CN102433000A - 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
- CN102433000A CN102433000A CN2011102332012A CN201110233201A CN102433000A CN 102433000 A CN102433000 A CN 102433000A CN 2011102332012 A CN2011102332012 A CN 2011102332012A CN 201110233201 A CN201110233201 A CN 201110233201A CN 102433000 A CN102433000 A CN 102433000A
- Authority
- CN
- China
- Prior art keywords
- prepreg
- repeating unit
- thermosetting resin
- compsn
- derived
- 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.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 92
- 239000011347 resin Substances 0.000 title claims abstract description 92
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 64
- 229910052751 metal Inorganic materials 0.000 title claims description 10
- 239000002184 metal Substances 0.000 title claims description 10
- 239000000203 mixture Substances 0.000 title abstract description 27
- 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
- 239000000463 material Substances 0.000 claims description 85
- 239000000758 substrate Substances 0.000 claims description 21
- 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 16
- 229920000728 polyester Polymers 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 8
- 239000012764 mineral filler Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 6
- 239000012766 organic filler Substances 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical group 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
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical class C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 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
- 239000004677 Nylon Substances 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 239000000835 fiber Substances 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
- 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
- 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 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 28
- 238000002360 preparation method Methods 0.000 description 26
- 239000002904 solvent Substances 0.000 description 22
- 229910052802 copper Inorganic materials 0.000 description 21
- 239000010949 copper Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 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 13
- 238000010438 heat treatment Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052736 halogen Inorganic materials 0.000 description 9
- 150000002367 halogens Chemical class 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 150000004665 fatty acids Chemical class 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000004744 fabric Substances 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
- 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
- 238000007598 dipping method Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 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
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 125000005518 carboxamido group Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000002148 esters Chemical class 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
- 239000000047 product Substances 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
- 229940044174 4-phenylenediamine Drugs 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
- 238000006424 Flood reaction Methods 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 compound [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
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 239000002648 laminated material Substances 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
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 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
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- PNZVFASWDSMJER-UHFFFAOYSA-N acetic acid;lead Chemical compound [Pb].CC(O)=O PNZVFASWDSMJER-UHFFFAOYSA-N 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
- 125000003368 amide group Chemical group 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
- 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
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 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
- 235000012204 lemonade/lime carbonate Nutrition 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
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 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
- IBGCXOFOCKCBNQ-UHFFFAOYSA-N nitro cyanate Chemical compound [O-][N+](=O)OC#N IBGCXOFOCKCBNQ-UHFFFAOYSA-N 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
- 238000003825 pressing Methods 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
- 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
- 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
CROSS-REFERENCE TO RELATED PATENT
The application requires the right of priority of on July 5th, 2010 at the korean patent application No.10-2010-0064397 of Korea S Department of Intellectual Property submission, and its disclosed content is all introduced the application as a reference.
Background of invention
1. technical field
One or more aspect of the present invention relates to the compsn that is used to prepare thermosetting resin, the cured prod of said composition, prepreg that comprises this cured prod and prepreg stacking material and comprises this prepreg or the clad stacking material and the printed substrate of prepreg stacking material; More specifically; The present invention relates to be used to prepare the compsn of thermosetting resin, said composition comprises aromatic polyester amide copolymer and the pyromellitic acid dianhydride with amino end group; The cured prod of said composition; The prepreg and the prepreg stacking material that comprise this cured prod; And the clad stacking material and the printed substrate that comprise this prepreg or prepreg stacking material.
2. background technology
According to the miniaturized and the multifunction trend of nearest electronics, carrying out the densification and the Miniaturization Research of printed substrate at present.The copper stacking material is widely used as the substrate for printed circuit board of electronics owing to its outstanding punch process property, Drilling processibility and low cost.
Be used for preparing the prepreg that the copper stacking material of printed substrate uses and require to have the following salient features that is suitable for semiconducting behavior and semiconductor package fabrication:
(1) corresponding to the low thermal coefficient of expansion of metal (integrated circuit substrate (IC)) thermal expansivity;
(2) ability of the low-dielectric in the high-frequency range more than 1GHz and dielectric stability
(3) under about 270 ℃ to the thermotolerance of reflow soldering process.
Prepreg is through flooding glass fabric with epoxy resin or bismaleimide-triazine resin, and dry then and this resins of semicure forms.Then, copper foil layer is stacked on prepreg or the prepreg stacking material, and this resin of completely solidified forms the copper clad stacking material.This copper clad stacking material is formed thin layer, and it is carried out pyroprocessing, such as under 270 ℃, carrying out reflow soldering process.When carrying out pyroprocessing, because prepreg is different with the thermal expansivity of copper clad stacking material, thermal distortion possibly take place in the copper clad stacking material of thin layer form, thereby causes copper clad stacking material productive rate to reduce.In addition, the high-hygroscopicity of epoxy resin or bismaleimide-triazine resin must be lowered.Especially, have bad dielectric properties (that is, the high-k in high-frequency range) in the high-frequency range of resin more than 1GHz, therefore be difficult to resin is applied on the semiconductor packages PC board that can receive high frequency and High-speed machining processing.Therefore, need a kind of prepreg of exploitation with low-dielectric ability.
Recently, through using aromatic polyester resin to replace epoxy resin or bismaleimide-triazine resin to prepare prepreg.Said prepreg prepares through using the organic or inorganic yarn fabric of aromatic polyester resin dipping.Especially, can use aromatic polyester resin and aromatic polyester yarn fabric to prepare the aromatic polyester prepreg.At length, aromatic polyester is dissolved in the solvent that contains halogen such as chlorine and prepares composition solution, floods the aromatic polyester yarn fabric with said composition solution, and the dry then product that obtains prepares the aromatic polyester prepreg.Yet in the method, the solvent that contains halogen is difficult to fully removed, and halogen can corrode Copper Foil.Therefore, the needs exploitation is a kind of uses non-halogen solvent to prepare the method for aromatic polyester prepreg.
