CN105669952B - 环氧树脂组合物、使用其的预浸料、带支撑体树脂膜、贴金属箔层叠板和多层印刷电路板 - Google Patents
环氧树脂组合物、使用其的预浸料、带支撑体树脂膜、贴金属箔层叠板和多层印刷电路板 Download PDFInfo
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- CN105669952B CN105669952B CN201610032246.6A CN201610032246A CN105669952B CN 105669952 B CN105669952 B CN 105669952B CN 201610032246 A CN201610032246 A CN 201610032246A CN 105669952 B CN105669952 B CN 105669952B
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- epoxy resin
- curing agent
- phosphorus
- chemical formula
- resin
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 94
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 94
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 229920005989 resin Polymers 0.000 title claims abstract description 51
- 239000011347 resin Substances 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 18
- 239000002184 metal Substances 0.000 title claims abstract description 18
- 239000011888 foil Substances 0.000 title claims abstract description 17
- 238000003475 lamination Methods 0.000 title claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 105
- 239000011574 phosphorus Substances 0.000 claims abstract description 105
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 88
- 239000000126 substance Substances 0.000 claims abstract description 85
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000000962 organic group Chemical group 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- -1 phosphorus compound Chemical class 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims description 15
- 125000004437 phosphorous atom Chemical group 0.000 claims description 8
- 238000001723 curing Methods 0.000 description 79
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 54
- 238000004519 manufacturing process Methods 0.000 description 35
- 239000002966 varnish Substances 0.000 description 25
- 229920003986 novolac Polymers 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000005011 phenolic resin Substances 0.000 description 14
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 13
- 229920001568 phenolic resin Polymers 0.000 description 13
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 12
- 229930003836 cresol Natural products 0.000 description 12
- 239000000945 filler Substances 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 10
- 229910019142 PO4 Inorganic materials 0.000 description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 10
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 10
- 235000021317 phosphate Nutrition 0.000 description 10
- 239000011120 plywood Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 150000004941 2-phenylimidazoles Chemical class 0.000 description 7
- 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 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000009751 slip forming Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 150000002366 halogen compounds Chemical class 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229940106691 bisphenol a Drugs 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
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- 239000004744 fabric Substances 0.000 description 3
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- 230000009477 glass transition Effects 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
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- 230000007423 decrease Effects 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- VLPFTAMPNXLGLX-UHFFFAOYSA-N trioctanoin Chemical compound CCCCCCCC(=O)OCC(OC(=O)CCCCCCC)COC(=O)CCCCCCC VLPFTAMPNXLGLX-UHFFFAOYSA-N 0.000 description 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000001246 bromo group Chemical class Br* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000007571 dilatometry Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
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Classifications
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- 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
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
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- 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
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- 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
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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Abstract
本发明提供环氧树脂组合物、使用其的预浸料、带支撑体树脂膜、贴金属箔层叠板和多层印刷电路板。本发明的环氧树脂组合物,含有(A)含磷固化剂和(B)环氧树脂,该(A)含磷固化剂是下述化学式(1)所示的磷化合物,化学式(1)中R所示的有机基团具有2个以上的酚羟基,该有机基团的分子量为190以上。
Description
本申请是申请日为2011年5月31日、申请号为201180026192.8、发明名称为“环氧树脂组合物、使用此环氧树脂组合物的预浸料、带支撑体树脂膜、贴金属箔层叠板和多层印刷电路板”的中国专利申请的分案申请。
技术领域
本发明涉及印刷电路板用环氧树脂组合物、使用了所述环氧树脂组合物的预浸料、带支撑体树脂膜、贴金属箔层叠板和多层印刷电路板。
背景技术
伴随个人电脑、手机等信息终端设备的普及,搭载于这些设备上的印刷电路板的小型化、高密度化在发展着。其安装形式由针脚插入型向表面安装型,进而向以使用了塑料基板的BGA(球栅阵列)为代表的面阵型发展着。像BGA这种裸芯片被直接安装的基板而言,芯片与基板的连接通常是通过采用热超声波压接的引线接合进行。在超声波压接中,安装裸芯片的基板被置于150℃以上的高温。因此,电绝缘性树脂需要能够耐受热超声波压接的温度条件的耐热性。
进而,有时也会要求将曾经安装的芯片由基板取下的所谓的修复性。将芯片由基板取下时,被施加与安装芯片时同等程度的热。此外,芯片被再次安装于基板时,会再次被加上热处理。由于反复加热,用以前的绝缘性树脂系时有时在预浸料的纤维基材与树脂之间会发生剥离。要求修复性的基板则要求具有针对反复暴露于高温的耐受性(耐热冲击性)。
虽然可以通过在环氧树脂中添加含有溴等卤素的卤素化合物来确保阻燃性,但有通过燃烧产生一氧化碳、氰化氢的情形。添加溴等卤素化合物的环氧树脂,在加热时溴会分解而引起耐热性的下降、可靠性的下降。因此,期待开发出不在环氧树脂中添加卤素化合物而能够确保阻燃性的成型品。
作为不添加卤素化合物而确保阻燃性的方法,可以举出配合氮、硅、氢氧化铝等填料的方法。其中尤其广泛使用配合磷化合物的方法。例如,使用作为磷酸酯系化合物的三苯基磷酸酯(TPP)和磷酸三甲苯酯(TCP)(例如参照专利文献1)。但是,这些磷化合物即使被添加到环氧树脂中,因不与环氧树脂发生反应,会发生所得到的成型品的吸湿后的耐热性、耐化学药品性等下降的问题。
对此,提出过使环氧树脂与磷化合物反应而合成含磷环氧树脂的方法(例如,参照专利文献2等)。但由于使用双氰胺(DICY)作为固化剂,所以有不得不使用二甲基甲酰胺(DMF)、二甲基乙酰胺(DMAc)等对环境高负荷的溶剂的问题。而且,不能称为能够充分地应对近来所要求的低吸湿性、耐热冲击性等。
进而,也可以举出例如将10-(2,5-二羟基苯基)-10H-9-氧杂-10-磷杂菲-10-氧化物(三光株式会社制,商品名:HCA-HQ)、10-(2,5-二羟基萘基)-10H-9-氧杂-10-磷杂菲-10-氧化物(三光株式会社制,商品名:HCA-NQ)等磷化合物、其衍生物用作固化剂的方法。
但这些固化剂因在溶剂中的溶解性低,所以需要预反应,使得制造工序变得繁杂等,有操作性低的问题。
现有技术文献
专利文献
专利文献1:日本特开2001-131393号公报
专利文献2:日本特开2002-265562号公报
发明内容
发明要解决的课题
本发明是为了解决以上问题而进行的,提供操作性优异、反应性高、阻燃性优异、进而被赋予了高耐热性的环氧树脂组合物。
为解决课题的手段
本发明与以下相关。
[1]一种环氧树脂组合物,含有(A)含磷固化剂和(B)环氧树脂,该(A)含磷固化剂是下述化学式(1)所示的磷化合物,化学式(1)中R所示的有机基团具有2个以上的酚羟基,该有机基团的分子量为190以上,
[化1]
[2]上述[1]所述的环氧树脂组合物,化学式(1)中R所示的有机基团具有下述结构单元,
[化2]
在上述结构单元中,*1各自与碳原子相结合。
[3]上述[1]所述的环氧树脂组合物,化学式(1)中R所示的有机基团具有1种或2种以上的选自下述化学式(2)、(3)、(4)、(5)和(6)中的结构,且具有2个以上的酚羟基,式(2)~(6)中的*表示与化学式(1)的磷原子直接结合的部位,
[化3]
[化4]
[化5]
[化6]
式(5)中的R1为氢原子或碳数1~3的烷基;R2为碳数1~4的烷基;n为芳香环的OR2基的数目,为1~3中的任一个;此外,RA为具有2个以上酚羟基的有机基团,
[化7]
式(6)中的R1为氢原子或碳数1~3的烷基;R2为碳数1~4的烷基;n为芳香环的OR2基的数目,为1~3中的任一个;此外,RB为具有2个以上酚羟基的有机基团。
[4]上述[2]或[3]所述的环氧树脂组合物,化学式(1)中R所示的有机基团具有1种或2种以上的选自下述化学式(7)、(8)和(9)中的结构,且具有2个以上的酚羟基,式(7)~(9)中的*表示与化学式(1)的磷原子直接结合的部位,
[化8]
[化9]
[化10]
[5]将上述[1]~[4]的任一项所述的环氧树脂组合物浸透在基材而成的预浸料。
[6]将上述[1]~[4]的任一项所述的环氧树脂组合物层叠在支撑体上而成的带支撑体树脂膜。
[7]使用上述[5]所述的预浸料或上述[6]所述的带支撑体树脂膜而成的贴金属箔层叠板。
[8]含有1层或2层以上的由上述[5]所述的预浸料形成的层、由上述[6]所述的带支撑体树脂膜形成的层、或者由上述[7]所述的贴金属箔层叠板形成的层的多层印刷电路板。
发明效果
依据本发明,通过使用上述化学式(1)所示的含磷固化剂,可以得到操作性优异、反应性高、阻燃性优异、进而具有高耐热性的环氧树脂组合物、预浸料、带支撑体树脂膜、贴金属箔层叠板、多层印刷电路板。
具体实施方式
[环氧树脂组合物]
本发明所涉及的环氧树脂组合物,含有下述化学式(1)所示的(A)含磷固化剂和(B)环氧树脂,该(A)含磷固化剂是下述化学式(1)所示的磷化合物,化学式(1)中R所示的有机基团具有2个以上的酚羟基,该有机基团的分子量为190以上是理想的。
[化11]
如果分子量在190以上,对溶剂的含磷固化剂的溶解性提高,操作性提高。由环氧树脂组合物得到的预浸料、带支撑体树脂膜、贴金属箔层叠版等成型品不仅阻燃性优异,而且耐热性、电性能、耐水性等特性也非常良好。
<含磷固化剂>
(含磷固化剂的结构)
(A)含磷固化剂是化学式(1)所示磷化合物,化学式(1)中R所示的有机基团具有下述结构单元是理想的。
[化12]
在上述结构单元中,*1各自与碳原子相结合。
而且,(A)含磷固化剂,化学式(1)中R所示的有机基团具有选自下述化学式(2)、(3)、(4)、(5)和(6)中的结构的1种或2种以上,具有2个以上的酚羟基。式(2)~(6)中的*表示与化学式(1)的磷原子直接结合的部位。
[化13]
[化14]
[化15]
[化16]
(式(5)中的R1为氢原子或碳数1~3的烷基,R2为碳数1~4的烷基,n为芳香环的OR2基的数目,为1~3中的任一个,此外,RA为具有2个以上酚羟基的有机基团。)
[化17]
(式(6)中的R1为氢原子或碳数1~3的烷基,R2为碳数1~4的烷基,n为芳香环的OR2基的数目,为1~3中的任一个,此外,RB为具有2个以上酚羟基的有机基团。)
化学式(1)中R所示的有机基团可以是具有选自下述化学式(7)、(8)和(9)中的结构的1种或2种以上,具有2个以上的酚羟基的有机基团。式(7)~(9)中的*表示与化学式(1)的磷原子直接结合的部位。
[化18]
[化19]
[化20]
由此环氧树脂得到的预浸料、带支撑体树脂膜、贴金属箔层叠版等成型品不仅阻燃性优异,而且耐热性、电性能、耐水性等特性也非常良好。
(含磷固化剂1)
(A)含磷固化剂可以为上述化学式(1)中R所示的有机基团具有上述化学式(2)的结构的磷化合物。具有上述化学式(2)所示的结构时,含有该含磷固化剂的环氧树脂组合物的耐热性会提高。而且,因含磷固化剂对作为反应体系的溶剂的溶解性提高,所以操作性会提高。尤其是具有上述化学式(2)所示结构的该含磷固化剂,因其为低粘度,所以操作性优异,可以提高生产率。
(含磷固化剂2)
(A)含磷固化剂可以为上述化学式(1)中R所示的有机基团具有上述化学式(3)的结构的磷化合物。具有上述化学式(3)所示的结构时,与(B)环氧树脂的反应性会提高。
(含磷固化剂3)
(A)含磷固化剂可以为上述化学式(1)中R所示的有机基团具有上述化学式(4)的结构的含磷化合物。具有上述化学式(4)所示的结构时,含有该含磷固化剂的环氧树脂组合物的耐热性会提高。
(含磷固化剂4)
(A)含磷固化剂可以为具有下述化学式(10)所示的结构单元A和化学式(11)所示的结构单元B的树脂。
[化21]
[化22]
即,该树脂可以具有结构单元A多个连续而成的单元,也可以具有结构单元B多个连续而成的单元,也可以具有结构单元A和结构单元B交替连接而成的单元,也可以具有前三者单元混合而成的结构。
当将具有上述结构单元的酚醛树脂用作含磷固化剂时,含有该含磷固化剂的环氧树脂组合物操作性优异,可获得高反应性。而且,阻燃性优异,具有高耐热性。
(含磷固化剂5)
(A)含磷固化剂可以为具有下述化学式(12)所示的结构单元C和化学式(13)所示的结构单元D的树脂。
[化23]
[化24]
即,该树脂可以具有结构单元C多个连续而成的单元,也可以具有结构单元D多个连续而成的单元,也可以具有结构单元C和结构单元D交替连接而成的单元,也可以具有前三者单元混合而成的结构。
当将具有上述结构单元的酚醛树脂用作含磷固化剂时,含有该含磷固化剂的环氧树脂组合物操作性优异,可获得高反应性。而且,阻燃性优异,具有高耐热性。
(含磷固化剂6)
(A)含磷固化剂可以为具有下述化学式(14)所示的结构单元E和化学式(15)所示的结构单元F的树脂。
[化25]
[化26]
即,该树脂可以具有结构单元E多个连续而成的单元,也可以具有结构单元F多个连续而成的单元,也可以具有结构单元E和结构单元F交替连接而成的单元,也可以具有前三者单元混合而成的结构。
当将具有上述结构单元的酚醛树脂用作含磷固化剂时,含有该含磷固化剂的环氧树脂组合物操作性优异,可获得高反应性。而且,阻燃性优异,具有高耐热性。
(含磷固化剂的制造方法)
化学式(1)所示的(A)含磷固化剂,由下述化学式(16)所示的磷化合物与具有酚羟基的化合物反应而得到。而且,根据情形,也可以添加对甲氧基苯甲醛。
[化27]
化学式(16)中X为H原子或卤素原子。
作为有可能用于含磷固化剂的制造的具有酚羟基的化合物,1分子中具有2个以上的酚羟基的化合物是理想的,有将苯酚、甲酚、二甲苯酚、间苯二酚、儿茶酚、双酚A、双酚F等苯酚类或α-萘酚、β-萘酚、二羟基萘等萘酚类和甲醛、乙醛、丙醛、苯甲醛、水杨醛等醛类在酸性催化剂下缩合或共缩合得到的树脂(酚醛清漆类)、聚对乙烯基苯酚树脂、由苯酚类和二甲氧基对二甲苯合成的具有苯二甲基的苯酚·芳烷基树脂等,单独或也可并用2种以上。
<环氧树脂>
作为用于本发明的环氧树脂组合物的(B)环氧树脂,分子内平均具有1.8个以上的环氧基是理想的。其中,当使用分子内平均具有1.8~2.5个(约2个)的环氧基的环氧树脂(2官能的环氧树脂)时,树脂的可塑化效果大。作为这样的分子内平均具有1.8~2.5个(约2个)的环氧基的环氧树脂,使用双酚A型环氧树脂的情形,成为粘接力等良好的固化物,使用双酚F型环氧树脂的情形,容易获得阻燃性,使用联苯型环氧树脂的情形,成为吸水率低、高Tg(玻璃化转变温度)的固化物。而且,通过使用萘型环氧树脂,可得到Tg高的固化物。
作为(B)环氧树脂使用分子内平均具有2.5~3.9个(约3个)的环氧基的环氧树脂(3官能的环氧树脂)的情形,可得到Tg更高的固化物。
而且,作为(B)环氧树脂使用苯酚酚醛清漆型环氧树脂的情形,成为高Tg且容易得到阻燃性的固化物。
<含磷量>
从阻燃性的观点来讲,环氧树脂组合物中的磷含量为树脂组合物固体成分全体的0.8~5.0质量%是理想的,1.0~2.5质量%为更加理想。磷含量不到树脂组合物固体成分全体的0.8质量%时,难以得到稳定的阻燃性,超过5.0质量%时,固化物的特性将恶化。
这里的磷含量是环氧树脂中的磷原子的含量,例如,分子量620的物质中有1个磷原子、并且配合有50质量%的该物质的话,就成为2.5质量%的磷含量(因磷原子的原子量约为31,所以31/620×0.5=0.025)。
<其他添加剂>
在本发明的环氧树脂组合物中,也可添加作为添加剂的无机充填剂、硅烷偶联剂。通过添加无机充填剂,可以得到在低热膨胀系数化、阻燃性提高方面优异的材料。而且,通过添加硅烷偶联剂,提高无机充填剂的分散性,可以得到在耐化学药品性、抗剥强度方面优异的材料。
此外,也可以添加在紫外线等下发出荧光的化学物质或树脂。由此,在用环氧树脂组合物制作的多层印刷电路板的电路形成后的检查中,使铜箔图案显出明显的剪影,由此识别图案的形状,外观检查变得容易。
<环氧树脂组合物的制造方法>
在得到本发明涉及的环氧树脂组合物时,可以使用溶剂也可以在无溶剂下进行。而且在得到这些环氧树脂组合物时,也可根据必要添加固化促进剂、其他特性赋予剂。
说明一例使用了溶剂的环氧树脂组合物的制作方法。在甲乙酮等溶剂中,配合(A)含磷固化剂、(B)环氧树脂、其他的固化剂成分、磷化合物等,搅拌至体系均匀。此后,例如,将氢氧化铝由上述溶剂制成浆体状并作为填料添加,再次搅拌。由此,可制作环氧树脂组合物的清漆。
[预浸料、带支撑体树脂膜、贴金属箔层叠板、多层印刷电路板]
将本发明涉及的环氧树脂组合物的清漆,使用逗点涂覆机、转印涂覆机、帘幕涂覆机、模涂机等,涂布在铜箔、铝箔等支撑体上,连续或非连续地加热干燥、B阶化(半固化),形成绝缘层,得到带支撑体树脂膜。上述带支撑体树脂膜的金属箔厚度、绝缘层树脂厚度虽然是任意的,但通常金属箔为8~80μm,绝缘层树脂厚度为20~200μm。
而且,将本发明涉及的环氧树脂组合物的清漆,涂布、浸透在玻璃布、玻璃非织造布,连续或非连续地加热干燥和B阶化,得到预浸料。在此预浸料的一面或两面配置金属箔(例如铜箔),层叠,加热成型,由此得到贴金属箔层叠板。
在贴金属箔层叠板或已形成电路图案的内层用基板的两面或单面,将上述带支撑体树脂膜的树脂面介由预浸料对置层叠,加热成型。进而在外层形成电路,得到多层印刷电路板。
实施例
以下由实施例具体说明本发明,但本发明并不局限于此。
[评价方法]
<阻燃性>
制作两面贴铜层叠板的试验片,由蚀刻把两面贴铜层叠板的铜箔除去,基于根据UL-94标准的垂直燃烧试验(V法)评价阻燃性。如果是V-O则阻燃性良好,如果是V-1则阻燃性不良。
<焊料耐热性>
将两面贴铜层叠板制作成50mm见方的试验片,使该试验片浮在加热至288℃的焊料耐热试验机,测定直到能够确认出膨胀等异常的时间。关于评价,“○分钟OK”表示到○分钟时未发生膨胀等异常,“○分钟NG”表示在○分钟时发生了膨胀等异常。
<玻璃化转变温度Tg>
玻璃化转变温度Tg是用TMA(热机械分析装置)(MAC Science公司制TMA-4000),在升温速度5℃/min的条件下测定。重复两次升温、降温,将第二次升温热膨胀曲线的拐点温度定义为Tg。
[制造例1~5]
<制造例1>
将作为环氧树脂的143g(树脂固体成分:70质量%(100g))甲酚酚醛清漆型环氧树脂(DIC株式会社制,商品名:EPICLON N-673-70M)、作为固化剂的35g甲酚酚醛清漆型酚醛树脂(DIC株式会社制,商品名:PHENOLITE KA-1163)、0.2g的2-苯基咪唑、作为含磷固化剂的30g下述化学式(1)和(4)所示的含磷酚醛树脂(道化学公司制,商品名:XZ-92741)、作为磷化合物的5g的1,3-亚苯基双(二-2,6-二甲苯基磷酸酯)(大八化学工业株式会社制,商品名:PX200)、100g的甲乙酮(MEK)进行配合,搅拌约1小时直到树脂均匀。之后,将作为填料的40g氢氧化铝(住友化学株式会社制,商品名:CL-303)以甲乙酮的浆体的形式添加,再搅拌1小时。由此,得到磷含量为1.6质量%的环氧树脂组合物清漆。
[化28]
[化29]
(在(4)中的*表示与化学式(1)的磷原子直接结合的部位。)
<制造例2>
除不使用1,3-亚苯基双(二-2,6-二甲苯基磷酸酯)(大八化学工业株式会社制,商品名:PX200)、不添加填料外,用与制造例1同样的工序制得环氧树脂组合物清漆。
<制造例3>
作为填料,代替CL303添加氢氧化铝(昭和电工株式会社制,商品名:HP-360),除此之外,用与制造例1同样的工序制得环氧树脂组合物清漆。
<制造例4>
作为填料,代替CL303添加勃姆石(河合石灰工业株式会社制,商品名:BMT),除此之外,用与制造例1同样的工序制得环氧树脂组合物清漆。
<制造例5>
作为填料,代替CL303添加粉碎二氧化硅(福岛窑业株式会社制,商品名:F05-30),除此之外,用与制造例1同样的工序制得环氧树脂组合物清漆。
[制造例6~8]
在制造例6~8中合成含磷固化剂,用合成的含磷固化剂制得环氧树脂组合物清漆。这里,含磷固化剂在180℃的熔融粘度及软化点是在以下条件下测定的。
在180℃的熔融粘度:在测定温度180℃,依据ASTM D4287,用ICI/锥板粘度计测得的粘度
软化点:依据JIS K7234,由B&R法测得的温度
<制造例6>
(含磷固化剂的合成)
在安装了温度计、冷却管、分馏管、氮气导入管和搅拌机的烧瓶中,装入192.4g(1.85mol)的苯酚酚醛清漆树脂、68.0g(0.50mol)的对甲氧基苯甲醛、108.0g(0.50mol)的9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(以下简称HCA),升温至180℃,在180℃反应8小时。
接着,在加热减压下除去水分,得到355g具有下述化学式(10)所示的结构单元A与化学式(11)所示的结构单元B的酚醛树脂(称作含磷固化剂X)。用上述方法测定含磷固化剂X的软化点的结果为125℃。另外,在180℃的熔融粘度为13dPa·s。此外,羟基当量为190g/eq,磷含量为4.2质量%。
[化30]
[化31]
(环氧树脂组合物清漆的制造)
接着,用含磷固化剂X作为含磷固化剂,制作环氧树脂组合物清漆。
将作为环氧树脂的100g的甲酚酚醛清漆型环氧树脂(DIC株式会社制,商品名:N-673-70M)、作为固化剂的20g的甲酚酚醛清漆型酚醛树脂(DIC株式会社制,商品名:PHENOLITE KA-1163)、0.2g的2-苯基咪唑、作为含磷固化剂的60g的含磷固化剂X、作为磷化合物的20g的1,3-亚苯基双(二-2,6-二甲苯基磷酸酯))(大八化学工业株式会社制,商品名:PX200)、80g的甲乙酮(MEK)进行配合,搅拌约1小时直到树脂均匀。此后,将作为填料的30g氢氧化铝(住友化学株式会社制,商品名:CL-303)以甲乙酮的浆体的形式添加,再搅拌1小时。由此,得到磷含量为1.4质量%的环氧树脂组合物清漆。
<制造例7>
(含磷固化剂的合成)
除使用330.4g(2.80mol)的双酚A酚醛清漆树脂代替制造例6中使用的苯酚酚醛清漆树脂外,与制造例6一样进行反应。得到490g具有下述化学式(12)所示的结构单元C和化学式(13)所示的结构单元D的酚醛树脂(称作含磷固化剂Y)。含磷固化剂Y的软化点为139℃(B&R法)。另外,含磷固化剂Y的熔融粘度为65dPa·s。此外,羟基当量为232g/eq、磷含量为3.1质量%。
[化32]
[化33]
(环氧树脂组合物清漆的制作)
接着,把含磷固化剂Y作为含磷固化剂使用,制作环氧树脂组合物清漆。
将作为环氧树脂的100g甲酚酚醛清漆型环氧树脂(DIC株式会社,商品名:N-673-70M)、作为固化剂的25g甲酚酚醛清漆型酚醛树脂(DIC株式会社制,商品名:PHENOLITE KA-1163)、0.2g的2-苯基咪唑、作为含磷固化剂的60g含磷固化剂Y,作为磷化合物的20g的1,3-亚苯基双(二-2,6-二甲苯基磷酸酯))(大八化学工业株式会社制,商品名:PX200)、80g的甲乙酮(MEK)进行配合,搅拌约1小时直到树脂均匀。此后,将作为填料的30g氢氧化铝(住友化学株式会社制,商品名:CL303)以甲乙酮的浆体的形式添加,再搅拌1小时。由此,得到磷含量为1.3质量%的环氧树脂组合物清漆。
<制造例8>
(含磷固化剂的合成)
除使用392.9g(2.35mol)的苯酚芳烷基树脂代替制造例6中所使用的苯酚酚醛清漆树脂以外,与制造例6一样进行反应。得到550g的具有下述化学式(14)所示的结构单元E和化学式(15)所示的结构单元F的酚醛树脂(称作含磷固化剂Z)。含磷固化剂Z的软化点为102℃(B&R法)。而且,含磷固化剂Z的熔融粘度为2.5dPa·s。此外,羟基当量为232g/eq,磷含量为2.7质量%。
[化34]
[化35]
(环氧树脂组合物清漆的制作)
接着,将含磷固化剂Z作为含磷固化剂使用,制作环氧树脂组合物清漆。
将作为环氧树脂的100g甲酚酚醛清漆型环氧树脂(DIC株式会社,商品名:N-673-70M)、作为固化剂的25g甲酚酚醛清漆型酚醛树脂(DIC株式会社制,商品名:PHENOLITE KA-1163)、0.2g的2-苯基咪唑、作为含磷固化剂的60g含磷固化剂Z、作为磷化合物的20g的1,3-亚苯基双(二-2,6-二甲苯基磷酸酯))(大八化学工业株式会社制,商品名:PX200)、80g的甲乙酮(MEK)进行配合,搅拌约1小时直到树脂均匀。此后,将作为填料的30g氢氧化铝(住友化学株式会社制,商品名:CL303)以甲乙酮的浆体的形式添加,再搅拌1小时。由此,得到磷含量为1.3质量%的环氧树脂组合物清漆。
[比较制造例1~3]
(比较制造例1)
将作为环氧树脂的143g甲酚酚醛清漆型环氧树脂(DIC株式会社,商品名:EPICLONN-673-70M)(树脂固体成分:70质量%(100g))、作为固化剂的35g甲酚酚醛清漆型酚醛树脂(DIC株式会社制,商品名:PHENOLITE KA-1163)、0.2g的2-苯基咪唑、作为磷化合物的40g的1,3-亚苯基双(二-2,6-二甲苯基磷酸酯))(大八化学工业株式会社制,商品名:PX200)、100g的甲乙酮进行配合,搅拌约1小时直到树脂均匀。此后,将作为填料的40g氢氧化铝(住友化学株式会社制,商品名:CL-303)以甲乙酮的浆体的形式添加,再搅拌1小时。由此得到磷含量为1.4质量%的环氧树脂组合物清漆。
(比较制造例2)
将作为环氧树脂的100g含磷环氧树脂(东都化成株式会社制,商品名:FX-298)、作为固化剂的35g的甲酚酚醛清漆型酚醛树脂(DIC株式会社制,商品名:PHENOLITE KA-1163)、0.2g的2-苯基咪唑、作为磷化合物的5g的1,3-亚苯基双(二-2,6-二甲苯基磷酸酯))(大八化学工业株式会社制,商品名:PX200)、100g的甲乙酮进行配合,搅拌约1小时直到树脂均匀。此后,将作为填料的40g的氢氧化铝(住友化学株式会社制,商品名:CL-303)以甲乙酮的浆体的形式添加,再搅拌1小时。由此得到磷含量为1.5质量%的环氧树脂组合物清漆。
(比较制造例3)
将作为环氧树脂的100g含磷环氧树脂(东都化成株式会社制,商品名:FX-298)、作为固化剂的20g的甲酚酚醛清漆型酚醛树脂(DIC株式会社制,商品名:PHENOLITE KA-1163)、5g的双氰胺(DICY)、0.2g的2-苯基咪唑、作为磷化合物的5g的1,3-亚苯基双(二-2,6-二甲苯基磷酸酯))(大八化学工业株式会社制,商品名:PX200)、70g的甲乙酮、30g的二甲基甲酰胺(DMF)进行配合,搅拌约1小时直到树脂均匀。此后,将作为填料的40g的氢氧化铝(住友化学株式会社制,商品名:CL-303)以甲乙酮的浆体的形式添加,再搅拌1小时。由此得到磷含量为1.5质量%的环氧树脂组合物清漆。
在表1表示制造例1~5、比较制造例1~3的环氧树脂组合物清漆的配合表。在表2表示制造例6~8的环氧树脂清漆的配合表。
表1
表2
[预浸料及贴铜层叠板的制作]
<实施例1~5>
将由制造例1~5制得的环氧树脂组合物清漆浸透到厚度为0.2mm的玻璃布(ASAHISCHWEBEL株式会社制,商品名:7629)后,在120℃下加热20分钟,干燥后得到预浸料。
在预浸料的两侧,将厚度为18μm的电解铜箔:F2-WS-18(古河电气工业株式会社制,商品名)重叠,使其粘接面与预浸料相合,在180℃、30分钟、4MPa的真空加压条件下,制得两面贴铜层叠板。
<实施例6~8>
使用由制造例6~8制得的环氧树脂组合物清漆,用与上述同样的方法得到预浸料。此外,制得两面贴铜层叠板。
<比较例1~3>
使用由比较制造例1~3制得的环氧树脂组合物清漆,用与上述同样的方法得到预浸料。此外,制得两面贴铜层叠板。
[结果]
将由上述方法得到的结果示于表3。
表3
可以确认,使用了上述化学式(1)所示的含磷固化剂的实施例1~8的层叠板具有阻燃性,耐热性高,并且Tg高。而且,与使用了以往的作为潜在性固化剂的双氰胺(DICY)的比较例3相比,实施例1~8的层叠板显示出充分的反应性。而且可以确认焊料耐热性优异,Tg也高,耐热性优异。
在实施例1~8,比起使用以往的作为固化剂的双氰胺(DICY)情形,即使不使用用于使双氰胺(DICY)溶解的沸点高、有吸湿性的二甲基甲酰胺(DMF),也能够将含磷固化剂溶解于作为通用溶剂的甲乙酮(MEK)中。另外,不使用如上述化学式(1)所示的含磷固化剂的比较例1~3,焊料耐热性差、Tg低、耐热性低。
Claims (5)
1.一种环氧树脂组合物,含有(A)含磷固化剂和(B)环氧树脂,
该(A)含磷固化剂是下述化学式(1)所示的磷化合物,
化学式(1)中R所示的有机基团为选自下述化学式(2)、(3)或(4)中的结构,且具有2个以上的酚羟基,该有机基团的分子量为190以上,
式(2)~(4)中的*表示与化学式(1)的磷原子直接结合的部位,
2.将上述权利要求1所述的环氧树脂组合物浸透在基材而成的预浸料。
3.将上述权利要求1或2所述的环氧树脂组合物层叠在支撑体上而成的带支撑体树脂膜。
4.使用上述权利要求2所述的预浸料或上述权利要求3所述的带支撑体树脂膜而成的贴金属箔层叠板。
5.含有1层或2层以上的由上述权利要求2所述的预浸料形成的层、由上述权利要求3所述的带支撑体树脂膜形成的层、或者由上述权利要求4所述的贴金属箔层叠板形成的层的多层印刷电路板。
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