US20030211303A1 - Microwave-transparent thermosetting resin compositions, electrical laminates obtained therefrom, and process of producing these - Google Patents
Microwave-transparent thermosetting resin compositions, electrical laminates obtained therefrom, and process of producing these Download PDFInfo
- Publication number
- US20030211303A1 US20030211303A1 US10/458,360 US45836003A US2003211303A1 US 20030211303 A1 US20030211303 A1 US 20030211303A1 US 45836003 A US45836003 A US 45836003A US 2003211303 A1 US2003211303 A1 US 2003211303A1
- Authority
- US
- United States
- Prior art keywords
- composition
- laminate
- group
- styrene
- conductive layer
- 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.)
- Abandoned
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 25
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims description 35
- 230000008569 process Effects 0.000 title description 6
- 239000000203 mixture Substances 0.000 claims abstract description 81
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 35
- 150000003673 urethanes Chemical class 0.000 claims abstract description 9
- 150000003440 styrenes Chemical class 0.000 claims abstract 3
- 239000000178 monomer Substances 0.000 claims description 27
- 239000000758 substrate Substances 0.000 claims description 25
- 239000011521 glass Substances 0.000 claims description 22
- -1 isocyanurate compound Chemical group 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 230000002787 reinforcement Effects 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000012545 processing Methods 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 10
- 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 8
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 238000005253 cladding Methods 0.000 claims description 8
- 239000003063 flame retardant Substances 0.000 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 8
- 239000012766 organic filler Substances 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 229910001369 Brass Inorganic materials 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000010951 brass Substances 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical group BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000011152 fibreglass Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000000518 rheometry Methods 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 239000002318 adhesion promoter Substances 0.000 claims description 4
- 239000003086 colorant Substances 0.000 claims description 4
- 238000010894 electron beam technology Methods 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 230000007246 mechanism Effects 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 229920005594 polymer fiber Polymers 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 claims description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims 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 claims description 3
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000007850 fluorescent dye Substances 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- JVPKLOPETWVKQD-UHFFFAOYSA-N 1,2,2-tribromoethenylbenzene Chemical compound BrC(Br)=C(Br)C1=CC=CC=C1 JVPKLOPETWVKQD-UHFFFAOYSA-N 0.000 claims description 2
- LIKGLDATLCWEDN-UHFFFAOYSA-N 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3-oxazolidine Chemical compound CCN1CCOC1(C)CCC(C)C LIKGLDATLCWEDN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- MRIZMKJLUDDMHF-UHFFFAOYSA-N cumene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1 MRIZMKJLUDDMHF-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 125000003700 epoxy group Chemical group 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
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims 3
- 150000003254 radicals Chemical class 0.000 claims 3
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical compound CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 claims 2
- GRKDVZMVHOLESV-UHFFFAOYSA-N (2,3,4,5,6-pentabromophenyl)methyl prop-2-enoate Chemical compound BrC1=C(Br)C(Br)=C(COC(=O)C=C)C(Br)=C1Br GRKDVZMVHOLESV-UHFFFAOYSA-N 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 abstract description 6
- 238000003475 lamination Methods 0.000 description 10
- 229920001567 vinyl ester resin Polymers 0.000 description 10
- 239000011889 copper foil Substances 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
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- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
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- 239000000615 nonconductor Substances 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004634 thermosetting polymer Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
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- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
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- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
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- OHGJVAFVIMGJTE-UHFFFAOYSA-L copper;naphthalene-2-carboxylate Chemical compound [Cu+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 OHGJVAFVIMGJTE-UHFFFAOYSA-L 0.000 description 1
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
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- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
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- 230000000704 physical effect Effects 0.000 description 1
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- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
- Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31598—Next to silicon-containing [silicone, cement, etc.] layer
- Y10T428/31601—Quartz or glass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31605—Next to free metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31645—Next to addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/31678—Of metal
- Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
- Y10T428/31696—Including polyene monomers [e.g., butadiene, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
- Y10T428/31699—Ester, halide or nitrile of addition polymer
Definitions
- the present invention relates to thermosetting resin compositions with excellent electrical properties; electrical laminates made therefrom; and methods of producing these.
- Electrical laminates such as circuit boards are produced by laminating sheets of electrical conducting material onto a base substrate of insulation material. The performance of the finished circuit board is effected by the electrical characteristics of the base substrate material.
- thermoset resin systems with acceptable electrical performance at high frequencies (>350 MHZ) are restricted in their applications due to high cost.
- the lower cost alternatives that are available do not perform satisfactorily at high frequencies due to unacceptable electrical properties, such as high dielectric constant (D k ), high dissipation factor (D f ), high variability of D k and D f with frequency, and consistency of D k and D f from lot to lot of production material.
- D k dielectric constant
- D f high dissipation factor
- D f high variability of D k and D f with frequency
- consistency of D k and D f from lot to lot of production material.
- Thermoplastic polymers such as polytetrafluoroethylene (PTFE) which have exceptional electrical performance at high frequencies are commercially available.
- PTFE polytetrafluoroethylene
- Thermoplastic polymers such as polytetrafluoroethylene (PTFE) which have exceptional electrical performance at high frequencies are commercially available.
- the primary drawbacks associated with these materials are very high raw material costs and special processing considerations that add substantial cost to the final product. Because of the physical properties, very high laminating temperatures and pressures are also required to fabricate an electrical laminate from PTFE. Furthermore, due to the inability to “wet” PTFE, costly and hazardous chemicals are required to modify its surface during fabrication of the circuit.
- thermoset material would have much greater mechanical properties over a much broader temperature range. Additionally, since thermoset materials have better mechanical properties, this would allow the circuit board fabricator to use conventional cost effective processes.
- thermosetting resin compositions and electrical laminates made therefrom, of low to moderate cost with acceptable electrical properties at frequencies up to at least 20 GHz.
- Such compositions would have great utility as circuit board substrates and the laminates made from these thermosetting resins can be utilized in many applications such as in the rapidly growing wireless communication market, in high speed computers, in high definition televisions, and in various other electrical and related applications.
- An object of the present invention is to provide a thermosetting resin composition which can be made flame retardant and which can be utilized in existing cost effective technologies to manufacture electrical laminates therefrom. Additionally, the present invention resin compositions can have utility as, for example, electrical insulators, encapsulants, insulating adhesives and in various other electrical and related applications generally know to those skilled in this art.
- thermosetting resin composition comprising (a) a terminally unsaturated urethane resin selected from the group of 1):
- R 1 is H or CH 3
- R 2 is an organic residue from a monohydric alcohol and R 3 is an organic residue from a diisocyanate
- R 1 is H or CH 3
- R 2 is an organic residue from a monohydric alcohol
- R 3 is an organic residue from a diisocyanate
- R 4 is an isocyanurate compound of the following structure
- the ratio of (a) to the sum of (b)1) and (b)2) is less than 0.15, and the ratio of (b)1) to (b)2) is less than 1.2.
- composition resins may also further contain monomers which would, for example, aid in the adhesion of a metal foil to the laminate; increase crosslink density and thermal performance; etc. Catalysts which, for example, induce free-radical cure may also be added.
- Other components may include moisture scavengers, compounds which increase or reduce the dielectric constant, and/or reduce the dissipation factor, polyethylene fillers, other fillers, organic or inorganic, which modify rheology, surface agents, viscosity and performance modifiers, wetting agents, air release agents, defoaming agents, flame retardant synergists, adhesion promoters, and other additional monomers and conventional additives known in the art.
- composition resins of the present invention which have excellent electrical properties and which may be flame retardant or heat resistant. Accordingly, the present invention further provides electrical laminates from about 0.003 inches to about 0.120 inches thick which may or may not be clad with an electrical conducting material on one or both sides.
