JP6932116B2 - Epoxy resin-containing varnish, epoxy resin composition-containing varnish, prepreg, resin sheet, printed wiring board, semiconductor device - Google Patents
Epoxy resin-containing varnish, epoxy resin composition-containing varnish, prepreg, resin sheet, printed wiring board, semiconductor device Download PDFInfo
- Publication number
- JP6932116B2 JP6932116B2 JP2018206652A JP2018206652A JP6932116B2 JP 6932116 B2 JP6932116 B2 JP 6932116B2 JP 2018206652 A JP2018206652 A JP 2018206652A JP 2018206652 A JP2018206652 A JP 2018206652A JP 6932116 B2 JP6932116 B2 JP 6932116B2
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- JP
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- Prior art keywords
- epoxy resin
- resin
- containing varnish
- prepreg
- varnish
- 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.)
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- 239000003822 epoxy resin Substances 0.000 title claims description 88
- 229920000647 polyepoxide Polymers 0.000 title claims description 88
- 229920005989 resin Polymers 0.000 title claims description 82
- 239000011347 resin Substances 0.000 title claims description 82
- 239000002966 varnish Substances 0.000 title claims description 61
- 239000004065 semiconductor Substances 0.000 title claims description 14
- 239000000203 mixture Substances 0.000 title description 29
- -1 prepreg Substances 0.000 title description 20
- 238000000034 method Methods 0.000 claims description 33
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 238000000465 moulding Methods 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 8
- 150000002576 ketones Chemical group 0.000 claims description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 4
- 239000010410 layer Substances 0.000 description 31
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- 238000001723 curing Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 21
- 239000002904 solvent Substances 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 150000002989 phenols Chemical class 0.000 description 13
- 239000011521 glass Substances 0.000 description 12
- 229910000679 solder Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000004891 communication Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000011256 inorganic filler Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910003475 inorganic filler Inorganic materials 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 239000007822 coupling agent Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical group O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 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
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
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- 238000005259 measurement Methods 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000013007 heat curing Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 150000004780 naphthols Chemical group 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
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- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 2
- IYSVFZBXZVPIFA-UHFFFAOYSA-N 1-ethenyl-4-(4-ethenylphenyl)benzene Chemical group C1=CC(C=C)=CC=C1C1=CC=C(C=C)C=C1 IYSVFZBXZVPIFA-UHFFFAOYSA-N 0.000 description 2
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical class OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical group OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 150000003935 benzaldehydes Chemical class 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 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
- 238000009835 boiling Methods 0.000 description 2
- 229940117916 cinnamic aldehyde Drugs 0.000 description 2
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- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- ZIXLDMFVRPABBX-UHFFFAOYSA-N alpha-methylcyclopentanone Natural products CC1CCCC1=O ZIXLDMFVRPABBX-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000003562 lightweight material Substances 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
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
本発明は溶液での安定性にすぐれるエポキシ樹脂含有ワニス、またそのワニスを用いたエポキシ樹脂組成物含有ワニスおよびその成型体に関し、誘電特性に優れた硬化物を与えるエポキシ樹脂に関する。 The present invention relates to an epoxy resin-containing varnish having excellent stability in a solution, an epoxy resin composition-containing varnish using the varnish, and a molded product thereof, and to an epoxy resin that gives a cured product having excellent dielectric properties.
さらに、本発明は高機能が要求される電気電子材料用途、特に半導体の封止剤、薄膜基板材料として好適なエポキシ樹脂組成物含有ワニス、プリプレグ、樹脂シート、プリント配線基板に関する。 Furthermore, the present invention relates to electrical and electronic material applications that require high functionality, particularly varnishes containing epoxy resin compositions, prepregs, resin sheets, and printed wiring boards that are suitable as semiconductor encapsulants and thin film substrate materials.
エポキシ樹脂組成物は作業性及びその硬化物の優れた電気特性、耐熱性、接着性、耐湿性(耐水性)等により電気・電子部品、構造用材料、接着剤、塗料等の分野で幅広く用いられている。 Epoxy resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties of the cured product, heat resistance, adhesiveness, moisture resistance (water resistance), etc. Has been done.
しかし近年、電気・電子分野においてはその発展に伴い、樹脂組成物の高純度化をはじめ耐湿性、密着性、誘電特性、フィラー(無機または有機充填剤)を高充填させるための低粘度化、成型サイクルを短くするための反応性のアップ等の諸特性の一層の向上が求められている。又、構造材としては航空宇宙材料、レジャー・スポーツ器具用途などにおいて軽量で機械物性の優れた材料が求められている。
特に近年、機械どうしの通信はもちろん、人と人との通信量が格段に増えていく中、情報量は膨大に肥大化していくことが想定される。
現在、スマートフォンやWifi等の通信の周波数が大きくなってきており、スマートフォンでは周波数700MHz〜3.4GHz、wifi等であれば2〜5GHz、等と通信の周波数帯が使用されてきており、幅広い周波数帯での誘電特性、特に誘電正接が重要になってきている。
また情報通信量が非常に多くなり、以下に早く多くの情報を伝えるかということが重要となってきており、高速通信化が基板にたいして重要なファクターとなる。
またスマートフォン等は年々薄型化、さらには電池の体積をとるために、小型化が大きく進んでいる。さらに年々機能を飛躍的に向上させる必要がる。このような環境の中、使用される基板の厚みは薄型化、多層化する必要があり、基板の耐熱性、剛性が製造における工程耐性として必要となってくることは明白である。
However, in recent years, with the development in the electric and electronic fields, the resin composition has been made highly purified, and has moisture resistance, adhesiveness, dielectric properties, and low viscosity for highly filling fillers (inorganic or organic fillers). Further improvement of various properties such as improvement of reactivity for shortening the molding cycle is required. Further, as a structural material, a lightweight material having excellent mechanical properties is required for aerospace materials, leisure / sports equipment applications, and the like.
Especially in recent years, it is expected that the amount of information will become enormously bloated as the amount of communication between machines as well as between people increases dramatically.
Currently, the communication frequency of smartphones and Wifi is increasing, and smartphones are using communication frequency bands such as 700MHz to 3.4GHz and wifi etc. are using communication frequency bands such as 2 to 5GHz. Incremental characteristics, especially dielectric tangent, are becoming important.
In addition, the amount of information communication has become extremely large, and it has become important to quickly transmit a large amount of information to the following, and high-speed communication is an important factor for the board.
In addition, smartphones and the like are becoming thinner year by year, and in order to take up the volume of batteries, miniaturization is progressing significantly. Furthermore, it is necessary to dramatically improve the functions year by year. In such an environment, the thickness of the substrate used needs to be thinned and multi-layered, and it is clear that the heat resistance and rigidity of the substrate are required for process resistance in manufacturing.
高速通信向けの材料としては、その特性からどうしてもポリフェニレンエーテルやBTレジン等といった特殊樹脂が主として使用されているが、単独では取り扱いが難しく、また特性が足りず、密着性や強度の改善のためエポキシ樹脂と併用される。また、パッケージ基板材料においてはエポキシ樹脂がメインで使われる場合も多いが、上記のとおり、今後高速通信が重要となってきた場合、誘電特性の改善のため、上述の特殊樹脂との組み合わせが増えてくることとなる。こういった特殊樹脂との組み合わせにおいてはワニスとしての安定性が無いと配合ができず、生産毎にワニスを作成し、もしくは分散して使用するということであると生産性が非常に悪い。さらに、ワニス作成時に相溶性が悪かったり、作成後まもなく結晶等が析出し分離すると安定した生産ができず、産業として成立が難しい。このためワニスとして安定的に生産できる高機能なエポキシ樹脂が求められている。
誘電特性の良いエポキシとしてビフェニレンアラルキルタイプのエポキシ樹脂が挙げられる。当該エポキシ樹脂は、非常に電気特性は良いものの、基板とする場合に溶剤への溶解性が悪く、溶解させても結晶が析出しやすいという傾向があるばかりか、耐熱性の改良が難しい(特許文献特開2012−229436号公報)。
一方、耐熱性の高いエポキシ樹脂は一般に架橋密度の高いエポキシ樹脂となる。
架橋密度の高いエポキシ樹脂は、その架橋密度が高いことが起因して、誘電特性が非常に悪くなりやすい。また、もろく、熱分解特性がわるくなる。架橋密度を下げるとこれらの特性は改善されるが、耐熱性が低くなり、ガラス転移点(Tg)が低下する。というトレードオフの関係にある。
As a material for high-speed communication, special resins such as polyphenylene ether and BT resin are mainly used due to their characteristics, but they are difficult to handle by themselves, and their characteristics are insufficient, so epoxy is used to improve adhesion and strength. Used in combination with resin. Epoxy resins are often used as the main material for package substrates, but as mentioned above, when high-speed communication becomes important in the future, the number of combinations with the above-mentioned special resins will increase in order to improve the dielectric properties. Will come. In combination with such a special resin, it cannot be blended unless it is stable as a varnish, and if the varnish is prepared or dispersed for each production, the productivity is very poor. Furthermore, if the compatibility is poor when the varnish is made, or if crystals or the like precipitate and separate shortly after the varnish is made, stable production cannot be achieved and it is difficult to establish an industry. Therefore, there is a demand for a highly functional epoxy resin that can be stably produced as a varnish.
