CN111662435A - Insulating substrate and preparation method and application thereof - Google Patents
Insulating substrate and preparation method and application thereof Download PDFInfo
- Publication number
- CN111662435A CN111662435A CN202010549211.6A CN202010549211A CN111662435A CN 111662435 A CN111662435 A CN 111662435A CN 202010549211 A CN202010549211 A CN 202010549211A CN 111662435 A CN111662435 A CN 111662435A
- Authority
- CN
- China
- Prior art keywords
- parts
- insulating substrate
- resin composition
- copper
- resin
- 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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- 239000000758 substrate Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 40
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011342 resin composition Substances 0.000 claims abstract description 36
- -1 cyclic olefin compound Chemical class 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 238000004891 communication Methods 0.000 claims abstract description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012779 reinforcing material Substances 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 66
- 239000011889 copper foil Substances 0.000 claims description 38
- 229910052802 copper Inorganic materials 0.000 claims description 29
- 239000010949 copper Substances 0.000 claims description 29
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 25
- 238000007731 hot pressing Methods 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 17
- 239000003365 glass fiber Substances 0.000 claims description 17
- 239000005011 phenolic resin Substances 0.000 claims description 17
- 229920001568 phenolic resin Polymers 0.000 claims description 17
- 239000004744 fabric Substances 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000000853 adhesive Substances 0.000 claims description 13
- 230000001070 adhesive effect Effects 0.000 claims description 13
- 239000011324 bead Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 13
- 239000003822 epoxy resin Substances 0.000 claims description 12
- 229920000647 polyepoxide Polymers 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 239000011256 inorganic filler Substances 0.000 claims description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 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
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000003063 flame retardant Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229920001187 thermosetting polymer Polymers 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012766 organic filler Substances 0.000 claims description 6
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 6
- 229940116351 sebacate Drugs 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 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 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- 239000004611 light stabiliser Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- 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 claims description 2
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 2
- STEYNUVPFMIUOY-UHFFFAOYSA-N 4-Hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CC(O)CC(C)(C)N1CCO STEYNUVPFMIUOY-UHFFFAOYSA-N 0.000 claims description 2
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004643 cyanate ester Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229920006132 styrene block copolymer Polymers 0.000 claims description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 claims description 2
- 239000013638 trimer 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
- 239000012776 electronic material Substances 0.000 abstract description 6
- 238000005476 soldering Methods 0.000 abstract description 6
- 238000002485 combustion reaction Methods 0.000 abstract description 5
- 230000009477 glass transition Effects 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003292 glue Substances 0.000 description 26
- 238000001723 curing Methods 0.000 description 16
- 238000003825 pressing Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000010998 test method Methods 0.000 description 7
- 238000004026 adhesive bonding Methods 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 239000004005 microsphere Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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- B32B15/00—Layered products comprising a layer of metal
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- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- 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
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- 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
- B32B37/1018—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 using only vacuum
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- 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
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- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/02—Halogenated hydrocarbons
- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0076—Curing, vulcanising, cross-linking
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- B32B2255/00—Coating on the layer surface
- B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
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- 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
- 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
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- 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
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/308—Heat stability
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
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- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention provides an insulating substrate and a preparation method and application thereof, belonging to the field of electronic materials. The insulating substrate is obtained by coating or impregnating a reinforcing material with a resin composition; the resin composition is prepared from the following raw materials in parts by weight: 9000-10000 parts of cyclic olefin compound containing one or two double bonds and at least one bridged ring, and 0.1-10 parts of ruthenium carbene catalyst. The invention adopts the specific resin composition to prepare the insulating substrate and further prepare the copper-clad plate, thereby not only effectively improving the glass transition temperature, but also effectively reducing the dielectric loss when in use and meeting the application requirement of high-frequency high-speed communication. Meanwhile, the prepared insulating substrate or copper-clad plate has good combustion resistance and dip soldering resistance, is not easy to absorb water, and is more suitable for preparing electronic materials. In addition, the preparation method is safe and environment-friendly. The resin composition disclosed by the invention is used for preparing the insulating substrate, and the prepared copper-clad plate can be used for high-frequency high-speed communication, particularly 5G communication, and has a good application prospect.
Description
Technical Field
The invention belongs to the field of electronic materials, and particularly relates to an insulating substrate, and a preparation method and application thereof.
Background
In many electronic products, a Printed Circuit Board (PCB) functions as a circuit interconnection and is an indispensable main part of the electronic products. Printed Circuit Boards (PCBs) are manufactured by etching a copper clad laminate (CCL, copper clad laminate for short) to obtain the associated circuitry. A Copper Clad Laminate (CCL) is a plate-like material formed by impregnating a reinforcing material with a resin, coating one or both surfaces with a copper foil, and performing hot pressing, and is a basic material for manufacturing a Printed Circuit Board (PCB).
