CN106939021A - A kind of phosphazene compound, pre-impregnated sheet, composite metal substrate and wiring board - Google Patents
A kind of phosphazene compound, pre-impregnated sheet, composite metal substrate and wiring board Download PDFInfo
- Publication number
- CN106939021A CN106939021A CN201610008890.XA CN201610008890A CN106939021A CN 106939021 A CN106939021 A CN 106939021A CN 201610008890 A CN201610008890 A CN 201610008890A CN 106939021 A CN106939021 A CN 106939021A
- Authority
- CN
- China
- Prior art keywords
- unsubstituted
- substituted
- alkyl
- combination
- group
- 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
- -1 phosphazene compound Chemical class 0.000 title claims abstract description 50
- 239000000758 substrate Substances 0.000 title claims abstract description 15
- 239000002131 composite material Substances 0.000 title claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 12
- 239000002184 metal Substances 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 125000003545 alkoxy group Chemical group 0.000 claims description 21
- 125000001072 heteroaryl group Chemical group 0.000 claims description 21
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 19
- 239000003822 epoxy resin Substances 0.000 claims description 18
- 229920000647 polyepoxide Polymers 0.000 claims description 18
- 238000006467 substitution reaction Methods 0.000 claims description 16
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 15
- 125000005248 alkyl aryloxy group Chemical group 0.000 claims description 12
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims description 12
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 230000000269 nucleophilic effect Effects 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 5
- UXJHQBVRZUANLK-UHFFFAOYSA-N azanylidyne(dichloro)-$l^{5}-phosphane Chemical compound ClP(Cl)#N UXJHQBVRZUANLK-UHFFFAOYSA-N 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000011188 CEM-1 Substances 0.000 claims description 4
- 239000011190 CEM-3 Substances 0.000 claims description 4
- 101100257127 Caenorhabditis elegans sma-2 gene Proteins 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000004437 phosphorous atom Chemical group 0.000 claims description 4
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000011889 copper foil Substances 0.000 claims description 2
- 239000011152 fibreglass Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims 1
- 239000003989 dielectric material Substances 0.000 abstract description 3
- 239000002585 base Substances 0.000 description 28
- 238000003756 stirring Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical group CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 150000002118 epoxides Chemical class 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 125000004104 aryloxy group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000053 physical method Methods 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- SPWIPDSCASBWFH-UHFFFAOYSA-N [P].N#CC#N Chemical compound [P].N#CC#N SPWIPDSCASBWFH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002576 ketones Chemical group 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical group [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 description 1
- 125000004457 alkyl amino carbonyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000004947 alkyl aryl amino group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 description 1
- 125000004644 alkyl sulfinyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N anhydrous methyl chloride Natural products ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 125000005100 aryl amino carbonyl group Chemical group 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 125000005129 aryl carbonyl group Chemical group 0.000 description 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 1
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004473 dialkylaminocarbonyl group Chemical group 0.000 description 1
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method 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
- 239000000126 substance Substances 0.000 description 1
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000004784 trichloromethoxy group Chemical group ClC(O*)(Cl)Cl 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- 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
- B32B15/09—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 polyesters
-
- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
-
- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/041—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
-
- 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
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
-
- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of phosphazene compound, pre-impregnated sheet, composite metal substrate and wiring board.The phosphazene compound with carboxylate has the molecular structure shown in formula (I).The present invention obtains the phosphazene compound with carboxylate by using the M groups of specific composition, and its solidfied material has low-dielectric, good heat resistance and mechanical performance, is a kind of dielectric materials with larger economy and environmentally friendly friendly.
Description
Technical field
The invention belongs to dielectric materials technical field, more particularly to it is a kind of phosphazene compound, pre-impregnated sheet, multiple
Close metal substrate and wiring board.
Background technology
Using mobile phone, computer, video camera, electronic game machine as representative electronic product, with air-conditioning, refrigerator,
Television image, sound equipment articles for use etc. for representative family expenses, office electric equipment products and other field use it is various
Product, for safety, significant portion of product requires that it possesses low-dielectric and heat resistance.
For electrical properties, dielectric constant and dielectric of the factor that need to mainly consider also including material are damaged
Consumption.Generally, due to substrate signal transfer rate and baseplate material dielectric constant square root into anti-
Than, therefore the dielectric constant of baseplate material is generally the smaller the better；On the other hand, represented because dielectric loss is smaller
The loss of signal transmission is fewer, therefore the transmission quality that the less material of dielectric loss can be provided is also more good
It is good.
Therefore, the material with low-k and low-dielectric loss how is developed, and is applied to high frequency
The manufacture of printed circuit board (PCB), is printed circuit board material field urgent problem to be solved at this stage.
The content of the invention
In view of this, one aspect of the present invention provides a kind of phosphazene compound with carboxylate, with low dielectric
Property, good heat resistance and mechanical performance, moreover, the phosphazene compound has the advantage of low cost.
