WO2012014715A1 - 硬化性樹脂組成物、その硬化物、フェノール系樹脂、エポキシ樹脂、及び半導体封止材料 - Google Patents
硬化性樹脂組成物、その硬化物、フェノール系樹脂、エポキシ樹脂、及び半導体封止材料 Download PDFInfo
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- WO2012014715A1 WO2012014715A1 PCT/JP2011/066342 JP2011066342W WO2012014715A1 WO 2012014715 A1 WO2012014715 A1 WO 2012014715A1 JP 2011066342 W JP2011066342 W JP 2011066342W WO 2012014715 A1 WO2012014715 A1 WO 2012014715A1
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- Prior art keywords
- resin
- group
- epoxy resin
- phenol
- phenolic
- Prior art date
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 208
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 206
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 158
- 239000011342 resin composition Substances 0.000 title claims abstract description 90
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 53
- 239000004065 semiconductor Substances 0.000 title claims abstract description 23
- 239000003566 sealing material Substances 0.000 title claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 110
- -1 anthranylmethyl groups Chemical group 0.000 claims abstract description 89
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims abstract description 39
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 31
- 125000001118 alkylidene group Chemical group 0.000 claims abstract description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 135
- 229920001187 thermosetting polymer Polymers 0.000 claims description 81
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 69
- 239000003795 chemical substances by application Substances 0.000 claims description 45
- 239000000155 melt Substances 0.000 claims description 24
- 239000011256 inorganic filler Substances 0.000 claims description 13
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 13
- 239000000463 material Substances 0.000 abstract description 19
- 238000002485 combustion reaction Methods 0.000 abstract description 2
- 238000013007 heat curing Methods 0.000 abstract 2
- 229920005989 resin Polymers 0.000 description 107
- 239000011347 resin Substances 0.000 description 107
- 238000000034 method Methods 0.000 description 65
- 229920003986 novolac Polymers 0.000 description 64
- 239000003063 flame retardant Substances 0.000 description 40
- 235000013824 polyphenols Nutrition 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 39
- 239000000047 product Substances 0.000 description 38
- 229910000679 solder Inorganic materials 0.000 description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 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 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- 238000005227 gel permeation chromatography Methods 0.000 description 25
- 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 24
- 229910001873 dinitrogen Inorganic materials 0.000 description 21
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 21
- 150000002989 phenols Chemical class 0.000 description 21
- 239000004593 Epoxy Substances 0.000 description 20
- 230000000694 effects Effects 0.000 description 20
- 238000005259 measurement Methods 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 17
- 239000003960 organic solvent Substances 0.000 description 17
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 16
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 15
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- 238000000691 measurement method Methods 0.000 description 15
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 14
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 14
- 125000001624 naphthyl group Chemical group 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 239000000945 filler Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 229910052736 halogen Inorganic materials 0.000 description 12
- 150000002367 halogens Chemical class 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- 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 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 11
- 125000003545 alkoxy group Chemical group 0.000 description 11
- 239000004305 biphenyl Substances 0.000 description 11
- 235000010290 biphenyl Nutrition 0.000 description 11
- 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 11
- 150000001875 compounds Chemical class 0.000 description 11
- 229930003836 cresol Natural products 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 10
- 239000012022 methylating agents Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- XMWGTKZEDLCVIG-UHFFFAOYSA-N 1-(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1 XMWGTKZEDLCVIG-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 125000003710 aryl alkyl group Chemical group 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- NQMUGNMMFTYOHK-UHFFFAOYSA-N 1-methoxynaphthalene Chemical group C1=CC=C2C(OC)=CC=CC2=C1 NQMUGNMMFTYOHK-UHFFFAOYSA-N 0.000 description 6
- GSKNLOOGBYYDHV-UHFFFAOYSA-N 2-methylphenol;naphthalen-1-ol Chemical compound CC1=CC=CC=C1O.C1=CC=C2C(O)=CC=CC2=C1 GSKNLOOGBYYDHV-UHFFFAOYSA-N 0.000 description 6
- PCVRSXXPGXRVEZ-UHFFFAOYSA-N 9-(chloromethyl)anthracene Chemical compound C1=CC=C2C(CCl)=C(C=CC=C3)C3=CC2=C1 PCVRSXXPGXRVEZ-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 6