In the production of a conventional single-sided or double-sided PCB, a series of operations (e.g., etching, plating, drilling, etc.) are performed on the copper-clad plate to form the desired conductive pattern circuit. In the process of manufacturing the multilayer printed circuit board, the unprocessed copper clad laminate is used as a base material to be manufactured into a conductive pattern circuit, and is directly pressed and molded by a hot press after being alternately pressed with a Bonding sheet (Bonding sheet) to be bonded together, so that more than three pattern circuit layers, namely the multilayer printed circuit board, are manufactured.
The aforementioned copper clad laminate for single-sided or double-sided PCB, as well as the copper clad laminate for multi-layer PCB and prepreg (insulating substrate) are all PCB-based materials, and are all the fields of copper clad laminate manufacturing industry technology. In the current production of Printed Circuit Boards (PCB), a copper clad laminate prepared from a glass fiber epoxy prepreg is mainly applied, thermosetting resin such as epoxy resin is dissolved in organic solvent such as toluene or butanone to form glue solution, then glass fiber cloth is immersed in the glue solution, and the solvent in the glue solution is volatilized through high-temperature heating to obtain the prepreg; and (3) pressing the prepreg and the copper foil together through a high-pressure high-temperature pressing machine, and finally obtaining the copper-clad plate through the complicated and high-energy-consumption process steps.
According to the traditional technology for preparing the copper-clad plate by using the solvent method, a large amount of organic solvent is consumed, the environmental pollution is caused, meanwhile, a large amount of heat is consumed in the solvent volatilization and solidification processes, the process is high in energy consumption, the performances such as dip-soldering resistance, peeling strength and the like are influenced due to the fact that the solvent cannot be completely volatilized, meanwhile, the epoxy resin material has the defects of high dielectric constant, high dielectric loss and the like, and the requirements of the high-frequency high-speed copper-clad plate in the current 5G communication cannot be met.
Patent CN107417864 discloses a polyphenylene ether prepolymer and a preparation method thereof, and also discloses a composition containing the polyphenylene ether prepolymer, and the resin composition is made into a prepreg, a laminated board or a printed circuit board. The polyphenyl ether prepolymer is obtained by reacting dicyclopentadiene monomer and vinyl-containing polyphenyl ether under a ruthenium catalyst. The prepolymer preparation process is relatively complicated and also requires the use of large amounts of organic solvents.
Disclosure of Invention
The invention aims to provide an insulating substrate and a preparation method and application thereof.
The invention provides an insulating substrate, which is obtained by coating or impregnating a reinforcing material with a resin composition; the resin composition is prepared from the following raw materials in parts by weight: 9000-10000 parts of cyclic olefin compound containing one or two double bonds and at least one bridged ring, and 0.1-10 parts of ruthenium carbene catalyst.
Further, the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cycloolefin compounds containing one or two double bonds and at least one bridged ring, and 1-6 parts of ruthenium carbene catalysts;
preferably, the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cycloolefin compounds containing one or two double bonds and at least one bridged ring, and 1-4 parts of ruthenium carbene catalysts;
more preferably, the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cyclic olefin compound containing one or two double bonds and at least one bridged ring, and 2 parts of ruthenium carbene catalyst.
Further, the resin composition also comprises the following raw materials in parts by weight: 0-5000 parts of organic filler, 0-10000 parts of inorganic filler, 0-10000 parts of thermosetting resin and 0-10000 parts of organic solvent;
preferably, the resin composition further comprises the following raw materials in parts by weight: 0-1000 parts of organic filler, 0-5000 parts of inorganic filler, 0-10000 parts of thermosetting resin and 0-10000 parts of organic solvent.
Further, the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cycloolefin compounds containing one or two double bonds and at least one bridged ring, and 1-6 parts of ruthenium carbene catalysts;
preferably, the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cycloolefin compounds containing one or two double bonds and at least one bridged ring, and 1-4 parts of ruthenium carbene catalysts;
more preferably, the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cyclic olefin compound containing one or two double bonds and at least one bridged ring, and 2 parts of ruthenium carbene catalyst.
Further, the cyclic olefin compound containing one or two double bonds and at least one bridged ring is one or a composition of more of dicyclopentadiene, cyclopentadiene trimer, cyclopentadiene tetramer and norbornene; the content of the dicyclopentadiene is 30-100%.
