CN112063025A - Thermosetting hydrocarbon polymer-based prepreg and copper-clad plate prepared from same - Google Patents
Thermosetting hydrocarbon polymer-based prepreg and copper-clad plate prepared from same Download PDFInfo
- Publication number
- CN112063025A CN112063025A CN202011039036.2A CN202011039036A CN112063025A CN 112063025 A CN112063025 A CN 112063025A CN 202011039036 A CN202011039036 A CN 202011039036A CN 112063025 A CN112063025 A CN 112063025A
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- Prior art keywords
- thermosetting
- matrix resin
- temperature
- initiator
- 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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- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 72
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 28
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 28
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 28
- 229920000642 polymer Polymers 0.000 title claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 63
- 239000011347 resin Substances 0.000 claims abstract description 63
- 238000002156 mixing Methods 0.000 claims abstract description 46
- 239000011159 matrix material Substances 0.000 claims abstract description 45
- 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 abstract description 27
- 239000003063 flame retardant Substances 0.000 claims abstract description 27
- 239000003999 initiator Substances 0.000 claims abstract description 26
- 238000010030 laminating Methods 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 14
- 238000001746 injection moulding Methods 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011889 copper foil Substances 0.000 claims abstract description 11
- 238000001125 extrusion Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- 238000003825 pressing Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229920000090 poly(aryl ether) Polymers 0.000 claims description 12
- 238000000354 decomposition reaction Methods 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 4
- 229910003080 TiO4 Inorganic materials 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
- 239000011324 bead Substances 0.000 claims description 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 229920002530 polyetherether ketone Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 229920001897 terpolymer Polymers 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000011256 inorganic filler Substances 0.000 claims description 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229910002929 BaSnO3 Inorganic materials 0.000 claims description 2
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 229910004774 CaSnO3 Inorganic materials 0.000 claims description 2
- 229910002971 CaTiO3 Inorganic materials 0.000 claims description 2
- 229910002976 CaZrO3 Inorganic materials 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229920000271 Kevlar® Polymers 0.000 claims description 2
- 229910003781 PbTiO3 Inorganic materials 0.000 claims description 2
- 229910020698 PbZrO3 Inorganic materials 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- 229910004410 SrSnO3 Inorganic materials 0.000 claims description 2
- 229910002370 SrTiO3 Inorganic materials 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 229910010252 TiO3 Inorganic materials 0.000 claims description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 2
- 229910007694 ZnSnO3 Inorganic materials 0.000 claims description 2
- 229910003122 ZnTiO3 Inorganic materials 0.000 claims description 2
- JCLOGSKIMBJQAA-UHFFFAOYSA-N [Mo].[Sn] Chemical compound [Mo].[Sn] JCLOGSKIMBJQAA-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- 229910021523 barium zirconate Inorganic materials 0.000 claims description 2
- YGBGWFLNLDFCQL-UHFFFAOYSA-N boron zinc Chemical compound [B].[Zn] YGBGWFLNLDFCQL-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052593 corundum Inorganic materials 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
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910001679 gibbsite Inorganic materials 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 238000007731 hot pressing Methods 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000004761 kevlar Substances 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000012766 organic filler Substances 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 claims description 2
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920006260 polyaryletherketone Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920006324 polyoxymethylene Polymers 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 150000003254 radicals Chemical group 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910014031 strontium zirconium oxide Inorganic materials 0.000 claims description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000004643 cyanate ester Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 238000004891 communication Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000005062 Polybutadiene Substances 0.000 description 14
- 229920002857 polybutadiene Polymers 0.000 description 14
- 238000001816 cooling Methods 0.000 description 7
- 239000002245 particle Substances 0.000 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 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 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 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 238000003889 chemical engineering Methods 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2447/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Derivatives of such polymers
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention belongs to the field of communication materials, and particularly relates to a thermosetting hydrocarbon polymer-based prepreg and a copper-clad plate prepared from the same. The invention prepares a thermosetting hydrocarbon polymer compound with well dispersed materials by carrying out fractional internal mixing and uniform mixing on thermosetting matrix resin, modified resin, filler, flame retardant and initiator. Subsequently, a prepreg with uniform thickness and smooth surface is produced by injection molding, extrusion or molding, and optionally post-heat treatment. Finally, the prepreg, the film and the copper foil are laminated together, and the thermosetting copper-clad plate is prepared by a laminating process, has excellent dielectric property, high mechanical strength and thermal conductivity, low thermal expansion coefficient and good uniformity of various properties, is suitable for manufacturing a multilayer copper-clad plate, and can meet various performance requirements of diversification and complication of functions of the copper-clad plate material in the current high-frequency and high-speed communication field.