- the electrical laminates of the present invention are produced by (a) continuous lamination or (b) a batch process:
- compositions of the present invention are uniquely suitable to the continuous lamination methods of Barrel et al. (U.S. Pat. No. 4,587,161 and No. 4,803,022).
- the combination of materials in the outlined ratios provides lower viscosities then previous compositions, (U.S. Pat. No. 4,420,509 and No. 4,446,173).
- Lower viscosities provide more rapid impregnation of reinforcements to allow higher line-speeds and consequently higher machine output.
- the desired composition is formulated with a free-radical source, (i.e., peroxide, azo-compound, etc.) to initiate cure.
- the material is postcured in a batch convection oven to further lower the dissipation factor of the laminate. Therefore, we have found the combination of continuous lamination with additional batch cure provides unexpected improvements in electrical performance. While the continuous lamination temperatures and times are known in the art, we have found the optimum secondary batch oven cure profile to be 350° F. for 1 hour dwell, (or range from 150° F. for 3 hours to 450° F. for 30 minutes).
- a layer of carrier film such as polyethylene terephthalate of 1.42 mills thick, was placed on a 1 ⁇ 4th inch thick glass plate of 1.25 by 1.25 ft. The dimensions of the film were large enough to protrude around the edges of the glass plate.
- Wire-wound rods are well known throughout the coatings industry.
- thermosetting resin composition may also further contain the above mentioned added components and may be cured by electron beam processing, radiation, heat with or without pressure, ultra violet light processing, and other conventional curing methods in conjunction with the appropriate initiators.
- the electrical laminates may further comprise an electrical conductive cladding on at least one side.
- FIG. 1 is an enlarged cross-sectional view of a part of an electrical laminate which comprises an electrically conductive metal layer 1 and a cross linked thin-wall body of the invented composition 2 .
- FIG. 2 is an enlarged cross-sectional view of an electrical laminate which exemplifies a double-sided metal clad electrical laminate, further provided with two metal conductive layers 1 , and an electrically insulating thin-wall body of the invented composition 2 .
- FIG. 3 is an enlarged cross-sectional view of an electrical laminate which exemplifies a multilayered electrical laminate, of the structure of a combination of single-sided and double sided metal clad electrical laminates as illustrated in FIG. 1 and FIG. 2.
- FIG. 4 is an enlarged cross-sectional view of an electrical laminate which comprises an electrically conductive layer 1 , a crosslinked thin-wall body of the invented composition 2 , and an uniformly dispersed inorganic or organic filler 3 .
- FIG. 5 is an enlarged cross-sectional view of an electrical laminate which comprises an electrically conductive metal layer 1 , a crosslinked thin-wall body of invented composition 2 , and nonwoven glass fibers 4 .
- FIG. 6 is an enlarged cross-sectional view of an electrical laminate which comprises an electrically conductive metal layer 1 , a crosslinked thin-wall body of invented composition 2 , and woven glass cloth 5 .
- FIG. 7 is an enlarged cross-section view of part of an example of a double-sided metal clad electrical laminate of FIG. 6 further provided with an electrically conductive metal layer 1 on the other surface.
- FIG. 8 is an enlarged cross-sectional view of an electrical laminate which comprises an electrically conductive metal layer 1 , a crosslinked thin-wall body of the invented composition 2 , and an aramid non-woven sheet 6 .
- the present invention comprises resin compositions of moderate cost with excellent electrical properties up to at least 20 GHz which may be flame retardant and heat resistant.
- the present compositions have utility as electrical insulators, electrical laminates, electrically insulating encapsulants, electrically insulating adhesives and other electrical and related applications.
- One component of these compositions is a terminally unsaturated urethane resin, known in the industry as a urethane vinyl ester:
- R 1 is H or CH 3
- R 2 is an organic residue from a monohydric alcohol
- R is an organic residue from a diisocyanate.
- This resin is manufactured by reacting a diisocyanate with two molar equivalents of monohydric alcohol containing a vinylidene group in the presence of a polar solvent (typically styrene) which also acts as a reactive monomer for crosslinking. Examples of this art are well known throughout the industry.
- the diisocyanate utilized may be aromatic or aliphatic, monomeric or polymeric, etc. The only requirements are that the diisocyanate contain isocyanate groups capable of reacting with the monohydric alcohol and not interfere with the subsequent crosslinking reactions.
- diisocyanate examples include 2,4 toluene diisocyanate, 2,6 toluene diisocyanate, 2,4′-diphenylmethane diisocyanate, and 2,6′-diphenyl methane diisocynate.
- monohydric alcohol that contains a vinylidene group examples include hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, and hydroxypropyl acrylate.
- compositions Another component of these compositions is a terminally unsaturated urethane resin, known in the industry as an isocyanurate vinyl ester:
- R 1 is H or CH 3
- R 2 is an organic residue from a monohydric alcohol
- R 3 is an organic residue from a diisocyanate
- R 4 is an isocyanurate compound of the following structure
- This resin is manufactured by the methods of Kuehn et al. (U.S. Pat. No. 4,145,544 and No. 4,243,788). For examples of these resins refer to the aforementioned patents.
- the main embodiment thereof is a printed circuit board laminate suitable for microwave antennas and the like.
- the preferred ratio for terminally unsaturated urethane resin to ethylenically unsaturated monomer has been determined to be less than 0.15. Or in the case where 1 mole of 2,4′-toluene diisocyanate is reacted with 2 moles of hydroxylpropyl methacrylate, less than 27% by weight of this resin (without monomer) is desired in ethylenically unsaturated monomer. In the case where an isocyanurate vinyl ester is manufactured from the same materials in different ratios, less than about 35% by weight of resin (without monomer) is desired in ethylenically unsaturated monomer.
- Examples 2 & 3 of TABLE 1 contain a urethane modified vinyl ester with a molecular weight of approximately 4200, styrene monomer of molecular weight 104.15, and dibromostryene of average molecular weight 263.95. Using this information, the ratios of urethane modified vinyl ester to total monomer would be 0.01 and 0.02 for Examples 2 & 3 respectively. Additionally, the ratio of styrene to dibromostyrene would be 0.50, and 1.16 for Examples 2 & 3 respectively.
- the second main component of these compositions is an ethylenically unsaturated monomer from the group of 1) styrene and 2) bromostyrene.
- bromostyrene include monobromostyrene, dibromostyrene, and tribromostyrene.
- the ideal molar ratio of styrene to bromostyrene has been found to be less than 1.2. Maintaining the desired ratios provides a composition with excellent electrical properties at microwave frequencies along with desirable thermal and mechanical properties.
- An optional component may be divinyl benzene (referred herein as DVB), or any other ethylenically multiunsaturated monomer.
- DVB can be about 0.1% to about 10% by weight; preferably about 0.5% to about 5% by weight of the total composition; more preferably about 1% to about 4% by weight of the total composition and most preferably about 2.5% by weight of the total composition.
- Divinyl benzene increases the crosslink density and therefore thermal performance of the composition.
- Other polyfunctional crosslinking monomers may also be use such as divinyl toluene and the like.
- the third and fourth components contribute to the mechanical and thermal properties of a composition but do not need to be present to obtain the excellent electrical properties.
- Catalysts and polymerization and U.V. initiators may also be components of the compositions of the present invention.
- catalyst which induce free-radical cure is t-butyl peroctoate at about 0.1 to about 2% by weight of the total composition (preferably about 0.2% by weight of the total composition); benzoate at about 0.1 to about 2% by weight of the total composition (preferably 0.25% by weight of the total.
- Alternate catalysts include benzoyl peroxide, cumene hydrogen peroxide and others known to those skilled in this art. Combination of catalysts may also be used. Curing mechanisms may be utilized including electron beam processing and ultra-violet light processing in conjunction with UV initiators, radiation, heating with or without pressure, and other conventional curing methods in conjunction with the appropriate initiators.
- Additional components such as moisture scavengers may also be added. Free moisture in the composition will negatively affect the dissipation factor. Therefore a component, such as 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3-oxazolidine (available from Angus Chemical Co.) can be added to minimize the free water in the composition. The oxazolidine compound will chemically react with the water to eliminate it. Alternately, a molecular sieve could be utilized. Molecular sieves are well known as moisture reducers throughout the coatings industry. Molecular sieves function by physically trapping the free water.
- Another additional component may be titanium dioxide which increases the dielectric constant, but reduces the dissipation factor. This combination of electrical properties is desirable for some specific high frequency applications.
- the titanium dioxide may be in a range of from about 1 to about 60% by weight of the total composition; preferably about 10 to about 40% by weight of the total composition; more preferably about 25% by weight of the total composition.
- polyethylene filler such as expanded polyethylene compound, available from American Fillers and Abrasives.
- the polyethylene will lower both the dielectric constant and dissipation factor.
- the polyethylene may be in a range of from about 1 to about 60% by weight of the total composition; preferably about 5 to about 40% by weight of the total composition; more preferably about 10% by weight of the total composition.
- additives include organic and/or inorganic fillers, for example, calcined kaolin, to modify rheology; surface active agents, to aid processing; other monomers, such as methyl methacrylate to modify viscosity and possibly performance; epoxies; colorants; fluorescent dyes; U.V.
- organic and/or inorganic fillers for example, calcined kaolin, to modify rheology; surface active agents, to aid processing; other monomers, such as methyl methacrylate to modify viscosity and possibly performance; epoxies; colorants; fluorescent dyes; U.V.
- blocking agents for example, wetting agents; air release agents; defoaming agents; flame retardant synergists (for example, antimony compounds); adhesion promoters (for example, epoxy resin “EPON 828” Shell Chemical Co.); additional monomers including styrene, vinyl toluene, t-butyl styrene, para-methyl styrene, diallyl phthalate, 2,4-ethyl-methyl imidazole, and other conventional additives.
- flame retardant synergists for example, antimony compounds
- adhesion promoters for example, epoxy resin “EPON 828” Shell Chemical Co.
- additional monomers including styrene, vinyl toluene, t-butyl styrene, para-methyl styrene, diallyl phthalate, 2,4-ethyl-methyl imidazole, and other conventional additives.
- the present invention further comprises electrical laminates utilizing the thermosetting resin compositions herein described which have excellent electrical properties and which may be flame retardant and heat resistant.
- the present thermosetting resin compositions can also be utilized in existing cost effective technologies to manufacture various types of electrical laminates. Examples of these technologies include, but are not limited to, continuous lamination, such as that described in U.S. Pat. No. 4,803,022 to Barell et al. which is incorporated herein by reference; production of printed circuit boards, such as described in U.S. Pat. Nos. 4,671,984 and 4,751,146 to Masahiko Maeda et al. which are incorporated herein by reference; production of electrical laminates such as described in U.S. Pat. No.
- An electrical laminate of the present invention is produced by infiltrating or impregnating at least one substrate, or multiple substrates, with a resin composition of the present invention to prepare resin-infiltrated or resin-impregnated substrates which are laminated by passage between rolls while removing interlaminar gas bubbles. Subsequently, the resulting laminate is heated, with or without pressure, to cure the resin composition whereby the electrical laminate is obtained. Other cure mechanisms can also be utilized.
- the electrical laminate of this invention can be continuously produced.
- organic peroxides can be used as curing catalysts.
- the organic peroxides include, for example, t-butyl perbenzoate, t-butyl peroxide, benzoyl peroxide, t-butyl peroctoate, t-butyl peroxy benzoate, dicumyl peroxide, etc.
- the curing can be controlled by use of curing accelerators or polymerization inhibitors. Characteristics of the resin composition can be improved by incorporating therein to plasticizers, stabilizers, thickeners, fillers, coloring agents, lubricants, etc.
- a copper-clad laminate can be obtained by subjecting substrates impregnated with an uncured resin composition and copper foil to laminated molding to unite them in a body, or by inserting an adhesive between substrates impregnated with an uncured resin and copper foil and then subjecting them to laminated molding to unite them in a body.
- a copper-clad laminate can be obtained by also preparing a laminate by laminate molding and then unite this laminate and a copper foil laminate in a body through an adhesive. Adhesives such as epoxy resins, butyryl-modified epoxy resins, etc. can be used.
- the present electrical laminates may be from about 0.001 to about 0.25 inches thick and may be metal clad on one or both sides or not clad in metal.
- a preferred embodiment is about 0.002 to about 0.20 inches thick.
- a more preferred embodiment is about 0.003 to about 0.120 inches thick.
- Suitable cladding metals include aluminum, silver, gold, brass and most preferably copper.
- the metal cladding may be in various forms and weight. The weight may range from about 0.25 to about 5 oz/ft 2 .
- the form can be any conventional type, such as, foil, an electrodeposited layer or rolled annealed metal, such as for example, rolled annealed copper.
- a preferred embodiment comprises a copper clad electrical laminate suitable for subsequent processing as a circuit board, stripline, microstripline microwave components and other related applications.
- the preferred embodiment of this composition is an electrical laminate from 0.003 to 0.120 inches thick with metal foil clad on one or both sides.
- Suitable reinforcement components include organic or inorganic fillers, woven fiberglass, glass paper, glass mat, glass cloth, polyimide paper (such as “THERMOUNT” from DuPont), woven polymeric fibers and non-woven polymer fiber reinforcements and the like.
- the reinforcement components of the laminates of the present invention may be in the range of about 25% to 75% by weight of the total laminate, preferably about 30% to about 40%, and more preferably about 35%.
- This embodiment of the present invention is clearly superior in electrical properties over presently available compositions.
- the unsaturated urethane resins are manufactured according to U.S. Pat. Nos. 4,587,161 and 4,803,022 of Kuehn et al., manufactured according to methods known in the art, or commercially available as Palatal 48001 KR (BASF, Germany) or 580-05 (Reichold Chemicals Inc., USA) in the case of a urethane vinyl ester, and as ITP 1041 and ITP 1070 (Reichold Chemicals Inc., USA), in the case of a isocyanurate vinyl ester.
- the ethylenically unsaturated monomers styrene and dibromonostyrene are commercially available.
- thermoset resin [0080] The typical cure schedule for the thermoset resin is:
- the general method of preparing electrical laminates from the resin compositions is as follows.
- the specific electrical laminates embodied in Examples 1 to 9 were made as indicated below and as further indicated in TABLE 1 which follows below. All laminates are 30 mil dielectric thickness with 18-20% by weight E-glass reinforcement.
- the resin composition is used to impregnate the reinforcement(s) in the lab according to the same method as above (a), with the following exceptions.
- the appropriate catalysts and promoters are chosen, and the laminate is left undisturbed and allowed to cure at room temperature for 1 to 24 hours.
- the catalyst half-life, quantity of catalyst, and type and amount of promoters will dictate the amount of time needed to cure at room temperature.
- composition can impregnate the reinforcement by our patented continuous lamination process, (Barrell et al. U.S. Pat. No. 4,803,022). These examples can be found in TABLE 1 under “Continuous” Cure Method.
- Example 2 Example 3
- Example 4 Example 5
- Example 6 Example 7
- Example 8 Example 9 Cure Method Room Temp. 200 F. 30 min. 200 F. 30 min. 200 F. 30 min. 200 F. 30 min. 200 F. 30 min. Continuous Continuous Post Cure 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350
- Example 1 Example 2
- Example 3 Example 4
- Example 5 Example 6
- Example 7 Example 8
- Example 9 1 MHz Dielectric Constant 3.03 2.65 2.68 2.59 2.6 2.63 2.7 2.99 3.20 1 MHz Dissipation Factor 0.0024 0.0043 0.0053 0.0037 0.0029 0.0034 0.0015 0.0034 0.0029 Db/inch @ 1 GHz N/A N/A N/A N/A N/A N/A 0.0253 0.0289 Db/inch @ 5 GHZ N/A N/A N/A N/A N/A N/A 0.1278 0.1249 Db/inch @ 10 GHz N/A N/A N/A N/A N/A N/A 0.3238 0.2774 2.1 GHz Dielectric Constant N/A 3.25 N/A N/A 3.31 N/A 2.89 N/A 3.15 2.1 GHz Dissipation Factor N/A 0.0046 N/A N/A 0.00298 N/A 0.00
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Abstract
The present invention relates to a thermosetting resin composition with excellent electrical properties comprising (a) one or more terminally unsaturated urethane resins, (b) styrene, and (c) brominated styrene. The aforementioned composition finds great utility as a printed circuit board laminate suitable for use at microwave frequencies.
Description
- This is a regular application based on Provisional Application No. 60/032,288 filed Dec. 3, 1996 and pursuant to 37 C.F.R. 1.53(b) this application claims the benefit of the filing date of same. The entire specification of Provisional Application No. 60/032,288 is herein incorporated by reference.
- The present invention relates to thermosetting resin compositions with excellent electrical properties; electrical laminates made therefrom; and methods of producing these.
- All publications and patent applications herein are incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference.
- Electrical laminates such as circuit boards are produced by laminating sheets of electrical conducting material onto a base substrate of insulation material. The performance of the finished circuit board is effected by the electrical characteristics of the base substrate material.
- Commercially available thermoset resin systems with acceptable electrical performance at high frequencies (>350 MHZ) are restricted in their applications due to high cost. The lower cost alternatives that are available do not perform satisfactorily at high frequencies due to unacceptable electrical properties, such as high dielectric constant (Dk), high dissipation factor (Df), high variability of Dk and Df with frequency, and consistency of Dk and Df from lot to lot of production material.
- Thermoplastic polymers such as polytetrafluoroethylene (PTFE) which have exceptional electrical performance at high frequencies are commercially available. The primary drawbacks associated with these materials are very high raw material costs and special processing considerations that add substantial cost to the final product. Because of the physical properties, very high laminating temperatures and pressures are also required to fabricate an electrical laminate from PTFE. Furthermore, due to the inability to “wet” PTFE, costly and hazardous chemicals are required to modify its surface during fabrication of the circuit.
- A thermoset material would have much greater mechanical properties over a much broader temperature range. Additionally, since thermoset materials have better mechanical properties, this would allow the circuit board fabricator to use conventional cost effective processes.
- A need exists for thermosetting resin compositions, and electrical laminates made therefrom, of low to moderate cost with acceptable electrical properties at frequencies up to at least 20 GHz. Such compositions would have great utility as circuit board substrates and the laminates made from these thermosetting resins can be utilized in many applications such as in the rapidly growing wireless communication market, in high speed computers, in high definition televisions, and in various other electrical and related applications.
- An object of the present invention is to provide a thermosetting resin composition which can be made flame retardant and which can be utilized in existing cost effective technologies to manufacture electrical laminates therefrom. Additionally, the present invention resin compositions can have utility as, for example, electrical insulators, encapsulants, insulating adhesives and in various other electrical and related applications generally know to those skilled in this art.
-
- where R1 is H or CH3, R2 is an organic residue from a monohydric alcohol and R3 is an organic residue from a diisocyanate;
-
-
-
- where m=1 to 3.
- Additionally, to achieve the desired properties (i.e., microwave transparency, fire retardation, and good thermal performance) the ratio of (a) to the sum of (b)1) and (b)2) is less than 0.15, and the ratio of (b)1) to (b)2) is less than 1.2.
- The composition resins may also further contain monomers which would, for example, aid in the adhesion of a metal foil to the laminate; increase crosslink density and thermal performance; etc. Catalysts which, for example, induce free-radical cure may also be added. Other components may include moisture scavengers, compounds which increase or reduce the dielectric constant, and/or reduce the dissipation factor, polyethylene fillers, other fillers, organic or inorganic, which modify rheology, surface agents, viscosity and performance modifiers, wetting agents, air release agents, defoaming agents, flame retardant synergists, adhesion promoters, and other additional monomers and conventional additives known in the art.
- Other objects of the present invention are to provide electrical laminates, and methods for producing these laminates containing the composition resins of the present invention, which have excellent electrical properties and which may be flame retardant or heat resistant. Accordingly, the present invention further provides electrical laminates from about 0.003 inches to about 0.120 inches thick which may or may not be clad with an electrical conducting material on one or both sides.
- The electrical laminates of the present invention are produced by (a) continuous lamination or (b) a batch process:
- (a) The compositions of the present invention are uniquely suitable to the continuous lamination methods of Barrel et al. (U.S. Pat. No. 4,587,161 and No. 4,803,022). The combination of materials in the outlined ratios provides lower viscosities then previous compositions, (U.S. Pat. No. 4,420,509 and No. 4,446,173). Lower viscosities provide more rapid impregnation of reinforcements to allow higher line-speeds and consequently higher machine output. In the continuous lamination process, the desired composition is formulated with a free-radical source, (i.e., peroxide, azo-compound, etc.) to initiate cure. Optionally, the material is postcured in a batch convection oven to further lower the dissipation factor of the laminate. Therefore, we have found the combination of continuous lamination with additional batch cure provides unexpected improvements in electrical performance. While the continuous lamination temperatures and times are known in the art, we have found the optimum secondary batch oven cure profile to be 350° F. for 1 hour dwell, (or range from 150° F. for 3 hours to 450° F. for 30 minutes).
- (b) The method to manufacture the laminate with a batch process involves
- 1) A layer of carrier film, such as polyethylene terephthalate of 1.42 mills thick, was placed on a ¼th inch thick glass plate of 1.25 by 1.25 ft. The dimensions of the film were large enough to protrude around the edges of the glass plate.
- 2) A one foot square piece of 1 oz. per sq. foot weight of copper foil was placed treatment side up on the carrier film.
- 3) A film of a resin composition, prepared according to the present invention, was metered onto the copper foil by using a wire-wound rod designed to provide a coating of the target thickness of the laminate. Wire-wound rods are well known throughout the coatings industry.
- 4) A layer of glass cloth, woven or nonwoven, was laid onto the resin film and allowed to saturate for approximately 2 minutes. If a plurality of layers were used, the layers were placed onto the resin film approximately 2 minutes apart to allow the resin mixture to saturate the glass.
- 5) An additional layer of copper foil, of the same size and weight as 2), was placed treatment side down on the laminate so as to align the edges with the first sheet of copper foil.
- 6) Another layer of carrier film, of the same size and dimensions as 1), was placed on top of the copper foil.
- 7) Two ½ inch wide by 12 inches long shims of the target laminate thickness were placed on opposing sides of the laminate, on top of the carrier film, but still on the glass plate.
- 8) A rod of ½ inch thick steel was placed on the shims at one edge of the laminate and gently pulled to the opposing edge while being forced by hand to ride on the shims. As the rod moved across the laminate, excess resin composition was allowed to drain out of the laminate.
- 9) Another plate of glass of equivalent dimensions as 1), was placed on top of the laminate.
- 10) The laminate was placed in a forced air convection oven at 150-250° F. for 15 minutes to 1 hour.
- 11) The laminate, still between the glass plates, was removed from the oven and allowed to cool to room temperature. At this time, the two glass plates and two layers of carrier film were removed.
- 12) Post cure from 350° F. for 1 hour in a forced air convention oven.