Further, the cyclic olefin compound containing one or two double bonds and at least one bridged ring is dicyclopentadiene;
or the cyclic olefin compound containing one or two double bonds and at least one bridge ring consists of dicyclopentadiene and norbornene; the mass ratio of dicyclopentadiene to norbornene is (5-10): 1;
preferably, the dicyclopentadiene and norbornene contain one or two functional groups; the functional group is one or more of methyl, methoxy, hydroxyl, carboxylic acid group, acrylate group and methacrylate group;
more preferably, the mass ratio of dicyclopentadiene to norbornene is 9: 1.
further, the structural formula of the ruthenium carbene catalyst is shown as formula I:
wherein L is1、L2、L3Is an independently selected electron donating group;
n is 0 or 1;
m is 0, 1 or 2;
k is 0 or 1;
X1and X2Are independently selected anionic ligands;
R1and R2Are respectively selected from H atom, hydrocarbon group and heteroatom-containing hydrocarbon group;
preferably, the first and second electrodes are formed of a metal,
Further, the inorganic filler is one or more of calcium carbonate, aluminum oxide, magnesium oxide, boron nitride, silica glass beads and silica hollow glass beads;
the thermosetting resin is one or more of epoxy resin, benzoxazine resin, cyanate ester resin, bismaleimide resin, polyphenyl ether resin and phenolic resin;
the organic filler is one or more of polystyrene, styrene-butadiene-styrene block copolymer, acrylonitrile-butadiene-styrene plastic, styrene-ethylene-butylene-styrene block copolymer, light stabilizer, antioxidant and flame retardant;
the organic solvent is toluene, methyl ethyl ketone, butanone, tetrahydrofuran or N, N-dimethylformamide;
preferably, the first and second electrodes are formed of a metal,
the inorganic filler is composed of alumina and silica glass beads, and the mass ratio of the alumina to the silica glass beads is (1-5): (1-5);
the light stabilizer is one or more of bis (1,2,2,6, 6-pentamethylpiperidinol) sebacate, succinic acid, 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol polymer, 3- [3- (2-H-benzotriazole-2-yl) -4-hydroxy-5-tert-butylphenyl ] -propionic acid-polyethylene glycol ester, bis (1,2,2,6, 6-pentamethyl-4-piperidine) sebacate and 1-methyl-8- (1,2,2,6, 6-pentamethyl-4-piperidine) sebacate;
the antioxidant is antioxidant TPP, antioxidant 164, antioxidant 1010, antioxidant BHT or antioxidant CA;
one or more of ammonium polyphosphate, red phosphorus, decabromodiphenylethane, hexabromocyclododecane, DOPO, DiDOPO and triphenyl phosphate serving as a flame retardant;
the organic solvent is toluene or butanone;
more preferably still, the first and second liquid crystal compositions are,
the mass ratio of the alumina to the silica glass beads is 3: 2.
further, the preparation method of the resin composition comprises the following steps: mixing the raw materials in the weight ratio to obtain the product.
Further, the reinforcing material is glass fiber cloth.
The invention also provides a preparation method of the insulating substrate, which comprises the following steps: coating or impregnating the reinforcing material with the resin composition, and heating and curing to obtain the composite material;
preferably, the temperature for heating and curing is 60-180 ℃ and the time is 1-20 minutes;
more preferably, the temperature for heating and curing is 60-100 ℃ and the time is 5-10 minutes.
The invention also provides the application of the insulating substrate in preparing the copper foil-clad laminated board; preferably, the copper clad laminate is a high-frequency high-speed copper clad laminate; more preferably, the copper clad laminate is a 5G communication high-frequency high-speed copper clad laminate.
The invention also provides a copper clad laminate which is obtained by pasting copper foil on the insulating substrate.
The invention also provides a preparation method of the copper clad laminate, which comprises the following steps: pasting a copper foil on the surface of the insulating substrate, and carrying out hot pressing to obtain the copper foil; the copper foil is adhered to one side or two sides of the insulating substrate.
Further, when the copper foil is pasted, an adhesive is coated on the surface of the insulating substrate or the surface of the copper foil;
preferably, the adhesive is one or more of epoxy resin, phenolic resin, polyphenyl ether resin and cyanate resin;
and/or the hot pressing is vacuum hot pressing or composite roller hot pressing.
Further, the temperature of the vacuum hot pressing is 60-150 ℃, and the time is 5-10 minutes;
and/or, the hot pressing of the composite roller is carried out after the normal temperature composite roller is hot pressed, and then curing is carried out;
preferably, hot pressing is carried out on the compound roller after 3-5 minutes of normal temperature compound, and the hot pressing of the compound roller is carried out for 2-5 minutes at the temperature of 60-100 ℃; the curing is carried out at 150-200 ℃ for 2-5 minutes.
The invention also provides application of the copper clad laminate in preparation of a printed circuit board.
In the invention, the normal temperature refers to room temperature, 25 +/-5 ℃; the overnight refers to 12. + -. 2 h.
The invention adopts the cycloolefine compounds containing one or two double bonds and at least one bridged ring as raw materials (such as dicyclopentadiene and norbornene) to obtain large-size materials (such as large-size polydicyclopentadiene) under the action of a specific ruthenium carbene catalyst. The material has no implosion bubbles, the mechanical property and the thermal stability are also obviously improved, the dielectric property is very excellent, and the material is suitable for manufacturing a high-frequency high-speed communication base material-Copper Clad Laminate (CCL) board and has very good application prospect.