To achieve these goals, present invention employs following technical scheme：
A kind of phosphazene compound, it has the molecular structure as shown in formula (I)：
Formula (I)；
In formula (I), R1Represent arbitrary organic group, R2For aliphatic group, R is to be carried by nucleopilic reagent
The inertia nucleophilic group of confession；M is phosphazenium groups；
A is integer more than zero, such as 1,2,3,4,5,6,7, b be the integer more than or equal to zero,
Such as 0,1,2,3,4,5,6,7, c be integer more than zero, such as 1,2,3,4,5,6,
7, and 2 times of total number equal to number of phosphorus atoms on M groups for the substituent being connected with M groups.
In the present invention, R1Arbitrary organic group is represented, condition is that atom is no more than normal valency, and
Stable compound can be produced." stable compound " be refer to it is sufficiently strong strongly from reactant mixture
Middle separation is to effective purity and is configured to compounds effective.
In the present invention, described " inertia nucleophilic group " refers to, a kind of functional group, and it is without active group
Group, it is not allowed to change places or reacted with the speed of a reality under conditions of conventional organic synthesis, its
Be free of what common sense was reacted to be remaining after nucleopilic reagent and chloro phosphazene compound nucleophilic substitution
Functional group.
Preferably, in formula (I), R1For aliphatic group and/or aryl, further preferably substitution or not
Substituted straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl,
Appointing in substituted or unsubstituted alkoxy, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl
A kind of or its at least two combination of meaning.
Preferably, R1For unsubstituted straight chained alkyl or branched alkyl, unsubstituted cycloalkyl, unsubstituted
In aralkyl, unsubstituted alkylaryl, unsubstituted aryl or unsubstituted heteroaryl any one or
The combination of person at least two.
Preferably, R1Without reactive group that can be with epoxy resin reaction generation secondary hydroxyl groups.
Preferably, R2For substituted or unsubstituted aralkyl, substituted or unsubstituted alkylaryl, substitution or
Any one in unsubstituted aryl or substituted or unsubstituted heteroaryl or its at least two combination.
Nucleopilic reagent containing hydroxyl such as alcohols or aldehydes matter, such as methanol, ethanol, propyl alcohol, phenol
Or hydroquinones etc., now R is CH3O-、CH3CH2-O-、CH3CH2CH-O-, phenoxy group or right
Hydroxyphenoxy.
In the present invention, it is preferred to, the inertia nucleophilic group is that R is selected from-OR13、 In any one or at least two
The combination planted；
R13For substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkyl, take
Generation or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, take
Generation or unsubstituted aralkoxy, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted carbonic ester
Base, substituted or unsubstituted sulfonate group, substituted or unsubstituted phosphonate group, substituted or unsubstituted virtue
In base or substituted or unsubstituted heteroaryl any one or at least two combination, R15、R16And R17
It independently is substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkyl, takes
Generation or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, take
Generation or unsubstituted aralkoxy, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted aryl or
Any one in substituted or unsubstituted heteroaryl, R18For substituted or unsubstituted straight chained alkyl or side chain
Alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alcoxyl
Base, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aralkoxy, substituted or unsubstituted alkane
In base aryloxy group, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl any one or extremely
Few two kinds combination, R22For substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted
Cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted ring
Alkoxy, substituted or unsubstituted aralkoxy, substituted or unsubstituted alkyl-aryloxy, substitution do not take
In the aryl in generation or substituted or unsubstituted heteroaryl any one or at least two combination, R23With
R24Independently be substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkyl,
Substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy,
Substituted or unsubstituted aralkoxy, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted aryl
Or in substituted or unsubstituted heteroaryl any one or at least two combination, R26And R27It is independent
Ground is substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkyl, substitution or not
Substituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substitution or not
Substituted aralkoxy, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted aryl or substitution or
In unsubstituted heteroaryl any one or at least two combination.
In foregoing description, substituted or unsubstituted straight chained alkyl or branched alkyl are preferably substitution or unsubstituted
C1~C12 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11) it is straight
Alkyl group or branched alkyl, preferably C1~C8 straight chained alkyls or branched alkyl, when carbon number is C1
For methyl, when carbon number is C2, as ethyl.
The substituted or unsubstituted cycloalkyl be preferably carbon number for C3~C12 (such as C4, C5,
C6, C7, C8, C9, C10 or C11) substituted or unsubstituted cycloalkyl.
Substituted or unsubstituted aryl is preferably phenyl, benzyl, 1,2,3,4- tetralyls,Deng.The example bag of phenyl
Include xenyl, terphenyl, benzyl, phenethyl or phenylpropyl etc..
Substituted or unsubstituted heteroaryl is five yuan or six membered heteroaryl.
Substituted or unsubstituted alkoxy be C1-C12 (such as C1, C2, C3, C4, C5, C6, C7,
C8, C9, C10 or C11) alkoxy.
Substituted or unsubstituted aralkyl is C7-C12 (such as C8, C9, C10 or C11) aralkyl.
Substituted or unsubstituted cycloalkyloxy is C3-C8 (such as C4, C5, C6, C7 or C8) cycloalkanes
Epoxide.
Substituted or unsubstituted aralkoxy is C7-C12 (such as C8, C9, C10 or C11) aralkyl oxygen
Base.
Substituted or unsubstituted alkyl-aryloxy is C7-C12 (such as C8, C9, C10 or C11) alkyl
Aryloxy group.
Preferably, the R is substituted or unsubstituted alkoxy or aryloxy.
The example of alkoxy includes, but are not limited to methoxyl group, ethyoxyl, isopropoxy, propoxyl group, fourth oxygen
Base and amoxy.Alkoxy grp can be replaced by substituents, such as alkenyl, alkynyl, halogen, hydroxyl,
Alkyl carbonyl oxy, aryl-carbonyl oxygen, alkoxy carbonyloxy group, aryloxy group carbonyloxy group, carboxylate, alkyl-carbonyl,
Aryl carbonyl, alkoxy carbonyl, amino carbonyl, alkyl amino-carbonyl, dialkyl amino carbonyl, alkylthio group
Carbonyl, alkoxy, phosphate, phosphonate radical are closed, phosphinic acids root is closed, amino (including alkyl amino, dioxane
Base amino, arylamino, ammonia diaryl base and alkyl aryl amino), acylamino- (including alkyl-carbonyl ammonia
Base, aryl-amino-carbonyl, carbamoyl and urea groups), amidino groups, imino group, sulfydryl, carbothioic acid ester,
Sulfuric ester, alkyl sulphinyl, sulfonic group, sulfamoyl, sulfonamido, nitromethyla, trifluoromethyl,
Cyano group, azido, heterocyclic radical, alkylaryl or aromatics or heteroaromatic group.The alkoxy grp of halogen substitution
Example include, but are not limited to a fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, a chloromethane epoxide,
Dichloro methoxyl group, trichloromethoxy.
The example of the aryloxy includes phenoxy group, benzyloxy, naphthoxy or biphenylyloxy, the aryl
Epoxide can be replaced by alkyl etc..
Preferably, the phosphazene compound be the phosphazene compound with following structure in any one or
At least two mixture：
A is 4, b
It is 2, R for 0, c1For methyl or phenyl, R2For ethyl；
A is 4, b
It is 1, R for 1, c1For methyl or phenyl, R2For ethyl；
A is 4, b
It is 2, R for 0, c1For methyl or phenyl, R2For ethyl.
Term " substituted " used in the present invention refers to any one or more hydrogen atoms on specified atom
The substituent substitution of designated groups is selected from, condition is that the specified atom is no more than normal valency, and is replaced
Result be to produce stable compound.When substituent is oxo group or ketone group (i.e.=O), then
2 hydrogen atoms on atom are substituted.Ketone substituent is not present on aromatic rings." stable compound "
It is to refer to sufficiently strong separate from reactant mixture to effective purity strongly and be configured to effective chemical combination
Thing.
In the present invention, it is preferred to, M is the phosphonitrile base M of ring three1, the phosphonitrile base M of ring more than four2Or non-annularity
Polyphosphazene base M3In any one or its at least two combination.
Preferably, M1Structure is：
M2Structure is：
Wherein, x is more than or equal to 4；
M3Structure is：
Wherein, y is more than or equal to 3.
Note, M1、M2In the expression of structural formula, there is symbolOnly " ring-type " is tied
A kind of signal of structure.M1、M2And M3InThe key connected on middle P atoms is only represented
Substituent substitution occurs on P atoms in three, is not to be construed as the expression of methyl.
Preferably, M represents the group for the phosphorus nitrogen skeleton being mainly made up of unsaturated phosphorus and nitrogen-atoms, i.e. phosphonitrile
Group, be specially：M includes at least 50wt% phosphonitrile base M of ring three1, at most 48wt% ring more than four
Phosphonitrile base M2And at most 48wt% non-annularity polyphosphazene base M3。
In the present invention, M1Content is at least 50wt%, i.e. M1Content can be 50wt~100wt%,
M1For bulk composition.Work as M1When content is 100wt%, then M is not contained2And M3.Typical case of the invention but
Nonrestrictive M1Content can for 50wt%, 51wt%, 55wt%, 58wt%, 60wt%,
65wt%, 70wt%, 74wt%, 75wt%, 80wt%, 85wt%, 90wt%, 92wt%, 95wt%,
98wt% or 100wt%.
In the present invention, M2Content is at most 48wt%, that is, is referred to, M2Content can be 0~48wt%.When
M2When content is 0wt%, that is, refers to, do not contain M2.The typical but non-limiting M of the present invention2Content can be with
For 0wt%, 2wt%, 5wt%, 8wt%, 11wt%, 14wt%, 17wt%, 20wt%, 23wt%,
26wt%, 29wt%, 32wt%, 35wt%, 38wt%, 42wt%, 45wt% or 48wt%.
In the present invention, M3Content is at most 48wt%, that is, is referred to, M3Content can be 0~48wt%.When
M3When content is 0wt%, that is, refers to, do not contain M3.The typical but non-limiting M of the present invention3Content can be with
For 0wt%, 2wt%, 5wt%, 8wt%, 11wt%, 14wt%, 17wt%, 20wt%, 23wt%,
26wt%, 29wt%, 32wt%, 35wt%, 38wt%, 42wt%, 45wt% or 48wt%.
In the present invention, if M1Content is less than 50wt%, or M2More than 48wt%, then with asphalt mixtures modified by epoxy resin
The reacted product of fat can damage heat resistance, water resistance and mechanical performance in use.If M3Content
More than 48%, then it would be possible to cause because viscosity is excessive in use with the reacted product of epoxy resin
It is inconvenient for use, and because of molecular weight the is excessive bad result such as make its performance suffer damage.
Another aspect of the present invention provides a kind of preparation method of the phosphazene compound with carboxylate, by party's legal system
Standby phosphazene compound has good heat resistance, good mechanical performance, and dielectric constant is low.
It is a kind of to prepare the above-mentioned method for stating phosphazene compound, phosphonitrile chloride and nucleopilic reagent are subjected to nucleophilic and taken
Obtained by generation reaction.
Nucleophilic displacement of fluorine can be prepared using method well known in the art, for example, refer to that " research of polyphosphazene is entered
Exhibition, Zhang Hongwei etc., material Leader 2010 year the 7th phase of volume 24 ".The instantiation of catalyst has chlorination
The Louis such as the metal chlorides such as zinc, magnesium chloride, aluminium chloride, boron trifluoride and its complex compound, NaOH
Alkali.These catalyst can one or more be used in mixed way, the present invention in have no special regulation.Phosphonitrile chlorine
Compound can be using most commonly used hexachlorocyclotriph,sphazene etc. of originating.To obtain the R in target product
Base, can add simultaneously can provide the nucleopilic reagent of R bases, and such as R is alkoxy or phenoxy group.
, can be first using a kind of nucleopilic reagent and phosphonitrile chlorination in the reaction of nucleopilic reagent and phosphonitrile chloride
Thing reacts, the chlorine in part substitution phosphonitrile chloride, then again with another nucleopilic reagent and phosphonitrile chloride
Reaction, to obtain the phosphazene compound of formula (I) structure.And can be by controlling the material between material
Magnitude relation, to obtain the phosphazene compound containing a M group or containing multiple M groups in structure.
Further aspect of the present invention provides a kind of with low-k and good heat resistance, good machinery
The composition epoxy resin of performance.
The above-mentioned phosphazene compound with carboxylate is added in the composition epoxy resin, curing agent is used as.
Known asphalt mixtures modified by epoxy resin can be used as the epoxy resin of composition epoxy resin, curing agent, other fillers
Fat.
The composition epoxy resin can also include other polyester in addition to the foregoing polyester containing phosphonitrile.
A kind of pre-impregnated sheet, its be impregnated with or be coated on base material by phosphazene compound with carboxylate described above and
Into.
Base material can be fiberglass substrate, polyester base material, polyimide base material, ceramic base material or carbon fiber
Base material etc..
Here, the concrete technology condition of its impregnation or coating is not particularly limited." pre-impregnated sheet " is also this area skill
" bonding sheet " known to art personnel.
The invention provides a kind of flexible copper-clad plate, the flexible copper-clad plate is of the present invention comprising more than one
Pre-impregnated sheet and the Copper Foil for the pre-impregnated sheet one or both sides being overlying on after overlapping.
A kind of composite metal substrate, it includes more than one such as above-mentioned pre-impregnated sheet and carries out surface metal-clad successively
Overlapping, pressing is formed.
Here, the material of surface metal-clad is the alloy of aluminium, copper, iron and its any combination.
The instantiation of composite metal substrate have CEM-1 copper-clad plates, CEM-3 copper-clad plates, FR-4 copper-clad plates,
FR-5 copper-clad plates, CEM-1 aluminium bases, CEM-3 aluminium bases, FR-4 aluminium bases or FR-5 aluminium bases.
A kind of wiring board, is formed in the Surface Machining circuit of above-mentioned composite metal substrate.
The raw material of composition epoxy resin has low-dielectric energy by being solidificated in be formed on composite metal substrate
Coating, can improve wiring board, such as electronic industry, electrically, Electric Industrial, communications and transportation, aviation boat
My god, toy industry etc. need the extensive use of the industries such as machine, equipment, instrument, the instrument of wiring board.
Above-mentioned term " ××× base or group ", which refers to, sloughs one or more hydrogen atoms in ××× molecular structure of compounds
Or remaining part after other atoms or atomic group.
The present invention obtains the phosphazene compound with carboxylate by using the M groups of specific composition so that should
Compound has a good low-dielectric energy, and its solidfied material has good heat resistance, mechanical performance and low
Dielectric constant and dielectric loss, be a kind of low dielectric material also with larger economy and environmentally friendly friendly
Material.Use the dielectric constant (1GHz) for the copper-clad plate that the resin combination obtains for 3.0-3.1, dielectric is damaged
Consume (1GHz) be 0.004-0.006, Tg can reach 175 DEG C and more than, T- peel strengths can reach
1.92kg/mm2And more than, interlaminar strength can reach 1.63kg/mm2And more than, saturated water absorption can
Reach less than 0.35%.
Embodiment
Technical scheme is further illustrated with reference to embodiment.
Embodiment 1
The structural formula of phosphazene compound of the present embodiment with carboxylate is as follows：
Hexachlorocyclotriph,sphazene 1mol, acetone are put into three mouthfuls of 2000ml glass reactors with agitating device
200ml, sodium methoxide 4mol, stir, while leading to nitrogen, are warming up to 60 DEG C, are instilled with 60min
20% sodium hydroxide solution 620g, keeps 60 DEG C of temperature, 15 hours of stirring reaction, then adds fourth two
Sour 2mol, continues stirring reaction 2 hours, after the completion of reaction, with inorganic in the method removal system of physics
Composition and moisture, are added dropwise 3mL 98% concentrated sulfuric acid, and add ethanol 2mol, in 40 DEG C of stirring reactions 2
Hour, after reaction, with the impurity and moisture in physical method removal system, solvent in system is distilled, is obtained
The carboxylate A1mol for being 150g/eq to the ester equivalent of said structure.
Proton nmr spectra sign is carried out to obtained compound A, it is as a result as follows：
1H NMR(CDCl3,500MHz):3.39 (hydrogen on m, 12H, methoxyl group), 2.52 (m, 4H,
CH3CH2OOC-CH 2),2.62(m,4H,CH3CH2OOC-CH2CH 2), 4.12 (m, 4H, CH3-CH 2),
1.30 (hydrogen in m, 6H, terminal methyl group).
The position of infrared spectrum characteristic peak：Ester carbonyl group 1730-1740cm-1, the C-O-C 1200cm of ester group-1,
The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P-N 874cm in phosphazene backbone-1, phosphonitrile bone
The characteristic absorption peak 1217cm of P=N keys in frame-1, P-N 874cm in phosphazene backbone-1, the absorption of methyl ether
Peak 2995.3cm-1, P-O-C key absworption peaks 1035cm-1, CH2- O absworption peak 2983cm-1。
O-cresol formaldehyde epoxy of the epoxide equivalent as 200g/eq is added using above-mentioned carboxylate A75g as curing agent
Resin 100g, curing accelerator pyridine 0.2g, prepares composition epoxy resin.Using the epoxy composite
The standard copper-clad plate sample for meeting the standards such as GB, UL is made according to general copper-clad plate production process for thing,
A copper-clad plates are named as, the performance of a copper-clad plates is tested, its result is represented in table -1.
Embodiment 2
The structural formula of phosphazene compound of the present embodiment with carboxylate is as follows：
Hexachlorocyclotriph,sphazene 1mol, acetone are put into three mouthfuls of 2000ml glass reactors with agitating device
200ml, sodium methoxide 4mol, stir, while leading to nitrogen, are warming up to 60 DEG C, are instilled with 60min
20% sodium hydroxide solution 620g, keeps 60 DEG C of temperature, 15 hours of stirring reaction, then adds fourth two
Sour 2mol, continues stirring reaction 2 hours, after the completion of reaction, with inorganic in the method removal system of physics
Composition and moisture, are added dropwise 3mL 98% concentrated sulfuric acid, and add phenol 2mol, in 40 DEG C of stirring reactions 3
Hour, after reaction, with the impurity and moisture in physical method removal system, solvent in system is distilled, is obtained
The carboxylate B 1mol for being 170g/eq to the ester equivalent of said structure.
Proton nmr spectra sign is carried out to obtained compound B, it is as a result as follows：
1H NMR(CDCl3,500MHz):7.0-7.3 (m, 10H, benzene ring hydrogen), 3.39 (s, 12H,
Hydrogen on methoxyl group), 2.52 (hydrogen on m, 8H, methylene).
The position of infrared spectrum characteristic peak：Ester carbonyl group 1730-1740cm-1, the C-O-C 1200cm of ester group-1,
The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P-N 874cm in phosphazene backbone-1, phosphonitrile bone
The characteristic absorption peak 1217cm of P=N keys in frame-1, P-N 874cm in phosphazene backbone-1, the absorption of methyl ether
Peak 2995.3cm-1, P-O-C key absworption peaks 1035cm-1, CH2- O absworption peak 2983cm-1。
O-cresol formaldehyde epoxy of the epoxide equivalent as 200g/eq is added using above-mentioned carboxylate B 85g as curing agent
Resin 100g, curing accelerator pyridine 0.2g, prepares composition epoxy resin.Using the epoxy composite
The standard copper-clad plate sample for meeting the standards such as GB, UL is made according to general copper-clad plate production process for thing,
B copper-clad plates are named as, the performance of b copper-clad plates is tested, its result is represented in table -1.
Embodiment 3
Phenol 1mol and succinic acid 1mol is put into three mouthfuls of 2000ml glass reactors with agitating device,
3mL 98% concentrated sulfuric acid is added dropwise, in 40 DEG C of stirring reactions 3 hours, after the completion of reaction, with the side of physics
Inorganic constituents and moisture in method removal system, and add hexachlorocyclotriph,sphazene 1mol, third in backward reactor
Ketone 200ml, sodium methoxide 4mol, stir, while leading to nitrogen, are warming up to 60 DEG C, with 60min drops
Enter 20% sodium hydroxide solution 620g, keep 60 DEG C of temperature, 15 hours of stirring reaction, then add fourth
Diacid 1mol, continues stirring reaction 2 hours, and adds hexachlorocyclotriph,sphazene 1mol in backward reactor,
Sodium methoxide 4mol, stirring reaction 10 hours adds succinic acid 1mol afterwards, continues stirring reaction 5 small
When, after the completion of reaction, with inorganic constituents and moisture in the method removal system of physics, 3mL 98% is added dropwise
The concentrated sulfuric acid, and add phenol 1mol, in 40 DEG C of stirring reactions 3 hours, after reaction, use physical method
Impurity and moisture in removal system, distill solvent in system, and the ester equivalent for obtaining said structure is 180
G/eq carboxylate C 1mol.
Proton nmr spectra sign is carried out to obtained compound C, it is as a result as follows：
1H NMR(CDCl3,500MHz):7.0-7.3 (m, 10H, benzene ring hydrogen), 3.39 (s, 24H,
Hydrogen on methoxyl group), 2.52 (hydrogen on m, 12H, methylene).
The position of infrared spectrum characteristic peak：Ester carbonyl group 1730-1740cm-1, the C-O-C 1200cm of ester group-1,
The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P-N 874cm in phosphazene backbone-1, phosphonitrile bone
The characteristic absorption peak 1217cm of P=N keys in frame-1, P-N 874cm in phosphazene backbone-1, the absorption of methyl ether
Peak 2995.3cm-1, P-O-C key absworption peaks 1035cm-1, CH2- O absworption peak 2983cm-1。
O-cresol formaldehyde epoxy of the epoxide equivalent as 200g/eq is added using above-mentioned carboxylate C 90g as curing agent
Resin 100g, curing accelerator pyridine 0.2g, prepares composition epoxy resin.Using the epoxy composite
The standard copper-clad plate sample for meeting the standards such as GB, UL is made according to general copper-clad plate production process for thing,
C copper-clad plates are named as, the performance of c copper-clad plates is tested, its result is represented in table -1.
Comparative example 1
Epoxide equivalent is 200g/eq o-cresol formaldehyde epoxy resin 200g, adds phenolic hydroxyl equivalent and is
105g/eq linear phenol-aldehyde resin curing agent 105g and six phenoxy group phosphorus cyanogen 70g as fire retardant and
0.2g pyridine, solution is dissolved into appropriate butanone, uses normal glass cloth, according to conventional preparation method,
The copper-clad plate d that resinous amount is 50% is obtained, the properties for covering copper d are represented in table -1.
Comparative example 2
Epoxide equivalent is 200g/eq o-cresol formaldehyde epoxy resin 200g, and adding has such as formula (1) knot
The resin compound 220g of structure, ester equivalent is the 220g/eq and six phenoxy group phosphorus cyanogen 70g as fire retardant
With 0.2g pyridine, solution is dissolved into appropriate butanone, normal glass cloth is used, according to conventional making side
Method, obtains the copper-clad plate e that resinous amount is 50%.The properties for covering copper e are represented in table -1.
Formula (1).
Embodiment and the test result of comparative example are as shown in following table -1 (in view of specific method of testing has been this area
Known to technical staff, method is no longer described in detail at this).
Table -1
As can be seen from Table 1, the present invention uses the compound for containing the molecular structure shown in formula I as solidification
Resin combination prepared by agent so that be by the dielectric constant (1GHz) of its copper-clad plate prepared
3.0-3.1, dielectric loss (1GHz) be 0.004-0.006, Tg can reach 175 DEG C and more than, T- peel off
Intensity can reach 1.92kg/mm2And more than, interlaminar strength can reach 1.63kg/mm2And more than, satisfy
Less than 0.35% is can reach with water absorption rate, hence it is evident that better than the performance of comparative example copper-clad plate.
Applicant state, the present invention illustrated by above-described embodiment the present invention phosphazene compound, pre-impregnated sheet,
Composite metal substrate and wiring board, but the invention is not limited in above-described embodiment, that is, do not mean that this hair
The bright above-described embodiment that has to rely on could be implemented.Person of ordinary skill in the field is it will be clearly understood that to this hair
Bright any improvement, addition, the concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention
Selection etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (10)
1. a kind of phosphazene compound, it is characterised in that it has the molecular structure as shown in formula (I)：
In formula (I), R1Represent arbitrary organic group, R2For aliphatic group, R is to be carried by nucleopilic reagent
The inertia nucleophilic group of confession；M is phosphazenium groups；
A is integer more than zero, and b is the integer more than or equal to zero, and c is the integer more than zero, and and M
The total number of the connected substituent of group is equal to 2 times of number of phosphorus atoms on M groups.
2. phosphazene compound as claimed in claim 1, it is characterised in that R1For aliphatic group and/or virtue
Alkyl, further preferred substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkanes
In base, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl
Any one or its at least two combination；
Preferably, R1For unsubstituted straight chained alkyl or branched alkyl, unsubstituted cycloalkyl, unsubstituted
In aralkyl, unsubstituted alkylaryl, unsubstituted aryl or unsubstituted heteroaryl any one or
The combination of person at least two；
Preferably, R1Without reactive group that can be with epoxy resin reaction generation secondary hydroxyl groups；
Preferably, R2For substituted or unsubstituted aralkyl, substituted or unsubstituted alkylaryl, substitution or
Any one in unsubstituted aryl or substituted or unsubstituted heteroaryl or its at least two combination；
Preferably, the inertia nucleophilic group is that R is selected from-OR13、-C≡C-R18、
R22-COO-、In any one or at least two combination；
R13For substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkyl, take
Generation or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, take
Generation or unsubstituted aralkoxy, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted carbonic ester
Base, substituted or unsubstituted sulfonate group, substituted or unsubstituted phosphonate group, substituted or unsubstituted virtue
In base or substituted or unsubstituted heteroaryl any one or at least two combination, R15、R16And R17
It independently is substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkyl, takes
Generation or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, take
Generation or unsubstituted aralkoxy, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted aryl or
In substituted or unsubstituted heteroaryl any one or at least two combination, R18To replace or not taking
The straight chained alkyl or branched alkyl in generation, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl,
Substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aralkoxy,
In substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl
Any one or at least two combination, R22For substituted or unsubstituted straight chained alkyl or branched alkyl,
Substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, take
Generation or the fragrant oxygen of unsubstituted cycloalkyloxy, substituted or unsubstituted aralkoxy, substituted or unsubstituted alkyl
Any one in base, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl or at least two
Combination, R23And R24It independently is substituted or unsubstituted straight chained alkyl or branched alkyl, substitution or not
Substituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substitution do not take
The cycloalkyloxy in generation, substituted or unsubstituted aralkoxy, substituted or unsubstituted alkyl-aryloxy, substitution
Or in unsubstituted aryl or substituted or unsubstituted heteroaryl any one or at least two combination,
R26And R27It independently is substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted ring
Alkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkanes
Epoxide, substituted or unsubstituted aralkoxy, substituted or unsubstituted alkyl-aryloxy, substitution or unsubstituted
Aryl or substituted or unsubstituted heteroaryl in any one or at least two combination；
Preferably, the phosphazene compound be the phosphazene compound with following structure in any one or
At least two mixture：
A is 4, b
It is 2, R for 0, c1For methyl or phenyl, R2For ethyl；
A is 4, b
It is 1, R for 1, c1For methyl or phenyl, R2For ethyl；
Or
A is 4, b
It is 2, R for 0, c1For methyl or phenyl, R2For ethyl.
3. the phosphazene compound according to claim 1 or 2 with carboxylate, it is characterised in that M
For the phosphonitrile base M of ring three1, the phosphonitrile base M of ring more than four2Or non-annularity polyphosphazene base M3In any one or
Its at least two combination；
Preferably, M1Structure is：
M2Structure is：
Wherein, x is more than or equal to 4；
M3Structure is：
Wherein, y is more than or equal to 3.
4. a kind of preparation method of the phosphazene compound with carboxylate as described in one of claim 1-3, its
It is characterised by, obtained by phosphonitrile chloride and nucleopilic reagent progress nucleophilic substitution.
5. a kind of composition epoxy resin, it is characterised in that include the band described in one of claim 1-3
The phosphazene compound of carboxylate.
6. a kind of pre-impregnated sheet, it is characterised in that it is contained by composition epoxy resin as claimed in claim 5
Soak or be coated on base material and form.
7. pre-impregnated sheet as claimed in claim 6, it is characterised in that the base material be fiberglass substrate,
Polyester base material, polyimide base material, ceramic base material or carbon fiber base material.
8. a kind of composite metal substrate, it is characterised in that it includes more than one such as claim 6 or 7
The pre-impregnated sheet carries out surface metal-clad, overlapping, pressing and formed successively；
Preferably, the material of the surface metal-clad is the alloy of aluminium, copper, iron and its any combination；
Preferably, the composite metal substrate is that CEM-1 copper-clad plates, CEM-3 copper-clad plates, FR-4 cover copper
Plate, FR-5 copper-clad plates, CEM-1 aluminium bases, CEM-3 aluminium bases, FR-4 aluminium bases or FR-5 aluminium bases
Plate.
9. a kind of flexible copper-clad plate, it is characterised in that the flexible copper-clad plate includes more than one such as right
It is required that pre-impregnated sheet described in 6 or 7 and the Copper Foil for the pre-impregnated sheet one or both sides being overlying on after overlapping.
10. a kind of wiring board, it is characterised in that in the surface of the composite metal substrate described in claim 8
Processing line is formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610008890.XA CN106939021A (en) | 2016-01-04 | 2016-01-04 | A kind of phosphazene compound, pre-impregnated sheet, composite metal substrate and wiring board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610008890.XA CN106939021A (en) | 2016-01-04 | 2016-01-04 | A kind of phosphazene compound, pre-impregnated sheet, composite metal substrate and wiring board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106939021A true CN106939021A (en) | 2017-07-11 |
Family
ID=59469352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610008890.XA Pending CN106939021A (en) | 2016-01-04 | 2016-01-04 | A kind of phosphazene compound, pre-impregnated sheet, composite metal substrate and wiring board |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106939021A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4191715A (en) * | 1978-07-03 | 1980-03-04 | Monsanto Company | Flame retarding compound |
| CN102503982A (en) * | 2011-10-31 | 2012-06-20 | 华中师范大学 | Phosphonitrilic chloride trimer epoxy compound with flame-retardant property and preparation and application thereof |
| JP2012177777A (en) * | 2011-02-25 | 2012-09-13 | Fujifilm Corp | Photosensitive composition, photosensitive film, photosensitive laminate, permanent pattern formation method and printed substrate |
| CN102977551A (en) * | 2011-09-02 | 2013-03-20 | 广东生益科技股份有限公司 | Halogen-free resin composition and method for preparing copper-clad plate from the halogen-free resin composition |
| JP2015205990A (en) * | 2014-04-21 | 2015-11-19 | 国立大学法人愛媛大学 | Flame-retardant polymer, production method thereof, and flame-retardant monomer |
| CN105153234A (en) * | 2014-06-13 | 2015-12-16 | 广东生益科技股份有限公司 | Phenoxy cyclotriphosphazene active ester, halogen free resin composition and application thereof |
-
2016
- 2016-01-04 CN CN201610008890.XA patent/CN106939021A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4191715A (en) * | 1978-07-03 | 1980-03-04 | Monsanto Company | Flame retarding compound |
| JP2012177777A (en) * | 2011-02-25 | 2012-09-13 | Fujifilm Corp | Photosensitive composition, photosensitive film, photosensitive laminate, permanent pattern formation method and printed substrate |
| CN102977551A (en) * | 2011-09-02 | 2013-03-20 | 广东生益科技股份有限公司 | Halogen-free resin composition and method for preparing copper-clad plate from the halogen-free resin composition |
| CN102503982A (en) * | 2011-10-31 | 2012-06-20 | 华中师范大学 | Phosphonitrilic chloride trimer epoxy compound with flame-retardant property and preparation and application thereof |
| JP2015205990A (en) * | 2014-04-21 | 2015-11-19 | 国立大学法人愛媛大学 | Flame-retardant polymer, production method thereof, and flame-retardant monomer |
| CN105153234A (en) * | 2014-06-13 | 2015-12-16 | 广东生益科技股份有限公司 | Phenoxy cyclotriphosphazene active ester, halogen free resin composition and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105646862B (en) | Polyester, pre-impregnated sheet, composite metal substrate and wiring board containing phosphonitrile | |
| EP3093329A1 (en) | Flame retardant compounds, hardeners and polyphenol-based epoxy resins | |
| CN108250676B (en) | A kind of phosphorous active ester and its halogen-free composition and copper clad foil substrate | |
| CN102276961A (en) | Halogen-free phosphorus-free epoxy resin composition, and semi-curing sheet and laminated sheet manufactured thereby | |
| CN105542128A (en) | Curing agent for epoxy resin as well as preparation method and application thereof | |
| CN107337694A (en) | A kind of phosphazene compound with silanol, fire retardant, composition epoxy resin and composite metal substrate | |
| CN106916281A (en) | Flame-retardant compound, curing agent and polyphenol base epoxy | |
| CN105646588A (en) | Phosphazene compound with carboxylic ester, presoaked plate, composite metal substrate and circuit board | |
| EP3263576A1 (en) | Phosphazene compound containing ester group, preparation method and use thereof | |
| US10233204B2 (en) | Phosphazene compound, and a composition, a prepreg and a wiring board comprising the same | |
| CN107522744A (en) | A kind of phosphazene compound, phosphonitrile epoxy resin, pre-impregnated sheet and composite metal substrate | |
| CN107337696A (en) | Phosphazene compound, curing agent, phosphonitrile epoxy resin and composite metal substrate and plastic packaging material with aldehyde radical | |
| CN106939021A (en) | A kind of phosphazene compound, pre-impregnated sheet, composite metal substrate and wiring board | |
| CN106939020A (en) | A kind of phosphazene compound, pre-impregnated sheet and composite metal substrate | |
| CN106939016A (en) | A kind of phosphazene compound, pre-impregnated sheet, composite metal substrate and wiring board | |
| CN107344952A (en) | A kind of phosphazene compound with alkynyl, composition epoxy resin, plastic packaging material and composite metal substrate | |
| CN106939017A (en) | A kind of phosphazene compound, pre-impregnated sheet, composite metal substrate and wiring board | |
| CN106939019A (en) | A kind of phosphazene compound, pre-impregnated sheet, composite metal substrate and wiring board | |
| CN106939018A (en) | A kind of phosphazene compound, pre-impregnated sheet and composite metal substrate | |
| CN106939022A (en) | A kind of phosphazene compound, pre-impregnated sheet and composite metal substrate | |
| CN107337697A (en) | Phosphazene compound, plastic packaging material and the composite metal substrate of the base containing DOPO | |
| CN107337698A (en) | Phosphazene compound, curing agent, phosphonitrile epoxy resin and composite metal substrate and plastic packaging material with amide groups | |
| CN107337693A (en) | Phosphazene compound, plastic packaging material and composite metal substrate containing phosphinate | |
| CN107573486A (en) | Sulfydryl phosphazene compound, curing agent and sulfydryl phosphonitrile epoxy resin | |
| CN108250674A (en) | A kind of halogen-free epoxy resin composition and use its prepreg and laminate |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170711 |
|
| RJ01 | Rejection of invention patent application after publication |