- The thermosetting resin composition may also further contain the above mentioned added components and may be cured by electron beam processing, radiation, heat with or without pressure, ultra violet light processing, and other conventional curing methods in conjunction with the appropriate initiators. The electrical laminates may further comprise an electrical conductive cladding on at least one side.
- One skilled in the art can easily make any necessary adjustments in accordance with the necessities of the particular situation.
- Further objects and advantages of the present invention will be clear from the description that follows.
- FIG. 1 is an enlarged cross-sectional view of a part of an electrical laminate which comprises an electrically
conductive metal layer 1 and a cross linked thin-wall body of the inventedcomposition 2. - FIG. 2 is an enlarged cross-sectional view of an electrical laminate which exemplifies a double-sided metal clad electrical laminate, further provided with two metal
conductive layers 1, and an electrically insulating thin-wall body of the inventedcomposition 2. - FIG. 3 is an enlarged cross-sectional view of an electrical laminate which exemplifies a multilayered electrical laminate, of the structure of a combination of single-sided and double sided metal clad electrical laminates as illustrated in FIG. 1 and FIG. 2.
- FIG. 4 is an enlarged cross-sectional view of an electrical laminate which comprises an electrically
conductive layer 1, a crosslinked thin-wall body of the inventedcomposition 2, and an uniformly dispersed inorganic or organic filler 3. - FIG. 5 is an enlarged cross-sectional view of an electrical laminate which comprises an electrically
conductive metal layer 1, a crosslinked thin-wall body of inventedcomposition 2, andnonwoven glass fibers 4. - FIG. 6 is an enlarged cross-sectional view of an electrical laminate which comprises an electrically
conductive metal layer 1, a crosslinked thin-wall body of inventedcomposition 2, and wovenglass cloth 5. - FIG. 7 is an enlarged cross-section view of part of an example of a double-sided metal clad electrical laminate of FIG. 6 further provided with an electrically
conductive metal layer 1 on the other surface. - FIG. 8 is an enlarged cross-sectional view of an electrical laminate which comprises an electrically
conductive metal layer 1, a crosslinked thin-wall body of the inventedcomposition 2, and anaramid non-woven sheet 6. - Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are described.
- The present invention comprises resin compositions of moderate cost with excellent electrical properties up to at least 20 GHz which may be flame retardant and heat resistant. The present compositions have utility as electrical insulators, electrical laminates, electrically insulating encapsulants, electrically insulating adhesives and other electrical and related applications.
-
- where R1 is H or CH3, R2 is an organic residue from a monohydric alcohol and R is an organic residue from a diisocyanate. This resin is manufactured by reacting a diisocyanate with two molar equivalents of monohydric alcohol containing a vinylidene group in the presence of a polar solvent (typically styrene) which also acts as a reactive monomer for crosslinking. Examples of this art are well known throughout the industry. The diisocyanate utilized may be aromatic or aliphatic, monomeric or polymeric, etc. The only requirements are that the diisocyanate contain isocyanate groups capable of reacting with the monohydric alcohol and not interfere with the subsequent crosslinking reactions. Examples of the diisocyanate are 2,4 toluene diisocyanate, 2,6 toluene diisocyanate, 2,4′-diphenylmethane diisocyanate, and 2,6′-diphenyl methane diisocynate. Examples of the monohydric alcohol that contains a vinylidene group are hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, and hydroxypropyl acrylate.
-
-
- This resin is manufactured by the methods of Kuehn et al. (U.S. Pat. No. 4,145,544 and No. 4,243,788). For examples of these resins refer to the aforementioned patents.
- It has been found that a combination of one or more of these resins with styrene and dibromostyrene in certain ratios will yield a composition with excellent properties suitable as a matrix resin for high frequency electrical applications. The main embodiment thereof, is a printed circuit board laminate suitable for microwave antennas and the like. The preferred ratio for terminally unsaturated urethane resin to ethylenically unsaturated monomer has been determined to be less than 0.15. Or in the case where 1 mole of 2,4′-toluene diisocyanate is reacted with 2 moles of hydroxylpropyl methacrylate, less than 27% by weight of this resin (without monomer) is desired in ethylenically unsaturated monomer. In the case where an isocyanurate vinyl ester is manufactured from the same materials in different ratios, less than about 35% by weight of resin (without monomer) is desired in ethylenically unsaturated monomer.
- One skilled in the art can readily obtain the aforementioned ratios from molecular weight and weight percent information. Examples 2 & 3 of TABLE 1 contain a urethane modified vinyl ester with a molecular weight of approximately 4200, styrene monomer of molecular weight 104.15, and dibromostryene of average molecular weight 263.95. Using this information, the ratios of urethane modified vinyl ester to total monomer would be 0.01 and 0.02 for Examples 2 & 3 respectively. Additionally, the ratio of styrene to dibromostyrene would be 0.50, and 1.16 for Examples 2 & 3 respectively.
- The second main component of these compositions is an ethylenically unsaturated monomer from the group of 1) styrene and 2) bromostyrene. Examples of bromostyrene include monobromostyrene, dibromostyrene, and tribromostyrene. Additionally, the ideal molar ratio of styrene to bromostyrene has been found to be less than 1.2. Maintaining the desired ratios provides a composition with excellent electrical properties at microwave frequencies along with desirable thermal and mechanical properties.
- An optional component may be divinyl benzene (referred herein as DVB), or any other ethylenically multiunsaturated monomer. DVB can be about 0.1% to about 10% by weight; preferably about 0.5% to about 5% by weight of the total composition; more preferably about 1% to about 4% by weight of the total composition and most preferably about 2.5% by weight of the total composition. Divinyl benzene increases the crosslink density and therefore thermal performance of the composition. Other polyfunctional crosslinking monomers may also be use such as divinyl toluene and the like.
- The third and fourth components contribute to the mechanical and thermal properties of a composition but do not need to be present to obtain the excellent electrical properties.
- Catalysts and polymerization and U.V. initiators may also be components of the compositions of the present invention. There are many choices available; particularly, catalyst which induce free-radical cure. The preferred catalyst is t-butyl peroctoate at about 0.1 to about 2% by weight of the total composition (preferably about 0.2% by weight of the total composition); benzoate at about 0.1 to about 2% by weight of the total composition (preferably 0.25% by weight of the total. Alternate catalysts include benzoyl peroxide, cumene hydrogen peroxide and others known to those skilled in this art. Combination of catalysts may also be used. Curing mechanisms may be utilized including electron beam processing and ultra-violet light processing in conjunction with UV initiators, radiation, heating with or without pressure, and other conventional curing methods in conjunction with the appropriate initiators.
- Additional components, such as moisture scavengers may also be added. Free moisture in the composition will negatively affect the dissipation factor. Therefore a component, such as 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3-oxazolidine (available from Angus Chemical Co.) can be added to minimize the free water in the composition. The oxazolidine compound will chemically react with the water to eliminate it. Alternately, a molecular sieve could be utilized. Molecular sieves are well known as moisture reducers throughout the coatings industry. Molecular sieves function by physically trapping the free water.
- Another additional component may be titanium dioxide which increases the dielectric constant, but reduces the dissipation factor. This combination of electrical properties is desirable for some specific high frequency applications. The titanium dioxide may be in a range of from about 1 to about 60% by weight of the total composition; preferably about 10 to about 40% by weight of the total composition; more preferably about 25% by weight of the total composition.
- Another component which may be added is polyethylene filler, (such as expanded polyethylene compound, available from American Fillers and Abrasives). The polyethylene will lower both the dielectric constant and dissipation factor. The polyethylene may be in a range of from about 1 to about 60% by weight of the total composition; preferably about 5 to about 40% by weight of the total composition; more preferably about 10% by weight of the total composition.
- Other optional additives include organic and/or inorganic fillers, for example, calcined kaolin, to modify rheology; surface active agents, to aid processing; other monomers, such as methyl methacrylate to modify viscosity and possibly performance; epoxies; colorants; fluorescent dyes; U.V. blocking agents; wetting agents; air release agents; defoaming agents; flame retardant synergists (for example, antimony compounds); adhesion promoters (for example, epoxy resin “EPON 828” Shell Chemical Co.); additional monomers including styrene, vinyl toluene, t-butyl styrene, para-methyl styrene, diallyl phthalate, 2,4-ethyl-methyl imidazole, and other conventional additives.
- The present invention further comprises electrical laminates utilizing the thermosetting resin compositions herein described which have excellent electrical properties and which may be flame retardant and heat resistant. The present thermosetting resin compositions can also be utilized in existing cost effective technologies to manufacture various types of electrical laminates. Examples of these technologies include, but are not limited to, continuous lamination, such as that described in U.S. Pat. No. 4,803,022 to Barell et al. which is incorporated herein by reference; production of printed circuit boards, such as described in U.S. Pat. Nos. 4,671,984 and 4,751,146 to Masahiko Maeda et al. which are incorporated herein by reference; production of electrical laminates such as described in U.S. Pat. No. 4,336,297 to Yasuo Fushiki et al. and U.S. Pat. No. 5,009,949 to Kazuyuki Tanaka et al. which are both incorporated herein by reference; continuous belt press lamination, such as the equipment offered by GreCon Corp.; and traditional press or vacuum press lamination.
- An electrical laminate of the present invention is produced by infiltrating or impregnating at least one substrate, or multiple substrates, with a resin composition of the present invention to prepare resin-infiltrated or resin-impregnated substrates which are laminated by passage between rolls while removing interlaminar gas bubbles. Subsequently, the resulting laminate is heated, with or without pressure, to cure the resin composition whereby the electrical laminate is obtained. Other cure mechanisms can also be utilized. The electrical laminate of this invention can be continuously produced.
- For curing the resin composition, organic peroxides can be used as curing catalysts. The organic peroxides include, for example, t-butyl perbenzoate, t-butyl peroxide, benzoyl peroxide, t-butyl peroctoate, t-butyl peroxy benzoate, dicumyl peroxide, etc. If necessary, the curing can be controlled by use of curing accelerators or polymerization inhibitors. Characteristics of the resin composition can be improved by incorporating therein to plasticizers, stabilizers, thickeners, fillers, coloring agents, lubricants, etc.
- A copper-clad laminate can be obtained by subjecting substrates impregnated with an uncured resin composition and copper foil to laminated molding to unite them in a body, or by inserting an adhesive between substrates impregnated with an uncured resin and copper foil and then subjecting them to laminated molding to unite them in a body. A copper-clad laminate can be obtained by also preparing a laminate by laminate molding and then unite this laminate and a copper foil laminate in a body through an adhesive. Adhesives such as epoxy resins, butyryl-modified epoxy resins, etc. can be used.
- The present electrical laminates may be from about 0.001 to about 0.25 inches thick and may be metal clad on one or both sides or not clad in metal. A preferred embodiment is about 0.002 to about 0.20 inches thick. A more preferred embodiment is about 0.003 to about 0.120 inches thick.
- Suitable cladding metals include aluminum, silver, gold, brass and most preferably copper. The metal cladding may be in various forms and weight. The weight may range from about 0.25 to about 5 oz/ft2. The form can be any conventional type, such as, foil, an electrodeposited layer or rolled annealed metal, such as for example, rolled annealed copper.
- A preferred embodiment comprises a copper clad electrical laminate suitable for subsequent processing as a circuit board, stripline, microstripline microwave components and other related applications. The preferred embodiment of this composition is an electrical laminate from 0.003 to 0.120 inches thick with metal foil clad on one or both sides.
- Suitable reinforcement components include organic or inorganic fillers, woven fiberglass, glass paper, glass mat, glass cloth, polyimide paper (such as “THERMOUNT” from DuPont), woven polymeric fibers and non-woven polymer fiber reinforcements and the like. The reinforcement components of the laminates of the present invention may be in the range of about 25% to 75% by weight of the total laminate, preferably about 30% to about 40%, and more preferably about 35%.
- The performance of this composition differs from similar materials mainly in electrical performance. These properties, especially dissipation factor, are very important when considering high frequency applications. Typical electrical properties of an 0.030″ thick laminate of approximate 20% (by weight) of fiberglass reinforcement are:
Frequency (GHz): 2.5 10.0 Dielectric constant: 3.20 3.22 Dissipation factor: 0.0031 0.0048 - The electrical properties of the same laminate at 1 MHZ are:
Dielectric constant: 3.20 Dissipation factor: 0.0029 - The above data shows the consistency of the dielectric constant and dissipation factor of a laminate comprising the inventive compositions across a wide range of frequencies. This feature is highly desirable for compositions utilized as dielectric materials.
- This embodiment of the present invention is clearly superior in electrical properties over presently available compositions.
- The invention will be further clarified by a consideration of the following examples which are to be considered as illustrative of the present invention. It should be understood that the invention is not limited to the specific details of the examples.
- The unsaturated urethane resins are manufactured according to U.S. Pat. Nos. 4,587,161 and 4,803,022 of Kuehn et al., manufactured according to methods known in the art, or commercially available as Palatal 48001 KR (BASF, Germany) or 580-05 (Reichold Chemicals Inc., USA) in the case of a urethane vinyl ester, and as ITP 1041 and ITP 1070 (Reichold Chemicals Inc., USA), in the case of a isocyanurate vinyl ester. The ethylenically unsaturated monomers styrene and dibromonostyrene are commercially available.
- The general method of preparing the resin compositions is as follows.
- 1) The ingredients, (listed in TABLE 1), are added to a mixing vessel.
- 2) The ingredients are mixed for 5 to 15 minutes with a Cowles dissolver operating at high sheer, about 100 to 500 rpm), at room temperature. Higher shear rates may be used, but could entrain air. Optionally, the mixture could be degassed in a vacuum (25-29 inches of Hg).
- 3) At this point, the composition is ready for use.
- The typical cure schedule for the thermoset resin is:
- a. 20 minutes at 210 degrees F, optionally up to 225 degrees F. Temperatures greater than 250° F. produce undesirable reactions during cure and yield poor quality product. Lower temperatures than 210° F. may be used with longer times.
- b. Depending upon the desired product, a post-cure is often necessary to optimize the electrical properties. One to three hours at 350° F. is preferred.
- The general method of preparing electrical laminates from the resin compositions is as follows. The specific electrical laminates embodied in Examples 1 to 9 were made as indicated below and as further indicated in TABLE 1 which follows below. All laminates are 30 mil dielectric thickness with 18-20% by weight E-glass reinforcement.
- 1) The ingredients, listed in TABLE 1, are added to a mixing vessel.
- 2) The ingredients are mixed for 5 to 15 minutes with a Cowles dissolver operating at high sheer, (about 100 to 500 rpm), at room temperature. Higher shear rates may be used, but could entrain air. Optionally, the mixture could be degassed in a vacuum (25-29 inches of Hg).
- 3) The mixture is heated to 85-100 degrees Fahrenheit, or any temperature below the point at which the catalyst undergoes considerable decomposition to form free radicals. The resin mixture is heated to facilitate impregnating the reinforcement.
- 4) The composition is utilized with one of the following processes:
- a. The resin mixture is used to impregnate the reinforcement(s) in the lab according to the method outlined in application No. 08/483,086, incorporated herein by reference. The residence times and temperatures can be found in TABLE 1. It has been discovered, that when using this lamination process, temperatures above 250° F. will produce poor quality laminates, and thus should be avoided.