Description
Technical Field
The invention belongs to the field of communication materials, and particularly relates to a thermosetting hydrocarbon polymer-based prepreg and a copper-clad plate prepared from the same.
Background
The copper-clad plate is widely applied to the fields of mobile phones, computers, wearable equipment, communication base stations, satellites, unmanned automobiles, unmanned aerial vehicles, intelligent robots and the like, and is one of key materials in electronic communication and information industries. The thermosetting hydrocarbon plate using polybutadiene as matrix resin is widely noticed due to the rapid development of 5G communication, and has the comprehensive advantages of low dielectric loss, low thermal expansion coefficient, high bending strength, high thermal-mechanical stability and the like. Traditional polybutadiene-based thermosetting hydrocarbon plates are usually prepared into prepregs through a sizing process.
In addition, as electronic products are rapidly developing towards miniaturization, light weight, thinning and multi-functionalization, the copper-clad plate used as a main carrier of electronic components has higher integration level and finer circuit arrangement. Therefore, the thermosetting hydrocarbon plate should have good heat conduction and dissipation functions, and also needs to have an extremely high dielectric constant and an extremely low dielectric loss in addition to the above excellent properties. In the traditional process, in order to improve the heat conductivity of the plate, high-filling-amount heat conduction materials or high-Dk inorganic fillers can be introduced into glue solution, and then the steps of gluing, baking, curing and the like are carried out. However, in the process, the solvent pollution is serious, and the addition amount of the heat conductive filler is limited, so that the thermal conductivity and Dk of the substrate are also limited, and the current requirements of high speed, high frequency, no damage and large-capacity information transmission are difficult to meet.
Patent publication No. CN 109943047A, publication No. 2019.06.28 discloses a thermosetting resin composition and a prepreg and a laminated board prepared by applying the thermosetting resin composition, wherein the thermosetting resin composition comprises the following components in parts by weight: (a) epoxy resin: 100 parts of (A); (b) unsaturated polyester active ester resin: 50-200 parts of a solvent; (c) vinyl-modified polyphenylene ether resin: 10-200 parts; (d) accelerator (b): 0.05-4 parts.
However, the prepreg disclosed in the patent has the problems of large dielectric loss and poor heat conduction effect.
Disclosure of Invention
The invention provides a thermosetting hydrocarbon polymer-based prepreg and a copper-clad plate prepared from the prepreg, wherein the prepreg and the copper-clad plate have the advantages of excellent dielectric property, high mechanical strength and thermal conductivity, low thermal expansion coefficient and good uniformity of various properties, are suitable for manufacturing a multilayer copper-clad plate, and can meet various performance requirements of diversification and complication of functions of the copper-clad plate material in the field of high-frequency and high-speed communication.
In order to solve the problems in the background technology, the invention prepares the thermosetting hydrocarbon polymer compound with well dispersed materials by carrying out fractional internal mixing and mixing on thermosetting matrix resin, modified resin, filler, flame retardant and initiator. Subsequently, a prepreg with uniform thickness and smooth surface is produced by injection molding, extrusion or molding, and optionally post-heat treatment. And finally, laminating the prepreg, the film and the copper foil together, and preparing the thermosetting copper-clad plate through a laminating process.
The invention provides a thermosetting hydrocarbon polymer-based prepreg, which is characterized in that thermosetting matrix resin, modified resin, a filler, a flame retardant and an initiator are subjected to step banburying and mixing uniformly to obtain a thermosetting hydrocarbon polymer compound, the compound is prepared into the prepreg with the thickness of 0.1-10 mm by an injection molding method, an extrusion method or a mould pressing method, the thermosetting matrix resin is high molecular weight polydiene and derivatives thereof with the melting point of 50-180 ℃, and is marked as matrix resin a, or is one or more of low molecular weight polydiene oligomers with the glass transition temperature of-90-10 ℃ and derivatives thereof, and is marked as matrix resin b.