Biphenylene aralkyl type epoxy resin can be mentioned as an epoxy having good dielectric properties. Although the epoxy resin has very good electrical characteristics, it has poor solubility in a solvent when used as a substrate, and even if it is dissolved, crystals tend to precipitate, and it is difficult to improve heat resistance (patented). Japanese Patent Application Laid-Open No. 2012-229436).
On the other hand, an epoxy resin having high heat resistance is generally an epoxy resin having a high crosslink density.
Epoxy resins with a high crosslink density tend to have very poor dielectric properties due to the high crosslink density. In addition, it is brittle and has poor thermal decomposition characteristics. Lowering the crosslink density improves these properties, but lowers the heat resistance and lowers the glass transition point (Tg). There is a trade-off relationship.
本発明においては溶剤での安定性が高いワニス状で取り扱えるエポキシ樹脂含有ワニスとそれを用いるエポキシ樹脂組成物ワニス、さらには機材への含浸をしたプリプレグおよび、または樹脂シート、およびそれらから製造される高い耐熱性と高度な誘電特性を有する積層板を提供することにある。 In the present invention, an epoxy resin-containing varnish that can be handled in the form of a varnish with high solvent stability, an epoxy resin composition varnish using the varnish, a prepreg impregnated into equipment, or a resin sheet, and a resin sheet thereof are produced. An object of the present invention is to provide a laminated plate having high heat resistance and high dielectric properties.
本発明者らは前記したような実状に鑑み、鋭意検討した結果、本発明を完成させるに至った。
すなわち本発明は
(1)下記一般式(1)で表されるエポキシ樹脂と有機溶剤からなるエポキシ樹脂含有ワニス、
(2)前項(1)に記載のエポキシ樹脂含有ワニスを用いたエポキシ樹脂組成物含有ワニス、
(3)前項(1)に記載のエポキシ樹脂含有ワニス又は前項(2)に記載のエポキシ樹脂組成物含有ワニスを用いてなるプリプレグ、
(4)前項(1)に記載のエポキシ樹脂含有ワニス又は前項(2)に記載のエポキシ樹脂組成物含有ワニスを用いてなる樹脂シート、
(5)前項(3)に記載のプリプレグおよび/または前項(4)に記載の樹脂シートを成形してなる積層板、
(6)前項(3)に記載のプリプレグおよび/または前項(4)に記載の樹脂シートを硬化してなるプリント配線基板、
(7)前項(5)に記載の積層板からなるプリント配線基板、
(8)前項(6)又は(7)のいずれか一項に記載のプリント配線板からなる半導体装置、
を、提供するものである。
The present inventors have completed the present invention as a result of diligent studies in view of the above-mentioned actual conditions.
That is, the present invention is (1) an epoxy resin-containing varnish composed of an epoxy resin represented by the following general formula (1) and an organic solvent.
(2) An epoxy resin composition-containing varnish using the epoxy resin-containing varnish according to (1) above.
(3) A prepreg using the epoxy resin-containing varnish according to the previous item (1) or the epoxy resin composition-containing varnish according to the previous item (2).
(4) A resin sheet using the epoxy resin-containing varnish according to the previous item (1) or the epoxy resin composition-containing varnish according to the previous item (2).
(5) A laminated board formed by molding the prepreg according to the previous item (3) and / or the resin sheet according to the previous item (4).
(6) A printed wiring board obtained by curing the prepreg according to the previous item (3) and / or the resin sheet according to the previous item (4).
(7) The printed wiring board made of the laminated board according to the previous item (5).
(8) The semiconductor device comprising the printed wiring board according to any one of (6) and (7) above.
Is provided.
本発明のエポキシ樹脂含有ワニスは高い耐熱性と高度な誘電特性を有するため積層板、プリント配線基板に有用である。 The epoxy resin-containing varnish of the present invention has high heat resistance and high dielectric properties, and is therefore useful for laminated boards and printed wiring boards.
本発明のエポキシ樹脂含有ワニスは、エポキシ樹脂と有機溶剤からなる。
本発明に使用するエポキシ樹脂は下記式(1)
The epoxy resin used in the present invention has the following formula (1).
必要に応じて、ジメチルアセトアミドやN−メチルピロリドン、ジメチルスルホキシド、カルビトールアセテートなどの高沸点溶剤を添加することは、溶剤乾燥時の表面改質のために有効であり、また、メタノール、エタノール、プロパノール、ブタノール等を添加することで乾燥時の状態を変えることも可能である。
ハロゲン系の溶剤の使用は環境問題から好ましくなく、ジエチルエーテル等はその危険性の高さから好ましくない。
なお、本発明のエポキシ樹脂含有ワニスは上述のエポキシ樹脂、溶剤以外に、後述するカップリング剤やゴム成分、ポリマー成分を添加しても均一の溶液となっている分(0℃〜50℃のいずれかの温度において1cm角の石英セルにおいて測定した際のヘイズが200以下となる)には構わない。
If necessary, addition of a high boiling point solvent such as dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, carbitol acetate is effective for surface modification during solvent drying, and methanol, ethanol, etc. It is also possible to change the state at the time of drying by adding propanol, butanol and the like.
The use of halogen-based solvents is not preferable due to environmental problems, and diethyl ether and the like are not preferable due to their high risk.
The epoxy resin-containing varnish of the present invention has a uniform solution even if a coupling agent, a rubber component, or a polymer component described later is added in addition to the above-mentioned epoxy resin and solvent (0 ° C to 50 ° C). The haze when measured in a 1 cm square quartz cell at any temperature is 200 or less).
樹脂濃度としては10〜80重量%である。特に好ましくは15〜75%である。濃度が濃い分には後の工程で希釈することができるので、大きな問題にはならないが、流動性が確保できないと取り扱いが困難であるばかりか、缶やドラムへの残量が多くなってしまい、廃棄物の量が増大、環境への負荷が大きくなる。 The resin concentration is 10 to 80% by weight. Particularly preferably, it is 15 to 75%. If the concentration is high, it can be diluted in a later process, so it will not be a big problem, but if the fluidity cannot be secured, it will be difficult to handle and the remaining amount in the can or drum will increase. , The amount of waste increases, and the burden on the environment increases.
樹脂粘度は0℃〜50℃のいずれかの温度において10mPa・s〜100Pa・sの範囲に入ることが好ましく、特に好ましくは100mPa・s〜80Pa・sである。粘度に関しては塗工工程によって適宜好適な粘度がある。例えば表面支持体にアプリケータ等で数十ミクン〜数百ミクロンで塗布する場合は5〜80Pa・s程度の粘度がハジキやできる樹脂シートの膜厚をコントロールするのによい。 The resin viscosity is preferably in the range of 10 mPa · s to 100 Pa · s at any temperature of 0 ° C. to 50 ° C., and is particularly preferably 100 mPa · s to 80 Pa · s. Regarding the viscosity, there is an appropriate viscosity depending on the coating process. For example, when the surface support is coated with an applicator or the like at a viscosity of several tens of mikun to several hundreds of microns, it is preferable to control the film thickness of the resin sheet having a viscosity of about 5 to 80 Pa · s, which can be repelled.
本発明のエポキシ樹脂含有ワニスの製造方法としては上記溶剤を撹拌しているところに、本発明で用いられるエポキシ樹脂を分割で添加し、徐々に溶解させながら均一な状態とする。
分割で溶解する時間は30〜10時間である。溶解の温度は樹脂の軟化点に対し、20℃以上下の温度か、もしくは樹脂の軟化点以上の温度で行うことが好ましい。樹脂の軟化点〜軟化点−20℃の温度領域(具体的に位は軟化点80℃であれば80〜60℃)では樹脂同士がブロッキングし、釜の破損、さらにはこれにより、釜内から金属がガラス片が異物として混入する可能性があり好ましくない。
In the method for producing the epoxy resin-containing varnish of the present invention, the epoxy resin used in the present invention is added in portions to the place where the solvent is agitated, and the varnish is gradually dissolved to obtain a uniform state.
