CN116396611A - 氰酸酯树脂组合物及用其制备的胶液、半固化片和覆铜板 - Google Patents
氰酸酯树脂组合物及用其制备的胶液、半固化片和覆铜板 Download PDFInfo
- Publication number
- CN116396611A CN116396611A CN202310170298.XA CN202310170298A CN116396611A CN 116396611 A CN116396611 A CN 116396611A CN 202310170298 A CN202310170298 A CN 202310170298A CN 116396611 A CN116396611 A CN 116396611A
- Authority
- CN
- China
- Prior art keywords
- cyanate
- resin composition
- prepreg
- weight percent
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 title claims abstract description 42
- 239000011342 resin composition Substances 0.000 title claims abstract description 28
- 239000003292 glue Substances 0.000 title claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 239000003822 epoxy resin Substances 0.000 claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 28
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 14
- 239000003063 flame retardant Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000004643 cyanate ester Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 239000011889 copper foil Substances 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 229920002857 polybutadiene Polymers 0.000 claims description 4
- 239000012779 reinforcing material Substances 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- -1 tetramethyl bisphenol F Chemical compound 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 claims description 2
- LOOCNDFTHKSTFY-UHFFFAOYSA-N 1,1,2-trichloropropyl dihydrogen phosphate Chemical compound CC(Cl)C(Cl)(Cl)OP(O)(O)=O LOOCNDFTHKSTFY-UHFFFAOYSA-N 0.000 claims description 2
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- HZEOUPCNUWSUFL-UHFFFAOYSA-N 4,5,5-trimethyl-4-pentan-3-yl-1H-imidazole Chemical compound C(C)C(C1(N=CNC1(C)C)C)CC HZEOUPCNUWSUFL-UHFFFAOYSA-N 0.000 claims description 2
- DYIZJUDNMOIZQO-UHFFFAOYSA-N 4,5,6,7-tetrabromo-2-[2-(4,5,6,7-tetrabromo-1,3-dioxoisoindol-2-yl)ethyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Br)C(Br)=C2Br)Br)=C2C(=O)N1CCN1C(=O)C2=C(Br)C(Br)=C(Br)C(Br)=C2C1=O DYIZJUDNMOIZQO-UHFFFAOYSA-N 0.000 claims description 2
- SPAUYKHQVLTCOL-UHFFFAOYSA-N C1(=CC=CC=C1)OP(OC1=CC=CC=C1)(O)=O.C1(=CC=CC=C1)C Chemical compound C1(=CC=CC=C1)OP(OC1=CC=CC=C1)(O)=O.C1(=CC=CC=C1)C SPAUYKHQVLTCOL-UHFFFAOYSA-N 0.000 claims description 2
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- SJPPCSAMRLODMM-UHFFFAOYSA-N P.COC1=CC(=CC=C1)OC.COC1=CC(=CC=C1)OC.COC1=CC(=CC=C1)OC Chemical compound P.COC1=CC(=CC=C1)OC.COC1=CC(=CC=C1)OC.COC1=CC(=CC=C1)OC SJPPCSAMRLODMM-UHFFFAOYSA-N 0.000 claims description 2
- REBHQKBZDKXDMN-UHFFFAOYSA-M [PH2]([O-])=O.C(C)[Al+]CC Chemical compound [PH2]([O-])=O.C(C)[Al+]CC REBHQKBZDKXDMN-UHFFFAOYSA-M 0.000 claims description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 229910002026 crystalline silica Inorganic materials 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000005350 fused silica glass Substances 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 229920006380 polyphenylene oxide Polymers 0.000 description 7
- 230000008901 benefit Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 150000001913 cyanates Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- 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
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- 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
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
本发明涉及一种氰酸酯树脂组合物及用其制备的胶液、半固化片和覆铜板，所述的氰酸酯树脂组合物中各组分按重量百分数计分别为：环氧树脂10～20wt％、氰酸酯树脂10～20wt％、热塑性弹性体1～5wt％、聚苯醚0～3wt％、表面活性剂0～1wt％、阻燃剂0～2wt％、填料55～70wt％以及固化剂0～0.2wt％。本发明氰酸酯树脂组合物中以CE树脂为主体，选用介电性能优异、耐湿热性和韧性优秀的PPO进行共混形成互穿网络结构，选用含有端活性基团的热塑性弹性体，氰酸酯基团能够与端活性基团生成嵌段结构，进而改善两相的界面连接性能，显著增强氰酸酯树脂的韧性。本发明制备的半固化片在具有良好的耐湿热性的同时，还具有较好的介电性能和热膨胀性能。
Description
技术领域
本发明属于覆铜板生产技术领域，具体涉及一种氰酸酯树脂组合物及用其制备的胶液、半固化片和覆铜板。
背景技术
电子工业、信息产业的高速发展依托于基础材料的进步，随着高速化和信号传输高频化阶段的到来，现有的电路基板材料在保证高Tg、低Dk/Df等性能的同时也带来高热膨胀系数和低尺寸稳定性，以上为保证覆铜板的可靠性，对基板材料的综合性能有了更高的需求。
环氧树脂、酚醛树脂、聚酰亚胺树脂、聚四氟乙烯树脂、聚酯树脂、聚苯醚树脂、氰酸酯树脂等树脂为现阶段最常用树脂各自具备其相应的优势与劣势。在高频高速化的方向上，环氧树脂及酚醛树脂因其介电性能上的劣势应用较少；聚四氟乙烯树脂机械性能及热膨胀性能的缺陷导致其在高频化上的应用较为艰难；氰酸酯具有高Tg、优良的电学性能(Dk＝2.8～3.2，Df＝0.002～0.008)和良好的力学性能，因此研究人员对其应用进行了深入探究。
现阶段氰酸酯仍存在以下问题：1)氰酸酯树脂在固化后极性极低并且分子链的刚性较强，因此，脆性较大，以其为主体的覆铜板柔韧性较差；2)氰酸酯树脂在高温潮湿的环境下，发生副反应，氰基官能团与水反应生成氨基甲酸酯，氨基甲酸酯热稳定性能差，容易受热分解影响树脂的热稳定性，即耐湿热性较差。
ZL 201010584888.X公开了一种氰酸酯树脂组合物及使用其制作的覆铜板，通过在双酚A氰酸酯的基础上引入酚醛树脂，促进氰酸酯-环氧树脂体系的固化，来改善氰酸酯耐湿热性，使其具有低介电常数和热膨胀性能。ZL 202210719104.2公开了一种低介电常数、低介电损耗、高Tg覆铜板的制备方法，通过添加双马来酰亚胺和SMA树脂，改善覆铜板的柔韧性使其具有极低的介电性能。
以上专利在一定程度解决了氰酸酯的耐湿热性和柔韧性，但是也会带来热膨胀性能的大幅度降低的问题。氰酸酯树脂(CE)作为高性能热固性树脂的代表，高频高速覆铜箔板常采用其作为主体材料。CE树脂交联密度大、结晶度高，赋予其低膨胀系数和较低介电性能等优点。与此同时，也暴露了其局限性，如固化后脆性较大等问题。
发明内容
本发明的目的是提供一种氰酸酯树脂组合物及用其制备的胶液、半固化片和覆铜板。
本发明的目的可以通过以下技术方案来实现：一种氰酸酯树脂组合物，包括环氧树脂、氰酸酯树脂、热塑性弹性体、聚苯醚、表面活性剂、阻燃剂、填料以及固化剂；所述的氰酸酯树脂组合物中各组分按重量百分数计分别为：
环氧树脂10～20wt％；
氰酸酯树脂10～20wt％；
热塑性弹性体1～5wt％；
聚苯醚0～3wt％；
表面活性剂0～1wt％；
阻燃剂0～2wt％；
填料55～70wt％；
固化剂0～0.2wt％。
进一步地，所述的环氧树脂包括双酚A型环氧树脂、双酚F型环氧树脂、苯酚型环氧树脂、含萘环结构环氧树脂或多官能团环氧树脂中的一种或多种。环氧树脂能提高体系交联密度，进而提高产品Tg温度，增强固化物的耐高温性能。
进一步地，所述的氰酸酯树脂包括双酚A型氰酸酯树脂、双酚E型氰酸酯树脂或四甲基双酚F型氰酸酯树脂。氰酸酯树脂能提供较好的介电性能和热膨胀性能。
进一步地，所述的热塑性弹性体包括氢化聚丁二烯共聚物；所述的氢化聚丁二烯共聚物包括丁二烯-苯乙烯共聚物、丁二烯-苯乙烯-丁二烯共聚物、苯乙烯-丁二烯-苯乙烯共聚物、丁二烯-异戊二烯共聚物、氢化苯乙烯-丁二烯嵌段共聚物或三元乙丙橡胶中的一种或多种。热塑性弹性体能够起到平衡综合性能的作用。
进一步地，所述的表面活性剂包括BYK-903或BYK-904中的一种或多种。
进一步地，所述的阻燃剂包括磷酸甲苯二苯酯、磷酸三氯丙基酯、六苯氧基环三磷腈、乙撑双四溴邻苯二甲酰亚胺、三(2,6-二甲氧基苯)膦或二乙基次膦酸铝中的一种或多种。阻燃剂能够提升氰酸酯树脂组合物的阻燃效果。
进一步地，所述的填料包括结晶型二氧化硅、熔融型二氧化硅、球型二氧化硅、碳酸钙、滑石碳化硅、碳酸钠或碳酸镁中的一种或多种。填料的主要作用在于提高热膨胀性能，增强机械性能和阻燃能力。
进一步地，所述的固化剂包括异辛酸锌、二乙基四甲基咪唑、2,3-二甲基-2,3-二苯基丁烷、4-二甲氨基吡啶、过氧化二叔丁基或过氧化二异丙苯中的一种或多种。LEWIS酸、质子酸、弱酸盐以及金属螯合物等固化剂能促进氰酸酯树脂交联，缩短固化时间。
本发明的目的之二在于，提供一种采用上述氰酸酯树脂组合物制得的胶液，所述的胶液包括环氧树脂、氰酸酯树脂、热塑性弹性体、聚苯醚、表面活性剂、阻燃剂、填料、固化剂以及有机溶剂；
所述的胶液的制备方法为将环氧树脂、氰酸酯树脂、热塑性弹性体、聚苯醚、表面活性剂、阻燃剂、填料以及固化剂加入有机溶剂中，混合均匀，即得到胶液；
所述的有机溶剂包括丙二醇甲醚、甲苯、环己酮、丁酮、丙酮、甲醇或二甲苯中的一种或多种；所述的有机溶剂的用量为氰酸酯树脂组合物固体总质量的30wt％。
本发明的目的之三在于，提供一种采用上述胶液制得的半固化片，所述的半固化片的制备步骤为先将增强材料浸渍在所述的胶液中形成层状物，再将该层状物经高温加热烘烤得到半固化片；所述的增强材料包括玻璃纤维布，其中，玻璃纤维布为市售可用于各种印刷电路板的玻璃纤维布；所述的烘烤温度为120～180℃。
本发明的目的之四在于，提供一种采用上述半固化片制得的覆铜板，所述的覆铜板的制备步骤为在半固化片的一侧或两侧覆盖金属铜箔，并进行加热加压压合得到覆铜板；所述的金属铜箔包括标准电解铜箔、反转铜箔、低轮廓铜箔或超低轮廓铜箔；所述的压合温度为170～240℃，压合压力为1.0～6.0MPa。
进一步地，可采用现有技术将上述覆铜板加工制成印刷电路板。
与现有技术相比，本发明具有以下优点：
1、本发明氰酸酯树脂组合物包括环氧树脂、氰酸酯树脂(CE)、热塑性弹性体、聚苯醚(PPO)、表面活性剂、阻燃剂、填料以及固化剂；本发明氰酸酯树脂组合物中以CE树脂为主体，选用介电性能优异、耐湿热性和韧性优秀的PPO进行共混形成互穿网络结构，选用含有端活性基团的热塑性弹性体，氰酸酯基团能够与端活性基团生成嵌段结构，进而改善两相的界面连接性能，显著增强氰酸酯树脂的韧性；本发明组合物不易析出；
2、本发明制备的半固化片在具有良好的耐湿热性的同时，还具有较好的介电性能和热膨胀性能；
3、本发明制备的半固化片的柔韧性较好，易于储存运输，具有良好的市场效益。
具体实施方式
下面对本发明的实施例作详细说明，以下实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
以下实施例中所使用的试剂皆为市售试剂。以下实施例中所使用的设备皆为市售设备。
按照下表所示的各组分制备胶液、半固化片以及覆铜板：
| 牌号 | 组分名称 |
| SEV-3410 | DCPD苯酚型环氧树脂 |
| NC-7000L | 含萘环结构环氧树脂 |
| 1250A80 | 多官能基环氧树脂 |
| SA-9000 | 改性聚苯醚 |
| BA-3000S | 氰酸脂树脂 |
| BYK-903 | 表面活性剂 |
| SG-P3 | 热塑性弹性体 |
| FB-3Y | 球型填料 |
| sc2300svj | 球型填料 |
| 异辛酸锌 | 固化剂 |
| SPB-100 | 阻燃剂 |
实施例1
将5.7wt％SEV-3410、5.8wt％1250A80、1.4wt％NC-7000L、13wt％BA-3000S、2.9wt％SPB-100、4.3wt％SG-P3、66.284wt％二氧化硅FB-3Y、0.016wt％异辛酸锌和0.6wt％BYK-903溶于甲苯和丁酮混合溶剂(甲苯和丁酮以2:1的体积比例混合，有机溶剂总质量占固体总质量的30wt％)中，搅拌分散均匀。用2116玻璃纤维布浸渍以上胶液，在180℃烤箱中烘干溶剂，制得半固化片。将12张和3张2116半固化片分别叠合，在两侧覆1OZ厚度的反转铜箔，在压机中真空固化2.5h，压合压力为6MPa，固化温度为220℃，制成覆铜层压板。选用3张2116半固化片压合而成的覆铜板用于测量10GHz下的介电常数与介电损耗。
采用与实施例1相同的方式制备实施例2-4以及对比例1-3所对应的胶液、半固化片以及覆铜板，其中，不同之处在于组合物的组分、用量和物理性能，如下表所示，表中各组分用量单位为wt％。
其中，各个特性参数的测试方法如下：
1)剥离强度的测试方法：参考IPC-TM-650 2.4.8所述方法测试；
2)Dk/Df的测试方法：参照IPC-TM-650 2.5.5.5.C，频率10GHz；
3)PCT的测试方法(121℃/100％RH/168小时)：选用上述的不含铜基板(12片半固化片压合而成)，参照IPC-TM-6502.6.16.1所述的方法经压力蒸煮测试(pressure cookingtest，PCT)分别进行吸湿168小时(相对湿度100％)测试后，浸入288℃锡炉10min，观察是否发生分层爆板；
4)冲击强度的测试方法：简支梁摆锤冲击强度，依据国标GB/T1451-2005方法测试。
实施例2与对比例1、2进行比较，氰酸脂的含量在高于16.9wt％时，基板柔韧性与耐湿热性大幅下降，因此应将氰酸脂含量控制在17wt％以内。改性聚苯醚的加入形成二维网状结构，能有效提高热膨胀系数和介电性能，对比例3相较于实施例3，对比例3的改性聚苯醚含量增加至5wt％，导致耐湿热性能以及电性能大幅衰减，因此改性聚苯醚含量应控制在3wt％以内，同时环氧树脂与热塑性弹性体的比例应在1:3以内，以达到最佳性能。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (10)
1.一种氰酸酯树脂组合物，其特征在于，所述的氰酸酯树脂组合物包括环氧树脂、氰酸酯树脂、热塑性弹性体、聚苯醚、表面活性剂、阻燃剂、填料以及固化剂；所述的氰酸酯树脂组合物中各组分按重量百分数计分别为：
环氧树脂10～20wt％；
氰酸酯树脂10～20wt％；
热塑性弹性体1～5wt％；
聚苯醚0～3wt％；
表面活性剂0～1wt％；
阻燃剂0～2wt％；
填料55～70wt％；
固化剂0～0.2wt％。
2.根据权利要求1所述的一种氰酸酯树脂组合物，其特征在于，所述的环氧树脂包括双酚A型环氧树脂、双酚F型环氧树脂、苯酚型环氧树脂、含萘环结构环氧树脂或多官能团环氧树脂中的一种或多种；所述的氰酸酯树脂包括双酚A型氰酸酯树脂、双酚E型氰酸酯树脂或四甲基双酚F型氰酸酯树脂。
3.根据权利要求1所述的一种氰酸酯树脂组合物，其特征在于，所述的热塑性弹性体包括氢化聚丁二烯共聚物；所述的氢化聚丁二烯共聚物包括丁二烯-苯乙烯共聚物、丁二烯-苯乙烯-丁二烯共聚物、苯乙烯-丁二烯-苯乙烯共聚物、丁二烯-异戊二烯共聚物、氢化苯乙烯-丁二烯嵌段共聚物或三元乙丙橡胶中的一种或多种。
4.根据权利要求1所述的一种氰酸酯树脂组合物，其特征在于，所述的表面活性剂包括BYK-903或BYK-904中的一种或多种。
5.根据权利要求1所述的一种氰酸酯树脂组合物，其特征在于，所述的阻燃剂包括磷酸甲苯二苯酯、磷酸三氯丙基酯、六苯氧基环三磷腈、乙撑双四溴邻苯二甲酰亚胺、三(2,6-二甲氧基苯)膦或二乙基次膦酸铝中的一种或多种。
6.根据权利要求1所述的一种氰酸酯树脂组合物，其特征在于，所述的填料包括结晶型二氧化硅、熔融型二氧化硅、球型二氧化硅、碳酸钙、滑石碳化硅、碳酸钠或碳酸镁中的一种或多种。
7.根据权利要求1所述的一种氰酸酯树脂组合物，其特征在于，所述的固化剂包括异辛酸锌、二乙基四甲基咪唑、2,3-二甲基-2,3-二苯基丁烷、4-二甲氨基吡啶、过氧化二叔丁基或过氧化二异丙苯中的一种或多种。
8.一种采用权利要求1所述氰酸酯树脂组合物制得的胶液，其特征在于，所述的胶液的制备方法为将环氧树脂、氰酸酯树脂、热塑性弹性体、聚苯醚、表面活性剂、阻燃剂、填料以及固化剂加入有机溶剂中，混合均匀，即得到胶液；
所述的有机溶剂包括丙二醇甲醚、甲苯、环己酮、丁酮、丙酮、甲醇或二甲苯中的一种或多种；所述的有机溶剂的用量为氰酸酯树脂组合物固体总质量的30wt％。
9.一种采用权利要求8所述的胶液制得的半固化片，其特征在于，所述的半固化片的制备步骤为先将增强材料浸渍在所述的胶液中形成层状物，再将该层状物烘烤得到半固化片；所述的增强材料包括玻璃纤维布；所述的烘烤温度为120～180℃。
10.一种采用权利要求9所述的半固化片制得的覆铜板，其特征在于，所述的覆铜板的制备步骤为在半固化片的一侧或两侧覆盖金属铜箔，并进行压合得到覆铜板；所述的金属铜箔包括标准电解铜箔、反转铜箔、低轮廓铜箔或超低轮廓铜箔；所述的压合温度为170～240℃，压合压力为1.0～6.0MPa。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310170298.XA CN116396611A (zh) | 2023-02-27 | 2023-02-27 | 氰酸酯树脂组合物及用其制备的胶液、半固化片和覆铜板 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310170298.XA CN116396611A (zh) | 2023-02-27 | 2023-02-27 | 氰酸酯树脂组合物及用其制备的胶液、半固化片和覆铜板 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116396611A true CN116396611A (zh) | 2023-07-07 |
Family
ID=87018630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310170298.XA Pending CN116396611A (zh) | 2023-02-27 | 2023-02-27 | 氰酸酯树脂组合物及用其制备的胶液、半固化片和覆铜板 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116396611A (zh) |
-
2023
- 2023-02-27 CN CN202310170298.XA patent/CN116396611A/zh active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108219371B (zh) | 环氧树脂组合物、预浸料、层压板和印刷电路板 | |
| EP3219758B1 (en) | Thermosetting resin composition and prepreg and laminated board prepared therefrom | |
| CN109777123B (zh) | 树脂组合物、印刷电路用预浸片及覆金属层压板 | |
| AU2011376206A1 (en) | Halogen-free resin composition and method for preparation of copper clad laminate with same | |
| CN109749396B (zh) | 一种聚苯醚树脂组合物及其应用 | |
| CN111378243B (zh) | 一种多功能改性树脂共混的半固化片碳氢组合物及应用及采用其制备高频高速覆铜板的方法 | |
| CN111635616B (zh) | 无卤阻燃热固性树脂组合物、印刷电路用预浸料及覆金属层压板 | |
| CN110669328A (zh) | 一种含磷阻燃bmi的树脂组合物及其应用 | |
| TWI656129B (zh) | 一種含有酯基的磷腈化合物、製備方法及用途 | |
| CN110724261B (zh) | 高耐热低介电聚苯醚型双马来酰亚胺树脂、层压板及其制备方法 | |
| CN109810517B (zh) | 树脂组合物、印刷电路用预浸片及覆金属层压板 | |
| JP5756922B2 (ja) | 樹脂組成物、樹脂ワニス、プリプレグ、金属張積層板、及びプリント配線板 | |
| CN109608828B (zh) | 一种热固性树脂组合物及使用其的预浸料、层压板和覆金属箔层压板 | |
| CN108219434B (zh) | 一种热固性树脂组合物、预浸料以及层压板 | |
| CN114149659B (zh) | 树脂组合物及其应用 | |
| CN105348741A (zh) | 用于高速基板的热固性树脂组合物、层压板 | |
| CN114634713B (zh) | 一种树脂组合物、预浸片及覆金属层压板 | |
| CN113121981B (zh) | 一种树脂组合物以及使用其的预浸片和绝缘板 | |
| CN116396611A (zh) | 氰酸酯树脂组合物及用其制备的胶液、半固化片和覆铜板 | |
| CN115181395A (zh) | 一种热固性树脂组合物及其应用 | |
| CN114292492A (zh) | 树脂组合物及应用 | |
| CN114230793A (zh) | 改性双马来酰亚胺预聚物及制备方法、应用 | |
| CN113185751A (zh) | 一种无卤硅系阻燃型乙烯基树脂及其制备方法和在覆铜板中的应用 | |
| CN114644824A (zh) | 阻燃型聚苯醚树脂组合物、覆铜板及其制备方法 | |
| CN112708128A (zh) | 改性聚苯醚树脂、聚苯醚复合材料及其制备方法、印制线路板 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |