CN102272200B - Aromatic polyester amide copolymer, high molecular film, prepreg, prepreg laminate, metal foil laminate, and printed circuit board - Google Patents
Aromatic polyester amide copolymer, high molecular film, prepreg, prepreg laminate, metal foil laminate, and printed circuit board Download PDFInfo
- Publication number
- CN102272200B CN102272200B CN2009801532722A CN200980153272A CN102272200B CN 102272200 B CN102272200 B CN 102272200B CN 2009801532722 A CN2009801532722 A CN 2009801532722A CN 200980153272 A CN200980153272 A CN 200980153272A CN 102272200 B CN102272200 B CN 102272200B
- Authority
- CN
- China
- Prior art keywords
- prepreg
- aromatic polyester
- polyester amide
- amide copolymer
- repeating unit
- 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.)
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 96
- 229920006149 polyester-amide block copolymer Polymers 0.000 title claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 29
- 239000011888 foil Substances 0.000 title claims abstract description 23
- 239000002120 nanofilm Substances 0.000 title abstract 2
- -1 aromatic diol Chemical class 0.000 claims abstract description 18
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 238000003475 lamination Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 17
- 238000005470 impregnation Methods 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 9
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- 150000004982 aromatic amines Chemical class 0.000 claims description 7
- 150000004984 aromatic diamines Chemical class 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012764 mineral filler Substances 0.000 claims description 6
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012766 organic filler Substances 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 2
- 229940018563 3-aminophenol Drugs 0.000 claims description 2
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 claims description 2
- SERBLGFKBWPCJD-UHFFFAOYSA-N 6-aminonaphthalen-2-ol Chemical class C1=C(O)C=CC2=CC(N)=CC=C21 SERBLGFKBWPCJD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 claims description 2
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical group C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000123 paper Substances 0.000 claims description 2
- 230000000306 recurrent effect Effects 0.000 abstract 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 description 36
- 238000000034 method Methods 0.000 description 27
- 239000002904 solvent Substances 0.000 description 21
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000004744 fabric Substances 0.000 description 11
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000005917 acylation reaction Methods 0.000 description 7
- 150000001408 amides Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000003368 amide group Chemical group 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 230000010933 acylation Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000011152 fibreglass Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 206010016654 Fibrosis Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000004761 fibrosis Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- LSACYLWPPQLVSM-UHFFFAOYSA-N isobutyric acid anhydride Chemical compound CC(C)C(=O)OC(=O)C(C)C LSACYLWPPQLVSM-UHFFFAOYSA-N 0.000 description 1
- JEHCHYAKAXDFKV-UHFFFAOYSA-J lead tetraacetate Chemical compound CC(=O)O[Pb](OC(C)=O)(OC(C)=O)OC(C)=O JEHCHYAKAXDFKV-UHFFFAOYSA-J 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- OKDQKPLMQBXTNH-UHFFFAOYSA-N n,n-dimethyl-2h-pyridin-1-amine Chemical compound CN(C)N1CC=CC=C1 OKDQKPLMQBXTNH-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0145—Polyester, e.g. polyethylene terephthalate [PET], polyethylene naphthalate [PEN]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
Disclosed are an aromatic polyester amide copolymer, a high molecular film, a prepreg, a prepreg laminate, a metal foil laminate, and a printed circuit board. The disclosed aromatic polyester amide copolymer comprises 20 to 25 mol % of an aromatic diol-derived recurrent unit (A) relative to the total recurrent unit, wherein said aromatic diol-derived recurrent unit (A) contains both a resorcinol-derived recurrent unit (RCN) and a recurrent unit (HQ) derived from at least one compound of biphenol and hydroquinone.
Description
Technical field
The invention discloses aromatic polyester amide copolymer, polymeric membrane, prepreg, the stacked body of prepreg, metal foil layer lamination and printed-wiring board (PWB).Disclose in more detail with respect to whole repeating units and contained 20～25 % by mole of repeating units (A) from aromatic diol, above-mentioned repeating unit from aromatic diol (A) contain simultaneously from Resorcinol repeating unit (RCN) and from the aromatic polyester amide copolymer of the repeating unit (HQ) of at least a kind of compound in xenol and quinhydrones, adopted the polymeric membrane of above-mentioned aromatic polyester amide copolymer, the stacked body of prepreg and prepreg, and the metal foil layer lamination and the printed-wiring board (PWB) that have adopted above-mentioned prepreg or the stacked body of prepreg.
Background technology
Nearest miniaturization, multifunction along with electronic machine, carrying out densification, the miniaturization of printed-wiring board (PWB), copper-clad laminate is due to punch process, drilling excellent in workability, and cheap and extensively utilize with substrate as the printed-wiring board (PWB) of electronic machine.
For the prepreg of such copper foil for printed circuit board plywood in order to be applicable to semi-conductive performance and semiconductor packages manufacturing process condition the main characteristic of needs below meeting.
(1) can tackle the low-thermal-expansion rate of thermal expansion metal rate
(2) low-k and the dielectric stability in the high-frequency region more than 1GHz
(3) to the thermotolerance of the reflow process of 270 ℃ of left and right
Above-mentioned prepreg be by the resin impregnated from epoxy or Bismaleimide Triazine after woven fiber glass, carry out drying and semicure and manufacture.Then, laminated copper foil on above-mentioned prepreg, make resin solidification and the manufacturing copper foil plywood.Can be through the high temperature operations such as reflow process of 270 ℃ after such copper-clad laminate filming, but while existing through such high-temperature process the copper-clad laminate of film morphology due to thermal distortion degradation problem under yield.In addition, epoxy resin or bismaleimide-triazine resin are due to the high-hygroscopicity of himself, so need to improve into agent of low hygroscopicity, particularly the dielectric characteristics in the high-frequency region more than 1GHz is poor, so exist, is difficult to be applicable to require the problem of printed-wiring board (PWB) of the semiconductor-sealing-purpose of high frequency, high speed processing.Therefore, need to not cause the prepreg of the low-dielectric of this problem.
In addition, recently, as the alternative scheme of epoxy resin or bismaleimide-triazine resin, also have the example of aromatic polyester for the formation of prepreg.Such prepreg is that aromatic polyester is contained and is immersed in organic cloth or non-woven cloth and manufactures.Particularly sometimes also use aromatic polyester resins and aromatic polyester cloth to manufacture the aromatic polyester prepreg.Specifically, aromatic polyester is dissolved in the solvent that contains the halogenss such as chlorine and manufactures liquid composite, after this liquid composite is contained and is immersed in aromatic polyester cloth, carry out drying and manufacture the aromatic polyester prepreg.But the method is difficult to the solvent that contains halogens is removed fully, halogens likely corrodes Copper Foil, so need to improve into the non-halogen solvent of use.
Summary of the invention
Technical task
An embodiment of the invention provide the aromatic polyester amide copolymer with low-thermal-expansion rate, low-k and low-dielectric loss.
Another embodiment of the invention provides prepreg and the stacked body of prepreg that has adopted above-mentioned aromatic polyester amide copolymer.
Another embodiment of the present invention provides metal foil layer lamination and the printed-wiring board (PWB) that has adopted above-mentioned prepreg or the stacked body of prepreg.
The problem solution
One aspect of the present invention is, with respect to whole repeating units, contain 20～25 % by mole of repeating units (A) from aromatic diol, described repeating unit from aromatic diol (A) contain simultaneously from Resorcinol repeating unit (RCN) and from the repeating unit (HQ) of at least a kind of compound in xenol and quinhydrones.
The content of the content of above-mentioned repeating unit (RCN) and above-mentioned repeating unit (HQ) meets following condition:
0＜n(RCN)/[n(RCN)+n(HQ)]＜1。
Wherein, n (RCN) and n (HQ) are respectively the repeating unit (RCN) that contains in above-mentioned aromatic polyester amide copolymer and the mole number of repeating unit (HQ).
Above-mentioned aromatic polyester amide copolymer also can contain 2～25 % by mole of repeating units (B) from aromatic hydroxy-carboxylic with respect to whole repeating units.
Above-mentioned aromatic polyester amide copolymer also can contain from the repeating unit (C) of the aromatic amine with phenolic hydroxyl group with from 20～25 % by mole of at least a repeating units in the repeating unit (C ') of aromatic diamine with respect to whole repeating units.
Above-mentioned aromatic polyester amide copolymer also can contain 35～48 % by mole of repeating units (D) from aromatic dicarboxylic acid with respect to whole repeating units.
Another aspect of the present invention is to provide the polymeric membrane that contains above-mentioned aromatic polyester amide copolymer.
Another aspect of the present invention is to provide the prepreg that contains the base material that is soaked with above-mentioned aromatic polyester amide copolymer.
Another aspect of the present invention is to provide the stacked body of the prepreg that comprises the above-mentioned prepreg more than 2.
Another aspect of the present invention is to provide the metal foil layer lamination that is formed with metallic film on the one side at least of above-mentioned prepreg or the stacked body of above-mentioned prepreg.
Another aspect of the present invention is to provide the printed-wiring board (PWB) that the metallic film etching of above-mentioned metal foil layer lamination is obtained.
Another aspect of the present invention is to provide the printed-wiring board (PWB) formed at least one type metal circuit pattern of above-mentioned polymeric membrane.
The invention effect
According to an embodiment of the invention, can provide the aromatic polyester amide copolymer with low-thermal-expansion rate, low-k and low-dielectric loss.
According to another implementation of the invention, by adopting above-mentioned aromatic polyester amide copolymer, can provide prepreg and the stacked body of prepreg with low-thermal-expansion rate, low-k and low-dielectric loss.
According to another embodiment of the present invention, can provide the metal foil layer lamination and the printed-wiring board (PWB) that adopt above-mentioned prepreg or the stacked body of prepreg.
Embodiment
Below to the aromatic polyester amide copolymer according to an embodiment of the invention with comprise by the prepreg of the base material of above-mentioned multipolymer impregnation and being elaborated.
According to the aromatic polyester amide copolymer of present embodiment, contain 20～25 % by mole of repeating units (A) from aromatic diol with respect to whole repeating units, described repeating unit from aromatic diol (A) contain simultaneously from Resorcinol repeating unit (RCN) and from the repeating unit (HQ) of at least a kind of compound in xenol and quinhydrones.When the content of above-mentioned repeating unit (A) was less than 20 % by mole, not preferred because the solubleness in solvent descends, while surpassing 25 % by mole, melt temperature was too high and not preferred.