The dissolution time in the division is 30 to 10 hours. The melting temperature is preferably 20 ° C. or higher or higher than the softening point of the resin with respect to the softening point of the resin. In the temperature range from the softening point of the resin to the softening point of -20 ° C (specifically, if the softening point is 80 ° C, the resin is 80 to 60 ° C), the resins are blocked from each other, causing damage to the kettle and further from the inside of the kettle. The metal is not preferable because the glass piece may be mixed as a foreign substance.
このようにして得られたエポキシ樹脂含有ワニスは100μm以下の目の細かさのフィルタで濾過して保管することが好ましい。特に好ましくは1〜78μmである。100μmをこえる目開きのフィルタの場合、異物が混入した場合、塗布後ムラになり、支持体を傷つけてしまう可能性があり好ましくない。1μmを切るフィルタの場合、濾過速度が非常に遅くなり、生産性が悪い。
濾過にかかる温度は10〜100℃であり、特に好ましくは20〜90℃である。
加温することで流動性が上がり濾過しやすくなるが、100℃を超えると溶剤の沸点にもよるが濾過液からの臭気が強くなり、人的な被害の可能性があり好ましくない。また10℃を切ると流動性の問題から濾過性が悪くなりやすいばかりか、生産に時間がかかり好ましくない。
このようにして得られる本発明のワニスは5℃で2か月以上、0℃で1か月以上結晶の析出、もしくは樹脂の析出が見られない。
The epoxy resin-containing varnish thus obtained is preferably filtered and stored with a filter having a fine mesh of 100 μm or less. Particularly preferably, it is 1 to 78 μm. In the case of a filter with an opening of more than 100 μm, if foreign matter is mixed in, it may become uneven after application and damage the support, which is not preferable. In the case of a filter of less than 1 μm, the filtration rate becomes very slow and the productivity is poor.
The temperature required for filtration is 10 to 100 ° C, particularly preferably 20 to 90 ° C.
By heating, the fluidity increases and it becomes easier to filter, but if it exceeds 100 ° C., the odor from the filtrate becomes stronger depending on the boiling point of the solvent, which is not preferable because there is a possibility of human damage. Further, if the temperature is lower than 10 ° C., not only the filterability tends to deteriorate due to the problem of fluidity, but also the production takes time, which is not preferable.
In the varnish of the present invention thus obtained, no precipitation of crystals or precipitation of resin is observed at 5 ° C. for 2 months or longer and at 0 ° C. for 1 month or longer.
本発明においては本発明のエポキシ樹脂含有ワニスを用いてプリプレグもしくは樹脂シートを成型することができる。 In the present invention, a prepreg or a resin sheet can be molded using the epoxy resin-containing varnish of the present invention.
本発明のエポキシ樹脂組成物含有ワニスには本発明のエポキシ樹脂含有ワニスを使用する。
本発明のエポキシ樹脂組成物含有ワニスにおいて他に添加する物質としては、特殊樹脂、併用する他のエポキシ樹脂、エポキシ樹脂用硬化剤、硬化促進剤、カップリング剤、無機充填剤であり、少なくともこれらから2種以上(すなわちエポキシ樹脂含有ワニスと合わせて3種以上)を含有する。
The epoxy resin-containing varnish of the present invention is used as the epoxy resin composition-containing varnish of the present invention.
Other substances to be added to the epoxy resin composition-containing varnish of the present invention include special resins, other epoxy resins used in combination, curing agents for epoxy resins, curing accelerators, coupling agents, and inorganic fillers, and at least these. Contains 2 or more types (that is, 3 or more types including epoxy resin-containing varnish).
特殊樹脂としては、前述に記載したものを含め、ポリフェニレンエーテル樹脂、ベンゾオキサジン樹脂、可溶性ポリイミド、可溶性ポリアミド、BTレジン、シアネート樹脂、マレイミド樹脂、スチレン/無水マレイン酸コポリマーもしくはその変性体等の樹脂が挙げられる。
これら樹脂の使用量は、樹脂全体の10〜90重量%であり、特に好ましくは20〜80重量%となる。
Examples of the special resin include those described above, and resins such as polyphenylene ether resin, benzoxazine resin, soluble polyimide, soluble polyamide, BT resin, cyanate resin, maleimide resin, styrene / maleic anhydride copolymer or a modified product thereof. Can be mentioned.
The amount of these resins used is 10 to 90% by weight, particularly preferably 20 to 80% by weight, based on the total amount of the resin.
本発明において用いられるエポキシ樹脂組成物と併用されうる他のエポキシ樹脂の具体例としては、ビスフェノール類(ビスフェノールA、ビスフェノールF、ビスフェノールS、ビフェノール、ビスフェノールAD等)またはフェノール類(フェノール、アルキル置換フェノール、芳香族置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、アルキル置換ジヒドロキシベンゼン、ジヒドロキシナフタレン等)と各種アルデヒド(ホルムアルデヒド、アセトアルデヒド、アルキルアルデヒド、ベンズアルデヒド、アルキル置換ベンズアルデヒド、ヒドロキシベンズアルデヒド、ナフトアルデヒド、グルタルアルデヒド、フタルアルデヒド、クロトンアルデヒド、シンナムアルデヒド等)との重縮合物;前記フェノール類と各種ジエン化合物(ジシクロペンタジエン、テルペン類、ビニルシクロヘキセン、ノルボルナジエン、ビニルノルボルネン、テトラヒドロインデン、ジビニルベンゼン、ジビニルビフェニル、ジイソプロペニルビフェニル、ブタジエン、イソプレン等)との重合物;前記フェノール類とケトン類(アセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン、ベンゾフェノン等)との重縮合物;前記フェノール類と芳香族ジメタノール類(ベンゼンジメタノール、ビフェニルジメタノール等)との重縮合物;前記フェノール類と芳香族ジクロロメチル類(α,α’−ジクロロキシレン、ビスクロロメチルビフェニル等)との重縮合物;前記フェノール類と芳香族ビスアルコキシメチル類(ビスメトキシメチルベンゼン、ビスメトキシメチルビフェニル、ビスフェノキシメチルビフェニル等)との重縮合物;前記ビスフェノール類と各種アルデヒドの重縮合物またはアルコール類等をグリシジル化したグリシジルエーテル系エポキシ樹脂、脂環式エポキシ樹脂、グリシジルアミン系エポキシ樹脂、グリシジルエステル系エポキシ樹脂等が挙げられるが、通常用いられるエポキシ樹脂であればこれらに限定されるものではない。これらは単独で用いてもよく、2種以上を用いてもよい。 Specific examples of other epoxy resins that can be used in combination with the epoxy resin composition used in the present invention include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or phenols (phenol, alkyl-substituted phenol). , Aromatically substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, alkyl substituted dihydroxybenzene, dihydroxynaphthalene, etc. and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaaldehyde, etc. Polycondensate with phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.); the phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroinden, divinylbenzene, divinylbiphenyl, diiso) Polymers of propenylbiphenyl, butadiene, isoprene, etc.; polycondensates of the phenols and ketones (acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone, etc.); phenols and aromatic dimethanols (benzene, etc.) Polycondensate with dimethanol, biphenyldimethanol, etc.; Polycondensate of the phenols with aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.); Polycondensate with bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.); , Alicyclic epoxy resin, glycidylamine-based epoxy resin, glycidyl ester-based epoxy resin and the like, but are not limited to these as long as they are commonly used epoxy resins. These may be used alone or two or more kinds may be used.