- b. the resin composition is used to impregnate the reinforcement(s) in the lab according to the same method as above (a), with the following exceptions. Rather than curing the laminate in an oven, the appropriate catalysts and promoters are chosen, and the laminate is left undisturbed and allowed to cure at room temperature for 1 to 24 hours. The catalyst half-life, quantity of catalyst, and type and amount of promoters will dictate the amount of time needed to cure at room temperature. These examples can be found in TABLE 1 under “Room Temp.” Cure Method.
- c. Alternately, the composition can impregnate the reinforcement by our patented continuous lamination process, (Barrell et al. U.S. Pat. No. 4,803,022). These examples can be found in TABLE 1 under “Continuous” Cure Method.
- 5) The laminate is post-cured for 1 hour at 350° F. Post-cure reduces the dissipation factor of the laminate. Therefore, a post-cure is desirable, but not required.
TABLE 1 Examples of New Invention Ingredient Designation Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Urethane Vinyl Ester 580-05 8.08 15.85 26.42 16.79 Isocyanate Vinyl Ester ITP 1041 26.90 16.14 Isocyanate Vinyl Ester ITP 1070 34.25 20.54 16.54 Monomer Styrene 6.88 13.50 22.50 22.02 13.21 14.68 8.81 14.08 14.30 Monomer Dibromostyrene 59.85 68.49 48.92 48.92 68.49 48.92 68.49 55.62 56.61 Monomer alpha-methyl styrene 2.52 Kaolin Filler Translink T-37 9.11 9.09 Quartz Filler Novakup 1250-172 23.94 Multifuntional Monomer Divinyl Benzene 1.55 1.54 Thickener Fumed Silica 0.45 1.47 1.47 1.47 1.47 1.47 1.47 1.45 Catalyst t-butyl peroctoate 0.48 0.20 Catalyst cummene hydroperoxide 0.50 0.49 0.49 0.49 0.49 0.49 0.49 Promoter copper napthenate 0.10 0.02 Promoter dimethyl aniline 0.20 0.10 0.10 0.10 0.10 0.10 0.10 Promoter 12% cobalt soln. 0.10 0.10 0.10 0.10 0.10 0.10 0.10 SUM 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Methods of Manufacturing Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Cure Method Room Temp. 200 F. 30 min. 200 F. 30 min. 200 F. 30 min. 200 F. 30 min. 200 F. 30 min. 200 F. 30 min. Continuous Continuous Post Cure 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. 1 hr @ 350 F. Properties of New Invention Electrical Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 1 MHz Dielectric Constant 3.03 2.65 2.68 2.59 2.6 2.63 2.7 2.99 3.20 1 MHz Dissipation Factor 0.0024 0.0043 0.0053 0.0037 0.0029 0.0034 0.0015 0.0034 0.0029 Db/inch @ 1 GHz N/A N/A N/A N/A N/A N/A N/A 0.0253 0.0289 Db/inch @ 5 GHZ N/A N/A N/A N/A N/A N/A N/A 0.1278 0.1249 Db/inch @ 10 GHz N/A N/A N/A N/A N/A N/A N/A 0.3238 0.2774 2.1 GHz Dielectric Constant N/A 3.25 N/A N/A 3.31 N/A 2.89 N/A 3.15 2.1 GHz Dissipation Factor N/A 0.0046 N/A N/A 0.00298 N/A 0.004 N/A 0.0041 Mechanical Copper Adhesion 4.0 N/A N/A N/A N/A N/A N/A 5.1 5.5 % Water Absorption N/A N/A N/A N/A N/A N/A N/A 0.05 0.06 Thermal Glass Transition Temperature 123 118 108 138 135 143 132 124 140 - Although the invention has been described in conjunction with specific embodiments, it is evident that many alternatives and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, the invention is intended to embrace all of the alternatives and variations that fall within the spirit and scope of the appended claims.
Claims (47)
1. A thermosetting resin composition, comprising:
(a) One or more terminally unsaturated urethanes selected from the group of:
1) one characterized by the formula:
where R1 is H or CH3, R2 is an organic residue from a monohydric alcohol and R3 is an organic residue from a diisocyanate;
2) and one characterized by the formula:
where R1 is H or CH3, R2 is an organic residue from a monohydric alcohol and R3 is an organic residue from a diisocyanate, and R4 is an isocyanurate compound of the following structure:
and
(b) Styrene monomer; and
(c) Bromostyrene, characterized by the formula:
wherein, the ratio of the sum of components (a) to the sum of components (b) and (c) is less than 0.2, and the ratio of (b) to (c) is less than 1.5.
2. The composition according to claim 1 further comprising a catalyst in about 0.1% to about 2% by weight of the total composition.
3. The composition according to claim 2 wherein the catalyst is selected from the group consisting of the t-butyl peroctoate, t-butyl peroxy benzoate, dicumyl peroxide, benzoyl peroxide, cumene hydrogen peroxide, t-butyl perbenzoate, t-butyl peroxide and combinations thereof.
4. The composition according to claim 3 wherein the catalyst comprises t-butyl peroctoate in about 0.2% by weight of the total composition.
5. The composition according to claim 3 wherein the catalyst comprises t-butyl peroxy benzoate in about 0.25% by weight of the total composition.
6. The composition according to claim 3 wherein the catalyst comprises dicumyl peroxide in about 0.25% by weight of the total composition.
7. The composition according to claim 1 wherein said styrene monomer is selected from the group consisting of styrene, halogenated styrene, and an alpha alkyl styrene.
8. The composition of claim 7 wherein said styrene monomer is an alpha alkyl styrene.
9. The composition of claim 7 wherein said styrene monomer is a halogenated styrene.
10. The composition of claim 9 wherein said halogenated styrene monomer is selected from the group consisting of dibromostyrene, tribromostyrene and pentabromobenzyl acrylate.
11. The composition of claim 1 further comprising divinyl benzene in about 0.1% to about 10% by weight of the total composition.
12. The composition of claim 11 wherein the divinyl benzene is from about 0.5% to about 5% by weight of the total composition.
13. The composition of claim 12 wherein the divinyl benzene is from about 1% to about 4% by weight of the total composition.
14. The composition of claim 1 further comprising additives selected from the group consisting of moisture scavengers, molecular sieves, organic fillers, inorganic fillers, oxides, polyethylene fillers, rheology modification fillers, surface active agents, monomers which modify viscosity and performance, colorants, fluorescent dyes, U.V. blockers, wetting agents, air release agents, defoamers, adhesion promoters, flame retardant synergists, styrene, vinyl toluene, t-butyl-styrene, paramethyl styrene, diallyl phthalate, 2,4,ethyl-methylimidazole, 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3-oxazolidine and combinations thereof.
15. The composition of claim 14 wherein the oxide comprises titanium dioxide.
16. The composition of claim 14 wherein the oxide comprises expanded polyethylene compounds.
17. The composition of claim 14 wherein the filler which modifies rheology is calcined kaolin.
18. The composition of claim 14 wherein the monomer which modifies viscosity and performance comprises methyl methacrylate.
19. A method of producing an electrical laminate comprising the steps of:
(1) impregnating at least one substrate with a thermosetting resin composition comprising catalysts which induce free radical cure, polymerization, or UV initiation, in about 0.1% to about 2% by weight of the total composition; and
(2) curing the resin impregnated substrate to produce an electrical laminate.
20. The method of claim 19 wherein the curing mechanism is selected from the group consisting of heating without pressure, heating with pressure, electron beam processing, and ultra-violet light processing in conjunction with U.V. initiators.
21. The method of claim 19 wherein the substrates are materials selected from the group consisting of organic or inorganic fillers, woven fiberglass, glass paper, glass cloth, glass mat, polyimide paper, woven polymeric fibers and non-woven polymer fiber reinforcements.
22. The method of claim 19 further comprising cladding an electrically conductive layer on at least one side of the impregnated substrate before curing.
23. The method of claim 19 further comprising cladding an electrically conductive layer on at least one side of the impregnated substrate after curing.
24. The method of claim 22 wherein the electrically conductive layer is a metal selected from the group of aluminum, silver, gold, brass and copper.
25. The method of claim 23 wherein the electrically conductive layer is a metal selected from the group consisting of aluminum, silver, gold, brass and copper.
26. The method of claim 19 wherein the impregnating step involves more than one substrate and the method further comprises laminating the substrates before the curing step.
27. The method of claim 26 wherein the curing mechanism is selected from the group consisting of heating without pressure, heating with pressure, electron beam processing, and ultra-violet light processing in conjunction with U.V. initiators.
28. The method of claim 26 wherein the substrates are materials selected from the group consisting of organic or inorganic fillers, woven fiberglass, glass paper, glass cloth, glass mat, polyimide paper, woven polymeric fibers and non-woven polymer fiber reinforcements.
29. The method of claim 26 further comprising cladding an electrically conductive layer on at least one side of the impregnated substrate before curing.
30. The method of claim 19 further comprising cladding an electrically conductive layer on at least one side of the impregnated substrate after curing.
31. The method of claim 29 wherein the electrically conductive layer is a metal selected from the group of aluminum, silver, gold, brass and copper.
32. The method of claim 30 wherein the electrically conductive layer is a metal selected from the group consisting of aluminum, silver, gold, brass and copper.
33. An electrical laminate obtained by
(1) impregnating at least one substrate with a thermosetting resin composition comprising:
(a) One or more terminally unsaturated urethanes selected from the group of:
1) one characterized by the formula:
where R1 is H or CH3, R2 is an organic residue from a monohydric alcohol and R3 is an organic residue from a diisocyanate;
2) and one characterized by the formula:
where R1 is H or CH3, R2 is an organic residue from a monohydric alcohol and R3 is an organic residue from a diisocyanate, and R4 is an isocyanurate compound of the following structure:
and
(b) Styrene monomer; and
(c) Bromostyrene, characterized by the formula:
wherein, the ratio of the sum of components (a) to the sum of components (b) and (c) is less than 0.2, and the ratio of (b) to (c) is less than 1.5; and (d) catalysts which induce free radical cure, polymerization, or UV initiation, in about 0.1% to about 2% by weight of the total composition; and
(2) curing the resin impregnated substrate to produce an electrical laminate.
34. The laminate of claim 33 wherein the composition resin further comprises a halogenated vinyl functional monomer.
35. The laminate of claim 34 wherein the composition further comprises glacial methacrylic acid.
36. The laminate of claim 35 wherein the composition further comprises divinyl benzene.
37. The laminate of claim 36 wherein the composition further comprises additional components selected from the group consisting of moisture scavengers, molecular sieves, organic fillers, inorganic fillers, monomers to increase or decrease the dielectric constant, monomer to reduce the dissipation factor, polyethylene fillers, monomers to modify rheology, surface active agents, monomers to modify viscosity and performance, colorants, fluorescent dye, U.V. blockers, wetting agents, air release agents, defoaming agents, flame retardant synergists, adhesion promoters, epoxies, styrene, vinyl toluene, t-butyl styrene, paramethyl styrene, diallyl phthalate, and 2,4,ethyl-methyl imidazole, 3-ethyl-2-methyl-2-3(3-methylbutyl)-1,3-oxazolidine, methyl methacrylate and combinations thereof.
38. The laminate of claim 37 wherein the substrates are materials selected from the group consisting of organic or inorganic fillers, woven fiberglass, glass paper, glass cloth, glass mat, polyimide paper, woven polymeric fibers and non-woven polymer fiber reinforcements.
39. The laminate of claim 38 further comprising an electrically conductive layer clad on at least one side of the cured impregnated substrate.
40. The laminate of claim 39 wherein the electrically conductive layer is a metal selected from the group of aluminum, silver, gold, brass and copper.
41. The laminate of claim 38 wherein more than one substrate is impregnated with the thermosetting resin and are laminated together before the curing step.
42 The laminate of claim 41 having an electrical conductive layer clad on at least one side of the laminated cured substrates.
43. The laminate of claim 42 wherein the electrical conductive layer is a metal selected from the group of aluminum, silver, gold, brass and copper.
44. An electrical laminate, comprising at least one reinforcement substrate and a crossed linked, thin wall thermosetting resin composition comprising:
(a) One or more terminally unsaturated urethanes selected from the group of:
1) one characterized by the formula:
where R1 is H or CH3, R2 is an organic residue from a monohydric alcohol and R3 is an organic residue from a diisocyanate;
2) and one characterized by the formula:
where R1 is H or CH3, R2 is an organic residue from a monohydric alcohol and R3 is an organic residue from a diisocyanate, and R4 is an isocyanurate compound of the following structure:
and
(b) Styrene monomer; and
(c) Bromostyrene, characterized by the formula:
wherein, the ratio of the sum of components (a) to the sum of components (b) and (c) is less than 0.2, and the ratio of (b) to (c) is less than 1.5; and (d) catalysts which induce free radical cure, polymerization, or UV initiation, in about 0.1% to about 2% by weight of the total composition.
45. The laminate of claim 44 further comprising an electrically conductive cladding on at least one side.
46. A multilayer electrical laminate comprising a combination of single sided and double sided laminates according to the laminate of claim 45 .
47. The laminate of claim 44 wherein the thickness range is from about 0.003 to about 0.120 inches thick.
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US10/458,360 US20030211303A1 (en) | 1996-12-03 | 2003-06-11 | Microwave-transparent thermosetting resin compositions, electrical laminates obtained therefrom, and process of producing these |
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US (3) | US6599619B1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10662304B2 (en) | 2013-12-31 | 2020-05-26 | Saint-Gobain Performance Plastics Corporation | Composites for protecting signal transmitters/receivers |
CN111800940A (en) * | 2019-04-05 | 2020-10-20 | Tdk株式会社 | Substrate and laminated substrate |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050121806A1 (en) * | 2003-12-04 | 2005-06-09 | White Electronic Designs Corporation | Method for attaching circuit elements |
US7597988B2 (en) * | 2004-12-29 | 2009-10-06 | Shen-Li High Tech Co., Ltd. | Integrated end-bus plate for fuel cell |
CN111218125A (en) * | 2020-03-05 | 2020-06-02 | 华威博奥(文安)电力设备有限公司 | Organic fire-resistant heat-insulating material and preparation method thereof |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4243788A (en) * | 1977-07-27 | 1981-01-06 | Ici Americas Inc. | Isocyanurate solutions |
US4803022A (en) * | 1987-05-06 | 1989-02-07 | Glasteel Industrial Laminates, Inc. | Method of continuously bonding and curing a zinc-coated metal-clad polyester-epoxy-glass fiber laminate |
-
1997
- 1997-12-03 US US08/984,157 patent/US6599619B1/en not_active Expired - Fee Related
-
2003
- 2003-06-11 US US10/458,361 patent/US20030215623A1/en not_active Abandoned
- 2003-06-11 US US10/458,360 patent/US20030211303A1/en not_active Abandoned
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10662304B2 (en) | 2013-12-31 | 2020-05-26 | Saint-Gobain Performance Plastics Corporation | Composites for protecting signal transmitters/receivers |
CN111800940A (en) * | 2019-04-05 | 2020-10-20 | Tdk株式会社 | Substrate and laminated substrate |
Also Published As
Publication number | Publication date |
---|---|
US20030215623A1 (en) | 2003-11-20 |
US6599619B1 (en) | 2003-07-29 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |