CN1161986A - 热固性树脂组合物、固化物、预成型料、金属铠装层压板和线路板 - Google Patents
热固性树脂组合物、固化物、预成型料、金属铠装层压板和线路板 Download PDFInfo
- Publication number
- CN1161986A CN1161986A CN97101088A CN97101088A CN1161986A CN 1161986 A CN1161986 A CN 1161986A CN 97101088 A CN97101088 A CN 97101088A CN 97101088 A CN97101088 A CN 97101088A CN 1161986 A CN1161986 A CN 1161986A
- Authority
- CN
- China
- Prior art keywords
- thermosetting resin
- compositions
- resin
- phenol
- hydroxyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 101
- 239000000463 material Substances 0.000 title claims description 39
- 239000011342 resin composition Substances 0.000 title abstract 3
- 239000002184 metal Substances 0.000 title 1
- 229920005989 resin Polymers 0.000 claims abstract description 128
- 239000011347 resin Substances 0.000 claims abstract description 128
- 229920003986 novolac Polymers 0.000 claims abstract description 51
- 239000000203 mixture Substances 0.000 claims description 65
- 229910052739 hydrogen Inorganic materials 0.000 claims description 48
- 239000001257 hydrogen Substances 0.000 claims description 48
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 29
- 239000004744 fabric Substances 0.000 claims description 15
- 239000012212 insulator Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 14
- -1 hydroxyl phenylenes Chemical class 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 239000004020 conductor Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
- 239000003973 paint Substances 0.000 claims description 7
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011152 fibreglass Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 6
- 239000007795 chemical reaction product Substances 0.000 claims 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 2
- 239000005011 phenolic resin Substances 0.000 abstract description 7
- 229920001568 phenolic resin Polymers 0.000 abstract description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 3
- BGDOLELXXPTPFX-UHFFFAOYSA-N 3,4-dihydro-2h-1,2-benzoxazine Chemical group C1=CC=C2ONCCC2=C1 BGDOLELXXPTPFX-UHFFFAOYSA-N 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 37
- 239000003795 chemical substances by application Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 238000005452 bending Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920003987 resole Polymers 0.000 description 8
- 238000001879 gelation Methods 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 150000003141 primary amines Chemical class 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 230000002650 habitual effect Effects 0.000 description 5
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 5
- 239000003566 sealing material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 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 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 244000124209 Crocus sativus Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- NSBIQPJIWUJBBX-UHFFFAOYSA-N n-methoxyaniline Chemical compound CONC1=CC=CC=C1 NSBIQPJIWUJBBX-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/28—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer impregnated with or embedded in a plastic substance
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
-
- 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
- B32B15/14—Layered products comprising a layer of metal next to a 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/08—Impregnating
-
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
-
- 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
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- 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
- B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
- B32B2315/08—Glass
- B32B2315/085—Glass fiber cloth or fabric
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/901—Printed circuit
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31515—As intermediate layer
- Y10T428/31522—Next to metal
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31529—Next to metal
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Textile Engineering (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
热固性树脂组合物(A)包含60-97重量%的含二氢苯并噁嗪环的热固性树脂和3-40重量%的酚醛清漆树脂,热固性树脂组合物(B)包含5-30重量%的含二氢苯并噁嗪环的热固性树脂和70-95重量%的酚醛清漆树脂。这些热固性树脂组合物固化迅速,它们的固化物具有优异的机械特性和不易燃性。
Description
本发明涉及热固性树脂组合物,该组合物具有优异的耐热性和不易燃性,可用作高功能成型材料、油漆、涂料、粘合剂、密封材料、印刷线路板的预成型料、金属铠装层压板、FRP和碳制品的原料。本发明还涉及热固性树脂组合物的固化物和用热固性树脂组合物制成的预成型料、金属铠装层压板和线路板。
热固性树脂如酚醛树脂、三聚氰胺树脂、环氧树脂、不饱和聚酯树脂和二(顺丁烯二酰亚胺)树脂等由于它们的可靠性和由热固性产生的耐热性,已被应用于各个工业领域。然而,这些树脂具有各自的缺点,例如,酚醛树脂和三聚氰胺树脂在固化时会产生挥发性副产物,环氧树脂和不饱和聚酯树脂的耐热性差,二(顺丁烯二酰亚胺)树脂非常昂贵,按照使用方法,需要忍受这些缺点。因此,现已开发了克服了这些缺点的新的热固性树脂。
一个例子是二氢苯并噁嗪化合物的开发(日本专利公开公报1974年第47387号和美国专利No.5,152,939说明书)。由于这些化合物是通过二氢苯并噁嗪环的开环聚合而热固的,在固化时,几乎不会产生挥发性物质。
对这些化合物的固化和反应性的研究已由Burke等在J.Am.Chem.Soc.3424(1956)和Riess等在Polym.Sci.Technol.27(1985)上分别报告。日本专利公开公报1995年第188364号公开了通过留下一定百分比的未环化的酚性羟基而在固化性上进行了改良的二氢苯并噁嗪化合物。
公开在日本专利公开公报1974年第47387号上的二氢苯并噁嗪化合物是通过开环聚合进行固化,以产生在耐热性和强度上优于已有的热固性树脂固化产品的固化树脂。然而,与酚醛树脂的惯用固化方法相比,通过开环聚合进行固化的方法所需时间长,并由于产能低,其使用受到限制。
如日本专利公开公报1995年第188364号所揭示的,分子中含有剩余的一定百分比的未转化成二氢苯并噁嗪环的酚性羟基的二氢苯并噁嗪化合物在固化性方面得到改善,但由于在化合物合成过程中加热而发生了开环聚合反应,使得合成难以稳定的进行。
虽然Burke等和Riess等报导了通过添加单官能团酚类化合物可改善固化性,但这些改善是不充分的,并由于交联点密度的降低,耐热性和机械强度出现下降。
本发明的目的在于提供含热固性树脂的组合物,所述热固性树脂含二氢苯并噁嗪环并在固化性上得到改善而不会损害其他特性如机械特性等。
本发明的另一个目的在于提供热固性树脂组合物的固化制品和通过使用所述热固性树脂组合物而制成的预成型料、金属铠装层压板以及线路板。
作为为达到上述目的而进行的研究的成果,本发明者发现,通过添加酚醛清漆树脂作为固化剂,可改善含二氢苯并噁嗪环的热固性树脂的固化性而不会损害包括机械特性在内的其他特性。本发明者还发现,将作为固化剂的含二氢苯并噁嗪环的热固性树脂添加至酚醛清漆树脂中,可使热固性树脂组合物在固化时不产生挥发性物质并在包括机械特性在内的各种特性方面有明显的提高。基于这些发现,本发明者完成了本发明。
即,本发明提供由60-97重量%的含二氢苯并噁嗪环的热固性树脂和3-40重量%的酚醛清漆树脂组成的热固性树脂组合物〔热固性树脂组合物(a)〕。
本发明还提供由5-30重量%的含二氢苯并噁嗪环的热固性树脂和70-95重量%的酚醛清漆树脂组成的热固性树脂组合物〔热固性树脂组合物(b)〕。
本发明还提供热固性树脂组合物(a)和(b)的固化制品。
本发明还提供通过将基料用含热固性树脂组合物(a)或(b)的清漆浸渍并随后加热干燥而制成的预成型料。
本发明还提供包含通过加热和加压,使二片或多片预成型料粘合而成的层压板和粘合在层压板的一面或两面上的金属箔的金属铠装层压板。
本发明还提供包含绝缘座和形成在绝缘座的内侧或一面或两面上的导线分布图的线路板,所述绝缘座包含热固性树脂组合物(a)或(b)的固化物的基体和加强基体的基料。
对可用于本发明的含二氢苯并噁嗪环的热固性树脂无任何限制,只要其含有二氢苯并噁嗪环并通过二氢苯并噁嗪环的开环聚合而固化即可。含二氢苯并噁嗪环的热固性树脂可由例如含酚性羟基、伯胺和甲醛的化合物如下式所示进行合成。
式中,R1表示甲基、苯基或被至少一个C1-3的烷基或烷氧基取代的苯基,上式中的亚苯基在它们的羟基的一个或两个邻位上有氢原子。
含酚性羟基的化合物的非限定性例子有多官能苯酚、双酚、双酚化合物、三苯酚化合物、四苯酚化合物和酚醛树脂。多官能苯酚的非限定性例子有儿茶酚、氢醌和间苯二酚。双酚化合物的非限定性例子有双酚A、双酚F和它们的位置异构体、双酚S和四氟双酚A。酚醛树脂的非限定性例子有苯酚-酚醛清漆树脂、可溶性酚醛树脂、酚醛改性二甲苯树脂、烷基酚树脂、三聚氰胺-酚醛树脂和酚醛改性聚丁二烯。
伯胺的非限定性例子有甲胺、苯胺和有取代的苯胺如甲苯胺和茴香胺。用脂肪族胺合成的热固性树脂可迅速固化,但耐热性差。用芳香族胺如苯胺合成的热固性树脂的固化物具有优异的耐热性,但固化速度较慢。
含二氢苯并噁嗪环的热固性树脂可通过下述方法制得:将含至少2个(各在它们的羟基的一个或两个两个邻位具有氢的)羟基亚苯基的化合物(以下称含活性羟基亚苯基的化合物)和伯胺的混合物加在加热至70℃或70℃以上的甲醛如甲醛水中,让混合物在70-110℃,最好在90-100℃反应20分钟至2小时,然后在120℃或120℃以下减压干燥。
在上述反应中,相对于含活性羟基亚苯基的化合物的1摩尔的所有酚性羟基,使用0.5-1.0摩尔,最好为0.6-1.0摩尔的伯胺,相对于1摩尔的伯胺,使用至少2摩尔的甲醛。若伯胺少于0.5摩尔,则交联点密度可能减少,耐热性会变得不充分。
在本发明中,含二氢苯并噁嗪环的热固性树脂可分别使用,也可两种以上合用。在制备本发明的热固性树脂组合物之前,可将热固性树脂在80-180℃,最好在120-160℃加热进行预聚合,以控制固化时间和熔体粘度。
在本发明中用于与热固性树脂混合的酚醛清漆树脂的非限定性例子有苯酚-酚醛清漆树脂、双酚-酚醛清漆树脂、酚醛改性二甲苯树脂和烷基酚树脂。
在本发明中,最好使用被称为高邻位酚醛清漆树脂(含至少50%的邻位率的酚醛清漆树脂)。这些高邻位酚醛清漆树脂可改善固化性而不会损害机械特性。
本发明的热固性树脂组合物(a)包含60-97重量%,最好为70-95重量%的含二氢苯并噁嗪环的热固性树脂和3-40重量%,最好为5-30重量%的酚醛清漆树脂。含二氢苯并噁嗪环的热固性树脂可自我固化,但一般需要很长的固化时间。添加3-40重量%的酚醛清漆树脂,可改善本发明的热固性树脂组合物(a)的固化性并可保持其良好的机械特性。若含二氢苯并噁嗪环的热固性树脂大于97重量%,则固化性的改善会变得不充分。
含二氢苯并噁嗪环的树脂的固化物的特征还在于,其吸水性低于已有的含环氧树脂和酚醛树脂的热固性树脂。这似乎是因为酚性羟基由于与氮原子的相互作用而被固定的缘故。为保持这一特征,本发明的热固性树脂组合物(a)由于所含的热固性树脂具有作为主要成分的二氢苯并噁嗪环,因此,该组合物(a)是令人满意的,并且,在该热固性树脂组合物中的酚性羟基和二氢苯并噁嗪环所含的氮原子最好以羟基/氮原子为不大于1.5,较好的为0.3-1.5,最好为0.5-1.10的数量比存在。
本发明的热固性树脂组合物(b)包含5-30重量%,最好是15-30重量%的含二氢苯并噁嗪环的热固性树脂和70-95重量%,最好为70-85重量%的酚醛清漆树脂。在含70-95重量%的酚醛清漆树脂的组合物(b)中,含二氢苯并噁嗪环的热固性树脂组合物起固化剂的作用。由于没有惯用的酚醛清漆树脂的固化剂六亚甲基四胺,热固性树脂组合物(b)可在不产生挥发性物质如氨的情况下进行固化,从而改善了工作效率。固化物在机械强度方面也得到了改善。
若酚醛清漆树脂大于40重量%或小于70重量%,则固化性得到改善,而固化物的机械强度可能下降。
当需要快速固化时,本发明的组合物(a)和(b)还可含少量惯用的酚醛树脂固化剂如六亚甲基四胺。即使附加使用这些惯用的固化剂,它们的量可减至使挥发性物质如氨的产生为最小的程度。当往热固性树脂组合物(a)或(b)中添加这些惯用的固化剂时,其较佳的添加量为占含二氢苯并噁嗪环的热固性树脂和酚醛清漆树脂总量的1-5重量%。
本发明的热固性树脂组合物可通过研磨含二氢苯并噁嗪环的热固性树脂和酚醛清漆树脂,然后将所得粉末混合,或最好用加热辊熔融混合或用溶剂混合成溶液而制备。
本发明的组合物还可根据需要,包含添加剂,例如,加强料如填料和补强纤维、防粘剂、着色剂和粘合剂。
填料的非限定性例子有有机填料如棉絮、α-纤维素、纸浆和木粉以及无机填料如锆粉、石英玻璃粉、滑石粉、碳酸钙粉、氢氧化镁粉、氧化镁粉、硅酸钙粉、硅石粉、沸石、粘土和云母。
加强纤维的非限定性例子有常产纤维、纱、棉布、玻璃布、无纺玻璃布、玻璃纤维、碳纤维、石英纤维、有机纤维、有机纤维布、无纺有机纤维布和纸。
加强料的量最好为10-300重量份比100重量份本发明的热固性树脂组合物。
本发明的热固性树脂组合物在固化性方面优于含二氢苯并噁嗪环的热固性树脂,因此,可通过用加热辊等捏和,然后于180-220℃,在20-70kgf/cm2的合模压力下压制成形或转移模塑15-30分钟来进行固化,以产生具有优异的机械特性和不易燃性的固化物。
固化物的特性可通过在180-220℃后固化5-120分钟来进一步加以改善。
本发明的热固性树脂组合物(a)和(b)还可根据用途,例如,用于制造金属铠装层压板、成型材料、密封材料和FRP树脂材料而含环氧树脂及其固化剂。
对可用作上述添加剂成分的环氧树脂无任何限制,非限定性例子有由苯酚和醛衍生的酚醛清漆树脂的环氧化产物,如苯酚-酚醛清漆环氧树脂、邻甲酚-酚醛清漆环氧树脂;可通过多醇如双酚A、双酚B、双酚F和双酚S与表氯醇的反应而得到的缩水甘油醚型环氧树脂;可通过多酸如邻苯二甲酸与表氯醇的反应而得到的缩水甘油酯型环氧树脂;可通过多胺如二氨基二苯基甲烷和异氰脲酸与表氯醇的反应而得到的缩水甘油胺型环氧树脂;可通过用过酸如过乙酸氧化烯键而得到的直链脂肪族型环氧树脂和脂环型环氧树脂;溴化环氧树脂。这些树脂可分别使用,也可两种以上合用。对环氧树脂的固化剂无任何限制,优选的例子为在固化过程中不产生挥发性物质的固化剂,尤其优选加聚型固化剂如酚醛清漆树脂、双氰胺、咪唑和三苯膦。当使用酚醛清漆树脂作为固化剂时,除用作热固性树脂组合物(a)和(b)的基本成分之一的酚醛清漆树脂之外,最好以酚醛清漆树脂的羟基/环氧树脂的环氧基的摩尔比为0.5-1.5的比例添加酚醛清漆树脂。
本发明的热固性树脂组合物(热固性树脂组合物(a)和(b))可合适地用作具有优异的耐热性、不易燃性和成型效率的高功能成型材料、油漆、涂料、粘合剂、密封材料、印刷线路板的预成型料、金属铠装层压板、FRP、碳制品等的树脂原料。
例如,本发明的热固性树脂组合物可单独或根据需要,与添加剂如填料、加强料、防粘剂和着色剂一起用作各种成型材料和用于包覆半导体装置的密封材料。
本发明的预成型料可通过用含本发明的热固性树脂组合物的油漆浸渍基料,然后加热干燥而制成。油漆可含添加剂如填料。
基料的非限定性例子有玻璃布、无纺玻璃布、有机纤维布、无纺有机纤维布和纸。
本发明的金属铠装层压板包括通过加热和加压,使二片或二片以上的预成型料粘合在一起而制成的层压板、粘合在层压板的一面或两面上的金属箔。例如,金属铠装层压板可通过将二片或多片预成型料叠层,将金属箔置于叠层的预成型料的一面或两面上,然后加热和加压,使叠层的预成型料和金属箔粘合在一起而制成。金属箔的非限定性例子有铜箔、镍箔、铝箔和SUS箔。
本发明的线路板包括绝缘座和形成在绝缘座的内侧或一面或两面上的导线分布图,所述绝缘座包含本发明的热固性树脂组合物的固化物的基体和加强基体的基料。基料的非限定性例子有玻璃布、无纺玻璃布、有机纤维布、无纺有机纤维布和纸。绝缘座可含其他添加剂如填料。
本发明的线路板包括具有形成在绝缘座的一面或两面上的导线分布图的印刷线路板和具有形成在绝缘座的内侧和一面或两面上的导线分布图的多层线路板。印刷线路板可通过在本发明的金属铠装层压板的金属箔上印刷以形成导线分布图,然后根据需要,用通孔将导线分布图连接而制成。多层印刷线路板可通过例如使用本发明的预成型料、金属铠装层压板和印刷线路板,按整体层压法(mass laminating method)或销式层压法(pin laminating method)加以制造。
本发明的线路板具有优异的耐热性和不易燃性,可用于各种电气和电子领域。
实施例1-13和比较例1-10〔1〕含二氢苯并噁嗪环的热固性树脂的合成(I)(1)苯酚-酚醛清漆树脂的合成
将1.9kg苯酚、1.15kg甲醛水(37%水溶液)和4g草酸放入5升的烧瓶中,然后加热回流6小时使其反应。在6666.1帕或更低的真空下除去未反应的苯酚和水。所得树脂的软化点为89℃(环球法),三聚物或高聚物/二聚物的比例为89/11(用凝胶渗透色谱法测得的峰面积比)。(2)二氢苯并噁嗪环的导入
将上面合成的1.7kg苯酚-酚醛清漆树脂(16摩尔羟基)与1.49kg(16摩尔)苯胺混合,然后将混合物在80℃搅拌5小时以形成均匀的混合液。将1.62kg甲醛水放入5升的烧瓶中并加热至90℃,然后用30分钟的时间逐渐加入酚醛清漆树脂/苯胺混合液。添加结束后,继续回流30分钟,然后在6666.1帕或更低的真空下于100℃加热2小时以除去缩合反应生成的水,得到其中的95%的活性羟基已转化成二氢苯并噁嗪环的热固性树脂(I)。〔2〕含二氢苯并噁嗪环的热固性树脂的合成(II)(1)苯酚-酚醛清漆树脂的合成
将1.9kg苯酚、1.10kg甲醛水(37%水溶液)和4g草酸放入5升的烧瓶中,重复合成(I)-(1)的步骤以合成苯酚-酚醛清漆树脂。所得树脂的软化点为84℃(环球法),三聚物或高聚物/二聚物的比例为82/18(用凝胶渗透色谱法测得的峰面积比)。(2)二氢苯并噁嗪环的导入
用与合成(I)-(2)相似的方法将二氢苯并噁嗪环导入在合成(II)-(1)中所得的苯酚-酚醛清漆树脂中。在所得热固性树脂(II)中,苯酚-酚醛清漆树脂的90%的活性羟基已转化成二氢苯并噁嗪环。〔3〕含二氢苯并噁嗪环的热固性树脂的合成(III)
重复合成(I)-(2)的步骤,不同之处在于,使用0.76kg(10摩尔羟基)双酚A、0.93kg(10摩尔)苯胺和1.62kg甲醛水(37%水溶液)作为原料,以得到其中的94%羟基已转化成二氢苯并噁嗪环的热固性树脂(III)。〔4〕酚醛清漆树脂的合成(A)
将2.4kg苯酚、0.02kg甲醛水(37%水溶液)、0.6kg仲甲醛、0.02kg乙酸锌、0.06kg苯甲酸和0.05kg水放入5升的烧瓶中,然后回流6小时使其反应。在6666.1帕或更低的真空下除去未反应的苯酚和水。所得树脂(A)的软化点为75-83℃(环球法),邻位率为70%(NMR)。〔5〕酚醛清漆树脂的合成(B)
将1.9kg苯酚、1.3kg甲醛水(37%水溶液)和15g草酸放入5升的烧瓶中,然后回流6小时使其反应。在6666.1帕或更低的真空下除去未反应的苯酚和水。所得树脂(B)的软化点为84℃(环球法),邻位率为40%(NMR)。〔6〕树脂组合物的制备
在实施例1-13和比较例6、8-10中,通过下述方法制备树脂组合物:将表1-4中所示酚醛清漆树脂放入烧瓶中,然后在110-120℃加热熔化树脂,接着添加表1-4所示的含二氢苯并噁嗪环的热固性树脂,将混合物混合5分钟以得到均匀的混合物。在比较例1-3中,仅使用表3所示的热固性树脂。在比较例4和5中,通过研磨表3所述的酚醛清漆树脂和六亚甲基四胺,然后在混合器中混合3分钟来制备树脂组合物。在比较例7中,将表4所示的热固性树脂溶解在熔融的苯酚中,并搅拌5分钟以得到均匀的混合物。〔7〕固化
将上面所得的树脂组合物研磨并填入容积为120×80×4mm的模具中,在1.96兆帕的压力下于180℃加热15分钟,以得到固化物。
按下述方法测定树脂组合物的特性。
胶凝时间为将0.3g树脂组合物在加热至180℃的胶凝计时器上每秒钟搅拌1次至树脂组合物停止绕线所需的时间。
抗弯强度和抗弯模量按照JISK6911以2mm/min的弯曲速率在23℃进行。
不易燃性的评价是通过使用3.6mm厚的试样,按照UL-94进行。
吸水性是通过按上述方法模塑的50×50×3mm的树脂板在PCT(高压锅测试器:121℃、2个大气压)中处理10小时前后的重量差算出。在实施例4(酚性OH/N=1.10)和比较例6(酚性OH/N=1.93)中,它们的吸水值分别为1.6%和3.2%,显示很大的差异。
实施例和比较例的树脂组合物的组成和特性显示在表1-10中。组成的重量单位是重量份。
表1
实 施 例
1 2 3 4 5 6 7含二氢苯并噁嗪环的热固性树脂(I) 5 10 30 70 97 10 70
(II) - - - - - - -
(III) - - - - - - -
酚醛清漆树脂A 95 90 70 30 3 - -
酚醛清漆树脂B - - - - - 90 30
表2
实 施 例
8 9 10 11 12 13含二氢苯并噁嗪环的热固性树脂(I) - - - - - -
(II) 10 70 70 - - -
(III) - - - 10 70 70
酚醛清漆树脂A 90 30 - 90 30 -
酚醛清漆树脂B - - 30 - - 30
表3
比 较 例
1 2 3 4 5含二氢苯并噁嗪环的热固性树脂(I) 100 - - - -
(II) - 100 - - -
(III) - - 100 - -
酚醛清漆树脂A - - - 85 -
酚醛清漆树脂B - - - - 85
六亚甲基四胺 - - - 15 15
表4
比 较 例
6 7 8 9 10含二氢苯并噁嗪环的热固性树脂(I) 50 70 40 2 98
(II) - - - - -
(III) - - - - -
酚醛清漆树脂A 50 - 60 98 2
酚醛清漆树脂B - - - - -
六亚甲基四胺 - - - - -
苯酚 - 30 - - -
表5
实 施 例
1 2 3 4 5胶凝时间(秒) 92 80 58 45 90
固化物外观 红色透明 红色透明 红色透明 红色透明 红色透明
表 面 光滑 光滑 光滑 光滑 光滑抗弯强度(兆帕) 157.2 158.8 157.6 159.5 159.0弯曲模量(兆帕) 5594 5650 5610 5620 5742
不易燃性 V-0 V-0 V-0 V-0 V-0
表6
实 施 例
6 7 8 9 10胶凝时间(秒) 95 70 132 120 142
固化物外观 红色透明 红色透明 红色透明 红色透明 红色透明
表 面 光滑 光滑 光滑 光滑 光滑抗弯强度(兆帕) 138.8 142.3 167.8 169.4 154.4弯曲模量(兆帕) 4841 4560 5453 5662 5482
不易燃性 V-0 V-0 V-0 V-0 V-0
表7
实 施 例
11 12 13胶凝时间(秒) 115 96 82固化物外观 红色透明 红色透明 红色透明
表 面 光滑 光滑 光滑抗弯强度(兆帕) 133.1 130.0 128.9弯曲模量(兆帕) 4621 4000 4050
不易燃性 V-0 V-0 V-0
表8
比 较 例
1 2 3 4胶凝时间(秒) 382 420 360 28固化物外观 红色透明 红色透明 橘黄色透明 棕色、不透明
表 面 光滑 光滑 光滑 许多小泡抗弯强度(兆帕) 158.8 171.5 137.2 25.5弯曲模量(兆帕) 5782 5684 4410 5120
不易燃性 V-0 V-0 V-0 V-0
表9
比 较 例
5 6 7 8 9胶凝时间(秒) 80 37 60 45 185固化物外观 棕色、不透明 红色透明 红色透明 红色透明 红色透明
表 面 许多小泡 光滑 光滑 光滑 光滑抗弯强度(兆帕) 92.6 120.5 90.3 100.5 140.3弯曲模量(兆帕) 464 5320 5400 5650 5451
不易燃性 V-0 V-0 V-0 V-0 V-0
表10
比 较 例
10胶凝时间(秒) 140
固化物外观 红色透明
表 面 光滑抗弯强度(兆帕) 152.5弯曲模量(兆帕) 5603
不易燃性 V-0
上表所示结果表明,本发明的热固性树脂组合物固化迅速,固化物具有优异的机械特性和不易燃性。因此,本发明的热固性树脂组合物可用作高功能成型材料、油漆、涂料、粘合剂、密封材料、预成型料、FRP和碳制品的原料。
Claims (19)
1.热固性树脂组合物,其特征在于,包含60-97重量%的含二氢苯并噁嗪环的热固性树脂和3-40重量%的酚醛清漆树脂。
2.如权利要求1所述的热固性树脂组合物,其特征在于,所述酚醛清漆树脂的邻位率至少为50%。
3.如权利要求1所述的热固性树脂组合物,其特征在于,热固性树脂组合物中的酚性羟基对二氢苯并噁嗪环中所含的氮原子的数量比为不大于1.5。
4.如权利要求1所述的热固性树脂组合物,其特征在于,所述含二氢苯并噁嗪环的热固性树脂是含至少2个均在其羟基的一个或两个邻位上有氢原子的羟基亚苯基的化合物与伯胺和甲醛的反应产物,化合物的酚性羟基与伯胺的摩尔比为1∶0.5-1.0,甲醛与伯胺的摩尔比至少为2。
5.如权利要求4所述的热固性树脂组合物,其特征在于,所述化合物是苯酚-酚醛清漆树脂或双酚A。
6.如权利要求1所述的热固性树脂组合物的固化物。
7.预成型料,其特征在于,通过用含权利要求1的热固性树脂组合物的油漆浸渍基料,然后加热干燥而制得。
8.如权利要求7所述的预成型料,其特征在于,所述基料是玻璃布、无纺玻璃布、有机纤维布、无纺有机纤维布或纸。
9.金属铠装层压板,其特征在于,包括通过加热和加压,使二片或二片以上的权利要求7的预成型料粘合在一起而制成的层压板和粘合在层压板的一面或两面上的金属箔。
10.线路板,其特征在于,包括绝缘座和形成在绝缘座的内侧或一面或两面上的导线分布图,所述绝缘座包含权利要求1的热固性树脂组合物的固化物的基体和加强基体的基料。
11.热固性树脂组合物,其特征在于,包含5-30重量%的含二氢苯并噁嗪环的热固性树脂和70-95重量%的酚醛清漆树脂。
12.如权利要求11所述的热固性树脂组合物,其特征在于,所述酚醛清漆树脂的邻位率为至少50%。
13.如权利要求11所述的热固性树脂组合物,其特征在于,所述含二氢苯并噁嗪环的热固性树脂是含至少2个均在其羟基的一个或两个邻位上有氢原子的羟基亚苯基的化合物与伯胺和甲醛的反应产物,化合物的酚性羟基与伯胺的摩尔比为1∶0.5-1.0,甲醛与伯胺的摩尔比至少为2。
14.如权利要求13所述的热固性树脂组合物,其特征在于,所述化合物是苯酚-酚醛清漆树脂或双酚A。
15.如权利要求11所述的热固性树脂组合物的固化物。
16.预成型料,其特征在于,通过用含权利要求11的热固性树脂组合物的油漆浸渍基料,然后加热干燥而制得。
17.如权利要求16所述的预成型料,其特征在于,所述基料是玻璃布、无纺玻璃布、有机纤维布、无纺有机纤维布或纸。
18.金属铠装层压板,其特征在于,包括通过加热和加压,使二片或二片以上的权利要求16的预成型料粘合在一起而制成的层压板和粘合在层压板的一面或两面上的金属箔。
19.线路板,其特征在于,包括绝缘座和形成在绝缘座的内侧或一面或两面上的导线分布图,所述绝缘座包含权利要求11的热固性树脂组合物的固化物的基体和加强基体的基料。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2429296 | 1996-02-09 | ||
JP024292/96 | 1996-02-09 | ||
JP167785/96 | 1996-06-27 | ||
JP16778596A JP3487083B2 (ja) | 1996-02-09 | 1996-06-27 | 熱硬化性樹脂組成物及びその硬化物 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1161986A true CN1161986A (zh) | 1997-10-15 |
CN1088727C CN1088727C (zh) | 2002-08-07 |
Family
ID=26361784
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN97101088A Expired - Lifetime CN1088727C (zh) | 1996-02-09 | 1997-02-05 | 热固性树脂组合物、固化物、预成型料、金属铠装层压板和线路板 |
Country Status (8)
Country | Link |
---|---|
US (1) | US5945222A (zh) |
EP (1) | EP0789056B1 (zh) |
JP (1) | JP3487083B2 (zh) |
KR (1) | KR100205271B1 (zh) |
CN (1) | CN1088727C (zh) |
DE (1) | DE69724169T2 (zh) |
MY (1) | MY121250A (zh) |
TW (1) | TW460537B (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100415826C (zh) * | 2003-07-10 | 2008-09-03 | 旭有机材工业株式会社 | 酚醛树脂组合物 |
CN101113284B (zh) * | 2006-07-24 | 2010-12-08 | 南亚塑胶工业股份有限公司 | 二氢苯并树脂合成及其应用 |
CN101376735B (zh) * | 2008-09-26 | 2011-11-30 | 广东生益科技股份有限公司 | 无卤阻燃树脂组合物以及用其制作的粘结片与覆铜箔层压板 |
CN101605837B (zh) * | 2007-02-08 | 2013-06-12 | 亨斯迈先进材料(瑞士)有限公司 | 热固性组合物 |
CN106188538A (zh) * | 2015-04-10 | 2016-12-07 | 台光电子材料股份有限公司 | 改性苯并噁嗪树脂、其组合物及应用 |
Families Citing this family (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1063262A4 (en) * | 1998-02-23 | 2001-07-11 | Asahi Chemical Ind | THERMO-CURABLE POLYPHENYLENE ETHER COMPOSITION, HARD RESIN COMPOSITION THEREOF AND LAYER STRUCTURE |
US6482946B1 (en) | 1999-11-05 | 2002-11-19 | Dow Global Technologies Inc. | High char yield benzoxazine compositions |
US6569918B2 (en) | 2000-02-04 | 2003-05-27 | Plastics Engineering Company | Polymer composition for curing novolac resins |
JP4734729B2 (ja) * | 2000-02-23 | 2011-07-27 | 東レ株式会社 | 複合材料成形用中間体及び繊維強化複合材料 |
US6437026B1 (en) | 2001-01-05 | 2002-08-20 | Cookson Singapore Pte Ltd. | Hardener for epoxy molding compounds |
JP3822549B2 (ja) * | 2002-09-26 | 2006-09-20 | 富士通株式会社 | 配線基板 |
ES2359226T3 (es) * | 2002-11-08 | 2011-05-19 | Icl-Ip America Inc. | Método para el curado de una composición de resina epoxi que contiene fosfonato reactivo. |
JP4576794B2 (ja) * | 2003-02-18 | 2010-11-10 | 日立化成工業株式会社 | 絶縁樹脂組成物及びその使用 |
JP4931418B2 (ja) * | 2003-07-10 | 2012-05-16 | 旭有機材工業株式会社 | フェノール樹脂組成物 |
US20070100116A1 (en) * | 2005-11-01 | 2007-05-03 | Zaldivar Rafael J | Low temperature processed resin for thermal and chemical protective coatings |
KR101051865B1 (ko) * | 2006-09-14 | 2011-07-25 | 파나소닉 전공 주식회사 | 프린트 배선판용 에폭시 수지 조성물, 수지 조성물 바니시,프리프레그, 금속 피복 적층체, 프린트 배선판 및 다층 프린트 배선판 |
ES2326681T3 (es) * | 2006-12-04 | 2009-10-16 | Nan Ya Plastics Corporation | Sintesis de una nueva dihidrobenzoxazina. |
ATE474875T1 (de) | 2007-02-08 | 2010-08-15 | Huntsman Adv Mat Switzerland | Wärmehärtbare zusammensetzung |
JP2009001692A (ja) | 2007-06-22 | 2009-01-08 | Akebono Brake Ind Co Ltd | 熱硬化性樹脂材料 |
US7642921B2 (en) * | 2007-07-23 | 2010-01-05 | Aquatic Safety Concepts, LLC | Electronic swimmer monitoring system |
US8227390B2 (en) | 2007-11-28 | 2012-07-24 | Akebono Brake Industry Co., Ltd. | Binder resin for friction material, binder resin composition for friction material, composite material for friction material containing the same, friction material and production method thereof |
WO2009109003A1 (en) * | 2008-03-03 | 2009-09-11 | Depco-Trh Pty Ltd | Heat reflective laminate |
CN101613530B (zh) * | 2008-06-23 | 2013-01-02 | 联茂电子股份有限公司 | 树脂组合物及其应用 |
EP2313452A1 (en) * | 2008-08-12 | 2011-04-27 | Huntsman Advanced Materials (Switzerland) GmbH | Thermosetting composition |
US9074049B2 (en) | 2009-10-21 | 2015-07-07 | Huntsman International Llc | Thermosetting composition |
WO2011099544A1 (ja) * | 2010-02-10 | 2011-08-18 | 日立化成工業株式会社 | 樹脂組成物、成形体及び複合成形体 |
TWI400292B (zh) * | 2010-06-14 | 2013-07-01 | Nanya Plastics Corp | Used in glass fiber laminates high glass transition temperature resin varnish composition |
TWI445727B (zh) * | 2010-10-21 | 2014-07-21 | Taiwan Union Technology Corp | 樹脂組合物及由其製成之預浸材與印刷電路板 |
JP5552075B2 (ja) * | 2011-02-17 | 2014-07-16 | Jfeケミカル株式会社 | 熱硬化性樹脂組成物およびその硬化物 |
JP5552074B2 (ja) * | 2011-02-17 | 2014-07-16 | Jfeケミカル株式会社 | 熱硬化性樹脂組成物およびその硬化物 |
TWI530528B (zh) | 2011-02-23 | 2016-04-21 | Toyo Boseki | Resin composition for electrical and electronic component packaging, manufacturing method of electrical and electronic parts, and electrical and electronic component package |
TWI421638B (zh) * | 2011-05-11 | 2014-01-01 | Chi Mei Corp | 正型感光性樹脂組成物及使用該組成物形成圖案的方法 |
WO2013031593A1 (ja) * | 2011-08-30 | 2013-03-07 | 東洋紡株式会社 | 電気電子部品封止用樹脂組成物、電気電子部品封止体の製造方法および電気電子部品封止体 |
CN104583309B (zh) | 2013-08-23 | 2017-10-03 | 台光电子材料(昆山)有限公司 | 树脂组成物及应用其之铜箔基板及印刷电路板 |
EP3265447B1 (en) * | 2015-03-04 | 2023-03-01 | Huntsman Advanced Materials Americas LLC | Benzoxazine low temperature curable composition |
TWI700320B (zh) | 2018-06-13 | 2020-08-01 | 台燿科技股份有限公司 | 樹脂組合物,以及使用該組合物所製得之預浸漬片、金屬箔積層板與印刷電路板 |
JP7026591B2 (ja) * | 2018-07-11 | 2022-02-28 | 日鉄ケミカル&マテリアル株式会社 | オキサジン樹脂組成物及びその硬化物 |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES414153A1 (es) | 1972-05-01 | 1976-06-01 | Lilly Co Eli | Un procedimiento de escision del grupo 7-carboxamido de unacefalosporina. |
ES414518A1 (es) * | 1972-05-09 | 1976-02-01 | Sued West Chemie Gmbh | Procedimiento para la preparacion de materiales sinteticos. |
JPS52809B2 (zh) * | 1973-11-16 | 1977-01-11 | ||
US4557979A (en) * | 1984-02-17 | 1985-12-10 | Monsanto Company | Process for deposition of resin dispersions on metal substrates |
JPH02138281A (ja) * | 1989-08-08 | 1990-05-28 | Dai Ichi Seiyaku Co Ltd | 3‐置換ピリドベンゾオキサジン |
DE4016296C1 (en) * | 1990-05-21 | 1991-09-05 | Gurit-Essex Ag, Freienbach, Ch | Flame retardant thermosetting adhesive for metals etc. - comprises oxa:aza:tetralin, halogenated epoxy] resins and opt. additives |
EP0493310A1 (de) * | 1990-12-21 | 1992-07-01 | Gurit-Essex AG | Zu schwerentflammbaren Kunststoffen härtbare Harzmischungen und deren Verwendung |
US5152939A (en) | 1991-03-12 | 1992-10-06 | Edison Polymer Innovation Corp. | Composite densification with benzoxazines |
JP3104314B2 (ja) * | 1991-05-16 | 2000-10-30 | 日立化成工業株式会社 | エポキシ樹脂組成物 |
JPH0567705A (ja) * | 1991-09-10 | 1993-03-19 | Hitachi Chem Co Ltd | 半導体封止用エポキシ樹脂組成物 |
JPH05211857A (ja) * | 1992-02-03 | 1993-08-24 | Houkou Suisan Kk | 水産練り製品 |
JPH06183855A (ja) * | 1992-04-23 | 1994-07-05 | Nippon Ceramic Co Ltd | セラミックス焦電体 |
JP3116634B2 (ja) * | 1993-01-29 | 2000-12-11 | ウシオ電機株式会社 | 誘電体バリヤ放電ランプ |
JPH06345898A (ja) * | 1993-06-08 | 1994-12-20 | Hitachi Chem Co Ltd | 成形材料用樹脂組成物及びこれを硬化させて得られる成形品 |
JP2774232B2 (ja) * | 1993-06-29 | 1998-07-09 | 帝人株式会社 | 紫外線吸収剤及びこれを含む高分子材料組成物 |
JP3329009B2 (ja) * | 1993-06-30 | 2002-09-30 | ソニー株式会社 | アクティブマトリクス表示装置 |
JPH0726115A (ja) * | 1993-07-09 | 1995-01-27 | Sumitomo Durez Co Ltd | 架橋構造を有する粉末フェノール樹脂 |
JPH07126484A (ja) * | 1993-11-04 | 1995-05-16 | Sumitomo Bakelite Co Ltd | フェノール樹脂成形材料 |
JPH07157496A (ja) * | 1993-12-07 | 1995-06-20 | Yamasa Shoyu Co Ltd | デオキシヌクレオシドの製造法 |
JP3434550B2 (ja) * | 1993-12-27 | 2003-08-11 | 日立化成工業株式会社 | 熱硬化性化合物、その硬化物及び熱硬化性化合物の製造方法 |
JPH07309997A (ja) * | 1994-05-17 | 1995-11-28 | Sumitomo Bakelite Co Ltd | フェノール樹脂成形材料 |
CN1058738C (zh) * | 1994-07-29 | 2000-11-22 | 四川联合大学 | 开环聚合酚醛树脂与纤维增强复合材料 |
JP3429090B2 (ja) * | 1994-12-28 | 2003-07-22 | 日立化成工業株式会社 | 熱硬化性樹脂組成物及びその硬化物 |
CN1059909C (zh) * | 1995-06-23 | 2000-12-27 | 四川联合大学 | 粒状多苯并嗪中间体及其制备方法 |
JPH0970844A (ja) * | 1995-09-05 | 1997-03-18 | Hitachi Chem Co Ltd | 紙基材フェノール樹脂積層板の製造方法 |
-
1996
- 1996-06-27 JP JP16778596A patent/JP3487083B2/ja not_active Expired - Lifetime
-
1997
- 1997-01-30 DE DE1997624169 patent/DE69724169T2/de not_active Expired - Lifetime
- 1997-01-30 US US08/791,813 patent/US5945222A/en not_active Expired - Lifetime
- 1997-01-30 EP EP19970300599 patent/EP0789056B1/en not_active Expired - Lifetime
- 1997-01-30 MY MYPI97000364A patent/MY121250A/en unknown
- 1997-02-03 TW TW86101243A patent/TW460537B/zh not_active IP Right Cessation
- 1997-02-05 CN CN97101088A patent/CN1088727C/zh not_active Expired - Lifetime
- 1997-02-06 KR KR1019970003795A patent/KR100205271B1/ko not_active IP Right Cessation
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100415826C (zh) * | 2003-07-10 | 2008-09-03 | 旭有机材工业株式会社 | 酚醛树脂组合物 |
CN101113284B (zh) * | 2006-07-24 | 2010-12-08 | 南亚塑胶工业股份有限公司 | 二氢苯并树脂合成及其应用 |
CN101605837B (zh) * | 2007-02-08 | 2013-06-12 | 亨斯迈先进材料(瑞士)有限公司 | 热固性组合物 |
CN101376735B (zh) * | 2008-09-26 | 2011-11-30 | 广东生益科技股份有限公司 | 无卤阻燃树脂组合物以及用其制作的粘结片与覆铜箔层压板 |
CN106188538A (zh) * | 2015-04-10 | 2016-12-07 | 台光电子材料股份有限公司 | 改性苯并噁嗪树脂、其组合物及应用 |
Also Published As
Publication number | Publication date |
---|---|
MY121250A (en) | 2006-01-28 |
EP0789056A3 (en) | 1997-12-29 |
JPH09272786A (ja) | 1997-10-21 |
JP3487083B2 (ja) | 2004-01-13 |
DE69724169D1 (de) | 2003-09-25 |
TW460537B (en) | 2001-10-21 |
KR970070124A (ko) | 1997-11-07 |
DE69724169T2 (de) | 2004-05-27 |
CN1088727C (zh) | 2002-08-07 |
KR100205271B1 (ko) | 1999-07-01 |
US5945222A (en) | 1999-08-31 |
EP0789056A2 (en) | 1997-08-13 |
EP0789056B1 (en) | 2003-08-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1088727C (zh) | 热固性树脂组合物、固化物、预成型料、金属铠装层压板和线路板 | |
CN1244660C (zh) | 室温固化耐高温型柔性环氧粘合剂及其制备方法 | |
TWI535749B (zh) | 熱固性組成物 | |
CN85107439A (zh) | 耐热聚合物树脂的组合物 | |
CN1717451A (zh) | 用于环氧树脂的硬化剂组合物 | |
CN1019810B (zh) | 经固化后成为不易燃并耐高温聚合物树脂的树脂混料及其应用 | |
CN1654539A (zh) | 热固性树脂组合物和薄膜制件 | |
CN101054508A (zh) | 一种复合环氧型电子封装材料及其制备方法 | |
CN1060771C (zh) | 芳酯化合物及其制法,用该化合物的环氧树脂组合物及其覆铜层合体 | |
CN1703436A (zh) | 非加热固化型粘合剂及使用该粘合剂的成形体的制造方法 | |
CN1111649A (zh) | 热固性化合物,其固化产品与制备该化合物的方法 | |
CN1305967C (zh) | 生物质树脂组合物、其制法和该生物质树脂组合物成型材料 | |
CN1189517C (zh) | 热固性树脂组合物 | |
CN1771274A (zh) | 印刷线路板用树脂组成物、半固化片及采用了半固化片的层叠板 | |
JP2001294689A (ja) | プリプレグ及び積層板 | |
JPH0826119B2 (ja) | エポキシ樹脂ラミネ−ト用ワニス | |
CN1769346A (zh) | 低膨胀介电组合物 | |
CN101061127A (zh) | 1,4-氢醌官能化的次膦酸酯和膦酸酯 | |
CN1075440C (zh) | 层压制品及其生产方法 | |
CN1630673A (zh) | 吲哚树脂、环氧树脂和含有这些树脂的树脂组合物 | |
CN1156504C (zh) | 生产高荧光酚-二羰基缩合物的方法,由其制造的环氧树脂、环氧树脂体系和层压材料 | |
JP6319703B1 (ja) | プロペニル基含有樹脂、樹脂組成物、樹脂ワニス、積層板の製造方法、熱硬化性成型材料および封止材 | |
CN1027278C (zh) | 热固化树脂组成物 | |
CN1157355C (zh) | 新型酯化合物及使用该化合物的热固树脂组合物 | |
JP3941659B2 (ja) | 熱硬化性樹脂組成物及びその硬化物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C06 | Publication | ||
PB01 | Publication | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CX01 | Expiry of patent term |
Granted publication date: 20020807 |
|
CX01 | Expiry of patent term |