本発明において用いられるエポキシ樹脂組成物を配合する場合、硬化剤を使用することができる。使用できる硬化剤の具体例としては、アミン化合物(アニリン樹脂を含む)や、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸などの酸無水物系化合物、ビスフェノール類、フェノール類(フェノール、アルキル置換フェノール、芳香族置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、アルキル置換ジヒドロキシベンゼン、ジヒドロキシナフタレン等)と各種アルデヒド(ホルムアルデヒド、アセトアルデヒド、アルキルアルデヒド、ベンズアルデヒド、アルキル置換ベンズアルデヒド、ヒドロキシベンズアルデヒド、ナフトアルデヒド、グルタルアルデヒド、フタルアルデヒド、クロトンアルデヒド、シンナムアルデヒド等)との重縮合物、フェノール類と各種ジエン化合物(ジシクロペンタジエン、テルペン類、ビニルシクロヘキセン、ノルボルナジエン、ビニルノルボルネン、テトラヒドロインデン、ジビニルベンゼン、ジビニルビフェニル、ジイソプロペニルビフェニル、ブタジエン、イソプレン等)との重合物、フェノール類とケトン類(アセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン、ベンゾフェノン等)との重縮合物、などが挙げられるがこれらに限定されるものではない。これらは単独で用いてもよく、2種以上併用してもよい。 When the epoxy resin composition used in the present invention is blended, a curing agent can be used. Specific examples of the curing agent that can be used include amine compounds (including aniline resin), phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and anhydrous. Acid anhydride compounds such as methylnadic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols, phenols (phenols, alkyl-substituted phenols, aromatic-substituted phenols, naphthols, alkyl-substituted naphthols, dihydroxybenzene, alkyl Polycondensate of substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaaldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), Polymers of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadien, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenols and ketones. Examples include, but are not limited to, polycondensates with other species (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.). These may be used alone or in combination of two or more.
本発明において用いられるエポキシ樹脂組成物において硬化剤を使用する場合の使用量は、エポキシ樹脂のエポキシ基1当量に対して0.6〜1.1当量が好ましい。エポキシ基1.1当量超える場合、また、0.6当量を切る場合、硬化剤が取り残されることとなり、硬化が不完全となり良好な硬化物性が得られない恐れがある。ただし、エポキシ樹脂と硬化可能な特殊樹脂が含有される場合はこの限りではなく、特殊樹脂によって消費されるエポキシの量を差し引いた残りのエポキシ基に対する硬化剤の量となるため、配合によって適宜調整が必要となる。 When a curing agent is used in the epoxy resin composition used in the present invention, the amount used is preferably 0.6 to 1.1 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin. If the epoxy group exceeds 1.1 equivalents, or if it is less than 0.6 equivalents, the curing agent will be left behind, and curing may be incomplete and good cured physical properties may not be obtained. However, this does not apply when the epoxy resin and the curable special resin are contained, and the amount of the curing agent is the amount of the curing agent for the remaining epoxy group after deducting the amount of epoxy consumed by the special resin. Is required.
本発明において用いられるエポキシ樹脂組成物においては、硬化促進剤を含有させても差し支えない。使用できる硬化促進剤の具体例としては2−メチルイミダゾール、2−エチルイミダゾール、2−エチル−4−メチルイミダゾール等のイミダゾ−ル類、2−(ジメチルアミノメチル)フェノール、1,8−ジアザ−ビシクロ(5,4,0)ウンデセン−7等の第3級アミン類、トリフェニルホスフィン等のホスフィン類、オクチル酸スズ等の金属化合物等が挙げられる。硬化促進剤は、エポキシ樹脂100重量部に対して0.1〜10.0重量部が必要に応じ用いられる。 The epoxy resin composition used in the present invention may contain a curing accelerator. Specific examples of the curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, and 1,8-diaza. Examples thereof include tertiary amines such as bicyclo (5,4,5) undecene-7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate. As the curing accelerator, 0.1 to 10.0 parts by weight is used as necessary with respect to 100 parts by weight of the epoxy resin.
本発明において用いられるエポキシ樹脂組成物には、必要に応じて難燃剤、充填剤等の添加剤を、硬化物の誘特性や耐熱性等の特性を悪化させない範囲で配合することができる。 If necessary, additives such as flame retardants and fillers can be added to the epoxy resin composition used in the present invention within a range that does not deteriorate the properties such as attracting properties and heat resistance of the cured product.
必要に応じて配合される充填剤は、特に限定されないが、無機充填剤としては溶融シリカ、結晶性シリカ、アルミナ、炭酸カルシウム、ケイ酸カルシウム、硫酸バリウム、タルク、クレー、酸化マグネシウム、酸化アルミニウム、酸化ベリリウム、酸化鉄、酸化チタン、窒化アルミニウム、窒化ケイ素、窒化ホウ素、マイカ、ガラス、石英、雲母などが挙げられる。さらに難燃効果を付与するため、水酸化マグネシウム、水酸化アルミニウムなどの金属水酸化物を使用することも好ましい。ただし、これらに限定されない。また2種以上を混合して使用しても良い。これら無機充填剤のうち、溶融シリカや結晶性シリカなどのシリカ類はコストが安く、電気信頼性も良好なため好ましい。
本発明において用いられるエポキシ樹脂組成物において、無機充填剤の使用量は内割りで通常10重量%〜95重量%、好ましくは10重量%〜80重量%、より好ましくは10重量%〜75重量%の範囲である。少なすぎると難燃性の効果が得られない、また弾性率が下がってしまう、また、多すぎると封止する溶液に溶かしたワニスとした際にフィラーが沈降してしまい、均質な成型体が得られない可能性がある。
なお、無機充填剤の形状、粒径等も特に限定されないが、通常、粒径0.01〜50μm、好ましくは0.1〜20μmのものである。
The filler to be blended as required is not particularly limited, but examples of the inorganic filler include fused silica, crystalline silica, alumina, calcium carbonate, calcium silicate, barium sulfate, talc, clay, magnesium oxide, aluminum oxide, and the like. Examples thereof include beryllium oxide, iron oxide, titanium oxide, aluminum nitride, silicon nitride, boron nitride, mica, glass, quartz and mica. Further, in order to impart a flame retardant effect, it is also preferable to use a metal hydroxide such as magnesium hydroxide or aluminum hydroxide. However, it is not limited to these. Further, two or more kinds may be mixed and used. Among these inorganic fillers, silicas such as fused silica and crystalline silica are preferable because they are inexpensive and have good electrical reliability.
In the epoxy resin composition used in the present invention, the amount of the inorganic filler used is usually 10% by weight to 95% by weight, preferably 10% by weight to 80% by weight, and more preferably 10% by weight to 75% by weight. Is the range of. If the amount is too small, the flame-retardant effect cannot be obtained, the elastic modulus decreases, and if the amount is too large, the filler will settle when the varnish is dissolved in the sealing solution, resulting in a homogeneous molded body. It may not be obtained.
The shape, particle size, etc. of the inorganic filler are not particularly limited, but are usually 0.01 to 50 μm, preferably 0.1 to 20 μm.
本発明において用いられるエポキシ樹脂組成物にはガラスクロスや無機充填剤と樹脂成分との接着性を高めるためにカップリング剤を配合することができる。カップリング剤としては従来公知のものをいずれも使用できるが、例えばビニルアルコキシシラン、エポキアルコキシシラン、スチリルアルコキシシラン、メタクリロキシアルコキシシラン、アクリロキシアルコキシシラン、アミノアルコキシシラン、メルカプトアルコキシシラン、イソシアナートアルコキシシランなどの各種アルコキシシラン化合物、アルコキシチタン化合物、アルミニウムキレート類などが挙げられる。これらは単独で使用しても2種以上併用しても良い。カップリング剤の添加方法は、カップリング剤であらかじめ無機充填剤表面を処理した後、樹脂と混合しても良いし、樹脂にカップリング剤を混合してから無機充填剤を混合しても良い。 The epoxy resin composition used in the present invention may contain a coupling agent in order to enhance the adhesiveness between the glass cloth or the inorganic filler and the resin component. As the coupling agent, any conventionally known one can be used, and for example, vinyl alkoxysilane, epoxyalkoxysilane, styrylalkoxysilane, methacryoxyalkoxysilane, acryloxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane, and isocyanatoalkoxy are used. Examples thereof include various alkoxysilane compounds such as silane, alkoxytitanium compounds, and aluminum chelates. These may be used alone or in combination of two or more. As a method of adding the coupling agent, the surface of the inorganic filler may be treated with the coupling agent in advance and then mixed with the resin, or the coupling agent may be mixed with the resin and then the inorganic filler may be mixed. ..
本発明において用いられるエポキシ樹脂組成物にさらに他の有機溶剤を添加してすることができる。用いられる溶剤としては、例えばγ−ブチロラクトン類、N−メチルピロリドン、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N,N−ジメチルイミダゾリジノン等のアミド系溶剤、テトラメチレンスルフォン等のスルフォン類、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルモノアセテート、プロピレングリコールモノブチルエーテル等のエーテル系溶剤、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン等のケトン系溶剤、トルエン、キシレンなどの芳香族系溶剤が挙げられる。溶剤は、得られたワニス中の溶剤を除く固形分濃度が通常10〜80重量%、好ましくは20〜70重量%となる範囲で使用する。 Other organic solvents can be added to the epoxy resin composition used in the present invention. Examples of the solvent used include γ-butyrolactones, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone and other amide solvents, tetramethylene sulfone and the like. Ethereal solvents such as sulfones, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, and ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone. Examples include solvents and aromatic solvents such as toluene and xylene. The solvent is used in a range in which the solid content concentration of the obtained varnish excluding the solvent is usually 10 to 80% by weight, preferably 20 to 70% by weight.
