CN102433000B - Composition for preparing thermosetting resin, cured product of the composition, prepreg and prepreg laminate having the cured product, and metal clad laminate and printed circuit board having the prepreg or the prepreg laminate - Google Patents
Composition for preparing thermosetting resin, cured product of the composition, prepreg and prepreg laminate having the cured product, and metal clad laminate and printed circuit board having the prepreg or the prepreg laminate Download PDFInfo
- Publication number
- CN102433000B CN102433000B CN201110233201.2A CN201110233201A CN102433000B CN 102433000 B CN102433000 B CN 102433000B CN 201110233201 A CN201110233201 A CN 201110233201A CN 102433000 B CN102433000 B CN 102433000B
- Authority
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- China
- Prior art keywords
- prepreg
- repeating unit
- composition
- thermosetting resin
- preparation
- Prior art date
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- 229920005989 resin Polymers 0.000 title claims abstract description 91
- 239000011347 resin Substances 0.000 title claims abstract description 91
- 239000000203 mixture Substances 0.000 title claims abstract description 90
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 64
- 229910052751 metal Inorganic materials 0.000 title claims description 9
- 239000002184 metal Substances 0.000 title claims description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 74
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims abstract description 51
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 19
- -1 aromatic diol Chemical class 0.000 claims abstract description 18
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 8
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims description 66
- 239000000463 material Substances 0.000 claims description 61
- 239000002648 laminated material Substances 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 18
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 14
- 229920000728 polyester Polymers 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 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
- 239000012764 mineral filler Substances 0.000 claims description 7
- 239000012766 organic filler Substances 0.000 claims description 6
- 229940090248 4-hydroxybenzoic acid Drugs 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
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 3
- 229940018563 3-aminophenol Drugs 0.000 claims description 3
- 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 3
- 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 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 239000000123 paper Substances 0.000 claims description 3
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 3
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 abstract 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 abstract 1
- 239000000047 product Substances 0.000 description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 28
- 239000002904 solvent Substances 0.000 description 23
- 229910052802 copper Inorganic materials 0.000 description 21
- 239000010949 copper Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 14
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 239000004744 fabric Substances 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- 229910052736 halogen Inorganic materials 0.000 description 9
- 150000002367 halogens Chemical class 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 8
- 150000004665 fatty acids Chemical class 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 7
- 238000005917 acylation reaction Methods 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 150000001408 amides Chemical class 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 2
- 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
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-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
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-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
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001263 acyl chlorides 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
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052454 barium strontium titanate Inorganic materials 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
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- 229940046892 lead acetate Drugs 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000003754 machining Methods 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
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-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
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 238000003756 stirring 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
- 230000008961 swelling Effects 0.000 description 1
- 229920005992 thermoplastic resin 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
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/12—Polyester-amides
-
- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
-
- 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
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- 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
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/65—Electrical insulator
Abstract
A composition for manufacturing thermosetting resin is provided to obtain a prepreg and a prepreg laminate, which have low thermal expansion ratio, low permittivity, dielectric loss and low moisture absorbency. A composition for manufacturing thermosetting resin comprises 100.0 parts by weight aromatic polyester amide copolymer and 10-900 parts by weight pyromellitic dianhydride. The aromatic polyester amide copolymer comprises: 10-30 mol% repeating unit, which has at least one terminal group among amino terminal group or hydroxy terminal group, originated from aromatic hydroxy carboxylic acid; 15-25 mol% repeating unit, which has phenolic hydroxy group, originated from aromatic amine or aromatic diamine; 15-25 mol% repeating unit originated from aromatic diol; and 30-60 mol% repeating unit originated from dicarboxylic acid.
Description
The cross reference of related application
This application claims the right of priority of the korean patent application No.10-2010-0064397 that on July 5th, 2010 submits in Korean Intellectual Property Office, and content disclosed in it all introduces the application as a reference.
Background of invention
2. background technology
According to miniaturization and the multifunction trend of nearest electronics, carry out densification and the Miniaturization Research of printed circuit board (PCB) at present.Layers of copper laminate materials, due to its outstanding punch process, Drilling processibility and low cost, is widely used as the substrate for printed circuit board of electronics.
Require that there is the following salient features being suitable for semiconducting behavior and semiconductor package fabrication for the preparation of the prepreg used in the layers of copper laminate materials of printed circuit board (PCB):
(1) corresponding to the low thermal coefficient of expansion of metal (integrated circuit substrate (IC)) thermal expansivity;
(2) the low-dielectric energy in the high-frequency range of more than 1GHz and dielectric stability
(3) thermotolerance to reflow soldering process at about 270 DEG C.
Prepreg is by carrying out impregnated glass fabric with epoxy resin or bismaleimide-triazine resin, and then dry and this resin of semicure is prepared from.Then, copper foil layer is stacked on prepreg or prepreg laminate materials, and solidifies this resin completely to form copper clad stacking material.This copper clad stacking material is formed thin layer, and pyroprocessing is carried out to it, such as at 270 DEG C, carry out reflow soldering process.When carrying out pyroprocessing, because prepreg is different with the thermal expansivity of copper clad stacking material, may there is thermal distortion in the copper clad stacking material of thin layer form, thus cause copper clad stacking material productive rate to reduce.In addition, the high-hygroscopicity of epoxy resin or bismaleimide-triazine resin must be lowered.Especially, (namely resin has bad dielectric properties in the high-frequency range of more than 1GHz, high-k in high-frequency range), be therefore difficult to resin to be applied to can be subject on the semiconductor packages printed-wiring board (PWB) of high frequency and High-speed machining process.Therefore, need to develop a kind of prepreg with low-dielectric energy.