The further preferable technical scheme is that the step-by-step banburying operation is sequentially divided into 2 steps:
s1, adding the thermosetting matrix resin, the modified resin, the filler and the flame retardant into an internal mixer for internal mixing for 1-300 min, wherein the rotating speed of a screw of the internal mixer is 15-900 rpm;
s2, adding an initiator to carry out banburying continuously, wherein the banburying time is 0.5-60 min, and the rotating speed of a screw of the banbury mixer is 15-300 rpm.
The further preferred technical scheme is as follows: in the step S1, when the thermosetting matrix resin is matrix resin a, the thermosetting matrix resin, the modified resin, the filler and the flame retardant are firstly mixed uniformly in a stirrer and then added into an internal mixer for internal mixing at the same time or step by step, wherein the internal mixing temperature is 0-150 ℃ higher than the melting point of the thermosetting matrix resin; and when the thermosetting matrix resin is matrix resin b, crushing and uniformly mixing the thermosetting matrix resin, the modified resin, the filler and the flame retardant in a low-temperature stirrer, then adding the mixture into an internal mixer for internal mixing, wherein the internal mixing temperature is controlled to be 0-40 ℃, the temperature of a cavity of the low-temperature stirrer is lower than the glass transition temperature of the polydiene, and preferably liquid nitrogen is used for cooling and insulating the cavity.
The further preferred technical scheme is as follows: in step S2, when the thermosetting matrix resin is the matrix resin a, the temperature of the internal mixer is controlled to be higher than the melting point of the thermosetting matrix resin by 0 to 30 ℃, and then the initiator is added into the internal mixer to continue internal mixing; when the thermosetting matrix resin is matrix resin b, controlling the temperature of an internal mixer to be 0-40 ℃, then adding an initiator to carry out internal mixing continuously, wherein the step-by-step internal mixing can be carried out by a continuous internal mixer or an intermittent internal mixer, and the intermittent internal mixer is preferred; the atmosphere in the sealed cavity can be air, and can also adopt protective gases such as nitrogen, argon and the like.
The further preferred technical scheme is as follows: the temperature of a machine barrel in the injection molding method and the extrusion method is 0-50 ℃ higher than the melting point of the thermosetting matrix resin, but is lower than the decomposition temperature when the half-life period of the initiator is 0.1h, and the retention time of the materials in the machine barrel is less than or equal to 3 min; in the injection molding method, the extrusion method or the mould pressing method, the temperature of a mould and the temperature of a hot-pressing roller are 0-100 ℃ higher than the decomposition temperature when the half-life period of the initiator is 3 hours; in the injection molding method and the mould pressing method, the heat preservation time of the materials in the mould is 30 s-3 h, a single set of mould can be adopted, multiple sets of moulds can be adopted for cyclic production, and the multiple sets of moulds are preferred.
The further preferred technical scheme is as follows: the prepreg is prepared by post-heat treatment after the compound is subjected to an injection molding method, an extrusion method or a mould pressing method, the post-heat treatment is divided into two stages, the baking temperature of the first stage is 10-30 ℃ higher than the decomposition temperature of the initiator when the half-life period is 1h, and the time is 10-120 min; the baking temperature of the second stage is 10-50 ℃ higher than the decomposition temperature of the initiator when the half-life period is 0.1h, the time is 1-60 min, and in the post-heat treatment process, the prepreg can be in a free state or can be placed in a mold.
The further preferred technical scheme is as follows: the thermosetting matrix resin accounts for 10-98 wt% of the prepreg, and the content of 1, 2-vinyl on a polydiene side chain is not less than 20%.
The further preferred technical scheme is as follows: the modified resin is one or a compound mixture of more of vinyl modified polyarylether, diene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, polydiene-styrene-divinylbenzene terpolymer and derivatives thereof,
wherein the number average molecular weight of the vinyl modified polyarylether is between 400 and 10000, a single macromolecular chain of the vinyl modified polyarylether at least contains 2 reactive vinyl functional groups and is positioned on the terminal group or the side group of the polyarylether main chain,
the number average molecular weight of the diene-maleic anhydride copolymer is 500-15000, the side group of the polydiene block at least contains a reactive carbon-carbon double bond,
the number average molecular weight of the styrene-maleic anhydride copolymer is 500-15000,
the number average molecular weight of the polydiene-styrene-divinylbenzene terpolymer is between 1000 and 15000, the lateral group of the polydiene block at least contains a reactive carbon-carbon double bond, the polystyrene block accounts for 10 to 60 percent, the divinylbenzene block accounts for 0.5 to 30 percent,
the amount of the modified resin accounts for 0-10 wt% of the prepreg.
The further preferred technical scheme is as follows: the filler is SiO2、Al2O3、TiO2、ZnO、MgO、Bi2O3、AlN、Si3N4、SiC、BN、Al(OH)3、Mg(OH)2、BaTiO3、SrTiO3、Mg2TiO4、Bi2(TiO3)3、PbTiO3、NiTiO3、CaTiO3、ZnTiO3、Zn2TiO4、BaSnO3、Bi2(SnO3)3、CaSnO3、PbSnO3、MgSnO3、SrSnO3、ZnSnO3、BaZrO3、CaZrO3、PbZrO3、MgZrO3、SrZrO3、ZnZrO3One or a mixture of more of inorganic fillers such as graphite, graphite oxide, graphite fluoride, talcum powder, mica powder, kaolin, clay, solid glass beads, hollow glass beads, glass fiber, basalt fiber, carbon fiber and the like, and one or a mixture of more of organic fillers such as polytetrafluoroethylene pre-sintered material, ultrahigh molecular weight polyethylene fiber, Kevlar fiber, polyimide, polyetherimide, polyether ether ketone, polyphenylene sulfide and the like, wherein the amount of the fillers is used0 to 90wt% of the sheet curing sheet,
the flame retardant is one or a mixture of more of aluminum-magnesium flame retardant, boron-zinc flame retardant, molybdenum-tin flame retardant, bromine flame retardant, antimony trioxide, phosphorus flame retardant, nitrogen flame retardant and derivatives thereof; the amount of the flame retardant is 0-50 wt% of the prepreg,
the initiator is a free radical initiator, the decomposition temperature of the initiator with the half-life period of 3h is higher than the melting point of the thermosetting matrix resin and is more than or equal to 50 ℃; the amount of the initiator accounts for 0.05-5 wt% of the thermosetting matrix resin.
A copper-clad plate manufactured by prepregs comprises the following specific steps: laminating a prepreg, a film and copper foil coated on the surface together, and preparing the thermosetting copper-clad plate by a laminating process; the number of the prepregs is more than or equal to 1, the number of the films is more than or equal to 0, and the number of the copper foils is 1 or 2; the laminating temperature of the laminating process is 150-270 ℃, the laminating pressure is 70-140 kg/cm2, and the laminating time is 0.5-12 h; the film is one or a mixture of more of fluorine-containing polymer, polyimide, polyolefin, polyaromatic hydrocarbon, polyamide, polyether ketone, polyether ether ketone, polyaryl ether, polyaryl sulfide, polyaryl ether sulfone, polyaryl ether ketone, polyaryl sulfide ketone, polyether sulfone ketone, polyaryl ether nitrile sulfone, polyaryl sulfide nitrile sulfone, polyphenyl quinoxaline, phenolic resin, epoxy resin, cyanate resin, polycarbonate, polyurethane and polyformaldehyde and derivatives thereof.
Detailed Description
The thermosetting hydrocarbon polymer-based prepreg and the copper-clad plate prepared by using the prepreg are further described in detail by embodiments. However, this example is provided only as an illustration and not as a limitation of the invention.
Example 1
80 parts of polybutadiene (Krevili Ricon 157), 20 parts of polybutadiene-maleic anhydride copolymer (Krevili Ricon130MA 8), 80 parts of BN (particle size 5 μm), and 25 parts of SiO2(Xinyi hongrun) and 35 parts of decabromodiphenylethane (Shandong sea king chemical) are added into a low-temperature stirrer for circulating cooling by liquid nitrogenCrushing, uniformly mixing, adding into a batch type internal mixer, setting the internal mixing temperature to be 30 ℃ and the screw rotating speed of the internal mixer to be 30rpm, internally mixing for 60min in air atmosphere, adding 2.5 parts of dibenzoyl peroxide (Qin Feng chemical engineering), keeping the cavity temperature and the screw rotating speed of the internal mixer unchanged, and continuously internally mixing for 20min in air atmosphere to obtain a thermosetting hydrocarbon polymer compound; then, transferring the compound into a flat cavity die with the thickness of 0.79mm, setting the temperature of the die to be increased to 90 ℃ according to the speed of 10 ℃/min, preserving heat for 2h, then continuing to be further increased to 120 ℃ according to the speed of 10 ℃/min, preserving heat for 0.5h, finally preserving heat for 15min at the temperature of 150 ℃, naturally reducing the temperature to room temperature, and stripping and taking out the compound from the die to obtain a prepreg; taking 1 prepreg and 2 loz copper foils and applying pressure of 110-130 kg/cm2And laminating for 4 hours at the temperature of 210 ℃ to obtain the thermosetting polybutadiene-based copper-clad plate with high thermal conductivity.
Example 2
Taking 60 parts of polybutadiene (Klivili Ricon 154), 20 parts of polybutadiene (Klivili Ricon 157), 20 parts of polybutadiene-maleic anhydride copolymer (Klivili Ricon130MA 20), 30 parts of BN (particle size of 5 microns), 40 parts of SiC (particle size of 6 microns), 20 parts of flame retardant magnesium hydroxide (American jaba MAGNIFIN H-5) and 30 parts of decabromodiphenylethane (Shandonghai Wang chemical) to be jointly added into a low-temperature stirrer for circulating cooling of liquid nitrogen, crushing and uniformly mixing, then adding into a batch internal mixer, setting the internal mixing temperature to be 35 ℃ and the screw rotating speed of the internal mixer to be 45rpm, adding 2.5 parts of dibenzoyl peroxide (Qinyi chemical engineering) after 80min internal mixing in air atmosphere, keeping the cavity temperature and the screw rotating speed of the internal mixer unchanged, and continuing internal mixing for 30min in air atmosphere to obtain a thermosetting hydrocarbon polymer compound; then, transferring the compound into a flat cavity die with the thickness of 1.56mm, setting the temperature of the die to be increased to 90 ℃ according to the speed of 5 ℃/min, preserving heat for 3h, then continuing to further increase the temperature to 120 ℃ according to the speed of 10 ℃/min, preserving heat for 1h, finally preserving heat for 30min at the temperature of 160 ℃, naturally reducing the temperature to room temperature, and stripping and taking out the compound from the die to obtain a prepreg; taking 1 prepreg and 2 loz copper foils and applying pressure of 120-140 kg/cm2And laminating for 4 hours at the temperature of 220 ℃ to obtain the thermosetting polybutadiene-based copper-clad plate with high thermal conductivity.
Example 3
Taking 40 parts of polybutadiene (Klivili Ricon 154), 45 parts of polybutadiene (Klivili Ricon 156), 15 parts of polybutadiene-maleic anhydride copolymer (Klivili Ricon130MA 10), 100 parts of BN (particle size of 5 microns), 20 parts of polytetrafluoroethylene pre-sintered material (Shandong Yue) and 28 parts of decabromodiphenylethane (Shandong sea King chemical) to be jointly added into a low-temperature stirrer for circulating cooling of liquid nitrogen for crushing and mixing uniformly, then adding into a batch internal mixer, setting the internal mixing temperature to be 35 ℃ and the screw rotating speed of the internal mixer to be 30rpm, carrying out internal mixing for 100min in air atmosphere, then adding 1.0 part of dibenzoyl peroxide (Qinfeng chemical engineering) and 1 part of dicumyl peroxide, keeping the cavity temperature and the screw rotating speed of the internal mixer unchanged, and carrying out internal mixing for 30min in air atmosphere continuously to obtain a thermosetting hydrocarbon polymer compound; the composite was then transferred to a 1.56mm thick flat cavity mold, and the mold temperature was set to 90 deg.C/minoC, keeping the temperature for 1h, and then continuing to follow the formula 5oC/min, further heating to 120 ℃, preserving heat for 1.5h, finally preserving heat for 1h at 170 ℃, naturally cooling to room temperature, stripping the prepreg from the mold, and taking out to obtain a prepreg; taking 1 prepreg and 2 loz copper foils and applying pressure of 120-140 kg/cm2And laminating for 5 hours at the temperature of 240 ℃ to obtain the thermosetting polybutadiene-based copper-clad plate with high thermal conductivity.
Example 4
Uniformly mixing 15 parts of JSR RB810 type polybutadiene and 85 parts of titanium dioxide by a stirrer, adding the mixture into a batch internal mixer for internal mixing, setting the internal mixing temperature to be 150 ℃ and the screw rotating speed of the internal mixer to be 60rpm, and reducing the temperature of the internal mixer to 100 after internal mixing for 60min in air atmosphereoC, adding 0.25 part of dicumyl peroxide, reducing the screw rotating speed of an internal mixer to 30rpm, and continuously carrying out internal mixing for 30min in an air atmosphere to obtain a thermosetting hydrocarbon polymer compound; the composite was then transferred to a 0.79mm thick flat cavity mold, and the mold temperature was setHeating to 130 deg.C at a rate of 10 deg.C/min and maintaining for 0.5h, further heating to 150 deg.C at a rate of 10 deg.C/min and maintaining for 1h, and finally 170 deg.CoC, after preserving heat for 1.5 hours, naturally cooling to room temperature, and stripping and taking out the prepreg from the mold to obtain a prepreg; taking 1 prepreg and 2 loz copper foils and applying pressure of 130-140 kg/cm2At a temperature of 240 deg.CoAnd C, laminating for 5.5 hours to obtain the thermosetting polybutadiene-based copper-clad plate with high Dk.
Example 5
Uniformly mixing 20 parts of JSR RB810 type polybutadiene, 30 parts of titanium dioxide, 45 parts of BN (particle size of 5 microns) and 5 parts of decabromodiphenylethane (Shandong Haiwang chemical) by a stirrer, adding the mixture into a batch internal mixer for internal mixing, setting the internal mixing temperature to 145 ℃ and the screw rotation speed of the internal mixer to 45rpm, carrying out internal mixing for 100min in an air atmosphere, reducing the temperature of the internal mixer to 95 ℃, adding 0.5 part of dicumyl peroxide, reducing the screw rotation speed of the internal mixer to 30rpm, and carrying out internal mixing for 30min in the air atmosphere continuously to obtain a thermosetting hydrocarbon polymer compound; the composite was then transferred to a 0.79mm thick flat cavity mold, and the mold temperature was set to rise to 130 deg.C/minoC, keeping the temperature for 0.5h, then continuously heating to 150 ℃ according to the speed of 10 ℃/min, keeping the temperature for 1h, and finally 170 DEG CoC, after preserving heat for 1.5 hours, naturally cooling to room temperature, and stripping and taking out the prepreg from the mold to obtain a prepreg; taking 1 prepreg and 2 loz copper foils and applying pressure of 130-140 kg/cm2And laminating for 6 hours at the temperature of 240 ℃ to obtain the thermosetting polybutadiene-based copper-clad plate with high thermal conductivity and high Dk.
In conclusion, the invention has good industrial production basis and wide application prospect.
The above examples are not intended to limit the amount of the composition of the present invention. Any minor modifications, equivalent changes and modifications to the above embodiments in accordance with the technical spirit or composition ingredients or contents of the present invention are within the scope of the technical solution of the present invention.
Claims (10)
1. A thermosetting hydrocarbon polymer-based prepreg characterized in that: the thermosetting type hydrocarbon polymer composite is prepared by uniformly mixing thermosetting type matrix resin, modified resin, filler, flame retardant and initiator in a banburying manner step by step, a prepreg with the thickness of 0.1-10 mm is prepared from the composite by an injection molding method, an extrusion method or a mould pressing method, the thermosetting type matrix resin is high molecular weight polydiene and derivatives thereof with the melting point of 50-180 ℃, and is marked as matrix resin a, or is marked as matrix resin b, and the mixture of one or more of low molecular weight polydiene oligomers and derivatives thereof with the glass transition temperature of-90-10 ℃.
2. The thermosetting hydrocarbon polymer-based prepreg according to claim 1, characterized in that the stepwise internal mixing operation comprises 2 steps in sequence:
s1, adding the thermosetting matrix resin, the modified resin, the filler and the flame retardant into an internal mixer for internal mixing for 1-300 min, wherein the rotating speed of a screw of the internal mixer is 15-900 rpm;
s2, adding an initiator to carry out banburying continuously, wherein the banburying time is 0.5-60 min, and the rotating speed of a screw of the banbury mixer is 15-300 rpm.
3. The thermosetting hydrocarbon polymer-based prepreg according to claim 2, characterized in that: in the step S1, when the thermosetting matrix resin is matrix resin a, the thermosetting matrix resin, the modified resin, the filler and the flame retardant are firstly mixed uniformly in a stirrer and then added into an internal mixer for internal mixing at the same time or step by step, wherein the internal mixing temperature is 0-150 ℃ higher than the melting point of the thermosetting matrix resin; and when the thermosetting matrix resin is matrix resin b, crushing and uniformly mixing the thermosetting matrix resin, the modified resin, the filler and the flame retardant in a low-temperature stirrer, then adding the mixture into an internal mixer for internal mixing, wherein the internal mixing temperature is controlled to be 0-40 ℃, and the cavity temperature of the low-temperature stirrer is lower than the glass transition temperature of the polydiene.
4. The thermosetting hydrocarbon polymer-based prepreg according to claim 2, characterized in that: in step S2, when the thermosetting matrix resin is the matrix resin a, the temperature of the internal mixer is controlled to be higher than the melting point of the thermosetting matrix resin by 0 to 30 ℃, and then the initiator is added into the internal mixer to continue internal mixing; and when the thermosetting matrix resin is the matrix resin b, controlling the temperature of the internal mixer to be 0-40 ℃, and then adding an initiator to carry out internal mixing continuously.
5. The thermosetting hydrocarbon polymer-based prepreg according to claim 1, characterized in that: the temperature of a machine barrel in the injection molding method and the extrusion method is 0-50 ℃ higher than the melting point of the thermosetting matrix resin, but is lower than the decomposition temperature when the half-life period of the initiator is 0.1h, and the retention time of the materials in the machine barrel is less than or equal to 3 min; in the injection molding method, the extrusion method or the mould pressing method, the temperature of a mould and the temperature of a hot-pressing roller are 0-100 ℃ higher than the decomposition temperature when the half-life period of the initiator is 3 hours; in the injection molding method and the mould pressing method, the heat preservation time of the material in the mould is 30 s-3 h.
6. The thermosetting hydrocarbon polymer-based prepreg according to claim 1, characterized in that: the prepreg is prepared by post-heat treatment after the compound is subjected to an injection molding method, an extrusion method or a mould pressing method, the post-heat treatment is divided into two stages, the baking temperature of the first stage is 10-30 ℃ higher than the decomposition temperature of the initiator when the half-life period is 1h, and the time is 10-120 min; the baking temperature of the second stage is 10-50 ℃ higher than the decomposition temperature of the initiator when the half-life period is 0.1h, and the time is 1-60 min.
7. The thermosetting hydrocarbon polymer-based prepreg according to claim 1, characterized in that: the thermosetting matrix resin accounts for 10-98 wt% of the prepreg, and the content of 1, 2-vinyl on a polydiene side chain is not less than 20%.
8. The thermosetting hydrocarbon polymer-based prepreg according to claim 1, characterized in that: the modified resin is one or a compound mixture of more of vinyl modified polyarylether, diene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, polydiene-styrene-divinylbenzene terpolymer and derivatives thereof,
wherein the number average molecular weight of the vinyl modified polyarylether is between 400 and 10000, a single macromolecular chain of the vinyl modified polyarylether at least contains 2 reactive vinyl functional groups and is positioned on the terminal group or the side group of the polyarylether main chain,
the number average molecular weight of the diene-maleic anhydride copolymer is 500-15000, the side group of the polydiene block at least contains a reactive carbon-carbon double bond,
the number average molecular weight of the styrene-maleic anhydride copolymer is 500-15000,
the number average molecular weight of the polydiene-styrene-divinylbenzene terpolymer is between 1000 and 15000, the lateral group of the polydiene block at least contains a reactive carbon-carbon double bond, the polystyrene block accounts for 10 to 60 percent, the divinylbenzene block accounts for 0.5 to 30 percent,
the amount of the modified resin accounts for 0-10 wt% of the prepreg.
9. The thermosetting hydrocarbon polymer-based prepreg according to claim 1, characterized in that: the filler is SiO2、Al2O3、TiO2、ZnO、MgO、Bi2O3、AlN、Si3N4、SiC、BN、Al(OH)3、Mg(OH)2、BaTiO3、SrTiO3、Mg2TiO4、Bi2(TiO3)3、PbTiO3、NiTiO3、CaTiO3、ZnTiO3、Zn2TiO4、BaSnO3、Bi2(SnO3)3、CaSnO3、PbSnO3、MgSnO3、SrSnO3、ZnSnO3、BaZrO3、CaZrO3、PbZrO3、MgZrO3、SrZrO3、ZnZrO3One or a mixture of more of inorganic fillers such as graphite, graphite oxide, graphite fluoride, talcum powder, mica powder, kaolin, clay, solid glass beads, hollow glass beads, glass fiber, basalt fiber, carbon fiber and the like, and one or a mixture of more of organic fillers such as polytetrafluoroethylene pre-sintered material, ultrahigh molecular weight polyethylene fiber, Kevlar fiber, polyimide, polyetherimide, polyether ether ketone, polyphenylene sulfide and the like, wherein the amount of the fillers accounts for 0-90 wt% of the sheet curing sheet,
the flame retardant is one or a mixture of more of aluminum-magnesium flame retardant, boron-zinc flame retardant, molybdenum-tin flame retardant, bromine flame retardant, antimony trioxide, phosphorus flame retardant, nitrogen flame retardant and derivatives thereof; the amount of the flame retardant is 0-50 wt% of the prepreg,
the initiator is a free radical initiator, the decomposition temperature of the initiator with the half-life period of 3h is higher than the melting point of the thermosetting matrix resin and is more than or equal to 50 ℃; the amount of the initiator accounts for 0.05-5 wt% of the thermosetting matrix resin.
10. The copper-clad plate manufactured by adopting the prepreg according to claim 1 is characterized by comprising the following specific steps: laminating a prepreg, a film and copper foil coated on the surface together, and preparing the thermosetting copper-clad plate by a laminating process; the number of the prepregs is more than or equal to 1, the number of the films is more than or equal to 0, and the number of the copper foils is 1 or 2; the laminating temperature of the laminating process is 150-270 ℃, and the laminating pressure is 70-140 kg/cm2The laminating time is 0.5-12 h; the film is fluorine-containing polymer, polyimide, polyolefin, polyaromatic hydrocarbon, polyamide, polyether ketone, polyether ether ketone, polyaryl ether, polyaryl sulfide, polyaryl ether sulfone, polyaryl ether ketone, polyaryl sulfide ketone, polyether sulfone ketone, polyaryl ether nitrile sulfone, polyaryl sulfide nitrile sulfone, polyphenyl quinoxaline, phenolic resin, epoxy resin, poly (arylene ether ketone), poly (arylene sulfide sulfone), poly (phenylene quinoxaline), poly (phenylene sulfide sulfone), poly (phenol-formaldehyde) resin,cyanate ester resin, polycarbonate, polyurethane and polyformaldehyde and their derivatives.
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| CN113896428A (en) * | 2021-09-14 | 2022-01-07 | 徐州工程学院 | Nematic liquid crystal orientation Kevlar/silicon carbide composite heat-conducting film, preparation method thereof and application thereof in electronic device heat management |
| CN114574122A (en) * | 2022-03-30 | 2022-06-03 | 常州中英科技股份有限公司 | High-thermal-conductivity bonding sheet for fluorine-containing resin-based high-frequency copper-clad plate |
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| CN113150457A (en) * | 2021-01-05 | 2021-07-23 | 广州辰东新材料有限公司 | Modified hydrocarbon-modified syndiotactic polystyrene composite material, copper-clad plate containing modified hydrocarbon-modified syndiotactic polystyrene composite material and preparation method of copper-clad plate |
| CN113896428A (en) * | 2021-09-14 | 2022-01-07 | 徐州工程学院 | Nematic liquid crystal orientation Kevlar/silicon carbide composite heat-conducting film, preparation method thereof and application thereof in electronic device heat management |
| CN113896428B (en) * | 2021-09-14 | 2022-12-16 | 徐州工程学院 | Nematic liquid crystal orientation Kevlar/silicon carbide composite heat-conducting film, preparation method thereof and application thereof in electronic device heat management |
| CN114574122A (en) * | 2022-03-30 | 2022-06-03 | 常州中英科技股份有限公司 | High-thermal-conductivity bonding sheet for fluorine-containing resin-based high-frequency copper-clad plate |
| CN114574122B (en) * | 2022-03-30 | 2023-09-08 | 常州中英科技股份有限公司 | Fluorine-containing resin-based high-frequency copper-clad plate high-heat-conductivity bonding sheet |
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Application publication date: 20201211 |