Summary of the invention
One or more aspect of the present invention is provided for preparing the compsn of thermosetting resin, and said compsn comprises aromatic polyester amide copolymer and the pyromellitic acid dianhydride with amino end group.
One or more aspect of the present invention provides thermosetting resin film, and it comprises the said cured prod that is used to prepare the compsn of thermosetting resin.
One or more aspect of the present invention provides prepreg and prepreg stacking material, and it comprises the said cured prod that is used to prepare the compsn of thermosetting resin.
The present invention also provides clad stacking material and the printed substrate that comprises said prepreg or prepreg stacking material.
According to an aspect of the present invention; A kind of compsn that is used to prepare thermosetting resin is provided; It comprises: the aromatic polyester amide copolymer with amino end group of 100 weight parts, said aromatic polyester amide copolymer comprises: about 10mol% to about 30mol% derived from the repeating unit A of aromatic hydroxycarboxylic acids, about 15mol% to about 25mol% be selected from by at least a repeating unit in the group of being formed derived from the repeating unit B of arylamine with derived from the repeating unit B ' of aromatic diamine, about 15mol% with phenolic hydroxyl group extremely about 30mol% derived from the repeating unit C of aromatic diol and about 30mol% extremely about 60mol% derived from the repeating unit D of aromatic dicarboxylic acid; And 10 to 900 weight part pyromellitic acid dianhydride.
Repeating unit A is derived from least a compound that is selected from PHB and 2-hydroxyl-6-naphthoic acid, and repeating unit B is derived from being selected from the amino-phenol by 3-, at least a compound in 4-amino-phenol and the group that 2-amino-the 6-naphthols is formed; Repeating unit B ' is derived from being selected from by 1; The 4-phenylenediamine, 1,3-phenylenediamine and 2; At least a compound in the group that the 6-naphthylene diamine is formed; Repeating unit C is derived from being selected from by Resorcinol, at least a compound in the group that xenol and Resorcinol are formed, and repeating unit D is derived from least a compound that is selected from m-phthalic acid and the naphthalic acid.
The amount of repeating unit B, repeating unit B ', repeating unit C and repeating unit D satisfies 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 respectively the mole numbers of repeating unit B, repeating unit B ', repeating unit C and repeating unit D in the aromatic polyester amide copolymer.
According to a further aspect in the invention, a kind of thermosetting resin film is provided, it comprises the said cured prod that is used to prepare the compsn of thermosetting resin.
According to a further aspect in the invention, a kind of prepreg is provided, said prepreg comprises base material and is contained in said in this base material and is used to prepare the cured prod of the compsn of thermosetting resin.
The total amount of the cured prod of the unit surface base material is comprised said compsn that is used to prepare thermosetting resin and said compsn can be at about 0.1g/m
2To about 1,000g/m
2Scope in.
Said base material can comprise and is selected from by the aromatic polyester fiber, aromatic polyester nylon, spun glass, thomel, at least a in the group that paper or their combination are formed.
Based on the said compsn that is used to prepare thermosetting resin with and total amount 100 weight parts of cured prod, said prepreg can further comprise at least a in organic filler and the mineral filler of 0.0001 to 100 weight part.
After the cured prod completely solidified that is being contained in the prepreg, when measuring the thermal expansivity of said prepreg, the thermal expansivity of said prepreg upwards is below the 20ppm/K at folk prescription.
After the cured prod completely solidified that is being contained in the prepreg, when under the 1GHz frequency, measuring specific inductivity and the dielectric loss of said prepreg, the specific inductivity of said prepreg can be below 4.0, and dielectric loss can be below 0.01.
After the cured prod completely solidified that is being contained in the prepreg, when measuring the modulus in flexure of said prepreg, the modulus in flexure of said prepreg can for about 10GPa to about 30GPa.
According to another aspect of the present invention, provide and comprise the prepreg stacking material of one deck prepreg at least.
According to another aspect of the present invention, the clad stacking material that comprises prepreg is provided; And at least one lip-deep layer of metal film at least that is configured in said prepreg.
Said prepreg can be the prepreg stacking material that comprises two-layer at least prepreg.
According to another aspect of the present invention, a kind of printed substrate is provided, it prepares through the tinsel on the said clad stacking material of etching.
According to another aspect of the present invention, a kind of printed substrate is provided, it forms through type metal circuitous pattern at least one surface of thermosetting resin film.
The detailed description of invention
Below, exemplary embodiment according to the present invention is described a kind of compsn that is used to prepare thermosetting resin, its cured prod and the prepreg that comprises this cured prod.
According to the embodiment of the present invention, the compsn that is used to prepare thermosetting resin comprises aromatic polyester amide copolymer and about 10 that 100 weight parts have amino end group to about 900 weight part pyromellitic acid dianhydrides.
When the amount of aromatic polyester amide copolymer and pyromellitic acid dianhydride was in above-mentioned scope, the cured prod (being cross-linked resin) that is used to prepare the compsn of thermosetting resin had low heat expansion property, low-dielectric and high crosslink density.Because high crosslink density, the cured prod of said compsn can have agent of low hygroscopicity, high-clarity and high modulus in flexure.
According to the embodiment of the present invention, the 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 at least a repeating unit in the group of being formed derived from the repeating unit B of arylamine with derived from the repeating unit B ' of aromatic diamine, about 15mol% with phenolic hydroxyl group extremely about 30mol% derived from the repeating unit C of aromatic diol and about 30mol% extremely about 60mol% derived from the repeating unit D of aromatic dicarboxylic acid.
When the amount of repeating unit A was in above-mentioned scope, said aromatic polyester amide copolymer had high physical strength and excellent thermal properties.When the total amount of repeating unit B and repeating unit B ' was in above-mentioned scope, the solvability of said aromatic polyester amide copolymer in solvent increased, and said aromatic polyester amide copolymer can have suitable melt temperature.When the amount of repeating unit C was in above-mentioned scope, the solvability of said aromatic polyester amide copolymer in solvent increased, and said aromatic polyester amide copolymer can have suitable melt temperature and high-clarity.When the amount of repeating unit D in above-mentioned scope, the solvability of said aromatic polyester amide copolymer in solvent increases, and said aromatic polyester amide copolymer can have low thermal coefficient of expansion and low-dielectric.
Repeating unit A can be derived from least a compound that is selected from PHB and 2-hydroxyl-6-naphthoic acid.Repeating unit B can be derived from being selected from by 1 derived from least a compound, the repeating unit B ' that are selected from by in 3-amino-phenol, 4-amino-phenol and the group that 2-amino-the 6-naphthols is formed; 4-phenylenediamine, 1; 3-phenylenediamine and 2, at least a compound in the group that the 6-naphthylene diamine is formed.Repeating unit C can be derived from being selected from by Resorcinol at least a compound in the group that xenol and Resorcinol are formed.Repeating unit D can be derived from least a compound that is selected from the group of being 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 satisfy 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 respectively the mole numbers of repeating unit B, repeating unit B ', repeating unit C and repeating unit D in the aromatic polyester amide copolymer.
When quantity than { [n (B)+n (B ')+n (C)]/n (D) } in above-mentioned scope the time, said aromatic polyester amide copolymer comprises a large amount of amino end group and/or hydroxyl end groups.In addition, between aromatic polyester amide copolymer and the epoxy resin curing reaction taking place, forms the thermosetting resin with high crosslink density.
For example, each repeating unit in the 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 independently be halogen atom, carboxyl, amino, nitro, cyanic acid, replacement or unsubstituted C separately
1-C
20Alkyl, replacement or unsubstituted C
1-C
20Alkoxyl group, replacement or unsubstituted C
2-C
20Thiazolinyl, replacement or unsubstituted C
2-C
20Alkynyl, replacement or unsubstituted C
1-C
20Assorted alkyl, replacement or unsubstituted C
6-C
30Aryl, replacement or unsubstituted C
7-C
30Aralkyl, replacement or unsubstituted C
5-C
30Heteroaryl, or replace or unsubstituted C
3-C
30Heteroarylalkyl.At least one Wasserstoffatoms of term used herein " substituted " expression compound by halogen atom, hydroxyl, alkyl, alkoxyl group, amino or these groups both replace at least.
The aromatic polyester amide copolymer can prepare through the polymerization following substances: (1) aromatic hydroxycarboxylic acids or its ester derivative; (2) be selected from by the arylamine with phenolic hydroxyl group or its amide derivatives, and at least a in the group formed 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 verivate, such as acyl chlorides or acid anhydrides, or can form the verivate of ester bond with pure and mild 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.
The aromatic polyester amide copolymer of preparation may be dissolved in the solvent as stated, and it can be the thermotropic liquor polyester amide copolymer, and it has optically anisotropic melt in formation below 400 ℃.For example, the melt temperature of said aromatic polyester amide copolymer can be about 250 to about 400 ℃ scope, and number-average molecular weight about 1,000 to about 20,000 scope.
The aromatic polyester amide copolymer can use following method preparation.That is: with fatty acid anhydride will be corresponding to hydroxyl or amino, the arylamine that corresponds respectively to repeating unit B and/or repeating unit B ' and/or the aromatic diamine of the aromatic hydroxycarboxylic acids of repeating unit A, carry out acidylate to obtain acylate corresponding to the aromatic diol of repeating unit C, then the acylate and the aromatic dicarboxylic acid that obtain are carried out transesterify to carry out melt polymerization.In this case, through regulating the consumption of fatty acid anhydride suitably, the aromatic polyester amide copolymer can have the amino end group and the predetermined polymerization degree.For example, when increasing the consumption of fatty acid anhydride, the quantity of amino end group reduces in the aromatic polyester amide copolymer, 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 is counted hydroxyl and amino total amount about 0.9 to about 1.2 times with chemical equivalent, for example 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 that generates contains amino end group; And the coloring phenomenon of aromatic polyester amide copolymer reduces, and some monomers of use can not distil from the aromatic polyester amide copolymer that generates, and the phenol gas of generation reduces.Acylation reaction can be carried out about 30 minutes to about 8 hours to about 170 ℃ TR about 130, for example, carried out about 2 to about 4 hours to about 160 ℃ TR about 140.
The fatty acid anhydride that uses in the 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 carboxamido-group exchange can be carried out in 130-400 ℃ TR, and temperature rise rate is 0.1-2 ℃/min, and for example, under 140-350 ℃ temperature, temperature rise rate is 0.3-1 ℃/min.
When carrying out the exchange of transesterify and carboxamido-group between fatty ester that obtains and the aromatic dicarboxylic acid; In order to increase speed of reaction; Molecular balance is moved, can shift out reaction system through evaporation or distillation as lipid acid and the unreacted fatty acid anhydride that by product generates.
Acylation reaction, transesterification reaction and amide exchange reaction can carry out in the presence of catalyzer.Catalyzer can be any known catalysts that is used to prepare vibrin, for example magnesium acetate, tin acetate (II), tetrabutyl titanate, sugar of lead, sodium acetate, potassium acetate, ANTIMONY TRIOXIDE SB 203 99.8 PCT, N, N-dimethyl aminopyridine and N-Methylimidazole.Catalyzer can add with monomer simultaneously, in the presence of catalyzer, carries out acylation reaction, transesterification reaction and amide exchange reaction then.
The polycondensation of transesterify and carboxamido-group exchange can be carried out through melt polymerization.Since the aromatic polyester amide copolymer that generates after a while with cross linking of epoxy resin, promptly solidify, can form cured prod, so solid state polymerization not necessarily with high-polymerization degree and high mechanical strength.
The polymerization reactor that melt polymerization uses does not receive particular restriction, can be any reactor drum that whisking appliance is housed that is generally used for the heavy viscous material reaction.In this respect, the reactor drum of melt polymerization can be identical with the reactor drum of acylation reaction, or use different reactor drums in each reaction.
According to current embodiment, the aromatic polyester amide copolymer contains amino end group, so the aromatic polyester amide copolymer can be highly cross-linked by pyromellitic acid dianhydride.