The mole number (n (HQ)) of the mole number of the above-mentioned repeating unit (RCN) contained in above-mentioned aromatic polyester amide copolymer in addition, (n (RCN)) and above-mentioned repeating unit (HQ) can meet following condition:
0＜n(RCN)/[n(RCN)+n(HQ)]＜1。
In addition, above-mentioned aromatic polyester amide copolymer also can contain 2～25 % by mole of repeating units (B) from aromatic hydroxy-carboxylic with respect to whole repeating units.
When the content of above-mentioned repeating unit (B) is less than 2 % by mole, not preferred due to the physical strength decline of aromatic polyester amide copolymer, while surpassing 25 % by mole, not preferred due to the thermal characteristics decline of aromatic polyester amide copolymer.
Above-mentioned repeating unit (B) can contain the repeating unit from least a kind of compound in P-hydroxybenzoic acid and 2-hydroxyl-6-naphthoic acid.
In addition, above-mentioned aromatic polyester amide copolymer also can contain from the repeating unit (C) of the aromatic amine with phenolic hydroxyl group with from 20～25 % by mole of at least a repeating units in the repeating unit (C ') of aromatic diamine with respect to whole repeating units.
In addition, when the total content of above-mentioned repeating unit (C) and repeating unit (C ') is less than 20 % by mole, not preferred because the solvability in solvent reduces, while surpassing 25 % by mole, because melt temperature is too high and not preferred.
Above-mentioned repeating unit (C) can contain from the repeating unit that is selected from the compound more than a kind in 3-amino-phenol, PAP and 2-amino-6-naphthols, above-mentioned repeating unit (C ') can contain from 1,4-phenylenediamine, 1, the repeating unit of the compound more than a kind in 3-phenylenediamine and 2,6-naphthylene diamine.
In addition, above-mentioned aromatic polyester amide copolymer also can contain 35～48 moles of ` of repeating unit (D) from aromatic dicarboxylic acid with respect to whole repeating units
When the content of above-mentioned repeating unit (D) is less than 35 % by mole, not preferred due to decreased solubility, while surpassing 48 % by mole, not preferred because thermotolerance, low-thermal-expansion, low dielectric characteristics descend.
Above-mentioned repeating unit (D) can contain from the repeating unit that is selected from the compound more than a kind in m-phthalic acid, naphthalic acid and terephthalic acid.
Specifically, any that the repeating unit separately that contains of above-mentioned aromatic polyester amide copolymer can be in following chemical formula means:
(1) from the repeating unit (A) of aromatic diol:
(2) from the repeating unit (B) of aromatic hydroxy-carboxylic:
(3) from the repeating unit (C) of the aromatic amine with phenolic hydroxyl group:
(4) from the repeating unit (C ') of aromatic diamine:
(5) from the repeating unit (D) of aromatic dicarboxylic acid:
<Chemical formula 16 >
In above-mentioned formula, R
1And R
2Identical or different, mean separately halogen atom, carboxyl, amino, nitro, cyano group, replacement or non-substituted C
1-C
20Alkyl, replacement or non-substituted C
1-C
20Alkoxyl group, replacement or non-substituted C
2-C
20Alkenyl, replacement or non-substituted C
2-C
20Alkynyl, replacement or non-substituted C
1-C
20Assorted alkyl, replacement or non-substituted C
6-C
30Aryl, replace or non-substituted C
7-C
30Aralkyl, replacement or non-substituted C
5-C
30Heteroaryl or replacement or non-substituted C
3-C
30Heteroaralkyl.In this manual, term " replacement " refers to that hydrogen is by halogen group, hydroxyl, alkyl, alkoxyl group, amido or replacing more than 2 kinds in them.
Such aromatic polyester amide copolymer can be by containing (1) in aromatic diol or its derivative that is used to form ester of Resorcinol and quinhydrones and/or xenol; (2) aromatic hydroxy-carboxylic or its are used to form the derivative of ester; (3) be selected from least a kind in the derivative that aromatic amine with phenolic hydroxyl group or its derivative that is used to form acid amides and aromatic diamine or its be used to form acid amides; And (4) aromatic dicarboxylic acid or its derivative that is used to form ester carry out polymerization and obtain.
The derivative that is used to form ester of above-mentioned aromatic diol can be that their hydroxyl reacts with carboxylic-acid and forms the material of ester bond.
In addition, the derivative that is used to form ester of above-mentioned aromatic hydroxy-carboxylic or aromatic dicarboxylic acid, the derivative that it can be acyl chlorides, the acid anhydrides isoreactivity is high, or can form with alcohols or glycols etc. the material of ester bond.
In addition, the derivative that is used to form acid amides of above-mentioned aromatic amine or aromatic diamine can be the material that its amido and carboxylic-acid form amido linkage.
The aromatic polyester amide copolymer of above-mentioned manufacture can be dissolved in solvent, can preferably can be formed in thermic (thermotropic) the liquid crystal polyester amide copolymer of 400 ℃ of anisotropic molten masses of following display optical.Specifically, the melt temperature of above-mentioned aromatic polyester amide copolymer can be 1,000～20,000 for 250 ℃～400 ℃, number-average molecular weight.
Above-mentioned aromatic polyester amide copolymer can be manufactured by the manufacture method of general aromatic polyester, for example can enumerate following methods: aromatic diol that will be corresponding with above-mentioned repeating unit (RCN) and repeating unit (HQ) difference, the aromatic hydroxy-carboxylic corresponding with above-mentioned repeating unit (B), the aromatic amine corresponding with above-mentioned repeating unit (C) and/or repeating unit (C ') and/or phenolic hydroxyl group or the amido of aromatic diamine utilize excessive fatty acid anhydride to carry out acylations and obtain the acyl group compound, make the acyl group obtained compound and aromatic dicarboxylic acid carry out transesterification reaction, thereby carry out melt polymerization.
In above-mentioned acylation reaction, the addition of fatty acid anhydride can be 1.0～1.2 times of equivalents of the total equivalent of phenolic hydroxyl group and amido, can be for example 1.04～1.07 times of equivalents.If the addition of above-mentioned fatty acid anhydride is many, have the painted obvious tendency of aromatic polyester amide copolymer, if few, have the tendency that the generation at the distillation such as polymkeric substance Raw monomer or phenols gas increases.Such acylation reaction preferably reacted 30 minutes～8 hours in 130～170 ℃, more preferably in 140～160 ℃, reacted 2～4 hours.
As the fatty acid anhydride used in above-mentioned acylation reaction, acetic anhydride, propionic anhydride, isobutyric anhydride, valeric anhydride, PIVALIC ACID CRUDE (25) acid anhydride, butyryl oxide etc. are arranged, without particular limitation of in this.In addition, mixing more than 2 kinds wherein can also be used.From economy and operability, consider, preferably use acetic anhydride.
Above-mentioned transesterification reaction and acid amides permutoid reaction are preferably implemented at 130～400 ℃ of heat-up rates with 0.1～2 ℃/minute, more preferably at 140～350 ℃ of heat-up rates with 0.3～1 ℃/minute, implement.
When the fatty acid ester that such amidation is obtained and carboxylic acid carry out transesterification reaction and acid amides permutoid reaction, move in order to make balance, the lipid acid of by-product and the utilization of unreacted acid anhydrides can be evaporated or distill and is discharged to outside reaction system.
Above-mentioned acylation reaction, transesterification reaction and acid amides permutoid reaction can be carried out under catalyzer exists.Above-mentioned catalyzer be in the past as polyester with catalyzer known catalyzer, magnesium acetate, tin acetate, tetrabutyl titanate, plumbic acetate, sodium-acetate, Potassium ethanoate, ANTIMONY TRIOXIDE SB 203 99.8 PCT, N are arranged, N-dimethyl aminopyridine, N-Methylimidazole etc.Above-mentioned catalyzer drops into monomer usually simultaneously when dropping into monomer, generation acylations and transesterification reaction under the existence of above-mentioned catalyzer.
Utilize the polycondensation of above-mentioned transesterification reaction and acid amides permutoid reaction usually to utilize melt polymerization to implement, can be used together melt polymerization and solid-state polymerization.
There is no particular limitation for the polymerizer of above-mentioned melt polymerization, can be the reactor that the general whipping device used in the high viscosity reaction is installed.Now, same reactor can be used as the reactor of acylations operation and the polymerizer of melt polymerization operation, also different reactors can be in each operation, used.
Above-mentioned solid-state polymerization can utilize following methods to implement: will from the prepolymer of discharging the melt polymerization operation pulverize and make flakey or Powdered after, make it carry out polymerization.Such solid-state polymerization is such as can be by processing and to implement in 1～30 hour with solid state heat at 200～350 ℃ in the inactive atmospheres such as nitrogen.In addition, above-mentioned solid-state polymerization can under agitation be implemented, and also can implement without under whipped state.In addition, the reactor that suitable whipping device is installed can also be come and uses as melt polymerization groove and solid-state polymerization groove.
The aromatic polyester amide copolymer of above-mentioned manufacture can have the following coefficient of thermal expansion of 3ppm/K.
The aromatic polyester amide copolymer obtained carries out moulding after can utilizing known method granulating, or utilizes known method fibrosis.In addition, such aromatic polyester amide copolymer can after being dissolved in solvent, be coated metallic film as will be described later, and then drying and thermal treatment forms polymeric membrane, can also be for the manufacture of cloth or non-woven fabrics.
According to the prepreg of present embodiment, comprise and contain the base material that is soaked with above-mentioned aromatic polyester amide copolymer.
Above-mentioned prepreg can be manufactured in accordance with the following methods: the composition solution that is dissolved with above-mentioned aromatic polyester amide polymer in solvent is contained to cloth (fabrics) and/or non-woven fabrics (non-fabrics) base material that is immersed in organic or inorganic, perhaps by the above-mentioned composition solution coat at above-mentioned cloth and/or non-woven fabrics base material, after moulding, except desolventizing.Now operable forming method can be enumerated solution impregnation method or varnish impregnation method.
With respect to above-mentioned aromatic polyester amide polymer 100 weight parts, the solvent that dissolves above-mentioned aromatic polyester amide copolymer can be with 100～100, the content of 000 weight part is used, when the content of above-mentioned solvent is less than 100 weight part, because solution viscosity rises, so add the existing problems in man-hour, while surpassing 100,000 weight part, because the amount of aromatic polyester amide copolymer is few, has the tendency that productivity descends, so not preferred.