更に本発明のエポキシ樹脂組成物含有ワニスには、必要に応じて公知の添加剤を配合することが出来る。用いうる添加剤の具体例としては、ポリブタジエン及びこの変性物、アクリロニトリル共重合体の変性物、ポリスチレン、ポリエチレン、フッ素樹脂、シリコーンゲル、シリコーンオイル、並びにカーボンブラック、フタロシアニンブルー、フタロシアニングリーン等の着色剤などが挙げられる。 Further, a known additive can be added to the epoxy resin composition-containing varnish of the present invention, if necessary. Specific examples of additives that can be used include polybutadiene and modified products thereof, modified products of acrylonitrile copolymer, polystyrene, polyethylene, fluororesin, silicone gel, silicone oil, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green. And so on.
本発明のプリプレグについて説明する。
本発明のプリプレグは上記樹脂組成物含有ワニスを繊維基材に含浸してなるものである。これにより、耐熱性、低膨張性および難燃性に優れたプリプレグを得ることができる。
前記繊維基材としては、例えばガラス織布、ガラス不繊布、ガラスペーパー等のガラス繊維基材、紙、アラミド、ポリエステル、芳香族ポリエステル、フッ素樹脂等の合成繊維等からなる織布や不織布、金属繊維、カーボン繊維、鉱物繊維等からなる織布、不織布、マット類等が挙げられる。これらの基材は単独又は混合して使用してもよい。これらの中でもガラス繊維基材が好ましい。これにより、プリプレグの剛性、寸法安定性を向上することができる。
ガラス繊維基材としては、Tガラス、Sガラス、Eガラス、NEガラス、および石英ガラスからなる群から選ばれる少なくとも一種を含むものが好ましい。
The prepreg of the present invention will be described.
The prepreg of the present invention is obtained by impregnating a fiber base material with the above resin composition-containing varnish. Thereby, a prepreg having excellent heat resistance, low expansion property and flame retardancy can be obtained.
Examples of the fiber base material include glass fiber base materials such as glass woven fabric, glass non-woven fabric, and glass paper, and woven fabrics, non-woven fabrics, and metals made of synthetic fibers such as paper, aramid, polyester, aromatic polyester, and fluororesin. Examples thereof include woven fabrics made of fibers, carbon fibers, mineral fibers and the like, non-woven fabrics, mats and the like. These substrates may be used alone or in combination. Among these, a glass fiber base material is preferable. As a result, the rigidity and dimensional stability of the prepreg can be improved.
The glass fiber base material preferably contains at least one selected from the group consisting of T glass, S glass, E glass, NE glass, and quartz glass.
前記樹脂組成物を前記繊維基材に含浸させる方法は、例えば基材を樹脂ワニスに浸漬する方法、各種コーターによる塗布する方法、スプレーによる吹き付ける方法等が挙げられる。これらの中でも、基材を樹脂ワニスに浸漬する方法が好ましい。これにより、基材に対する樹脂組成物の含浸性を向上することができる。なお、基材を樹脂ワニスに浸漬する場合、通常の含浸塗布設備を使用することができる。
例えば、本発明のエポキシ樹脂組成物をそのままで、又は溶媒に溶解若しくは分散させたワニスの形態で、ガラス布等の基材に含浸させた後、乾燥炉中等で通常、80〜200℃(ただし、溶媒を使用した場合は溶媒の揮発可能な温度以上とする)、好ましくは150〜200℃の温度で、1〜30分間、好ましくは1〜15分間乾燥させることによってプリプレグが得られる。
また後述する樹脂シートをガラスクロスに押し付け、転写し、プリプレグを得るという手法も適用可能である。
Examples of the method of impregnating the fiber base material with the resin composition include a method of immersing the base material in a resin varnish, a method of applying with various coaters, a method of spraying with a spray, and the like. Among these, the method of immersing the base material in the resin varnish is preferable. Thereby, the impregnation property of the resin composition with respect to the base material can be improved. When the base material is immersed in the resin varnish, ordinary impregnation coating equipment can be used.
For example, after impregnating a base material such as a glass cloth with the epoxy resin composition of the present invention as it is or in the form of a varnish dissolved or dispersed in a solvent, it is usually 80 to 200 ° C. (however, in a drying furnace or the like). The prepreg is obtained by drying at a temperature of 150 to 200 ° C. for 1 to 30 minutes, preferably 1 to 15 minutes.
Further, a method of pressing a resin sheet, which will be described later, against a glass cloth and transferring the resin sheet to obtain a prepreg can also be applied.
本発明の樹脂シートについて説明する。
本発明のエポキシ樹脂組成物含有ワニスを用いた樹脂シートは上記ワニスをそれ自体公知のグラビアコート法、スクリーン印刷、メタルマスク法、スピンコート法などの各種塗工方法により平面状支持体に乾燥後の厚さが所定の厚さ、たとえば5〜100μmになるように塗布後、乾燥して得られるが、どの塗工方法を用いるかは支持体の種類、形状、大きさ、塗工の膜厚、支持体の耐熱性等により適宜選択される。平面支持体としては、たとえばポリアミド、ポリアミドイミド、ポリアリレート、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエーテルケトン、ポリエーテルイミド、ポリエーテルエーテルケトン、ポリケトン、ポリエチレン、ポリプロピレン、テフロン(登録商標)等の各種高分子、および/またはその共重合体から作られるフィルム、あるいは銅箔等の金属箔等が挙げられる。
塗布後、乾燥し、シート状の組成物を得ることができる(本発明のシート)が、本シートをさらに加熱することでシート状の硬化物とすることもできる。また一度の加熱で溶剤乾燥と硬化工程を兼ねてもよい。
本発明のエポキシ樹脂組成物は上記支持体の両面もしくは片面に上記方法で塗工、加熱することにより、該支持体の両面または片面に本発明の硬化物の層を形成することができる。また硬化前に被着体を貼り合わせ、硬化させることで積層体を作成することも可能である。
また本発明の樹脂シートは支持体から剥がすことで接着シートとして使用することもでき、被着体に接触させ、必要に応じて圧力と熱をかけ、硬化とともに接着させるということもできる。
The resin sheet of the present invention will be described.
The resin sheet using the epoxy resin composition-containing varnish of the present invention is obtained by drying the varnish onto a flat support by various coating methods such as a gravure coating method, a screen printing method, a metal mask method, and a spin coating method, which are known per se. It is obtained by coating and drying so that the thickness of the resin is a predetermined thickness, for example, 5 to 100 μm, but which coating method is used depends on the type, shape, size, and coating thickness of the support. , It is appropriately selected depending on the heat resistance of the support and the like. Examples of the flat support include various heights such as polyamide, polyamideimide, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyetherketone, polyetherimide, polyetheretherketone, polyketone, polyethylene, polypropylene, and Teflon (registered trademark). Examples thereof include a film made of molecules and / or a copolymer thereof, a metal foil such as copper foil, and the like.
After coating, it can be dried to obtain a sheet-like composition (the sheet of the present invention), but a sheet-like cured product can also be obtained by further heating the sheet. Further, the solvent drying and the curing process may be combined by one heating.
By applying and heating the epoxy resin composition of the present invention on both sides or one side of the support by the above method, a layer of the cured product of the present invention can be formed on both sides or one side of the support. It is also possible to create a laminated body by laminating and curing the adherends before curing.
Further, the resin sheet of the present invention can be used as an adhesive sheet by peeling it from the support, or it can be brought into contact with an adherend, and if necessary, pressure and heat are applied to bond the resin sheet as it cures.
本発明の積層板について説明する。
本発明で用いられる積層板は、上記のプリプレグおよび/または樹脂シートを加熱加圧成形してなるものである。これにより、耐熱性、低膨張性および難燃性に優れたプリント配線板を得ることができる。プリプレグおよび/または樹脂シート1枚のときは、その上下両面もしくは片面に金属箔を重ねる。また、プリプレグおよび/または樹脂シートを2枚以上積層することもできる。プリプレグおよび/または樹脂シート2枚以上積層するときは、積層したプリプレグおよび/または樹脂シートの最も外側の上下両面もしくは片面に金属箔あるいはフィルムおよび/または樹脂シートを重ねる。次に、プリプレグおよび/または樹脂シートと金属箔とを重ねたものを加熱加圧成形することでプリント配線板を得ることができる。前記加熱する温度は、特に限定されないが、120〜220℃が好ましく、特に150〜200℃が好ましい。前記加圧する圧力は、特に限定されないが、1.5〜5MPaが好ましく、特に2〜4MPaが好ましい。また、必要に応じて高温漕等で150〜300℃の温度で後硬化を行ってもかまわない。
The laminated board of the present invention will be described.
The laminated board used in the present invention is formed by heat-press molding the above-mentioned prepreg and / or resin sheet. Thereby, a printed wiring board having excellent heat resistance, low expansion property and flame retardancy can be obtained. In the case of one prepreg and / or resin sheet, metal foil is laminated on both the upper and lower sides or one side thereof. Further, two or more prepregs and / or resin sheets can be laminated. When two or more prepregs and / or resin sheets are laminated, a metal foil or film and / or resin sheet is laminated on the outermost upper and lower sides or one side of the laminated prepreg and / or resin sheet. Next, a printed wiring board can be obtained by heat-press molding a stack of a prepreg and / or a resin sheet and a metal foil. The heating temperature is not particularly limited, but is preferably 120 to 220 ° C, particularly preferably 150 to 200 ° C. The pressurizing pressure is not particularly limited, but is preferably 1.5 to 5 MPa, particularly preferably 2 to 4 MPa. Further, if necessary, post-curing may be performed at a temperature of 150 to 300 ° C. in a high-temperature tank or the like.
本発明のプリント配線基板について説明する。
プリント配線板は、前記積層板を内層回路板として用いる。積層板の片面又は両面に回路形成する。場合によっては、ドリル加工、レーザー加工によりスルーホールを形成し、めっき等で両面の電気的接続をとることもできる。
The printed wiring board of the present invention will be described.
As the printed wiring board, the laminated board is used as an inner layer circuit board. A circuit is formed on one side or both sides of the laminated board. In some cases, through holes can be formed by drilling or laser processing, and both sides can be electrically connected by plating or the like.
前記内装回路基板に市販又は本発明の樹脂シート、または前記本発明のプリプレグを重ね合わせて加熱加圧成形し、多層プリント配線基板を得ることができる。
具体的には、上記樹脂シートの絶縁層側と内層回路板とを合わせて、真空加圧式ラミネーター装置などを用いて真空加熱加圧成形させ、その後、熱風乾燥装置等で絶縁層を加熱硬化させることにより得ることができる。
ここで加熱加圧成形する条件としては特に限定されないが、一例を挙げると、温度60〜160℃、圧力0.2〜3MPaで実施することができる。また、加熱硬化させる条件としては特に限定されないが、一例を挙げると、温度140〜240℃、時間30〜120分間で実施することができる。
あるいは、前記本発明のプリプレグを内層回路板に重ね合わせ、これを平板プレス装置などを用いて加熱加圧成形することにより得ることができる。ここで加熱加圧成形する条件としては特に限定されないが、一例を挙げると、温度140〜240℃、圧力1〜4MPaで実施することができる。このような平板プレス装置等による加熱加圧成形では、加熱加圧成形と同時に絶縁層の加熱硬化が行われる。
A commercially available resin sheet of the present invention or the prepreg of the present invention or the prepreg of the present invention is superposed on the internal circuit board and heat-press molded to obtain a multilayer printed wiring board.
Specifically, the insulating layer side of the resin sheet and the inner layer circuit board are combined and vacuum-heated and pressure-molded using a vacuum-pressurized laminator device or the like, and then the insulating layer is heat-cured by a hot-air drying device or the like. Can be obtained by
Here, the conditions for heat and pressure molding are not particularly limited, but for example, the molding can be carried out at a temperature of 60 to 160 ° C. and a pressure of 0.2 to 3 MPa. The conditions for heat curing are not particularly limited, but for example, it can be carried out at a temperature of 140 to 240 ° C. and a time of 30 to 120 minutes.
Alternatively, the prepreg of the present invention can be obtained by superimposing the prepreg on the inner layer circuit board and heat-pressing molding using a flat plate press or the like. Here, the conditions for heat and pressure molding are not particularly limited, but for example, the molding can be carried out at a temperature of 140 to 240 ° C. and a pressure of 1 to 4 MPa. In the heat-pressurizing molding using such a flat plate press or the like, the insulating layer is heat-cured at the same time as the heat-pressurizing molding.
また、本発明に係る多層プリント配線基板の製造方法は、前記樹脂シート、または本発明のプリプレグを、内層回路基板の内層回路パターンが形成された面に重ね合わせて連続積層する工程、及び導体回路層をセミアディティブ法等のビルドアップ工法で形成する工程を含む。 Further, the method for manufacturing a multilayer printed wiring board according to the present invention includes a step of superimposing the resin sheet or the prepreg of the present invention on a surface of an inner layer circuit board on which an inner layer circuit pattern is formed, and continuously laminating the conductor circuit. It includes a step of forming a layer by a build-up method such as a semi-additive method.
前記樹脂シート、または本発明のプリプレグより形成された絶縁層の硬化は、次のレーザー照射および樹脂残渣の除去を容易にし、デスミア性を向上させるため、半硬化状態にしておく場合もある。また、一層目の絶縁層を通常の加熱温度より低い温度で加熱することにより一部硬化(半硬化)させ、絶縁層上に、一層ないし複数の絶縁層をさらに形成し半硬化の絶縁層を実用上問題ない程度に再度加熱硬化させることにより絶縁層間および絶縁層と回路との密着力を向上させることができる。この場合の半硬化の温度は、80℃〜200℃が好ましく、100℃〜180℃がより好ましい。尚、次工程においてレーザーを照射し、絶縁層に開口部を形成するが、その前に基材を剥離する必要がある。基材の剥離は、絶縁層を形成後、加熱硬化の前、または加熱硬化後のいずれに行っても特に問題はない。
なお、前記多層プリント配線基板を得る際に用いられる内層回路板は、例えば、銅張積層板の両面に、エッチング等により所定の導体回路を形成し、導体回路部分を黒化処理したものを好適に用いることができる。
The curing of the insulating layer formed from the resin sheet or the prepreg of the present invention may be left in a semi-cured state in order to facilitate the next laser irradiation and removal of the resin residue and improve the desmear property. Further, the first layer of the insulating layer is partially cured (semi-cured) by heating at a temperature lower than the normal heating temperature, and one or more insulating layers are further formed on the insulating layer to form a semi-cured insulating layer. By heat-curing again to the extent that there is no problem in practical use, the adhesion between the insulating layers and the insulating layer and the circuit can be improved. The semi-curing temperature in this case is preferably 80 ° C. to 200 ° C., more preferably 100 ° C. to 180 ° C. In the next step, the laser is irradiated to form an opening in the insulating layer, but it is necessary to peel off the base material before that. There is no particular problem in peeling the base material after forming the insulating layer, before heat curing, or after heat curing.
The inner layer circuit board used for obtaining the multilayer printed wiring board is preferably, for example, one in which a predetermined conductor circuit is formed on both sides of a copper-clad laminate by etching or the like and the conductor circuit portion is blackened. Can be used for.
レーザー照射後の樹脂残渣等は過マンガン酸塩、重クロム酸塩等の酸化剤などにより除去することが好ましい。また、平滑な絶縁層の表面を同時に粗化することができ、続く金属メッキにより形成する導電配線回路の密着性を上げることができる。 It is preferable to remove the resin residue and the like after laser irradiation with an oxidizing agent such as permanganate and dichromate. Further, the surface of the smooth insulating layer can be roughened at the same time, and the adhesion of the conductive wiring circuit formed by the subsequent metal plating can be improved.
次に、外層回路を形成する。外層回路の形成方法は、金属メッキにより絶縁樹脂層間の接続を図り、エッチングにより外層回路パターン形成を行う。樹脂シート、またはプリプレグを用いたときと同様にして、多層プリント配線基板を得ることができる。
尚、金属箔を有する樹脂シート、またはプリプレグを用いた場合は、金属箔を剥離することなく、導体回路として用いるためにエッチングにより回路形成を行ってもよい。その場合、厚い銅箔を使用した基材付き絶縁樹脂シートを使うと、その後の回路パターン形成においてファインピッチ化が困難になるため、1〜5μmの極薄銅箔を使うか、または12〜18μmの銅箔をエッチングにより1〜5μmに薄くするハーフエッチングする場合もある。
Next, the outer layer circuit is formed. As for the method of forming the outer layer circuit, the insulating resin layers are connected by metal plating, and the outer layer circuit pattern is formed by etching. A multilayer printed wiring board can be obtained in the same manner as when a resin sheet or a prepreg is used.
When a resin sheet having a metal foil or a prepreg is used, the circuit may be formed by etching for use as a conductor circuit without peeling the metal foil. In that case, if an insulating resin sheet with a base material using a thick copper foil is used, it becomes difficult to achieve a fine pitch in the subsequent circuit pattern formation. Therefore, an ultrathin copper foil of 1 to 5 μm is used, or 12 to 18 μm is used. In some cases, the copper foil is half-etched to thin it to 1 to 5 μm by etching.
さらに絶縁層を積層し、前記同様回路形成を行っても良いが、多層プリント配線板の設計上、最外層には、回路形成後、ソルダーレジストを形成する。ソルダーレジストの形成方法は、特に限定されないが、例えば、ドライフィルムタイプのソルダーレジストを積層(ラミネート)し、露光、および現像により形成する方法、または液状レジストを印刷したものを露光、および現像により形成する方法によりなされる。なお、得られた多層プリント配線板を半導体装置に用いる場合、半導体素子を実装するため接続用電極部を設ける。接続用電極部は、金めっき、ニッケルメッキおよび半田めっき等の金属皮膜で適宜被覆することができる。このような方法により多層プリント配線板を製造することができる。 Further, an insulating layer may be laminated to form a circuit in the same manner as described above, but due to the design of the multilayer printed wiring board, a solder resist is formed on the outermost layer after the circuit is formed. The method for forming the solder resist is not particularly limited, but for example, a method of laminating a dry film type solder resist and forming it by exposure and development, or a method of printing a liquid resist and forming it by exposure and development. It is done by the method of When the obtained multilayer printed wiring board is used in a semiconductor device, a connection electrode portion is provided to mount the semiconductor element. The connecting electrode portion can be appropriately coated with a metal film such as gold plating, nickel plating, and solder plating. A multilayer printed wiring board can be manufactured by such a method.
次に、本発明の半導体装置について説明する。
前記で得られた多層プリント配線板に半田バンプを有する半導体素子を実装し、半田バンプを介して、前記多層プリント配線板との接続を図る。そして、多層プリント配線板と半導体素子との間には液状封止樹脂を充填し、半導体装置を形成する。半田バンプは、錫、鉛、銀、銅、ビスマスなどからなる合金で構成されることが好ましい。
半導体素子と多層プリント配線板との接続方法は、フリップチップボンダーなどを用いて基板上の接続用電極部と半導体素子の半田バンプとの位置合わせを行ったあと、IRリフロー装置、熱板、その他加熱装置を用いて半田バンプを融点以上に加熱し、多層プリント配線板と半田バンプとを溶融接合することにより接続する。尚、接続信頼性を良くするため、予め多層プリント配線板上の接続用電極部に半田ペースト等、比較的融点の低い金属の層を形成しておいても良い。この接合工程に先んじて、半田バンプおよび、または多層プリント配線板上の接続用電極部の表層にフラックスを塗布することで接続信頼性を向上させることもできる。
Next, the semiconductor device of the present invention will be described.
A semiconductor element having solder bumps is mounted on the multilayer printed wiring board obtained above, and the connection with the multilayer printed wiring board is achieved via the solder bumps. Then, a liquid sealing resin is filled between the multilayer printed wiring board and the semiconductor element to form a semiconductor device. The solder bump is preferably composed of an alloy made of tin, lead, silver, copper, bismuth or the like.
The connection method between the semiconductor element and the multilayer printed wiring board is as follows: After aligning the connection electrode part on the substrate and the solder bump of the semiconductor element using a flip chip bonder or the like, an IR reflow device, a hot plate, etc. The solder bumps are heated above the melting point using a heating device, and the multilayer printed wiring board and the solder bumps are melt-bonded to connect them. In order to improve the connection reliability, a metal layer having a relatively low melting point such as solder paste may be formed in advance on the connection electrode portion on the multilayer printed wiring board. Prior to this joining step, the connection reliability can be improved by applying flux to the solder bumps or the surface layer of the connection electrode portion on the multilayer printed wiring board.
基板としてはマザーボード、ネットワーク基板、パッケージ基板等に使用され、基板として使用される。特にパッケージ基板としては片面封止材料用の薄層基板として有用である。また半導体封止材として使用した場合、その配合から得られる半導体装置としてはとしては、例えばDIP(デュアルインラインパッケージ)、QFP(クワッドフラットパッケージ)、BGA(ボールグリッドアレイ)、CSP(チップサイズパッケージ)、SOP(スモールアウトラインパッケージ)、TSOP(シンスモールアウトラインパッケージ)、TQFP(シンクワッドフラットパッケージ)等が挙げられる。 As a board, it is used for a motherboard, a network board, a package board, etc., and is used as a board. In particular, as a package substrate, it is useful as a thin-layer substrate for a single-sided sealing material. When used as a semiconductor encapsulant, the semiconductor devices obtained from the formulation include, for example, DIP (dual in-line package), QFP (quad flat package), BGA (ball grid array), and CSP (chip size package). , SOP (Small Outline Package), TSOP (Thin Small Outline Package), TQFP (Syncwad Flat Package) and the like.
以下に合成例および実施例を挙げて本発明の特徴をさらに具体的に説明する。以下に示す材料、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。
ここで、各物性値の測定条件は下記の通りである。
・エポキシ当量
JIS K−7236に記載された方法で測定し、単位はg/eq.である。
・軟化点
JIS K−7234に準拠した方法で測定し、単位は℃である。
The features of the present invention will be described in more detail with reference to Synthesis Examples and Examples. The materials, treatment contents, treatment procedures, etc. shown below can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limited by the specific examples shown below.
Here, the measurement conditions for each physical property value are as follows.
Epoxy equivalent Measured by the method described in JIS K-7236, the unit is g / eq. Is.
-Softening point Measured by a method conforming to JIS K-7234, the unit is ° C.
合成例1
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながらWO2007/007827に準拠して製造した下記式で表されるフェノール樹脂((a)/(b)=1.3 n=0.5 水酸基当量134g/eq. 軟化点93℃)134部、エピクロロヒドリン450部、メタノール54部を加え、撹拌下で溶解し、70℃にまで昇温した。次いでフレーク状の水酸化ナトリウム42.5部を90分かけて分割添加した後、更に70℃で1時間反応を行った。反応終了後,水洗し、塩を除いた後、得られた有機層をロータリーエバポレーターを用いて減圧下、過剰のエピクロルヒドリン等の溶剤類を留去した。残留物にメチルイソブチルケトン500部を加え溶解し、撹拌下で30重量%の水酸化ナトリウム水溶液17部を加え、1時間反応を行った後、油層の洗浄水が中性になるまで水洗を行い、得られた溶液から、ロータリーエバポレーターを用いて減圧下にメチルイソブチルケトン等を留去することで本発明のエポキシ樹脂(EP1)195部を得た。得られたエポキシ樹脂のエポキシ当量は211g/eq.軟化点71℃、150℃における溶融粘度(ICI溶融粘度 コーン#1)は0.34Pa・sであった。
A phenol resin represented by the following formula ((a) / (b) = 1.3 n = 0.5) manufactured in accordance with WO2007 / 007827 while performing nitrogen purging on a flask equipped with a stirrer, a reflux condenser, and a stirrer. Hydroxy group equivalent 134 g / eq. Softening point 93 ° C.) 134 parts, epichlorohydrin 450 parts, and methanol 54 parts were added, dissolved under stirring, and the temperature was raised to 70 ° C. Next, 42.5 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then the reaction was further carried out at 70 ° C. for 1 hour. After completion of the reaction, the mixture was washed with water to remove salts, and the obtained organic layer was subjected to reduced pressure using a rotary evaporator to distill off excess solvents such as epichlorohydrin. 500 parts of methyl isobutyl ketone was added to the residue to dissolve it, 17 parts of a 30 wt% sodium hydroxide aqueous solution was added under stirring, the reaction was carried out for 1 hour, and then the oil layer was washed with water until the washing water became neutral. From the obtained solution, 195 parts of the epoxy resin (EP1) of the present invention was obtained by distilling off methyl isobutyl ketone and the like under reduced pressure using a rotary evaporator. The epoxy equivalent of the obtained epoxy resin is 211 g / eq. The melt viscosity (ICI melt viscosity cone # 1) at the softening points of 71 ° C. and 150 ° C. was 0.34 Pa · s.
実施例1、比較例1
合成例1で得られたエポキシ樹脂(EP1)、比較用のエポキシ樹脂((NC−3000 日本化薬製))について、樹脂濃度が60重量%になるように溶剤としてメチルエチルケトンに溶解させエポキシ樹脂ワニスを得た。
得られた本発明のエポキシ樹脂含有ワニスは含有するエポキシ樹脂の分子量がほぼ同等にもかかわらず、5℃で2か月以上、0℃で1か月以上結晶の析出、もしくは樹脂の析出が見られなかった。一方、比較用のエポキシ樹脂含有ワニスは2週間目の段階で結晶の析出が確認できた。
Example 1, Comparative Example 1
The epoxy resin (EP1) obtained in Synthesis Example 1 and the comparative epoxy resin ((NC-3000 Nippon Kayaku)) were dissolved in methyl ethyl ketone as a solvent so that the resin concentration was 60% by weight, and the epoxy resin varnish was used. Got
Although the obtained epoxy resin-containing varnish of the present invention has almost the same molecular weight of the epoxy resin contained in the varnish, precipitation of crystals or resin is observed at 5 ° C. for 2 months or longer and at 0 ° C. for 1 month or longer. I couldn't. On the other hand, in the epoxy resin-containing varnish for comparison, crystal precipitation was confirmed at the stage of the second week.
実施例2
エポキシ樹脂組成物含有ワニスとして合成例1で得られた(EP1)を21部、硬化剤(日本化薬製 ビフェニルアラルキル樹脂 KAYAHARD GPH-65)20部、硬化促進剤0.2部、メチルエチルケトン40部を加え、均一に溶解したものを用意し、を調整した。得られたワニスを、ポリイミド(ユーピレックス)に100ミクロンのアプリケータを用いて塗布後、120℃10分、窒素ガスを流しながら熱風乾燥器で乾燥をおこない、本発明の樹脂シートを得た。得られた樹脂シートのDSCを測定すると82℃から発熱ピークがあり、硬化可能なシートであることを確認した。
Example 2
21 parts of (EP1) obtained in Synthesis Example 1 as an epoxy resin composition-containing varnish, 20 parts of a curing agent (Biphenyl aralkyl resin KAYAHARD GPH-65 manufactured by Nippon Kayaku), 0.2 parts of a curing accelerator, 40 parts of methyl ethyl ketone. Was added, and a uniformly dissolved product was prepared and adjusted. The obtained varnish was applied to polyimide (UPIREX) using a 100-micron applicator, and then dried at 120 ° C. for 10 minutes with a hot air dryer while flowing nitrogen gas to obtain a resin sheet of the present invention. When the DSC of the obtained resin sheet was measured, a heat generation peak was observed from 82 ° C., and it was confirmed that the sheet was curable.
実施例3
合成例1で得られたエポキシ樹脂(EP1)を、エポキシ当量1モル当量に対し、硬化剤を等当量で配合し、触媒をエポキシ樹脂100重量部に対し、1重量部となる割合で配合し、これをメチルエチルケトンで樹脂濃度80%に調整し、エポキシ樹脂組成物含有ワニスとして表1に示す組成にて調整した。それぞれ得られたワニスを、ポリイミド(ユーピレックス)に100ミクロンのアプリケータを用いて塗布後、120℃10分、窒素ガスを流しながら熱風乾燥器で乾燥をおこない、本発明の樹脂シートを得た。
Example 3
The epoxy resin (EP1) obtained in Synthesis Example 1 was blended with an equal equivalent of a curing agent to 1 molar equivalent of epoxy equivalent, and the catalyst was blended at a ratio of 1 part by weight to 100 parts by weight of the epoxy resin. , This was adjusted to a resin concentration of 80% with methyl ethyl ketone, and adjusted with the composition shown in Table 1 as an epoxy resin composition-containing varnish. The obtained varnishes were applied to polyimide (UPIREX) using a 100-micron applicator, and then dried at 120 ° C. for 10 minutes with a hot air dryer while flowing nitrogen gas to obtain the resin sheet of the present invention.
比較例2
実施例3において、エポキシ樹脂(EP1)を表1に示す他のエポキシ樹脂に変えた以外は、同様の配合・方法にてそれぞれ比較用樹脂シートを得た。
Comparative Example 2
In Example 3, a comparative resin sheet was obtained by the same formulation and method except that the epoxy resin (EP1) was changed to another epoxy resin shown in Table 1.
実施例4〜6
実施例3で得られた樹脂シートを10枚ポリイミドより剥がし、熱板プレス上に設置した、その後10kg/cm2、温度180℃で10分の加熱加圧形成を行い、積層板を作製した。作製した積層板について、下記の項目及び方法でその特性の測定を行った。測定結果を表1に示す。
・弾性率(DMA)
動的粘弾性測定器:TA−instRuments、DMA−2980
測定温度範囲:−30〜280℃
温速度:2℃/分
試験片サイズ:5mm×50mmに切り出した物を使用した
Tg:DMA測定に於けるTan−δのピーク点をTgとした。
・ガラス転移温度(Tg)
熱機械測定装置(TMA):熱機械測定装置TA−instRuments製 TMA Q400EM製
昇温速度:2℃/分
・誘電率、誘電正接
空洞共振器を使用し、関東電子応用化学製 1GHz用の治具を用いて測定(0.5mmx70mmに切り出したものを使用)
Examples 4-6
The resin sheet obtained in Example 3 was peeled off from 10 sheets of polyimide, placed on a hot plate press, and then heat-pressurized at 10 kg / cm2 and a temperature of 180 ° C. for 10 minutes to prepare a laminated plate. The characteristics of the produced laminated board were measured by the following items and methods. The measurement results are shown in Table 1.
・ Elastic modulus (DMA)
Dynamic viscoelasticity measuring instrument: TA-instRuments, DMA-2980
Measurement temperature range: -30 to 280 ° C
Temperature rate: 2 ° C./min Specimen size: A material cut out to 5 mm × 50 mm was used. Tg: The peak point of Tan-δ in the DMA measurement was defined as Tg.
・ Glass transition temperature (Tg)
Thermomechanical measuring device (TMA): Thermomechanical measuring device TA-instRuments TMA Q400EM Heating rate: 2 ° C / min / dielectric constant, using a dielectric loss tangent cavity resonator, a jig for 1 GHz manufactured by Kanto Electronics Applied Chemistry Measured using (use the one cut out to 0.5 mm x 70 mm)
比較例3〜9
実施例4〜6において、本発明の樹脂シートを比較例2にて得られた比較用樹脂シートに変えた以外は同様の方法にて比較用積層板を作製した。測定結果を表1に示す。
In Examples 4 to 6, comparative laminates were produced in the same manner except that the resin sheet of the present invention was changed to the comparative resin sheet obtained in Comparative Example 2. The measurement results are shown in Table 1.
また、表1で得られた硬化物性を、横軸に耐熱性(TMA Tg)と縦軸に誘電正接をプロットしたグラフを図1に示し、横軸に耐熱性(DMA Tg)と縦軸に誘電正接をプロットしたグラフを図2に示す。 Further, the cured physical properties obtained in Table 1 are shown in FIG. 1 by plotting heat resistance (TMA Tg) on the horizontal axis and dielectric loss tangent on the vertical axis, and heat resistance (DMA Tg) on the horizontal axis and vertical axis. A graph plotting the dielectric loss tangent is shown in FIG.
(図1)
(Fig. 1)
(図2)
(Fig. 2)
図1、図2より、他のエポキシ樹脂含有ワニスを用いた場合は、耐熱性の向上に比例し誘電特性が高く(悪く)なっていること及びその傾きがほぼ一定であることが分かる。これに対し本発明のエポキシ樹脂含有ワニスを用いた場合は、耐熱性向上に伴う誘電特性の悪化は緩やか傾きになっていることがわかった。
すなわち、本発明のエポキシ樹脂含有ワニスを用いる樹脂組成物は耐熱性に対して誘電正接が低い傾向があり、高度な耐熱性と誘電特性を両立することがわかる。
From FIGS. 1 and 2, it can be seen that when another epoxy resin-containing varnish is used, the dielectric property becomes higher (worse) in proportion to the improvement in heat resistance and the inclination thereof is almost constant. On the other hand, when the epoxy resin-containing varnish of the present invention was used, it was found that the deterioration of the dielectric property accompanying the improvement in heat resistance had a gentle slope.
That is, it can be seen that the resin composition using the epoxy resin-containing varnish of the present invention tends to have a low dielectric loss tangent with respect to heat resistance, and has both high heat resistance and dielectric properties.
Claims (6)
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