Recently, by using aromatic polyester resin to replace epoxy resin or bismaleimide-triazine resin to prepare prepreg.Described prepreg is prepared by using the organic or inorganic yarn fabric of aromatic polyester resin dipping.Especially, aromatic polyester resin and aromatic polyester yarn fabric can be used to prepare aromatic polyester prepreg.In detail, aromatic polyester is dissolved in prepares composition solution containing the solvent of halogen as chlorine, carries out dipping aromatic polyester yarn fabric with described composition solution, then dryly obtains product to prepare aromatic polyester prepreg.But in the method, the solvent containing halogen is difficult to be completely removed, and halogen can corrode Copper Foil.Therefore, need to develop a kind of non-halogen solvent that uses to prepare the method for aromatic polyester prepreg.
1. technical field
One or more aspect of the present invention relates to for the preparation of the composition of thermosetting resin, the solidifying product of said composition, the prepreg comprising this solidifying product and prepreg laminate materials and the clad stacking material and the printed circuit board (PCB) that comprise this prepreg or prepreg laminate materials, more specifically, the present invention relates to the composition for the preparation of thermosetting resin, said composition comprises the aromatic polyester amide copolymer and pyromellitic acid dianhydride with amino end group; The solidifying product of said composition; Comprise prepreg and the prepreg laminate materials of this solidifying product; And comprise clad stacking material and the printed circuit board (PCB) of this prepreg or prepreg laminate materials.
Summary of the invention
One or more aspect of the present invention is provided for the composition preparing thermosetting resin, and described composition comprises the aromatic polyester amide copolymer and pyromellitic acid dianhydride with amino end group.
One or more aspect of the present invention provides thermosetting resin film, and it comprises the described solidifying product for the preparation of the composition of thermosetting resin.
One or more aspect of the present invention provides prepreg and prepreg laminate materials, and it comprises the described solidifying product for the preparation of the composition of thermosetting resin.
The present invention goes back clad stacking material and the printed circuit board (PCB) that providing package contains described prepreg or prepreg laminate materials.
According to an aspect of the present invention, a kind of composition for the preparation of thermosetting resin is provided, it comprises: the aromatic polyester amide copolymer with amino end group of 100 weight parts, described aromatic polyester amide copolymer comprises: about 10mol% to about 30mol% is derived from the repeating unit A of aromatic hydroxycarboxylic acids, about 15mol% to about 25mol% is selected from by derived from least one repeating unit had in the repeating unit B of arylamine of phenolic hydroxyl group and the group that forms derived from the repeating unit B ' of aromatic diamine, about 15mol% to about 30mol% is derived from the repeating unit D of the repeating unit C of aromatic diol and about 30mol% to about 60mol% derived from aromatic dicarboxylic acid, and 10 to 900 weight part pyromellitic acid dianhydrides.
Repeating unit A is derived from least one compound be selected from P-hydroxybenzoic acid and 2-hydroxyl-6-naphthoic acid, repeating unit B is derived from being selected from by 3-amino-phenol, at least one compound in the group that PAP and 2-amino-6-naphthols form, repeating unit B ' is derived from being selected from by 1, 4-phenylenediamine, 1, 3-phenylenediamine and 2, at least one compound in the group that 6-naphthylene diamine forms, repeating unit C is derived from being selected from by Resorcinol, at least one compound in the group that xenol and Resorcinol form, and repeating unit D is derived from least one compound be selected from m-phthalic acid and naphthalic acid.
The amount of repeating unit B, repeating unit B ', repeating unit C and repeating unit D meets following condition:
1.0≤[n(B)+n(B’)+n(C)]/n(D)＜1.5，
Wherein, n (B), n (B '), n (C) and n (D) are the mole number of repeating unit B, repeating unit B ', repeating unit C and repeating unit D in aromatic polyester amide copolymer respectively.
According to a further aspect in the invention, provide a kind of thermosetting resin film, it comprises the described solidifying product for the preparation of the composition of thermosetting resin.
According to a further aspect in the invention, provide a kind of prepreg, described prepreg comprises base material and is contained in the solidifying product of the described composition for the preparation of thermosetting resin in this base material.
The total amount of the solidifying product of the described composition for the preparation of thermosetting resin that unit surface base material comprises and described composition can at about 0.1g/m
2to about 1,000g/m
2scope in.
Described base material can comprise and is selected from by aromatic polyester fibres, aromatic polyester nylon, glass fibre, carbon fiber, at least one in the group that paper or their combination form.
Based on total amount 100 weight part of the described composition for the preparation of thermosetting resin and its solidifying product, described prepreg can comprise at least one in the organic filler of 0.0001 to 100 weight part and mineral filler further.
When being contained in after the solidifying product in prepreg solidifies completely, when measuring the thermal expansivity of described prepreg, the thermal expansivity of described prepreg is being below 20ppm/K in one direction.
When being contained in after the solidifying product in prepreg solidifies completely, when measuring specific inductivity and the dielectric loss of described prepreg under 1GHz frequency, the specific inductivity of described prepreg can be less than 4.0, and dielectric loss can be less than 0.01.
When being contained in after the solidifying product in prepreg solidifies completely, when measuring the modulus in flexure of described prepreg, the modulus in flexure of described prepreg can be about 10GPa to about 30GPa.
According to another aspect of the present invention, providing package contains the prepreg laminate materials of at least one deck prepreg.
According to another aspect of the present invention, providing package is containing the clad stacking material of prepreg; And at least layer of metal film be configured at least one surface of described prepreg.