The invention adopts the specific resin composition to prepare the insulating substrate and further prepare the copper-clad plate, thereby not only effectively improving the glass transition temperature of the copper-clad plate or the insulating substrate, but also obviously reducing the dielectric constant and the dielectric loss of the copper-clad plate or the insulating substrate compared with the prior art, effectively reducing the dielectric loss when in use, meeting the requirements of the current high-frequency high-speed communication application, in particular meeting the requirements of the high-frequency high-speed copper-clad plate such as 5G communication and the like. Meanwhile, the insulating substrate or the copper-clad plate prepared from the resin composition has good combustion resistance and dip soldering resistance, is not easy to absorb water, is more suitable for the technical field of electronics, and is further used for preparing printed circuit boards or other electronic materials. In addition, the preparation method does not need to use an organic solvent, reduces the pollution to operators and atmosphere to the minimum degree, and is safer and more environment-friendly; the cyclic olefin compound can be cured within minutes or even seconds by ring-opening shift polymerization, and compared with epoxy resin which requires several hours of curing time, the efficiency is improved, and the energy consumption is reduced. The resin composition is used for preparing the insulating substrate, and the prepared high-frequency high-speed copper-clad plate can be used for communication, particularly 5G communication, can realize the processing of a novel copper-clad plate with low dielectric constant and low dielectric loss and no solvent, and has good application prospect.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Detailed Description
The raw materials and equipment used in the embodiment of the present invention are known products and obtained by purchasing commercially available products.
Embodiment 1 preparation of high-frequency high-speed copper-clad plate
The dicyclopentadiene and ruthenium carbene catalyst is prepared by mixing the following components in a weight ratio of 10000: 2, stirring and mixing uniformly to obtain glue solution, selecting 200 x 200mm E-glass fiber cloth, uniformly coating the glue solution, and curing at 60 ℃ for 10 minutes to obtain the insulating substrate. Coating phenolic resin adhesive on the surface of a copper foil with the thickness of 35 microns (or coating the phenolic resin adhesive on two sides of an insulating substrate), then respectively placing two copper foils on two sides of the insulating substrate, placing the two copper foils in a vacuum hot press and pressing the two copper foils to obtain a copper-clad plate, wherein the temperature and time of vacuum hot pressing are 150 ℃ for 10 minutes.
Embodiment 2 preparation of high-frequency high-speed flame-retardant copper-clad plate
Dicyclopentadiene, a ruthenium carbene catalyst, silica glass microspheres and decabromodiphenylethane are mixed according to the weight ratio of 10000: 2: 5000: 1000, stirring and mixing uniformly to obtain glue solution, selecting 200X 200mm E-glass fiber cloth, uniformly coating the glue solution, and curing at 60 ℃ for 10 minutes to obtain the insulating substrate. Coating phenolic resin adhesive on the surface of a copper foil with the thickness of 35 microns (or coating the phenolic resin adhesive on two sides of an insulating substrate), then respectively placing two copper foils on two sides of the insulating substrate, placing the two copper foils in a vacuum hot press and pressing the two copper foils to obtain a copper-clad plate, wherein the temperature and time of vacuum hot pressing are 150 ℃ for 10 minutes.
Embodiment 3 preparation of high-frequency high-speed copper-clad plate of the invention
Cycloolefin compound (composed of dicyclopentadiene and norbornene, the weight ratio of dicyclopentadiene to norbornene is 9: 1), ruthenium carbene catalyst, silica glass beads and hexabromocyclododecane according to the weight ratio of 10000: 2: 5000: 1000, stirring and mixing uniformly to obtain glue solution, selecting 200X 200mm E-glass fiber cloth, uniformly coating the glue solution, and curing at 60 ℃ for 10 minutes to obtain the insulating substrate. Coating phenolic resin adhesive on the surface of a copper foil with the thickness of 35 microns (or coating the phenolic resin adhesive on two sides of an insulating substrate), then respectively placing two copper foils on two sides of the insulating substrate, placing the two copper foils in a vacuum hot press and pressing the two copper foils to obtain a copper-clad plate, wherein the temperature and time of vacuum hot pressing are 150 ℃ for 10 minutes.
Embodiment 4 preparation of the high-temperature-resistant high-frequency high-speed copper-clad plate
Dicyclopentadiene, a ruthenium carbene catalyst, silica glass microspheres and hexabromocyclododecane are mixed according to the weight ratio of 10000: 4: 5000: 1000, stirring and mixing uniformly to obtain glue solution, selecting 200X 200mm E-glass fiber cloth, uniformly coating the glue solution, and curing at 60 ℃ for 10 minutes to obtain the insulating substrate. Coating phenolic resin adhesive on the surface of a copper foil with the thickness of 35 microns (or coating the phenolic resin adhesive on two sides of an insulating substrate), then respectively placing two copper foils on two sides of the insulating substrate, placing the two copper foils in a vacuum hot press and pressing the two copper foils to obtain a copper-clad plate, wherein the temperature and time of vacuum hot pressing are 150 ℃ for 10 minutes.
Embodiment 5 preparation of high-frequency high-speed flame-retardant epoxy resin copper-clad plate
Dicyclopentadiene, a ruthenium carbene catalyst, epoxy resin, silica glass microspheres and hexabromocyclododecane are mixed according to the weight ratio of 10000: 6: 10000: 5000: 1000, stirring and mixing uniformly to obtain glue solution, selecting 200X 200mm E-glass fiber cloth, uniformly coating the glue solution, and curing at 60 ℃ for 10 minutes to obtain the insulating substrate. And respectively placing copper foils with the thickness of 35 microns on two surfaces of an insulating substrate, placing the insulating substrate in a vacuum hot press, and pressing the insulating substrate in the vacuum hot press to obtain the copper-clad plate, wherein the temperature and time of the vacuum hot press are 150 ℃ for 10 minutes.
Embodiment 6 preparation of high-frequency high-speed flame-retardant phenolic resin copper-clad plate
Dicyclopentadiene, a ruthenium carbene catalyst, phenolic resin, an inorganic filler (the inorganic filler is composed of alumina powder and silica glass beads, the weight ratio of the alumina powder to the silica glass beads is 300: 200), hexabromocyclododecane according to the weight ratio of 10000: 4: 10000: 5000: 1000, stirring and mixing uniformly to obtain glue solution, selecting 200X 200mm E-glass fiber cloth, uniformly coating the glue solution, and curing at 60 ℃ for 10 minutes to obtain the insulating substrate. And respectively placing copper foils with the thickness of 35 microns on two surfaces of an insulating substrate, placing the insulating substrate in a vacuum hot press, and pressing the insulating substrate in the vacuum hot press to obtain the copper-clad plate, wherein the temperature and time of the vacuum hot press are 150 ℃ for 10 minutes.
Embodiment 7 continuous preparation of high-frequency high-speed copper-clad plate
Dicyclopentadiene, a ruthenium carbene catalyst, silica glass microspheres and decabromodiphenylethane are mixed according to the weight ratio of 10000: 2: 5000: 1000, stirring and mixing uniformly to obtain a glue solution, placing the glue solution in a gluing tank, passing E-glass fiber cloth through the gluing tank, uniformly coating the glue solution, coating a phenolic resin adhesive on the surface of a copper foil with the thickness of 35 microns, passing two copper foils and the glass fiber cloth coated with the glue solution through a normal-temperature compounding roller (3 minutes) and a hot-pressing compounding roller (60 ℃ for 2 minutes), respectively passing the two copper foils on two sides of the glass fiber cloth when passing through the compounding rollers, then passing through a curing furnace (150 ℃ for 2 minutes), and shearing to obtain the copper-clad plate.
Example 8 continuous preparation of phenolic resin high-frequency high-speed copper-clad plate without solvent
Dicyclopentadiene, a ruthenium carbene catalyst, phenolic resin, silica glass microspheres and hexabromocyclododecane are mixed according to the weight ratio of 10000: 4: 10000: 5000: 1000, stirring and mixing uniformly to obtain a glue solution, placing the glue solution in a gluing tank, passing E-glass fiber cloth through the gluing tank, uniformly coating the glue solution, passing 35-micron-thick copper foils and the glass fiber cloth coated with the glue solution through a normal-temperature compounding roller (3 minutes) and a hot-pressing compounding roller (60 ℃,2 minutes), passing through the compounding rollers, respectively placing two copper foils on two sides of the glass fiber cloth, then passing through a curing oven (180 ℃, 5 minutes), and shearing to obtain the copper-clad plate.
Embodiment 9 preparation of high-frequency high-speed copper-clad plate of the invention
Embodiment 10 preparation of high-frequency high-speed copper-clad plate of the invention
Embodiment 11 preparation of high-frequency high-speed copper-clad plate of the invention
Replacement of only the ruthenium carbene catalyst in example 1 byThe remaining conditions were unchanged.
Comparative example 1 preparation of solvent type epoxy resin copper-clad plate
Butanone, epoxy resin, a curing agent, silica glass microspheres and hexabromocyclododecane are mixed according to the weight ratio of 100: 100: 10: 50: 10 to obtain a glue solution, putting the glue solution into a gluing tank, passing the E-glass fiber cloth through the gluing tank, uniformly coating the glue solution, passing through a thermal curing furnace (155 ℃, 10 minutes), and removing an organic solvent butanone to obtain the insulating substrate. Then attaching 35 micron copper foil on the upper and lower sides of the insulating substrate, placing the insulating substrate in a vacuum hot press for pressing to obtain the copper-clad plate, wherein the temperature rise procedure is as follows: the temperature is raised from room temperature to 150 ℃ for 15 minutes and maintained for 30 minutes, then raised to 190 ℃ for 5 minutes and maintained for 2 hours, and finally cooled for 30 minutes. And obtaining the copper-clad plate.
The advantageous effects of the present invention are demonstrated by specific test examples below.
Test example 1 detection of Performance of copper clad laminate
The copper-clad plates prepared in examples 1 to 11 and comparative example 1 were compared in terms of performance, and the performance test items and results are shown in table 1. The test method used for each performance test item is as follows:
glass transition temperature test method: testing according to GB/T1033.1-2008;
the dielectric constant test method comprises the following steps: testing by ASTM D150(10 GHz);
the dielectric loss test method comprises the following steps: testing by ASTM D150(10 GHz);
the peel strength test method comprises the following steps: measured according to IPC-TM-650 method;
the combustion resistance test method comprises the following steps: measured according to the UL94 method;
dip-soldering resistance (delamination) test method: immersing a sample (100X 100mm substrate) kept in a pressure cooker at 121 ℃ and 105kPa for 2 hours in a solder bath heated to 260 ℃ for 20 seconds to visually observe whether or not delamination occurs and whether or not white spots or wrinkles occur;
water absorption test method: the measurement was carried out according to the IPC-TM-6502.6.2.1 method.
TABLE 1 comparison of the Properties of the copper-clad plates
As can be seen from the test results of table 1: compared with the copper-clad plate prepared by the prior art, the copper-clad plate prepared by the insulating substrate prepared by the special resin composition has higher glass transition temperature, smaller dielectric constant and less dielectric loss, and has excellent performances; the dielectric constant of the copper clad laminate is lower than 4, the dielectric loss is not higher than 0.009, even lower than 0.003, the loss in the circuit use process can be effectively reduced, the requirements of the current high-frequency high-speed communication application are met, and particularly the requirements of the copper clad laminate serving as the high-frequency high-speed copper clad laminate in the current 5G communication are met. Meanwhile, the copper-clad plate prepared by the insulating substrate has good combustion resistance and dip soldering resistance, is not easy to absorb water, is more suitable for the technical field of electronics, and is further used for preparing printed circuit boards or other electronic materials.
In conclusion, the insulating substrate is prepared by adopting the specific resin composition, the copper-clad plate is further prepared, the glass transition temperature of the copper-clad plate or the insulating substrate is effectively improved, the dielectric constant and the dielectric loss of the copper-clad plate or the insulating substrate are obviously reduced compared with the prior art, the dielectric loss can be effectively reduced when the copper-clad plate or the insulating substrate is used, the requirements of the current high-frequency high-speed communication application can be met, and particularly the requirements of the high-frequency high-speed copper-clad plate such as 5G communication and the like can be met. Meanwhile, the insulating substrate or the copper-clad plate prepared from the resin composition has good combustion resistance and dip soldering resistance, is not easy to absorb water, is more suitable for the technical field of electronics, and is further used for preparing printed circuit boards or other electronic materials. In addition, the preparation method does not need to use an organic solvent, reduces the pollution to operators and atmosphere to the minimum degree, and is safer and more environment-friendly; the cyclic olefin compound can be cured within minutes or even seconds by ring-opening shift polymerization, and compared with epoxy resin which requires several hours of curing time, the efficiency is improved, and the energy consumption is reduced. The resin composition is used for preparing the insulating substrate, and the prepared high-frequency high-speed copper-clad plate can be used for communication, particularly 5G communication, can realize the processing of a novel copper-clad plate with low dielectric constant and low dielectric loss and no solvent, and has good application prospect.
Claims (17)
1. An insulating substrate, characterized in that: it is obtained by coating or impregnating a reinforcing material with a resin composition; the resin composition is prepared from the following raw materials in parts by weight: 9000-10000 parts of cyclic olefin compound containing one or two double bonds and at least one bridged ring, and 0.1-10 parts of ruthenium carbene catalyst.
2. The insulating substrate according to claim 1, wherein: the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cycloolefin compounds containing one or two double bonds and at least one bridged ring, and 1-6 parts of ruthenium carbene catalysts;
preferably, the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cycloolefin compounds containing one or two double bonds and at least one bridged ring, and 1-4 parts of ruthenium carbene catalysts;
more preferably, the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cyclic olefin compound containing one or two double bonds and at least one bridged ring, and 2 parts of ruthenium carbene catalyst.