As the solvent that dissolves above-mentioned aromatic polyester amide copolymer, preferred non-halogen solvent.But the present invention is not limited thereto, aprotic, polar based compound, halogenated phenol, orthodichlorobenzene, chloroform, methylene dichloride, tetrachloroethane etc. can be used separately or will more than 2 kinds, use together in addition.Particularly above-mentioned aromatic polyester amide copolymer is soluble in non-halogen solvent, can not use the solvent that contains halogens, therefore, can prevent from advance containing its metal foil layer lamination or the problem that is corroded and so on due to halogens of the tinsel of printed-wiring board (PWB) when use contains the solvent of halogens.
As above-mentioned base material, can use cloth and/or the non-woven fabrics of aromatic polyester fiber, glass fibre, carbon fiber, paper or their mixture and so on.
While in above-mentioned prepreg manufacturing process, using the impregnation method, by the composition solution that is dissolved with aromatic polyester amide copolymer in solvent contain the time that is immersed in above-mentioned base material usually be preferably 0.001 minute～1 hour.The above-mentioned impregnation time is less than 0.001 minute, and above-mentioned aromatic polyester amide copolymer impregnation equably surpasses 1 hour, and productivity descends.
In addition, the composition solution that is dissolved with above-mentioned aromatic polyester amide copolymer in solvent is contained to the temperature that is immersed in above-mentioned base material and can be the scope of 20～190 ℃, preferably at room temperature carry out.
In addition, above-mentioned aromatic polyester amide copolymer is preferably 0.1～1,000g/m in the per unit area impregnation amount of above-mentioned base material
2Scope.Above-mentioned impregnation amount is less than 0.1g/m
2The time, because productivity descends, thus not preferred, surpass 1,000g/m
2The time, be not suitable for the miniaturization of printed-wiring board (PWB).
In solvent, be dissolved with in the composition solution of above-mentioned aromatic polyester amide copolymer, in the scope of not damaging the object of the invention, in order to regulate specific inductivity and coefficient of thermal expansion, can also be added with the mineral filler of silicon-dioxide, aluminium hydroxide, calcium carbonate, the organic fillers such as epoxy resin cured product, crosslinked acrylic resin.Particularly can add the mineral filler of high-k.As such mineral filler, can utilize the titanates such as barium titanate, strontium titanate, the material that the part of the titanium of barium titanate or barium is replaced with other metal etc.With respect to aromatic polyester amide copolymer 100 weight parts, such mineral filler or the content of organic filler are preferably the ratio of 0.0001～100 weight part.When the addition of above-mentioned mineral filler or organic filler is less than 0.0001 weight part, has the tendency that is difficult to fully to improve the specific inductivity of prepreg or reduces coefficient of thermal expansion, while surpassing 100 weight part, have the tendency of aromatic polyester amide copolymer as the effect reduction of tackiness agent.
According to the prepreg of present embodiment, have cloth and/or the non-woven fabrics of the organic or inorganic of the aromatic polyester amide copolymer of agent of low hygroscopicity and low dielectric characteristics and physical strength excellence due to use, so excellent in dimensional stability, thermal distortion is few, hard, be conducive to via drilling processing and stacked processing.
In the impregnation method of manufacturing above-mentioned prepreg, the composition solution that is dissolved with above-mentioned aromatic polyester amide copolymer in solvent is contained and is immersed in above-mentioned base material, perhaps by the above-mentioned composition solution coat after above-mentioned base material, there is no particular limitation for the method for removing above-mentioned solvent, but preferably utilize the solvent evaporation.Can enumerate such as the evaporation that utilizes the methods such as heating, decompression, ventilation.Wherein, consider aspect the suitability during having prepreg manufacturing process now, production efficiency, operability that the preferred solvent heating evaporation more preferably utilizes the heating of ventilating to evaporate.
Above-mentioned desolventizing in operation, about Heating temperature, preferably to the composition solution of the aromatic polyester amide copolymer that obtains in manufacture method of the present invention, in the scope of 20～190 ℃ predrying 1 minute～2 hours, in the scope of 190～350 ℃, implement the thermal treatment of 1 minute～10 hours.
The prepreg according to present embodiment obtained so preferably has approximately 5～200 μ m, the thickness of 30～150 μ m more preferably from about.In addition, unidirectional coefficient of thermal expansion of above-mentioned prepreg is below 10ppm/K, and specific inductivity is below 3.5, and dielectric loss (dielectric loss) is below 0.01.Wherein, when so-called dielectric loss means the additional alternating-electric field of dielectric substance, the power loss disappeared with hot form in dielectric substance.When above-mentioned coefficient of thermal expansion surpasses 10ppm/K, due to the peeling that prepreg occurs, so not preferred.In addition, above-mentioned specific inductivity surpass 3.5 or dielectric loss surpass at 0.01 o'clock, due to the insulating substrate be not suitable as in high-frequency region, so not preferred.
The above-mentioned prepreg of stacked regulation number, be heated and pressurize, thereby can manufacture the stacked body of prepreg.
In addition, can also configure the metallic films such as Copper Foil, silver foil, aluminium foil at the one or both sides of above-mentioned prepreg or the stacked body of above-mentioned prepreg, with above-mentioned same heating and pressurization, thereby can manufacture the metal foil layer lamination.
In above-mentioned metal foil layer lamination, there is no particular limitation for the stacked body of prepreg or prepreg and metallic film thickness separately, but be preferably 0.1～300 μ m.When the thickness of above-mentioned prepreg or the stacked body of prepreg is less than 0.1 μ m, because the man-hour that adds of carrying out winding method, crackle easily occurred, thus not preferred, while surpassing 300 μ m, because the thickness limited multilayer laminated number of plies is limited, so not preferred.When the thickness of above-mentioned metallic film was less than 0.1 μ m, crackle easily occurred during due to layer metal film, thus not preferred, while surpassing 300 μ m, to multilayer laminated unfavorable, so not preferred.
The heating that above-mentioned metal foil layer lamination is suitable for while manufacturing and pressurization operation are preferably carried out in 150～180 ℃ of temperature, pressure 9～20MPa left and right, but can consider reactivity, the pressing device of prepreg characteristic or aromatic polyester amide copolymer composition performance, as the thickness of the metal foil layer lamination of target etc., suitably determine, therefore there is no particular limitation.
In addition, according to the metal foil layer lamination of present embodiment, in order to improve the bonding strength between the stacked body of prepreg and metallic film, can further comprise the bond layer be clipped between them.As above-mentioned bond layer, can use thermoplastic resin composition or compositions of thermosetting resin.In addition, the thickness of above-mentioned bond layer is preferably 0.1～100 μ m.When above-mentioned thickness is less than 0.1 μ m, not preferred because bonding strength reduces, while surpassing 100 μ m, because thickness is blocked up and not preferred.
In addition, the metallic film of the above-mentioned metal foil layer lamination of etching forms circuit, thereby can manufacture printed-wiring board (PWB).In addition, at least one type metal circuit pattern of above-mentioned polymeric membrane, thereby can manufacture printed-wiring board (PWB).In addition, can also at above-mentioned printed-wiring board (PWB), form through hole etc. as required.The multilayer printed circuit board of present embodiment can be manufactured by the following method: for example, according to the thickness of the insulation layer as target, the above-mentioned prepreg of configuration regulation number between the structural woods such as internal layer base material or metallic film, in heating with add to depress and carry out moulding.Heating now and pressurized conditions can the condition when manufacturing above-mentioned metal foil layer lamination similarly suitably determine.In addition, as above-mentioned internal layer base material, can enumerate the stacked body of the prepreg of using as electrically insulating material, metal foil layer lamination or printed-wiring board (PWB) etc. as an example, can also be by also using more than 2 kinds in them.
Below enumerate embodiment and illustrate in greater detail the present invention, but the invention is not restricted to this.
Embodiment 1
In the reactor that possesses whipping appts, torque meter, nitrogen ingress pipe, thermometer and reflux exchanger, drop into P-hydroxybenzoic acid 138.1g (1.0 moles), PAP 245.54g (2.3 moles), quinhydrones 185.8g (1.7 moles), Resorcinol 61.9g (0.6 mole), m-phthalic acid 747.6g (4.5 moles) and acetic anhydride 1,123g (11 moles).
After with nitrogen, fully replacing above-mentioned inside reactor, through 30 minutes, be warming up to 150 ℃ under stream of nitrogen gas, refluxed 3 hours while maintain this temperature.
Then, on one side the acetic acid that will distillate and the distillation of unreacted acetic anhydride remove, through 180 minutes, be warming up to 320 ℃ on one side, the etching that moment of torsion is risen finishes as reaction, discharges content.The solids component obtained is cooled to room temperature, after with pulverizing mill, pulverizing, under nitrogen atmosphere at 260 ℃ maintain 5 hour and on one side carry out solid-state polymerization on one side, obtained the aromatic polyester amide copolymer powder.
The aromatic polyester amide copolymer powder 400g obtained is like this added in N-Methyl pyrrolidone (NMP) 600g, stirred 4 hours in normal temperature, obtained the composition solution of aromatic polyester amide copolymer.
Under normal temperature, impregnation woven fiber glass in said composition solution (IPC 1078), pass through between two rods it, thereby remove unnecessary composition solution, makes thickness certain.Then, content is placed in the dried by hot air stream at high temperature machine, under 120 ℃ except after desolventizing, 300 ℃ of lower thermal treatments 60 minutes, thereby obtained aromatic polyester amide copolymer is contained the prepreg of the form that is immersed in woven fiber glass.
Comparative example 1
As aromatic diol, do not use quinhydrones fully and only use Resorcinol 253.23g (2.3 moles), in addition, manufacture aromatic polyester amide copolymer according to the method identical with above-described embodiment 1.In addition, according to the method identical with above-described embodiment 1, manufacture aromatic polyester amide copolymer composition solution and prepreg.
Comparative example 2
As aromatic diol, do not use Resorcinol fully and only use quinhydrones 253.23g (2.3 moles), in addition, manufacture aromatic polyester amide copolymer according to the method identical with above-described embodiment 1.In addition, according to the method identical with above-described embodiment 1, manufacture aromatic polyester amide copolymer composition solution and prepreg.
Comparative example 3
Use P-hydroxybenzoic acid 138.1g (1.0 moles), PAP 109.1g (1.0 moles), quinhydrones 289.6g (2.63 moles), Resorcinol 95.8g (0.87 mole), m-phthalic acid 747.6g (4.5 moles) and acetic anhydride 1,123g (11 moles), in addition, according to the method identical with above-described embodiment 1, manufacture aromatic polyester amide copolymer.In addition, according to the method identical with above-described embodiment 1, manufacture aromatic polyester amide copolymer composition solution and prepreg.
With comparative example 1～3, contrast, the toner of the prepreg of manufacturing in following enforcement above-described embodiment 1 comes off and the electrical characteristic evaluation.
At first, the prepreg of manufacturing in the prepreg of acquisition in above-described embodiment 1 and comparative example 1～3 in bathing, is flooded 3 times respectively in the weldering that the scolding tin temperature is 290 ℃, and each 10 seconds, and observe its condition of surface.Confirmed that the prepreg of manufacturing in embodiment 1 does not deform or bubbles, but the prepreg of manufacturing in comparative example 1～3, its surperficial part comes off, and the distortion of prepreg self has also occurred.
In addition, to the prepreg of manufacturing in the prepreg that obtains in embodiment 1 and comparative example 1～3, utilize electric impedance analyzer to measure specific inductivity and dielectric loss separately, the specific inductivity of the prepreg obtained in acetonideexample 1 is shown as 3.0 (1GHz), dielectric loss is shown as 0.005, shows low value at high-frequency region.But, the specific inductivity of the prepreg obtained in comparative example 1 is shown as 3.4 (1GHz), dielectric loss is shown as 0.007, the specific inductivity of the prepreg obtained in comparative example 2 is shown as 3.6 (1GHz), dielectric loss is shown as 0.008, the specific inductivity of the prepreg obtained in comparative example 3 is shown as 3.4 (1GHz), dielectric loss is shown as 0.007, has shown the value higher than the situation of embodiment 1.
In addition, to the prepreg of manufacturing in the prepreg that obtains in embodiment 1 and comparative example 1～3, (TMA company, Q400) measure coefficient of thermal expansion separately, and the coefficient of thermal expansion of the prepreg obtained in acetonideexample 1 has shown 9.2ppm/K in 50～120 ℃ of temperature ranges to utilize TMA.But, the coefficient of thermal expansion of the prepreg obtained in comparative example 1 is shown as 14.5ppm/K, the coefficient of thermal expansion of the prepreg obtained in comparative example 2 is shown as 11.5ppm/K, the coefficient of thermal expansion of the prepreg obtained in comparative example 3 is shown as 12.4ppm/K, shown the value higher than the situation of embodiment 1 (>10ppm/K).
On the other hand, as mentioned above, can, according to using prepreg to manufacture the manufacture method in the past of the stacked body of prepreg, metal foil layer lamination and printed-wiring board (PWB), utilize the prepreg of manufacturing in the above-described embodiments to manufacture the stacked body of prepreg, metal foil layer lamination and printed-wiring board (PWB).
The present invention is illustrated as a reference with embodiment, but this illustration only, so long as those skilled in the art just should be appreciated that other the embodiment that can carry out thus various deformation and be equal to.Therefore, real technical protection scope of the present invention should be determined according to the technological thought of claims.
Claims (17)
1. aromatic polyester amide copolymer, it is characterized in that, with respect to whole repeating units, contain repeating unit A20 from aromatic diol～25 % by mole, the described A of repeating unit from aromatic diol contains simultaneously from the repeating unit RCN of Resorcinol with from the repeating unit HQ of a kind of compound in xenol and quinhydrones at least, with respect to whole repeating units, also contain repeating unit B2 from aromatic hydroxy-carboxylic～25 % by mole, with respect to whole repeating units, also contain from the repeating unit C of the aromatic amine with phenolic hydroxyl group with from 20～25 % by mole of at least a repeating units in the repeating unit C ' of aromatic diamine, with respect to whole repeating units, also contain repeating unit D35 from aromatic dicarboxylic acid～48 % by mole.
2. aromatic polyester amide copolymer according to claim 1, is characterized in that, described repeating unit B is from least a kind of compound in P-hydroxybenzoic acid and 2-hydroxyl-6-naphthoic acid.
3. aromatic polyester amide copolymer according to claim 1, it is characterized in that, described repeating unit C is from the compound more than a kind in the group of selecting free 3-amino-phenol, PAP and 2-amino-6-naphthols to form, described repeating unit C ' is from choosing free 1,4-phenylenediamine, 1, the compound more than a kind in the group that 3-phenylenediamine and 2,6-naphthylene diamine form.
4. aromatic polyester amide copolymer according to claim 1, is characterized in that, described repeating unit D is from the compound more than a kind in the group of selecting free m-phthalic acid, naphthalic acid and terephthalic acid to form.
5. aromatic polyester amide copolymer according to claim 1, is characterized in that, number-average molecular weight is 1,000～20,000, and melt temperature is 250～400 ℃.
6. a polymeric membrane, is characterized in that, contains the described aromatic polyester amide copolymer of any one in claim 1～5.
7. a prepreg, is characterized in that, contains the have the right base material of the described aromatic polyester amide copolymer of any one in requirement 1～5 of impregnation.
8. prepreg according to claim 7, is characterized in that, described aromatic polyester amide copolymer is 0.1～1,000g/m in the per unit area impregnation amount of described base material
2Scope.
9. prepreg according to claim 7, is characterized in that, described base material comprises at least a kind in the group of selecting free aromatic polyester fiber, glass fibre, carbon fiber and paper composition.
10. prepreg according to claim 7, is characterized in that, take and also contain organic filler or the mineral filler of adding with respect to described aromatic polyester amide copolymer 100 weight parts as the ratio of 0.0001～100 weight part in described base material.
11. prepreg according to claim 7, is characterized in that, unidirectional coefficient of thermal expansion is below 10ppm/K.
12. prepreg according to claim 7, is characterized in that, specific inductivity is below 3.5, and dielectric loss is below 0.01.
13. the stacked body of prepreg, is characterized in that, comprises the prepreg claimed in claim 7 more than 2.
14. a metal foil layer lamination, is characterized in that, comprise prepreg claimed in claim 7 and be configured in described prepreg at least the one side at least one metallic film.
15. metal foil layer lamination according to claim 14 is characterized in that described prepreg is at least 2, is the stacked body of prepreg.
16. a printed-wiring board (PWB), is characterized in that, the metallic film etching of the described metal foil layer lamination of claim 14 is obtained.
17. a printed-wiring board (PWB), is characterized in that, at least one type metal circuit pattern of polymeric membrane claimed in claim 6 and form.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020080138702A KR101595121B1 (en) | 2008-12-31 | 2008-12-31 | Aromatic liquid-crystalline polyester amide copolymer prepreg or prepreg laminates having the copolymer and metal clad laminates and print wiring board having the prepreg or the prepreg laminates |
| KR10-2008-0138702 | 2008-12-31 | ||
| PCT/KR2009/007763 WO2010077014A2 (en) | 2008-12-31 | 2009-12-24 | Aromatic polyester amide copolymer, high molecular film, prepreg, prepreg laminate, metal foil laminate, and printed circuit board |
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| CN102272200B true CN102272200B (en) | 2013-11-27 |
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| KR101798237B1 (en) * | 2011-05-06 | 2017-11-15 | 심천 워트 어드밴스드 머티리얼즈 주식회사 | Wholly aromatic polyester amide copolymer resin, polymer film having the copolymer resin, flexible metal clad laminate having the polymer film, and flexible printed circuit board having the metal clad laminate |
| WO2017043439A1 (en) * | 2015-09-09 | 2017-03-16 | 住友化学株式会社 | Aromatic polyester, liquid aromatic-polyester composition, process for producing aromatic-polyester film, and aromatic-polyester film |
| CN106633044A (en) * | 2016-11-30 | 2017-05-10 | 彭州市运达知识产权服务有限公司 | Liquid crystal polyarylester and preparation method thereof |
| KR102049024B1 (en) | 2017-03-22 | 2019-11-26 | 주식회사 엘지화학 | Resin composition for semiconductor package, prepreg and metal clad laminate using the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4874800A (en) * | 1986-10-17 | 1989-10-17 | Polyplastics Co., Ltd. | Polyester resin composition |
| JP2008291168A (en) * | 2007-05-28 | 2008-12-04 | Sumitomo Chemical Co Ltd | Method for producing liquid crystal polymer film and substrate for printed circuit board |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3619867B2 (en) * | 1993-09-03 | 2005-02-16 | 株式会社高分子加工研究所 | Production method of thermotropic liquid crystal polymer filament |
| US6132884A (en) * | 2000-01-14 | 2000-10-17 | Ticona Llc | Process for producing amorphous anisotrophic melt-forming polymers having a high degree of stretchability and polymers produced by same |
| US7227179B2 (en) | 2002-09-30 | 2007-06-05 | World Properties, Inc. | Circuit materials, circuits, multi-layer circuits, and methods of manufacture thereof |
-
2008
- 2008-12-31 KR KR1020080138702A patent/KR101595121B1/en active IP Right Grant
-
2009
- 2009-12-24 WO PCT/KR2009/007763 patent/WO2010077014A2/en active Application Filing
- 2009-12-24 CN CN2009801532722A patent/CN102272200B/en active Active
- 2009-12-24 JP JP2011543429A patent/JP2012514066A/en active Pending
- 2009-12-30 TW TW98145785A patent/TW201035168A/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4874800A (en) * | 1986-10-17 | 1989-10-17 | Polyplastics Co., Ltd. | Polyester resin composition |
| JP2008291168A (en) * | 2007-05-28 | 2008-12-04 | Sumitomo Chemical Co Ltd | Method for producing liquid crystal polymer film and substrate for printed circuit board |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20100080081A (en) | 2010-07-08 |
| CN102272200A (en) | 2011-12-07 |
| WO2010077014A3 (en) | 2010-09-16 |
| WO2010077014A2 (en) | 2010-07-08 |
| JP2012514066A (en) | 2012-06-21 |
| KR101595121B1 (en) | 2016-02-17 |
| TW201035168A (en) | 2010-10-01 |
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