Described prepreg can be the prepreg laminate materials comprising at least two-layer prepreg.
According to another aspect of the present invention, provide a kind of printed circuit board (PCB), it is prepared by the tinsel etched on described clad stacking material.
According to another aspect of the present invention, provide a kind of printed circuit board (PCB), its by thermosetting resin film at least one on the surface type metal circuitous pattern formed.
The detailed description of invention
Below, exemplary embodiment according to the present invention describes a kind of composition for the preparation of thermosetting resin, its solidifying product and comprise the prepreg of this solidifying product.
According to the embodiment of the present invention, the composition for the preparation of thermosetting resin comprises aromatic polyester amide copolymer and about 10 to the about 900 weight part pyromellitic acid dianhydrides that 100 weight parts have amino end group.
When the amount of aromatic polyester amide copolymer and pyromellitic acid dianhydride is in above-mentioned scope, the solidifying product (i.e. cross-linked resin) for the preparation of the composition of thermosetting resin has low heat expansion property, low-dielectric and high crosslink density.Due to high crosslink density, the solidifying product of described composition can have agent of low hygroscopicity, high-clarity and high modulus in flexure.
According to the embodiment of the present invention, aromatic polyester amide copolymer comprise about 10mol% to about 30mol% derived from the repeating unit A of aromatic hydroxycarboxylic acids, about 15mol% to about 25mol% be selected from by derived from least one repeating unit, the about 15mol% that have in the repeating unit B of arylamine of phenolic hydroxyl group and the group that forms derived from the repeating unit B ' of aromatic diamine to about 30mol% derived from the repeating unit D of the repeating unit C of aromatic diol and about 30mol% to about 60mol% derived from aromatic dicarboxylic acid.
When the amount of repeating unit A is in above-mentioned scope, described aromatic polyester amide copolymer has high physical strength and excellent thermal properties.When the total amount of repeating unit B and repeating unit B ' is in above-mentioned scope, described aromatic polyester amide copolymer solvability in a solvent increases, and described aromatic polyester amide copolymer can have suitable melt temperature.When the amount of repeating unit C is in above-mentioned scope, described aromatic polyester amide copolymer solvability in a solvent increases, and described aromatic polyester amide copolymer can have suitable melt temperature and high-clarity.When the amount of repeating unit D is in above-mentioned scope, described aromatic polyester amide copolymer solvability in a solvent increases, and described aromatic polyester amide copolymer can have low thermal coefficient of expansion and low-dielectric.
Repeating unit A can derived from least one compound be selected from P-hydroxybenzoic acid and 2-hydroxyl-6-naphthoic acid.Repeating unit B can derived from least one compound be selected from the group that is made up of 3-amino-phenol, PAP and 2-amino-6-naphthols, repeating unit B ' can derived from being selected from by 1,4-phenylenediamine, 1, at least one compound in the group that 3-phenylenediamine and 2,6-naphthylene diamine form.Repeating unit C can derived from being selected from by Resorcinol, at least one compound in the group that xenol and Resorcinol form.Repeating unit D can derived from least one compound be selected from the group that is made up of m-phthalic acid and naphthalic acid.
The amount of repeating unit B, repeating unit B ', repeating unit C and repeating unit D can meet following condition:
1.0≤[n(B)+n(B’)+n(C)]/n(D)＜1.5，
Wherein, n (B), n (B '), n (C) and n (D) are the mole number of repeating unit B, repeating unit B ', repeating unit C and repeating unit D in aromatic polyester amide copolymer respectively.
When number ratio { [n (B)+n (B ')+n (C)]/n (D) } is in above-mentioned scope, described aromatic polyester amide copolymer comprises a large amount of amino end groups and/or hydroxyl end groups.In addition, between aromatic polyester amide copolymer and epoxy resin, there is curing reaction, form the thermosetting resin with high crosslink density.
Such as, each repeating unit in aromatic polyester amide copolymer can be represented by following arbitrary general formula:
(1) derived from the repeating unit A of aromatic hydroxycarboxylic acids:
General formula 1
General formula 2
General formula 3
General formula 4
General formula 5
(2) derived from the repeating unit B of arylamine with phenolic hydroxyl group:
General formula 6
General formula 7
General formula 8
(3) derived from the repeating unit B ' of aromatic diamine:
General formula 9
General formula 10
General formula 11
(4) derived from the repeating unit C of aromatic diol:
General formula 12
General formula 13
General formula 14
General formula 15
(5) derived from the repeating unit D of aromatic dicarboxylic acid:
General formula 16
General formula 17
General formula 18
General formula 19
General formula 20
General formula 21
General formula 22
General formula 23
Wherein, R
1and R
2can be independently halogen atom, carboxyl, amino, nitro, cyano group, substituted or unsubstituted C separately
1-C
20alkyl, substituted or unsubstituted C
1-C
20alkoxyl group, substituted or unsubstituted C
2-C
20thiazolinyl, substituted or unsubstituted C
2-C
20alkynyl, substituted or unsubstituted C
1-C
20assorted alkyl, substituted or unsubstituted C
6-C
30aryl, substituted or unsubstituted C
7-C
30aralkyl, substituted or unsubstituted C
5-C
30heteroaryl or substituted or unsubstituted C
3-C
30heteroarylalkyl.Term used herein " replacement " represent compound at least one hydrogen atom by halogen atom, hydroxyl, alkyl, alkoxyl group, amino or these groups at least both replace.
Aromatic polyester amide copolymer is prepared by polymerization following substances: (1) aromatic hydroxycarboxylic acids or its ester derivative; (2) be selected from by arylamine or its amide derivatives with phenolic hydroxyl group, and at least one in the group that forms of aromatic diamine or its amide derivatives; (3) aromatic diol or its ester derivative; And (4) aromatic dicarboxylic acid or its ester derivative.
The ester derivative of aromatic hydroxycarboxylic acids or aromatic dicarboxylic acid can be highly active derivative, such as acyl chlorides or acid anhydrides, or can form the derivative of ester bond with alcohol and glycol etc.
In the amide derivatives of arylamine or aromatic diamine, its amino can form amido linkage with carboxylic acid.
In the ester derivative of aromatic diol, its hydroxyl can form ester bond with carboxylic acid.
In a solvent, it can be thermotropic liquor polyester amide copolymer to the aromatic polyester amide copolymer solubilized of preparation described above, and it is formed below 400 DEG C has optically anisotropic melt.Such as, the melt temperature of described aromatic polyester amide copolymer can in the scope of about 250 to about 400 DEG C, and number-average molecular weight is in the scope of about 1,000 to about 20,000.
Aromatic polyester amide copolymer can use following method to prepare.That is: with fatty acid anhydride by correspond to repeating unit A aromatic hydroxycarboxylic acids hydroxyl or amino, the arylamine corresponding respectively to repeating unit B and/or repeating unit B ' and/or aromatic diamine, carry out acidylate to obtain acylate corresponding to the aromatic diol of repeating unit C, then the acylate of acquisition and aromatic dicarboxylic acid are carried out transesterify to carry out melt polymerization.In this case, by regulating the consumption of fatty acid anhydride suitably, aromatic polyester amide copolymer can have amino end group and the predetermined polymerization degree.Such as, when increasing the consumption of fatty acid anhydride, in aromatic polyester amide copolymer, the quantity of amino end group reduces, and the quantity of carboxyl end groups and the polymerization degree increase.When reducing the consumption of fatty acid anhydride, the quantity of amino end group increases, and the quantity of carboxyl end groups and the polymerization degree reduce.
In acylation reaction, the consumption of fatty acid anhydride counts about 0.9 to about 1.2 times of hydroxyl and amino total amount with chemical equivalent, such as about 0.95 to about 1.05 times.When the consumption of fatty acid anhydride is in above-mentioned scope, the aromatic polyester amide copolymer generated contains amino end group, and the coloring phenomenon of aromatic polyester amide copolymer reduces, some monomers of use can not distil from the aromatic polyester amide copolymer generated, and the phenol gas of generation reduces.Acylation reaction can carry out about 30 minutes to about 8 hours in the temperature range of about 130 to about 170 DEG C, such as, carries out about 2 to about 4 hours in the temperature range of about 140 to about 160 DEG C.
The fatty acid anhydride used in acylation reaction can comprise diacetyl oxide, propionic anhydride, isobutyric anhydride, valeric anhydride, trimethylacetic acid acid anhydride, butyryl oxide or their combination, but is not limited to them.
Transesterify and amide group exchange and can carry out in the temperature range of 130-400 DEG C, and temperature rise rate is 0.1-2 DEG C/min, and such as, at the temperature of 140-350 DEG C, temperature rise rate is 0.3-1 DEG C/min.
Transesterify and amide group is carried out when exchanging between the fatty acid ester obtained and aromatic dicarboxylic acid, in order to increase speed of reaction, molecular balance is moved, the lipid acid generated and unreacted fatty acid anhydride can be shifted out reaction system by evaporating or distilling as by product.
Acylation reaction, transesterification reaction and amide exchange reaction can carry out in the presence of a catalyst.Catalyzer can be any known catalysts for the preparation of vibrin, such as magnesium acetate, tin acetate (II), tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, ANTIMONY TRIOXIDE SB 203 99.8 PCT, N, N-dimethyl aminopyridine and N-Methylimidazole.Catalyzer can add with monomer simultaneously, then carries out acylation reaction, transesterification reaction and amide exchange reaction in the presence of a catalyst.
The polycondensation that transesterify and amide group exchange can be undertaken by melt polymerization.Due to generate aromatic polyester amide copolymer after a while with cross linking of epoxy resin, namely solidify, the solidifying product with high-polymerization degree and high mechanical strength can be formed, so solid state polymerization is not necessarily.
The polymerization reactor that melt polymerization uses, not by particular restriction, can be any reactor that agitator is housed being generally used for heavy viscous material reaction.In this respect, the reactor of melt polymerization can be identical with the reactor of acylation reaction, or use different reactors in each reaction.
According to current embodiment, aromatic polyester amide copolymer contains amino end group, so aromatic polyester amide copolymer can be highly cross-linked by pyromellitic acid dianhydride.
The aromatic polyester amide copolymer of preparation described above can have the thermal expansivity of below 3ppm/K.
According to the embodiment of the present invention, the composition for the preparation of thermosetting resin can be prepared by the aromatic polyester amide copolymer and pyromellitic acid dianhydride mixing predetermined proportion.
Thermosetting resin film can be prepared by the composition for the preparation of thermosetting resin by common solvent casting method.
For the preparation of thermosetting resin composition solubilized in a solvent.So can use the composition dipping for the preparation of thermosetting resin or coated substrate, then thermofixation (usually, semicure) product prepares prepreg.In this case, by using thermofixation, make crosslinking reaction to occur to prepare cross-linked resin between the composition of the composition for the preparation of thermosetting resin be contained in prepreg.That is, for the preparation of the amino end group in the aromatic polyester amide copolymer of the composition of the composition of thermosetting resin, with other composition in composition, namely pyromellitic acid dianhydride is partial cross-linked to form cross-linked resin (i.e. solidifying product).Because described solidifying product has the physical properties of aromatic polyester amide copolymer, solidifying product can have agent of low hygroscopicity and high modulus in flexure, and low thermal coefficient of expansion, low-k and low-dielectric loss.
Term used herein " semicure " represents to be wherein the state that part is carried out for the preparation of the solidification process of the composition of resin.Can not melting still can soften during the resin heating generated by semicure composition, can be swelling but can not dissolve in a solvent.Usually, the resin obtained by semicure composition is called B b stage resin b.Term " completely solidification " represents the state that the solidification process of wherein composition has carried out completely.The resin that complete curing composition generates can not soften when heating, and can not dissolve in a solvent.Usually, the resin obtained by complete curing composition is called C b stage resin b.
In addition, also can be used for other field except prepreg for the preparation of the composition of thermosetting resin.
Composition solution by dipping in composition solution or can be coated on organic or inorganic yarn fabric and/or non-woven fabric by prepreg, then prepared by dry and semicure composition solution, wherein, composition solution prepares by being dissolved in by the composition for the preparation of thermosetting resin in solvent.Dipping is undertaken by solution impregnation or varnish impregnation.
Based on the composition for the preparation of thermosetting resin of 100 weight parts, can be 100 to 100,000 weight part for dissolving the consumption of the solvent of aromatic polyester amide copolymer.When the consumption of solvent is in above-mentioned scope, the composition for the preparation of thermosetting resin fully dissolves in a solvent, and the gain in yield of composition for the preparation of thermosetting resin.
Can be non-halogen solvent for dissolving the solvent of aromatic polyester amide copolymer, but be not limited thereto.Such as solvent can be aprotic, polar based compound, halogenation phenol, o-dichlorobenzene, chloroform, methylene dichloride, tetrachloroethane or their combination.
Especially, because the composition for the preparation of thermosetting resin even can be dissolved in non-halogen solvent, therefore may avoid using the solvent containing halogen.So the tinsel of the clad stacking material or printed circuit board (PCB) that comprise the solidifying product of composition can be avoided being corroded, and containing when halogen solvent, it may be corroded in use.
Base material can comprise aromatic polyester fibres, aromatic polyester nylon, glass fibre, carbon fiber, paper or comprise in them at least both yarn fabric and/or non-woven fabric.
When impregnation steps is used in the preparation method of prepreg, base material can be combined thing solution impregnation, such as about 0.001 minute to about 1 hour.When dipping time is in above-mentioned scope, base material is combined the homogeneous dipping of thing solution, and the gain in yield of prepreg.
In addition, described base material can be combined thing solution impregnation in the temperature range of 20-190 DEG C.
The pickup of composition on unit surface base material for the preparation of thermosetting resin can about 0.1 to about 1,000g/m
2scope in.When the pickup of the composition for the preparation of thermosetting resin is in above-mentioned scope, the productive rate of prepreg improves, and carries out its handling ease.So, in prepreg, after semicure process, can be about 0.1g/m for the preparation of the amount of the composition of thermosetting resin and the solidifying product of composition based on the base material of unit surface
2to about 1,000g/m
2.
In order to control specific inductivity and thermal expansivity, mineral filler can be added in composition solution, such as silica, aluminium hydroxide or calcium carbonate; And/or organic filler such as cured epoxy resin or crosslink propylene aldehyde radical material (crosslinked acryl).Mineral filler can be titanate, such as barium titanate or strontium titanate, or replaces the compound of titanium in barium titanate or barium with other metallic member.Be 100 weight parts based on the composition for the preparation of thermosetting resin, the mineral filler contained in described composition solution and/or the consumption of organic filler can be 0.0001 to 100 weight parts.If when the consumption of mineral filler and/or organic filler is in above-mentioned scope, the thermal expansivity of prepreg reduces, and can play the effect of tackiness agent after semicure process fully for the preparation of the composition of thermosetting resin and the solidifying product of composition.Therefore, after semicure process, the mineral filler contained in prepreg and/or the amount of organic filler can be 0.0001 to 100 weight parts, based on the total amount for the preparation of the composition of thermosetting resin and the solidifying product of composition of 100 weight parts.
Owing to comprising the solidifying product of the composition for the preparation of thermosetting resin according to the prepreg of embodiment of the present invention, it has low thermal coefficient of expansion, low-dielectric, agent of low hygroscopicity and high modulus in flexure, and described organic or inorganic yarn fabric and/or organic or inorganic non-woven fabric have high mechanical strength, therefore prepreg has outstanding dimensional stability, be difficult to thermal distortion, and can be flexible or hard.Due to these characteristics, prepreg is applicable to through hole boring process and lamination process.So prepreg can be used as flexible matrix material in various field.
In the pickling process technique preparing prepreg, after with composition solution base material being flooded or applying, can evaporation of solvent be passed through, but be not limited thereto except the method for desolventizing.Such as, evaporation can be undertaken by heating evaporation, vacuum-evaporation or ventilation evaporation.Solvent also can by removing to 2 hours the prepreg drying being impregnated with composition solution at the temperature of 20-190 DEG C for 1 minute.
Then, dry prepreg heats 1 to 8 hour at the temperature of 120-320 DEG C, is contained in the composition for the preparation of thermosetting resin in prepreg with semicure.
According to current embodiment, the thickness of the prepreg of preparation can be about 5 μm to about 200 μm, such as about 30 μm to about 150 μm.
Be contained in after the solidifying product in prepreg (that is, semicure resin=B b stage resin b) solidifies completely, the one-directional thermal expansion coefficient of the prepreg of measurement can be below 20ppm/K.If when the described thermal expansivity of prepreg is in above-mentioned scope, then the clad stacking material comprising prepreg can not peel off.
In addition, be contained in after the solidifying product in prepreg solidifies completely, the specific inductivity of the prepreg measured under 1GHz frequency and dielectric loss are respectively less than less than 4.0 and 0.01.Term used herein " dielectric loss " represents the energy waste of the dielectric materials represented with heat energy when applying alternating-electric field on the dielectric material.If when specific inductivity and dielectric loss are respectively in above-mentioned scope, the prepreg comprising solidifying product is applicable to the insulating substrate in high frequency field.
Be contained in after the solidifying product in prepreg solidifies completely, the modulus in flexure of prepreg can be about 10GPa to about 30GPa.When the modulus in flexure of prepreg is in above-mentioned scope, warpage may can not be there is.
The thermal expansivity of prepreg, specific inductivity and modulus in flexure can use following method to measure usually.That is: metal foil layer is stacked on two surfaces of prepreg, then this layer laminate heated and apply pressure to prepare clad stacking material, then remove tinsel from clad stacking material, wherein said prepreg is prepared by the base material be impregnated with for the preparation of the composition of thermosetting resin by semicure.Then, the thermal expansivity of prepreg, dielectricity and modulus in flexure can be measured by analyzing prepreg.Wherein when heating and pressurize, described semicure resin is completely crued.
Meanwhile, prepreg laminate materials, also by the prepreg of stacked predefined quantity, then heats this layer laminate and applies pressure to prepare.When heating and pressurize, semicure resin solidifies be transformed into cross-linked resin completely.
Clad stacking material also by the tinsel that configures such as Copper Foil, silver foil or aluminium foil a to surface or two surfaces of prepreg or prepreg laminate materials, then heats this layer laminate and applies pressure to prepare.If semicure resin, when heating and pressurize, semicure resin solidifies be transformed into cross-linked resin completely.
The thickness of the tinsel of prepreg or prepreg laminate materials and clad stacking material respectively can in the scope of 0.1 μm to 300 μm.If the thickness of prepreg or prepreg laminate materials is in above-mentioned scope, can not break in winding process, and can obtain there is thickness limited multilayer laminated material.If the thickness of tinsel is in above-mentioned scope, during lamination, tinsel can not be broken, and can obtain multilayer laminated material.
When preparing clad stacking material, heating and pressurized conditions can be, such as 150 DEG C to 250 DEG C with 10Mpa to 30Mpa.But this condition can unrestrictedly change according to the thickness of the character of prepreg, activity for the preparation of the composition of thermosetting resin, the performance of printing device, the clad stacking material of expectation.
According to current embodiment, clad stacking material can comprise the binder layer be between prepreg laminate materials and tinsel further, to strengthen bounding force therebetween.Binder layer can be prepared by thermoplastic resin or thermosetting resin.In addition, the thickness of binder layer can in the scope of 0.1 to 100 μm.If the thickness of binder layer is in above-mentioned scope, bounding force increases, and binder layer has suitable thickness.
Printed circuit board (PCB) also forms circuit thereon by the tinsel on etching metal covering stacking material to be prepared.Printed circuit board (PCB) also can by thermosetting resin film at least one on the surface type metal schematic circuit prepare.If needed, printed circuit board (PCB) also can have through hole.
Multilayer printed circuit board according to embodiment can be prepared in the following way, such as, when considering the thickness of insulating layer that will be formed, between the composition prepreg of predetermined number being configured in such as inner substrate or tinsel, then this layer laminate being heated and applying pressure.In this respect, heating can be identical with the condition that those prepare clad stacking material with the condition of pressurization.In addition, can inner substrate be used as the prepreg laminate materials of electrically insulating material, clad stacking material or printed circuit board (PCB), or also can use above-mentioned at least both combination.
Below, one or more embodiment of the present invention will be described in detail by following embodiment.But these embodiments not meaning that limit the scope of one or more embodiment of the present invention.
Embodiment
(preparation of copper clad stacking material)
embodiment 1
first step: the preparation of aromatic polyester amide copolymer
179.6g (1.3mol) P-hydroxybenzoic acid, 245.5g (2.3mol) PAP, 198.2g (1.8mol) Resorcinol, 44.0g (0.4mol) Resorcinol, 731.0g (4.4mol) m-phthalic acid and 1123g (11mol) diacetyl oxide are joined in the reactor that agitator, torquer, nitrogen inlet, thermometer and reflux exchanger are housed.Inside reactor nitrogen fully purges, and then in nitrogen atmosphere, in 30 minutes, temperature is elevated to 150 DEG C.Keep the temperature of 150 DEG C, reactor is refluxed 3 hours.
Subsequently, while the acetic acid flowed out by distillation removing and unreacted diacetyl oxide, the temperature of reactor is elevated to 320 DEG C of insulations 180 minutes.The time point that torque starts to increase is considered to reaction end, then releases the content in reactor.By the pressed powder cool to room temperature obtained, and the pressed powder that grinding obtains, aromatic polyester amide copolymer powder is obtained when not carrying out any independent solid state polymerization.
second step: for the preparation of the preparation of the composition solution of thermosetting resin
The aromatic polyester amide copolymer powder prepared by 500g first step and 50g pyromellitic acid dianhydride join in the N-Methyl pyrrolidone (NMP) of 450g, and at 25 DEG C, stir the mixture 4 hours to obtain the composition solution for the preparation of thermosetting resin solution.
third step: the preparation of prepreg
At room temperature, glass woven cloth (IPC1078) is flooded with the composition solution prepared in second step, then make it remove excessive composition solution by two roller and obtain impartial thickness.Then, the glass woven cloth product obtained is put into hot air dryer, at 180 DEG C except desolventizing is to obtain prepreg.
4th step: the preparation of copper clad stacking material
Be that the electrolytic copper foil of 18 μm is configured on two opposites of prepreg prepared by third step by thickness, obtain stacking material, then use hot plate pressing machine (hot plate press) by this stacking material under 200 DEG C and 30Mpa heating and pressurizing 3 hours with obtained clad stacking material.
embodiment 2
By mode in the same manner as in Example 1 for the preparation of the composition preparing thermosetting resin, except using aromatic polyester amide copolymer powder and the 495g pyromellitic acid dianhydride of preparation in 55g embodiment 1.In addition, prepreg and copper clad stacking material has been prepared by mode in the same manner as in Example 1.
comparative example 1
Only use the aromatic polyester amide copolymer powder of preparation in 550g embodiment 1 for the preparation of the composition (not using pyromellitic acid dianhydride) preparing thermosetting resin.In addition, prepreg and copper clad stacking material has been prepared by mode in the same manner as in Example 1.
comparative example 2
By mode in the same manner as in Example 1 for the preparation of the composition preparing thermosetting resin, except using aromatic polyester amide copolymer powder and the 26g pyromellitic acid dianhydride of preparation in 524g embodiment 1.In addition, prepreg and copper clad stacking material has been prepared by mode in the same manner as in Example 1.
comparative example 3
By mode in the same manner as in Example 1 for the preparation of the composition preparing thermosetting resin, except using aromatic polyester amide copolymer powder and the 495.5g pyromellitic acid dianhydride of preparation in 54.5g embodiment 1.In addition, prepreg and copper clad stacking material has been prepared by mode in the same manner as in Example 1.
evaluation operation example
After 2 Copper Foils removing copper clad stacking material prepared by embodiment 1-2 and comparative example 1-3, analyze prepreg part, measure the cross-linking density of prepreg, thermal expansivity, specific inductivity, dielectric loss and modulus in flexure.Result is shown in table 1.
Table 1
| Assessment item | Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| The cross-linking density (%) of resin | 99.8 | 99.8 | 0 | 99.8 | 99.8 |
| The thermal expansivity (ppm/K) of prepreg | 12 | 16 | 12 | 12 | 21 |
| The specific inductivity (@1GHz) of prepreg | 3.8 | 3.9 | 3.6 | 3.7 | 4.5 |
| The dielectric loss (@1GHz) of prepreg | 0.007 | 0.009 | 0.006 | 0.006 | 0.012 |
| The modulus in flexure (Gpa) of prepreg | 13 | 19 | 6 | 8 | 20 |
In Table 1, cross-linking density is analyzed exothermic peak by using differential scanning calorimeter (DSC, TA Instrument, DSC2910) and measures, and this exothermic peak is by being elevated to 300 DEG C to obtain from room temperature with the temperature rise rate of 20 DEG C/min.Thermal expansivity is measured at the temperature of 50 DEG C to 200 DEG C by using TMA (TMA Q400).Specific inductivity and dielectric loss are by room temperature using impedometer to measure.Modulus in flexure uses IPC-TM650 to measure.
As shown in table 1, copper clad stacking material prepared by embodiment 1 and 2 and comparative example 2 and 3 comprises cross-linked resin.But copper clad stacking material prepared by comparative example 1 does not comprise any cross-linked resin.So the copper clad stacking material that copper clad stacking material prepared by embodiment 1 and 2 and comparative example 2 and 3 is prepared than comparative example 1 has better thermotolerance, chemical resistant properties and physical strength.The part (corresponding to prepreg) not comprising Copper Foil of copper clad stacking material prepared by embodiment 1 and 2 has low thermal coefficient of expansion, low-k, low-dielectric loss and high modulus in flexure.But the part not comprising Copper Foil of copper clad stacking material prepared by comparative example 1 and 2 has low modulus in flexure.In addition, compare with 2 and comparative example 1 with embodiment 1 with 2, the part that copper clad stacking material prepared by comparative example 3 does not comprise Copper Foil has high thermal expansion coefficient and bad (that is, high) dielectric properties.
According to the embodiment of the present invention, provide a kind of composition for the preparation of thermosetting resin, it comprises the aromatic polyester amide copolymer and pyromellitic acid dianhydride with amino end group, and said composition may be dissolved in non-halogen solvent.
According to another implementation of the invention, thermosetting resin film, prepreg and prepreg laminate materials are provided, it comprises the described solidifying product for the preparation of the composition of thermosetting resin, thus has low thermal coefficient of expansion, low-k, low-dielectric loss, agent of low hygroscopicity and high modulus in flexure.
According to another implementation of the invention, provide clad stacking material and printed circuit board (PCB), it comprises described prepreg or prepreg laminate materials.
Although shown particularly with reference to exemplary of the present invention and described the present invention, but should be understood that, when not deviating from the spirit and scope of the present invention defined by the following claims, those skilled in the art can carry out the various changes in form and details.
Claims (16)
1., for the preparation of a composition for thermosetting resin, described composition comprises:
The aromatic polyester amide copolymer with amino end group of 100 weight parts, described aromatic polyester amide copolymer comprises: 10mol% to 30mol% derived from repeating unit A, the 15mol% to 25mol% of aromatic hydroxycarboxylic acids be selected from by derived from least one repeating unit had in the repeating unit B of arylamine of phenolic hydroxyl group and the group that forms derived from the repeating unit B ' of aromatic diamine, 15mol% to 30mol% derived from the repeating unit C and 30mol% to 60mol% of aromatic diol derived from the repeating unit D of aromatic dicarboxylic acid; And
10 weight part to 900 weight part pyromellitic acid dianhydrides.
2. the composition for the preparation of thermosetting resin according to claim 1, wherein, repeating unit A derived from least one compound be selected from P-hydroxybenzoic acid and 2-hydroxyl-6-naphthoic acid,
Wherein repeating unit B is derived from least one compound be selected from the group that is made up of 3-amino-phenol, PAP and 2-amino-6-naphthols,
Wherein repeating unit B ' is derived from least one compound be selected from the group that is made up of Isosorbide-5-Nitrae-phenylenediamine, 1,3-phenylenediamine and 2,6-naphthylene diamine,
Wherein repeating unit C is derived from least one compound be selected from the group that is made up of Resorcinol, xenol and Resorcinol, and
Wherein repeating unit D is derived from least one compound be selected from m-phthalic acid and naphthalic acid.
3. the composition for the preparation of thermosetting resin according to claim 1, wherein, the amount of repeating unit B, repeating unit B ', repeating unit C and repeating unit D meets following condition:
1.0≤[n(B)+n(B’)+n(C)]/n(D)<1.5，
Wherein n (B), n (B '), n (C) and n (D) represent the mole number of repeating unit B, repeating unit B ', repeating unit C and repeating unit D in aromatic polyester amide copolymer respectively.
4. a thermosetting resin film, comprises the solidifying product of the composition for the preparation of thermosetting resin according to any one of claim 1-3.
5. a prepreg, comprises:
Base material; With
Be contained in the solidifying product of the composition for the preparation of thermosetting resin according to any one of the claim 1-3 in described base material.
6. prepreg according to claim 5, wherein, the base material of per unit area comprise for the preparation of the composition of thermosetting resin and the total amount of its solidifying product at 0.1g/m
2to 1000g/m
2scope in.
7. prepreg according to claim 5, wherein, described base material comprises and is selected from by aromatic polyester fibres, aromatic polyester nylon, glass fibre, at least one in the group that carbon fiber, paper or their combination form.
8. prepreg according to claim 5, based on total amount 100 weight part of the described composition for the preparation of thermosetting resin and its solidifying product, comprises at least one in the organic filler of 0.0001 weight part to 100 weight part and mineral filler further.
9. prepreg according to claim 5, wherein, when being contained in after the solidifying product in prepreg solidifies completely, when measuring the thermal expansivity of described prepreg, the thermal expansivity of described prepreg is being below 20ppm/K in one direction.
10. prepreg according to claim 5, wherein, when being contained in after the solidifying product in prepreg solidifies completely, when measuring specific inductivity and the dielectric loss of described prepreg under 1GHz frequency, the specific inductivity of described prepreg is less than 4.0, and dielectric loss is less than 0.01.
11. prepregs according to claim 5, wherein, when being contained in after the solidifying product in prepreg solidifies completely, when measuring the modulus in flexure of prepreg, the modulus in flexure of described prepreg is being 10GPa to 30GPa.
12. 1 kinds of prepreg laminate materials, comprise at least one deck prepreg according to claim 5.
13. 1 kinds of clad stacking materials, comprise:
Prepreg according to claim 5; With
Be configured at least layer of metal film at least one surface of described prepreg.
14. clad stacking materials according to claim 13, wherein, described prepreg is the prepreg laminate materials comprising at least two-layer prepreg.
15. 1 kinds of printed circuit board (PCB)s, are formed by the tinsel etched on clad stacking material according to claim 13.
16. 1 kinds of printed circuit board (PCB)s, by thermosetting resin film according to claim 4 at least one on the surface type metal circuit pattern formed.
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| KR10-2010-0064397 | 2010-07-05 | ||
| KR1020100064397A KR101708934B1 (en) | 2010-07-05 | 2010-07-05 | Composition for preparing thermosetting resin, cured product of the composition, prepreg and prepreg laminate having the cured product, and metal clad laminate and printed circuit board having the prepreg or the prepreg laminate |
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| CN102433000B true CN102433000B (en) | 2015-06-17 |
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| JP (1) | JP5721570B2 (en) |
| KR (1) | KR101708934B1 (en) |
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| JP6474261B2 (en) * | 2015-01-22 | 2019-02-27 | 上野製薬株式会社 | Laminate |
| CN111393635B (en) * | 2020-04-07 | 2024-02-09 | 宁波长阳科技股份有限公司 | Liquid crystal polymer copper-clad plate and preparation method thereof |
| CN111703150A (en) * | 2020-05-13 | 2020-09-25 | 电子科技大学 | Method for reducing dielectric loss of polyolefin composite substrate material |
| TWI789796B (en) * | 2021-06-23 | 2023-01-11 | 律勝科技股份有限公司 | Polymer and application thereof |
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| EP1561786A4 (en) * | 2002-10-16 | 2007-07-18 | Pi R & D Co Ltd | Solution compositions of block copolyimides comprising pyromellitic dianhydride and process for production thereof |
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| Publication number | Publication date |
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| TW201202341A (en) | 2012-01-16 |
| KR101708934B1 (en) | 2017-03-08 |
| CN102433000A (en) | 2012-05-02 |
| TWI503370B (en) | 2015-10-11 |
| JP2012012605A (en) | 2012-01-19 |
| JP5721570B2 (en) | 2015-05-20 |
| KR20120003667A (en) | 2012-01-11 |
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