3. The insulating substrate according to claim 1 or 2, wherein: the resin composition also comprises the following raw materials in parts by weight: 0-5000 parts of organic filler, 0-10000 parts of inorganic filler, 0-10000 parts of thermosetting resin and 0-10000 parts of organic solvent;
preferably, the resin composition further comprises the following raw materials in parts by weight: 0-1000 parts of organic filler, 0-5000 parts of inorganic filler, 0-10000 parts of thermosetting resin and 0-10000 parts of organic solvent.
4. The insulating substrate according to claim 1 or 2, wherein: the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cycloolefin compounds containing one or two double bonds and at least one bridged ring, and 1-6 parts of ruthenium carbene catalysts;
preferably, the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cycloolefin compounds containing one or two double bonds and at least one bridged ring, and 1-4 parts of ruthenium carbene catalysts;
more preferably, the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cyclic olefin compound containing one or two double bonds and at least one bridged ring, and 2 parts of ruthenium carbene catalyst.
5. The insulating substrate according to claim 1 or 2, wherein: the cyclic olefin compound containing one or two double bonds and at least one bridged ring is one or a composition of more of dicyclopentadiene, cyclopentadiene trimer, cyclopentadiene tetramer and norbornene; the content of the dicyclopentadiene is 30-100%.
6. The insulating substrate according to claim 5, wherein: the cyclic olefin compound containing one or two double bonds and at least one bridged ring is dicyclopentadiene;
or the cyclic olefin compound containing one or two double bonds and at least one bridge ring consists of dicyclopentadiene and norbornene; the mass ratio of dicyclopentadiene to norbornene is (5-10): 1;
preferably, the dicyclopentadiene and norbornene contain one or two functional groups; the functional group is one or more of methyl, methoxy, hydroxyl, carboxylic acid group, acrylate group and methacrylate group;
more preferably, the mass ratio of dicyclopentadiene to norbornene is 9: 1.
7. the insulating substrate according to claim 1 or 2, wherein: the structural formula of the ruthenium carbene catalyst is shown as a formula I:
wherein L is1、L2、L3Is an independently selected electron donating group;
n is 0 or 1;
m is 0, 1 or 2;
k is 0 or 1;
X1and X2Are independently selected anionic ligands;
R1and R2Are respectively selected from H atom, hydrocarbon group and heteroatom-containing hydrocarbon group;
preferably, the first and second electrodes are formed of a metal,
8. The insulating substrate according to claim 1 or 2, wherein: the inorganic filler is one or more of calcium carbonate, aluminum oxide, magnesium oxide, boron nitride, silica glass beads and silica hollow glass beads;
the thermosetting resin is one or more of epoxy resin, benzoxazine resin, cyanate ester resin, bismaleimide resin, polyphenyl ether resin and phenolic resin;
the organic filler is one or more of polystyrene, styrene-butadiene-styrene block copolymer, acrylonitrile-butadiene-styrene plastic, styrene-ethylene-butylene-styrene block copolymer, light stabilizer, antioxidant and flame retardant;
the organic solvent is toluene, methyl ethyl ketone, butanone, tetrahydrofuran or N, N-dimethylformamide;
preferably, the first and second electrodes are formed of a metal,
the inorganic filler is composed of alumina and silica glass beads, and the mass ratio of the alumina to the silica glass beads is (1-5): (1-5);
the light stabilizer is one or more of bis (1,2,2,6, 6-pentamethylpiperidinol) sebacate, succinic acid, 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol polymer, 3- [3- (2-H-benzotriazole-2-yl) -4-hydroxy-5-tert-butylphenyl ] -propionic acid-polyethylene glycol ester, bis (1,2,2,6, 6-pentamethyl-4-piperidine) sebacate and 1-methyl-8- (1,2,2,6, 6-pentamethyl-4-piperidine) sebacate;
the antioxidant is antioxidant TPP, antioxidant 164, antioxidant 1010, antioxidant BHT or antioxidant CA;
one or more of ammonium polyphosphate, red phosphorus, decabromodiphenylethane, hexabromocyclododecane, DOPO, DiDOPO and triphenyl phosphate serving as a flame retardant;
the organic solvent is toluene or butanone;
more preferably still, the first and second liquid crystal compositions are,
the mass ratio of the alumina to the silica glass beads is 3: 2.
9. the insulating substrate according to claim 1 or 2, wherein: the preparation method of the resin composition comprises the following steps: mixing the raw materials in the weight ratio to obtain the product.
10. The insulating substrate according to claim 1 or 2, wherein: the reinforced material is glass fiber cloth.
11. A method for producing an insulating substrate according to any one of claims 1 to 10, characterized in that: it comprises the following steps: coating or impregnating the reinforcing material with the resin composition, and heating and curing to obtain the composite material;
preferably, the temperature for heating and curing is 60-180 ℃ and the time is 1-20 minutes;
more preferably, the temperature for heating and curing is 60-100 ℃ and the time is 5-10 minutes.
12. Use of the insulating substrate according to any one of claims 1 to 10 for the preparation of a copper clad laminate; preferably, the copper clad laminate is a high-frequency high-speed copper clad laminate; more preferably, the copper clad laminate is a 5G communication high-frequency high-speed copper clad laminate.
13. A copper clad laminate characterized in that: the insulating substrate is obtained by attaching a copper foil to the insulating substrate according to any one of claims 1 to 10.
14. A method for producing the copper clad laminate as claimed in claim 13, characterized in that: it comprises the following steps: pasting a copper foil on the surface of the insulating substrate, and carrying out hot pressing to obtain the copper foil; the copper foil is adhered to one side or two sides of the insulating substrate.
15. The method of claim 14, wherein: coating an adhesive on the surface of the insulating substrate or the surface of the copper foil during copper foil pasting;
preferably, the adhesive is one or more of epoxy resin, phenolic resin, polyphenyl ether resin and cyanate resin;
and/or the hot pressing is vacuum hot pressing or composite roller hot pressing.
16. The method of claim 15, wherein: the temperature of the vacuum hot pressing is 60-150 ℃, and the time is 5-10 minutes;
and/or, the hot pressing of the composite roller is carried out after the normal temperature composite roller is hot pressed, and then curing is carried out;
preferably, hot pressing is carried out on the compound roller after 3-5 minutes of normal temperature compound, and the hot pressing of the compound roller is carried out for 2-5 minutes at the temperature of 60-100 ℃; the curing is carried out at 150-200 ℃ for 2-5 minutes.
17. Use of the copper clad laminate of claim 13 in the preparation of a printed circuit board.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113061395A (en) * | 2021-03-24 | 2021-07-02 | 深圳市纽菲斯新材料科技有限公司 | Thermosetting resin composition and preparation method and application thereof |
CN115216101A (en) * | 2021-08-06 | 2022-10-21 | 派迈新材料(成都)有限责任公司 | Heat-insulating material and application thereof in preparation of heat-insulating pipeline and pipeline coating |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1675278A (en) * | 2002-06-28 | 2005-09-28 | 日本瑞翁株式会社 | Processes for producing thermoplastic resins, crosslinked resins and crosslinked resin composite materials |
JP2008143956A (en) * | 2006-12-06 | 2008-06-26 | Nippon Zeon Co Ltd | Polymerizable composition, crosslinkable resin and method for producing the same |
CN105229040A (en) * | 2013-02-27 | 2016-01-06 | 马特里亚公司 | Metal carbene olefin metathesis dual catalyst composition |
CN107417864A (en) * | 2016-05-24 | 2017-12-01 | 台光电子材料股份有限公司 | Polyphenylene oxide prepolymer, its preparation method, resin combination and its product |
CN112662129A (en) * | 2020-12-21 | 2021-04-16 | 上海中化科技有限公司 | Resin composition, composite material and preparation method thereof |
-
2020
- 2020-06-16 CN CN202010549211.6A patent/CN111662435A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1675278A (en) * | 2002-06-28 | 2005-09-28 | 日本瑞翁株式会社 | Processes for producing thermoplastic resins, crosslinked resins and crosslinked resin composite materials |
JP2008143956A (en) * | 2006-12-06 | 2008-06-26 | Nippon Zeon Co Ltd | Polymerizable composition, crosslinkable resin and method for producing the same |
CN105229040A (en) * | 2013-02-27 | 2016-01-06 | 马特里亚公司 | Metal carbene olefin metathesis dual catalyst composition |
CN107417864A (en) * | 2016-05-24 | 2017-12-01 | 台光电子材料股份有限公司 | Polyphenylene oxide prepolymer, its preparation method, resin combination and its product |
CN112662129A (en) * | 2020-12-21 | 2021-04-16 | 上海中化科技有限公司 | Resin composition, composite material and preparation method thereof |
Non-Patent Citations (3)
Title |
---|
WYREBEK P: "Looking for the Noncyclic(amino)(alkyl)carbene Ruthenium Catalyst for Ethenolysis of Ethyl Oleate: Selectivity Is on Target", 《ACS OMEGA》 * |
刘勇: "《材料物理性能》", 30 September 2015, 北京航空航天大学出版社 * |
刘瑞雪等: "《高分子材料》", 30 April 2018, 河南大学出版社 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113061395A (en) * | 2021-03-24 | 2021-07-02 | 深圳市纽菲斯新材料科技有限公司 | Thermosetting resin composition and preparation method and application thereof |
CN115216101A (en) * | 2021-08-06 | 2022-10-21 | 派迈新材料(成都)有限责任公司 | Heat-insulating material and application thereof in preparation of heat-insulating pipeline and pipeline coating |
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