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- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 6
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 6
- VSWALKINGSNVAR-UHFFFAOYSA-N naphthalen-1-ol;phenol Chemical compound OC1=CC=CC=C1.C1=CC=C2C(O)=CC=CC2=C1 VSWALKINGSNVAR-UHFFFAOYSA-N 0.000 description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- MPCHQYWZAVTABQ-UHFFFAOYSA-N 2-(chloromethyl)naphthalene Chemical compound C1=CC=CC2=CC(CCl)=CC=C21 MPCHQYWZAVTABQ-UHFFFAOYSA-N 0.000 description 5
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- 238000006735 epoxidation reaction Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- 150000003018 phosphorus compounds Chemical class 0.000 description 5
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- 238000001228 spectrum Methods 0.000 description 5
- PENXUAAQSIVXBE-UHFFFAOYSA-N 1-(dichloromethyl)naphthalene Chemical compound C1=CC=C2C(C(Cl)Cl)=CC=CC2=C1 PENXUAAQSIVXBE-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
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- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 4
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- 239000002841 Lewis acid Substances 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 238000010533 azeotropic distillation Methods 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 125000006267 biphenyl group Chemical group 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
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- 239000011889 copper foil Substances 0.000 description 4
- 150000007973 cyanuric acids Chemical class 0.000 description 4
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- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 230000001035 methylating effect Effects 0.000 description 4
- 150000004780 naphthols Chemical class 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- 238000001721 transfer moulding Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
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- 125000005843 halogen group Chemical group 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
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- 239000012433 hydrogen halide Substances 0.000 description 3
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- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 3
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- KGSFMPRFQVLGTJ-UHFFFAOYSA-N 1,1,2-triphenylethylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 KGSFMPRFQVLGTJ-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- WBODDOZXDKQEFS-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-phenylbenzene Chemical group CC1=C(C)C(C)=CC(C=2C=CC=CC=2)=C1C WBODDOZXDKQEFS-UHFFFAOYSA-N 0.000 description 2
- RRCDOVBQOMYGGJ-UHFFFAOYSA-N 1-(methoxymethyl)naphthalene Chemical compound C1=CC=C2C(COC)=CC=CC2=C1 RRCDOVBQOMYGGJ-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
- OGRAOKJKVGDSFR-UHFFFAOYSA-N 2,3,5-trimethylphenol Chemical compound CC1=CC(C)=C(C)C(O)=C1 OGRAOKJKVGDSFR-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—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 epoxy compounds used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/295—Organic, e.g. plastic containing a filler
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/296—Organo-silicon compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the cured product obtained according to the present invention is excellent in heat resistance, moisture resistance reliability, flame retardancy, dielectric properties, curability during curing reaction, and suitable for semiconductor encapsulant, printed circuit board, paint, casting application, etc.
- the present invention relates to a thermosetting resin composition that can be used, a cured product thereof, a phenol-based resin, an epoxy resin, and a semiconductor sealing material using the thermosetting resin composition.
- Thermosetting resin compositions containing an epoxy resin and its curing agent as essential components are excellent in various physical properties such as high heat resistance, moisture resistance, and low viscosity.
- Electronic components such as semiconductor encapsulants and printed circuit boards, electronic Widely used in parts field, conductive adhesives such as conductive paste, other adhesives, matrix for composite materials, paints, photoresist materials, developer materials, etc.
- Examples of the phenol resin and epoxy resin for encapsulating electronic components that meet the required characteristics include, for example, a benzylated phenol resin obtained by reacting a phenol resin with a benzylating agent such as benzyl chloride, and the benzylated phenol resin as an epihalohydrin.
- a benzylated phenol resin obtained by reacting a phenol resin with a benzylating agent such as benzyl chloride
- the benzylated phenol resin as an epihalohydrin.
- the reacted epoxy resin for example, refer patent document 1
- the phenol resin obtained by reacting a phenolic compound and dichloromethylnaphthalene and the phenol resin obtained by reacting the said dichloromethylnaphthalene.