The aromatic polyester amide copolymer of preparation can have the thermal expansivity below the 3ppm/K as stated.
According to the embodiment of the present invention, the compsn that is used to prepare thermosetting resin can prepare through aromatic polyester amide copolymer and the pyromellitic acid dianhydride that mixes predetermined proportion.
Thermosetting resin film can be prepared by the compsn that is used to prepare thermosetting resin through common solvent casting method.
The compsn that is used for preparing thermosetting resin may be dissolved in solvent.So can use the compsn dipping or the coated substrate that are used to prepare thermosetting resin, thermofixation then (semicure usually) product prepares prepreg.In this case, between the composition of compsn that being used in the prepreg prepare thermosetting resin crosslinking reaction takes place and prepare cross-linked resin through using thermofixation, make to be contained in.Promptly be, be used for preparing the amino end group of aromatic polyester amide copolymer of composition of the compsn of thermosetting resin, with other composition in the compsn, promptly pyromellitic acid dianhydride is partial cross-linked to form cross-linked resin (being cured prod).Because said cured prod has the physical properties of aromatic polyester amide copolymer, cured prod can have agent of low hygroscopicity and high modulus in flexure, and low thermal coefficient of expansion, low-k and low-dielectric loss.
The solidification process that term used herein " semicure " expression wherein is used to prepare the compsn of resin is the state that part is carried out.Can fusion during the resin heating that generates through the semicure compsn but can soften, can swelling but in solvent, can not dissolve.Usually, the resin that obtains through the semicure compsn is called the B b stage resin b.The state that the solidification process of compsn has wherein carried out fully represented in term " completely solidified ".The resin that the completely solidified compsn generates can not soften when heating, in solvent, can not dissolve.Usually, the resin that obtains through the completely solidified compsn is called the C b stage resin b.
In addition, the compsn that is used to prepare thermosetting resin also can be used for other field except that prepreg.
Prepreg can or be coated in composition solution on organic or inorganic yarn fabric and/or the non-woven fabric through dipping in composition solution; Dry then and semicure composition solution prepares; Wherein, composition solution is to be dissolved in solvent through the compsn that will be used for preparing thermosetting resin to prepare.Dipping can carry out through solution impregnation or varnish impregnation.
Based on the compsn that is used to prepare thermosetting resin of 100 weight parts, the consumption that is used to dissolve the solvent of aromatic polyester amide copolymer can be 100 to 100,000 weight parts.When the consumption of solvent was in above-mentioned scope, the compsn that is used for preparing thermosetting resin fully was dissolved in solvent, and was used to prepare the gain in yield of the compsn of thermosetting resin.
The solvent that is used to dissolve the aromatic polyester amide copolymer can be non-halogen solvent, but is not limited thereto.For example solvent can be aprotic, polar based compound, halogenation phenol, neighbour-dichlorobenzene, chloroform, methylene dichloride, tetrachloroethane or their combination.
Special, owing to be used for preparing the compsn of thermosetting resin even can be dissolved in non-halogen solvent, therefore possibly avoid the use of the solvent that contains halogen.So the clad stacking material or the tinsel of printed substrate that comprise the cured prod of compsn can be avoided being corroded, it possibly be corroded under the situation of halogen solvent and contain in use.
Base material can comprise aromatic polyester fiber, aromatic polyester nylon, spun glass, thomel, paper or comprise in them both yarn fabrics and/or non-woven fabric at least.
When impregnation steps is used for the preparation method of prepreg, the base material thing solution impregnation that can be combined, for example about 0.001 minute to about 1 hour.When time of immersion is in above-mentioned scope, base material the be combined dipping of thing solution homogeneous and the gain in yield of prepreg.
In addition, the said base material thing solution impregnation that can in 20-190 ℃ TR, be combined.
The pickup of compsn on the unit surface base material that is used to prepare thermosetting resin can be about 0.1 to about 1,000g/m
2Scope in.When the pickup of the compsn that is used to prepare thermosetting resin was in above-mentioned scope, the productive rate of prepreg improved, and its handling ease is carried out.So in prepreg, through after the semicure process, the amount of cured prod that is used to prepare compsn and the compsn of thermosetting resin can be about 0.1g/m based on the base material of unit surface
2To about 1,000g/m
2
In order to control specific inductivity and thermal expansivity, can in composition solution, add mineral filler, for example silica, white lake or lime carbonate; And/or organic filler for example cured epoxy resin or crosslink propylene aldehyde radical material (crosslinked acryl).Mineral filler can be a titanate, for example barium titanate or strontium titanate, the perhaps titanium in other metal section and part replacement barium titanate of usefulness or the compound of barium.Compsn based on being used to prepare thermosetting resin is 100 weight parts, and the mineral filler that contains in the said composition solution and/or the consumption of organic filler can be 0.0001 to 100 weight parts.If the consumption of mineral filler and/or organic filler is in above-mentioned scope the time, the thermal expansivity of prepreg reduces, and the cured prod that is used to prepare compsn and the compsn of thermosetting resin can play the effect of tackiness agent fully after the semicure process.Therefore, after the semicure process, the mineral filler that contains in the prepreg and/or the amount of organic filler can be 0.0001 to 100 weight parts, based on the total amount of cured prod of compsn and compsn that is used to prepare thermosetting resin of 100 weight parts.
Owing to comprise the cured prod of the compsn that is used to prepare 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 said organic or inorganic yarn fabric and/or organic or inorganic non-woven fabric have high mechanical strength; Therefore prepreg has outstanding dimensional stability, is difficult to thermal distortion, and can be flexible or hard.Because these characteristics, prepreg are applicable to through hole boring and handle and lamination process.So prepreg can be used as the flexible substrate material in various fields.
In the pickling process technology of preparation prepreg, after with composition solution base material being flooded or applying, can remove through evaporation and desolvate, be not limited thereto but remove the method for desolvating.For example, evaporation can be carried out through heating evaporation, vacuum-evaporation or the evaporation of ventilating.Solvent also can be through removing the prepreg that is impregnated with composition solution under 20-190 ℃ temperature in dry 1 minute to 2 hours.
Then, the exsiccant prepreg heated under 120-320 ℃ temperature 1 to 8 hour, was contained in being used in the prepreg with semicure and prepared the compsn of thermosetting resin.
According to current embodiment, the thickness of the prepreg of preparation can be extremely about 200 μ m of about 5 μ m, and for example about 30 μ m are to about 150 μ m.
After cured prod in being contained in prepreg (that is, the semicure resin=B b stage resin b) completely solidified, the unidirectional heat coefficient of expansion of the prepreg of measurement can be below the 20ppm/K.If the said thermal expansivity of prepreg is in above-mentioned scope the time, the clad stacking material that then comprises prepreg can not peel off.
In addition, after the cured prod completely solidified in being contained in prepreg, be respectively below 4.0 with below 0.01 at the specific inductivity of the prepreg of measuring under the 1GHz frequency and dielectric loss.The energy waste of the dielectric materials that term used herein " dielectric loss " expression is represented with heat energy when on dielectric materials, applying alternating-electric field.If specific inductivity and dielectric loss are respectively in above-mentioned scope the time, the prepreg that comprises cured prod is applicable to the insulating substrate in high frequency field.
After the cured prod completely solidified in being contained in prepreg, the modulus in flexure of prepreg can for about 10GPa to about 30GPa.When the modulus in flexure of prepreg was in above-mentioned scope, warpage maybe not can take place.
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 is heated and exerts pressure and prepare the clad stacking material; Remove tinsel from the clad stacking material then, wherein said prepreg is to prepare through the base material that semicure is impregnated with the compsn that is used to prepare thermosetting resin.Then, can measure thermal expansivity, dielectricity and the modulus in flexure of prepreg through analyzing prepreg.Wherein when heating and pressurization, said semicure resin is completely crued.
Simultaneously, the prepreg stacking material also can be through the prepreg of range upon range of set amount in advance, then to this layer laminate heating and exert pressure and prepare.When heating and pressurization, semicure resin completely solidified is transformed into cross-linked resin.
The clad stacking material also can be through configuration such as the tinsel of Copper Foil, silver foil or aluminium foil on surface of prepreg or prepreg stacking material or two surfaces, then to this layer laminate heating and exert pressure and prepare.If the semicure resin, when heating and pressurization, semicure resin completely solidified is transformed into cross-linked resin.
The thickness of the tinsel of prepreg or prepreg stacking material and clad stacking material respectively can be in the scope of 0.1 μ m to 300 μ m.If the thickness of prepreg or prepreg stacking material in above-mentioned scope, can not break, and can obtain to have thickness limited multilayer laminated material in winding process.If the thickness of tinsel is in above-mentioned scope, tinsel can not broken during lamination, and can obtain multilayer laminated material.
When preparation clad stacking material, heating with pressurized conditions can be, for example 150 ℃ to 250 ℃ and 10Mpa to 30Mpa.But, this condition can be unrestrictedly according to the character of prepreg, the thickness of clad stacking material that is used to prepare performance, the expectation of activity, the printing device of the compsn of thermosetting resin changes.
According to current embodiment, the clad stacking material can further comprise the binder layer that is between prepreg stacking material and the tinsel, to strengthen the bounding force between the two.Binder layer can be prepared by thermoplastic resin or thermosetting resin.In addition, the thickness of binder layer can be in the scope of 0.1 to 100 μ m.If the thickness of binder layer is in above-mentioned scope, bounding force increases, and binder layer has suitable thickness.
Printed substrate can and form circuit above that through the tinsel on the etching metal covering stacking material and prepare.Printed substrate also can prepare through type metal schematic circuit at least one surface of thermosetting resin film.If desired, printed substrate also can have through hole.
Multilayer printed circuit board according to embodiment can prepare through following mode; For example; Under the situation of considering the thickness of insulating layer that will form, the prepreg of predetermined number is configured between the composition such as inner base material or tinsel, then to this layer laminate heating and exert pressure.In this respect, heating can be identical with those conditions that prepare the clad stacking material with the condition of pressurization.In addition, the prepreg stacking material, clad stacking material or the printed substrate that are used as electrically insulating material can be used as inner base material, perhaps also can use above-mentioned both combinations at least.
Below, one or more embodiments of the present invention will be elaborated through following embodiment.But these embodiment and the scope to one or more embodiments of the present invention that do not mean that limit.
Embodiment
(preparation of copper clad stacking material)
Embodiment 1
First step: the preparation of aromatic polyester amide copolymer
179.6g (1.3mol) PHB, 245.5g (2.3mol) 4-amino-phenol, 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 drum that whisking appliance, torquer, nitrogen inlet, TM and reflux exchanger are housed.Inside reactor fully purges with nitrogen, in nitrogen atmosphere, in 30 minutes, temperature is elevated to 150 ℃ then.Keep 150 ℃ temperature, reactor drum was refluxed 3 hours.
Subsequently, removing effusive acetate and unreacted diacetyl oxide through distillation when, the temperature of reactor drum is elevated to 320 ℃ of insulations 180 minutes.The time point that torque begins to increase is considered to reaction end, emits the content in the reactor drum then.With the pressed powder cool to room temperature that obtains, and grind the pressed powder that obtains, under the situation of not carrying out any independent solid state polymerization, obtain aromatic polyester amide copolymer powder.
Second step: be used to prepare the preparation of the composition solution of thermosetting resin
In the N-Methyl pyrrolidone (NMP) that the aromatic polyester amide copolymer powder of 500g first step preparation and 50g pyromellitic acid dianhydride are joined 450g, and under 25 ℃, stir the mixture and be used to prepare the composition solution of thermosetting resin solution in 4 hours with acquisition.
Third step: the preparation of prepreg
At room temperature, (IPC1078) floods with the composition solution for preparing in second step with the glass woven, makes it remove excessive composition solution and obtain impartial thickness through two rollers then.Then, the glass woven product that obtains is put into hot air dryer, remove at 180 ℃ and desolvate to obtain prepreg.
The 4th step: the preparation of copper clad stacking material
With thickness is on two opposites of the electrolytic copper foil of the 18 μ m prepreg that is configured in the third step preparation; Obtain stacking material, use then hot plate pressing machine (hot plate press) with this stacking material 200 ℃ with 30Mpa under heating and pressurizing 3 hours to make the clad stacking material.
Embodiment 2
Through with embodiment 1 in identical mode prepare the compsn that is used to prepare thermosetting resin, except using the aromatic polyester amide copolymer powder and the 495g pyromellitic acid dianhydride of preparation among the 55g embodiment 1.In addition, through with embodiment 1 in identical mode prepared prepreg and copper clad stacking material.
The comparative example 1
Only use the aromatic polyester amide copolymer powder of preparation among the 550g embodiment 1 to prepare the compsn (not using pyromellitic acid dianhydride) that is used to prepare thermosetting resin.In addition, through with embodiment 1 in identical mode prepared prepreg and copper clad stacking material.
The comparative example 2
Through with embodiment 1 in identical mode prepare the compsn that is used to prepare thermosetting resin, except using the aromatic polyester amide copolymer powder and the 26g pyromellitic acid dianhydride of preparation among the 524g embodiment 1.In addition, through with embodiment 1 in identical mode prepared prepreg and copper clad stacking material.
The comparative example 3
Through with embodiment 1 in identical mode prepare the compsn that is used to prepare thermosetting resin, except using the aromatic polyester amide copolymer powder and the 495.5g pyromellitic acid dianhydride of preparation among the 54.5g embodiment 1.In addition, through with embodiment 1 in identical mode prepared prepreg and copper clad stacking material.
Estimate embodiment
Behind 2 Copper Foils of the copper clad stacking material of removing embodiment 1-2 and comparative example 1-3 preparation, analyze the prepreg part, measured cross-linking density, thermal expansivity, specific inductivity, dielectric loss and the modulus in flexure of prepreg.The result is shown in table 1.
Table 1
| Assessment item | Embodiment 1 | Embodiment 2 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| The cross-linking density of resin (%) | 99.8 | 99.8 | 0 | 99.8 | 99.8 |
| The thermal expansivity of prepreg (ppm/K) | 12 | 16 | 12 | 12 | 21 |
| The specific inductivity of prepreg (1GHz) | 3.8 | 3.9 | 3.6 | 3.7 | 4.5 |
| The dielectric loss of prepreg (1GHz) | 0.007 | 0.009 | 0.006 | 0.006 | 0.012 |
| The modulus in flexure of prepreg (Gpa) | 13 | 19 | 6 | 8 | 20 |
[0169]In table 1, (DSC, TA Instrument DSC2910) analyze exothermic peak and measure cross-linking density, and this exothermic peak obtains through being elevated to 300 ℃ from room temperature with the temperature rise rate of 20 ℃/min through using differential scanning calorimeter.Thermal expansivity is measured under 50 ℃ to 200 ℃ temperature through using TMA (TMA Q400).Specific inductivity and dielectric loss are measured through at room temperature using impedometir.Modulus in flexure uses IPC-TM650 to measure.
As shown in table 1, embodiment 1 and 2 and comparative example 2 and 3 the preparation the copper clad stacking material comprise cross-linked resin.But the copper clad stacking material of comparative example's 1 preparation does not comprise any cross-linked resin.So, embodiment 1 and 2 and the copper clad stacking material comparison of comparative example 2 and 3 preparations have better thermotolerance, chemical resistant properties and physical strength than the copper clad stacking material of embodiment 1 preparation.The part that does not comprise Copper Foil (corresponding to prepreg) of the copper clad stacking material of embodiment 1 and 2 preparations has low thermal coefficient of expansion, low-k, low-dielectric loss and high modulus in flexure.But the part that does not comprise Copper Foil of the copper clad stacking material of comparative example 1 and 2 preparations has low modulus in flexure.In addition, with embodiment 1 with 2 and comparative example 1 compare with 2, the part that the copper clad stacking material of comparative example 3 preparation 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, a kind of compsn that is used to prepare thermosetting resin is provided, it comprises aromatic polyester amide copolymer and the pyromellitic acid dianhydride with amino end group, and said composition may be dissolved in the non-halogen solvent.
According to another implementation of the invention; Thermosetting resin film, prepreg and prepreg stacking material are provided; It comprises the said cured prod that is used to prepare the compsn of thermosetting resin, thereby 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, clad stacking material and printed substrate are provided, it comprises said prepreg or prepreg stacking material.
Although showed particularly and described the present invention with reference to exemplary of the present invention; But should be understood that; Under the situation that does not deviate 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 on form and the details.
Claims (16)
1. compsn that is used to prepare thermosetting resin, said compsn comprises:
The aromatic polyester amide copolymer with amino end group of 100 weight parts, said aromatic polyester amide copolymer comprises: about 10mol% to about 30mol% derived from the repeating unit A of aromatic hydroxycarboxylic acids, about 15mol% to about 25mol% be selected from by at least a repeating unit in the group of being formed derived from the repeating unit B of arylamine with derived from the repeating unit B ' of aromatic diamine, about 15mol% with phenolic hydroxyl group extremely about 30mol% derived from the repeating unit C of aromatic diol and about 30mol% extremely about 60mol% derived from the repeating unit D of aromatic dicarboxylic acid; And
About 10 weight parts to about 900 weight part pyromellitic acid dianhydrides.
2. the compsn that is used to prepare thermosetting resin according to claim 1, wherein, repeating unit A is derived from least a compound that is selected from PHB and 2-hydroxyl-6-naphthoic acid,
Wherein repeating unit B is derived from being selected from by at least a compound in 3-amino-phenol, 4-amino-phenol and the group that 2-amino-the 6-naphthols is formed,
Wherein repeating unit B ' is derived from being selected from by 1,4-phenylenediamine, 1, and 3-phenylenediamine and 2, at least a compound in the group that the 6-naphthylene diamine is formed,
Wherein repeating unit C is derived from least a compound that is selected from the group of being made up of Resorcinol, xenol and Resorcinol, and
Wherein repeating unit D is derived from least a compound that is selected from m-phthalic acid and the naphthalic acid.
3. the compsn that is used to prepare thermosetting resin according to claim 1, wherein, the amount of repeating unit B, repeating unit B ', repeating unit C and repeating unit D satisfies 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 the aromatic polyester amide copolymer respectively.
4. thermosetting resin film comprises among the claim 1-3 each described cured prod that is used to prepare the compsn of thermosetting resin.
5. prepreg comprises:
Base material; With
Be contained among the claim 1-3 in the said base material each described cured prod that is used to prepare the compsn of thermosetting resin.
6. prepreg according to claim 5, wherein, the compsn that base material comprised is used to prepare thermosetting resin of per unit area with and the total amount of cured prod at about 0.1g/m
2To about 1000g/m
2Scope in.
7. prepreg according to claim 5, wherein, said base material comprises and being selected from by aromatic polyester fiber, aromatic polyester nylon, spun glass, at least a in the group that thomel, paper or their combination are formed.
8. prepreg according to claim 5; Based on the said compsn that is used to prepare thermosetting resin with and total amount 100 weight parts of cured prod, further comprise at least a in organic filler and the mineral filler of about 0.0001 weight part to about 100 weight parts.
9. prepreg according to claim 5, wherein, after the cured prod completely solidified that is being contained in the prepreg, when measuring the thermal expansivity of said prepreg, the thermal expansivity of said prepreg upwards is below the 20ppm/K at folk prescription.
10. prepreg according to claim 5; Wherein, after the cured prod completely solidified that is being contained in the prepreg, when under the 1GHz frequency, measuring specific inductivity and the dielectric loss of said prepreg; The specific inductivity of said prepreg is below 4.0, and dielectric loss is below 0.01.
11. prepreg according to claim 5, wherein, after the cured prod completely solidified that is being contained in the prepreg, when measuring the modulus in flexure of prepreg, the modulus in flexure of said prepreg is that about 10GPa is to about 30GPa.
12. a prepreg stacking material comprises the described prepreg of one deck claim 5 at least.
13. a clad stacking material comprises:
The described prepreg of claim 5; With
Be configured at least one lip-deep layer of metal film at least of said prepreg.
14. clad stacking material according to claim 13, wherein, said prepreg is the prepreg stacking material that comprises two-layer at least prepreg.
15. a printed substrate forms through the tinsel on the described clad stacking material of etching claim 13.
16. a printed substrate forms through type metal circuit pattern at least one surface of the described thermosetting resin film of claim 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102433000A true CN102433000A (en) | 2012-05-02 |
| CN102433000B CN102433000B (en) | 2015-06-17 |
Family
ID=45599397
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110233201.2A Active CN102433000B (en) | 2010-07-05 | 2011-07-05 | 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 |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5721570B2 (en) |
| KR (1) | KR101708934B1 (en) |
| CN (1) | CN102433000B (en) |
| TW (1) | TWI503370B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393635A (en) * | 2020-04-07 | 2020-07-10 | 宁波长阳科技股份有限公司 | Liquid crystal polymer copper-clad plate and preparation method thereof |
| CN115505124A (en) * | 2021-06-23 | 2022-12-23 | 律胜科技股份有限公司 | Polymer and use thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6474261B2 (en) * | 2015-01-22 | 2019-02-27 | 上野製薬株式会社 | Laminate |
| CN111703150A (en) * | 2020-05-13 | 2020-09-25 | 电子科技大学 | Method for reducing dielectric loss of polyolefin composite substrate material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5962608A (en) * | 1997-02-14 | 1999-10-05 | Reliance Electric Industrial Co. | Polymers made with metal oxide sols |
| CN1957042A (en) * | 2004-05-26 | 2007-05-02 | 宝理塑料株式会社 | Thermoplastic resin composition |
| CN101184798A (en) * | 2005-05-27 | 2008-05-21 | 纳幕尔杜邦公司 | Resin compositions with a low coefficient of thermal expansion and articles therefrom |
| CN101687983A (en) * | 2007-05-23 | 2010-03-31 | 三星精密化学株式会社 | Aromatic liquid-crystalline polyester amide copolymer, prepreg including the same, prepreg laminate including the prepreg, metal film laminate including the prepreg, and printed wiring board including |
| US20100124037A1 (en) * | 2008-11-18 | 2010-05-20 | Samsung Electronics Co., Ltd. | Thermosetting composition and printed circuit board using the same |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2947884B2 (en) * | 1990-06-27 | 1999-09-13 | 三井化学株式会社 | Aromatic polyester amide |
| JPH051269A (en) * | 1991-06-24 | 1993-01-08 | Toray Ind Inc | Adhesive resin composition |
| EP0599886B1 (en) * | 1991-08-19 | 2001-03-21 | Mississippi Polymer Technologies, Inc. | Macromonomers having reactive end groups |
| US5290452A (en) * | 1991-12-05 | 1994-03-01 | Exxon Research & Engineering Co. | Crosslinked polyester amide membranes and their use for organic separations |
| JPH07238236A (en) * | 1994-03-01 | 1995-09-12 | Nippon Ester Co Ltd | Resin composition for powder coating |
| JP4220794B2 (en) * | 2002-02-01 | 2009-02-04 | 積水化学工業株式会社 | Insulating substrate material, printed circuit board, laminate, copper foil with resin, copper clad laminate, polyimide film, TAB film and prepreg |
| US20060004180A1 (en) * | 2002-10-16 | 2006-01-05 | Hiroshi Itatani | Solution compositions of block copolyimides comprising pyromellitic dianhydride and process for production thereof |
| WO2008114674A1 (en) * | 2007-03-14 | 2008-09-25 | Zeon Corporation | Insulating composite body, method for producing the same, and use of insulating composite body |
| JP5231174B2 (en) * | 2007-11-02 | 2013-07-10 | 三星電子株式会社 | Substrate-forming composition, prepreg, substrate and thermosetting aromatic oligomer |
| JP5221937B2 (en) * | 2007-11-16 | 2013-06-26 | 株式会社オートネットワーク技術研究所 | Acid anhydride-introduced polymer and polymer composition, covered electric wire and wire harness |
-
2010
- 2010-07-05 KR KR1020100064397A patent/KR101708934B1/en active IP Right Grant
-
2011
- 2011-07-05 JP JP2011149284A patent/JP5721570B2/en active Active
- 2011-07-05 TW TW100123643A patent/TWI503370B/en active
- 2011-07-05 CN CN201110233201.2A patent/CN102433000B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5962608A (en) * | 1997-02-14 | 1999-10-05 | Reliance Electric Industrial Co. | Polymers made with metal oxide sols |
| CN1957042A (en) * | 2004-05-26 | 2007-05-02 | 宝理塑料株式会社 | Thermoplastic resin composition |
| CN101184798A (en) * | 2005-05-27 | 2008-05-21 | 纳幕尔杜邦公司 | Resin compositions with a low coefficient of thermal expansion and articles therefrom |
| CN101687983A (en) * | 2007-05-23 | 2010-03-31 | 三星精密化学株式会社 | Aromatic liquid-crystalline polyester amide copolymer, prepreg including the same, prepreg laminate including the prepreg, metal film laminate including the prepreg, and printed wiring board including |
| US20100124037A1 (en) * | 2008-11-18 | 2010-05-20 | Samsung Electronics Co., Ltd. | Thermosetting composition and printed circuit board using the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393635A (en) * | 2020-04-07 | 2020-07-10 | 宁波长阳科技股份有限公司 | Liquid crystal polymer copper-clad plate and preparation method thereof |
| 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 |
| CN115505124A (en) * | 2021-06-23 | 2022-12-23 | 律胜科技股份有限公司 | Polymer and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5721570B2 (en) | 2015-05-20 |
| KR101708934B1 (en) | 2017-03-08 |
| TW201202341A (en) | 2012-01-16 |
| JP2012012605A (en) | 2012-01-19 |
| KR20120003667A (en) | 2012-01-11 |
| TWI503370B (en) | 2015-10-11 |
| CN102433000B (en) | 2015-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100929383B1 (en) | Aromatic liquid crystal polyester amide copolymer, prepreg employing the above-mentioned aromatic liquid crystal polyester amide copolymer, laminate and printed wiring board employing the prepreg | |
| CN106010421B (en) | Adhesive composition, film-like adhesive material, adhesive layer, adhesive sheet, copper-clad laminate, wiring board, and printed wiring board | |
| US9161443B2 (en) | Wholly aromatic polyester amide copolymer resin, polymer film including the wholly aromatic polyester amide copolymer resin, flexible metal-clad laminate including the polymer film, and flexible printed circuit board including the flexible metal-clad laminate | |
| CN102433000B (en) | 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 | |
| KR101111644B1 (en) | Aromatic 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 | |
| KR101054271B1 (en) | A prepreg and a prepreg laminated body which employ | adopted the aromatic polyester amide copolymer, the said aromatic polyester amide copolymer, and the metal foil laminated board and printed wiring board which employ | adopted the said prepreg or the prepreg laminated body. | |
| CN102272200B (en) | Aromatic polyester amide copolymer, high molecular film, prepreg, prepreg laminate, metal foil laminate, and printed circuit board | |
| KR101054272B1 (en) | Prepreg and prepreg laminates employing a multi-type polyester amide copolymer, the multi-polyester amide copolymer, and a metal foil laminate and printed wiring board employing the prepreg or prepreg laminate | |
| JP6047426B2 (en) | Composition for manufacturing thermosetting resin, cured product thereof, prepreg containing the cured product, and metal foil laminate and printed wiring board using the prepreg | |
| TWI557175B (en) | Composition for preparing thermosetting resin, cured product of the composition, prepreg having the cured product, and metal clad laminate and printed circuit board having the prepreg | |
| CN102432999B (en) | Composition for preparing thermosetting resin, cured product of the composition, prepreg and prepreg laminate having the cured product, and printed circuit board having the prepreg or the prepreg laminate | |
| KR101007233B1 (en) | Thermosetting resin composition, cross-linked thermosetting resin composition, prepreg or prepreg laminates having the cross-linked product, and metal clad laminates and print wiring board having the prepreg or the prepreg laminates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: SHENZHEN WOTE ADVANCED MATERIALS CO., LTD. Free format text: FORMER OWNER: SAMSUNG FINE CHEMICALS CO., LTD. Effective date: 20150128 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; TO: 518052 SHENZHEN, GUANGDONG PROVINCE |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20150128 Address after: 518052 Guangdong city of Shenzhen province Nanshan District Nantou two road crossing forward hot electrons strategic emerging industrial park 10 Applicant after: Shenzhen Wote Advanced Materials Co., Ltd. Address before: Ulsan, South Korea Applicant before: Samsung Fine Chemicals Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder |
Address after: 518000 31 / F, block B, building 7, Wanke Yuncheng phase 3, Nanshan District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Water New Material Co.,Ltd. Address before: 518052 Guangdong city of Shenzhen province Nanshan District Nantou two road crossing forward hot electrons strategic emerging industrial park 10 Patentee before: Shenzhen Water New Material Co.,Ltd. |
|
| CP02 | Change in the address of a patent holder | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211130 Address after: 401220 No. 10, Huabei 2nd Road, Yanjia street, Changshou District, Chongqing Patentee after: Chongqing Wote Zhicheng New Material Technology Co.,Ltd. Address before: 518000 31 / F, block B, building 7, international innovation Valley, Vanke Yuncheng phase 3, Nanshan District, Shenzhen City, Guangdong Province Patentee before: Shenzhen Water New Material Co.,Ltd. |