- the thing using the epoxy resin made to react with epihalohydrin (for example, refer patent document 2, 3) is disclosed.
- the epoxy resin and the phenol resin according to Patent Document 1 have a low moisture absorption rate and have improved moisture resistance and solder resistance to some extent. It is inferior in flame retardancy, and cannot be used for halogen-free material design, and the epoxy resin and phenol resin (curing agent) described in Patent Documents 2 and 3 have a certain degree of flame retardancy improving effect. Since the viscosity of the product is high, the fluidity at the time of molding is inferior, and it cannot be used at all for electronic parts that have been fine pitched in recent years.
- the problem to be solved by the present invention is that the composition is excellent in fluidity of the composition, and also has a moisture resistance reliability suitable for recent electronic component-related materials and a thermosetting that realizes halogen-free and high flame resistance for environmental harmony.
- the present invention provides a conductive resin composition, a cured product thereof, a semiconductor sealing material using the composition, and a phenolic resin and an epoxy resin that provide these performances.
- the present inventors basically have a structure in which a plurality of phenolic hydroxyl group-containing aromatic skeletons (ph) are bonded via an alkylidene group or an aromatic hydrocarbon structure-containing methylene group.
- ph phenolic hydroxyl group-containing aromatic skeletons
- the present invention is a thermosetting resin composition
- a thermosetting resin composition comprising an epoxy resin (A) and a phenolic resin (B) as essential components, wherein the phenolic resin (B) comprises a plurality of phenolic hydroxyl group-containing aromatics.
- the skeleton (ph) has a phenol resin structure having a structure in which the skeleton (ph) is bonded through an alkylidene group or an aromatic hydrocarbon structure-containing methylene group as a basic skeleton, and the aromatic nucleus of the phenol resin structure has a naphthylmethyl group or
- the present invention relates to a thermosetting resin composition (hereinafter, abbreviated as “thermosetting resin composition (I)”), which is a phenol-based resin having an antonylmethyl group.
- the present invention further contains an inorganic filler in a proportion of 70 to 95% by mass in the composition.
- the present invention relates to a semiconductor sealing material.
- the present invention further relates to a cured product obtained by curing reaction of the thermosetting resin composition (I).
- the present invention further relates to an epoxy resin cured product obtained by curing reaction of the thermosetting resin composition (I).
- the present invention further has a phenolic resin structure having a structure in which a plurality of phenolic hydroxyl group-containing aromatic skeletons (ph) are bonded via an alkylidene group or an aromatic hydrocarbon structure-containing methylene group as a basic skeleton,
- the present invention relates to a phenol-based resin characterized by having a naphthylmethyl group or an antonylmethyl group in the aromatic nucleus of the phenol resin structure.
- the present invention further relates to a thermosetting resin composition
- a thermosetting resin composition comprising an epoxy resin (A ′) and a curing agent (B ′) as essential components, wherein the epoxy resin (A ′) contains a plurality of glycidyloxy group-containing fragrances.
- the epoxy resin (A ′) contains a plurality of glycidyloxy group-containing fragrances.
- the present invention relates to a thermosetting resin composition having an antonylmethyl group (hereinafter, this thermosetting resin composition is abbreviated as “thermosetting resin composition (II)”).
- an inorganic filler is further contained in the composition in an amount of 70 to 95% by mass. It is related with the semiconductor sealing material characterized by containing by a ratio.
- the present invention further relates to a cured product obtained by curing reaction of the thermosetting resin composition (II).
- the present invention further has an epoxy resin structure having, as a basic skeleton, a structure in which a plurality of glycidyloxy group-containing aromatic skeletons (ep) are bonded via an alkylidene group or an aromatic hydrocarbon structure-containing methylene group, Further, the present invention relates to an epoxy resin characterized by having a naphthylmethyl group or an antonylmethyl group in the aromatic nucleus of the epoxy resin structure.
- thermosetting resin composition that is excellent in fluidity of the composition, is moisture-resistant and suitable for recent electronic component-related materials, and is halogen-free and highly flame retardant for harmony with the environment. Hardened
- FIG. 1 is a GPC chart of the phenol resin (A-1) obtained in Example 1.
- FIG. 2 is a C 13 NMR chart of the phenol resin (A-1) obtained in Example 1.
- FIG. 3 is an MS spectrum of the phenol resin (A-1) obtained in Example 1.
- 4 is a GPC chart of the phenol resin (A-2) obtained in Example 2.
- FIG. 5 is a GPC chart of the phenol resin (A-3) obtained in Example 3.
- FIG. 6 is a GPC chart of the phenol resin (A-4) obtained in Example 4.
- FIG. 7 is a GPC chart of the phenol resin (A-5) obtained in Example 5.
- FIG. 8 is a GPC chart of the epoxy resin (E-1) obtained in Example 6.
- FIG. 1 is a GPC chart of the phenol resin (A-1) obtained in Example 1.
- FIG. 2 is a C 13 NMR chart of the phenol resin (A-1) obtained in Example 1.
- FIG. 3 is an MS spectrum of the phenol resin (A-
- FIG. 9 is a C 13 NMR chart of the epoxy resin (E-1) obtained in Example 6.
- FIG. 10 is the MS spectrum of the epoxy resin (E-1) obtained in Example 6.
- FIG. 11 is a GPC chart of the epoxy resin (E-2) obtained in Example 7.
- FIG. 12 is a GPC chart of the epoxy resin (E-3) obtained in Example 8.
- FIG. 13 is a GPC chart of the epoxy resin (E-4) obtained in Example 9.
- FIG. 14 is a GPC chart of the epoxy resin (E-5) obtained in Example 10.
- thermosetting resin composition (I) of the present invention is first a thermosetting resin composition containing an epoxy resin (A) and a phenolic resin (B) as essential components, and the phenolic resin (B).
- a thermosetting resin composition containing an epoxy resin (A) and a phenolic resin (B) as essential components, and the phenolic resin (B).
- the aromatic nucleus of the resin structure has a naphthylmethyl group or an antonylmethyl group.
- the phenolic resin (B) has a phenolic resin structure whose basic skeleton is a structure in which a phenolic hydroxyl group-containing aromatic skeleton (ph) is bonded via an alkylidene group or an aromatic hydrocarbon structure-containing methylene group.
- the aromatic nucleus of the phenol resin structure has a naphthylmethyl group or an antonylmethyl group, the aromatic nucleus of the resin itself can be enhanced and the fluidity of the resin itself can be maintained, and the semiconductor sealing material application
- such a phenolic resin (B) is the novel phenolic resin of the present invention.
- the content of naphthylmethyl group or anthonylmethyl group in the aromatic nucleus of the phenol resin structure is naphthylmethyl group or antonylmethyl when the total number of phenolic hydroxyl group-containing aromatic skeletons (ph) is 100.
- a ratio in which the total number of groups is 10 to 200 is preferable from the viewpoint of further improving the balance between moisture resistance reliability and flame retardancy.
- the range of 15 to 120 is preferable because it has a high effect of improving curability, moldability, moisture resistance reliability, and flame retardancy, and the range of 20 to 100 is more compatible with fillers such as silica. It is preferable because it is excellent in impregnation into a glass substrate and the effect of the present invention is remarkable, and the range of 20 to 80 is particularly preferable.
- Patent Documents 2 and 3 described above describe that dichloromethylnaphthalene used as a condensing agent contains naphthylmethyl chloride as an impurity, and the content of the impurity is 10% by mass. It is described that heat resistance is reduced unless the following is set. However, in the present invention, when a naphthylmethyl group or an antonylmethyl group is positively introduced into the resin structure and the total proportion of the phenolic hydroxyl group-containing aromatic skeleton (ph) is 100, 10 By setting the ratio to ⁇ 200, no decrease in heat resistance is recognized, and the moisture resistance reliability typified by moisture resistance and solder resistance is remarkably improved.
- thermosetting resin composition in the present invention has a very low viscosity despite containing a bulky condensed polycyclic skeleton, and is improved in impregnation into an inorganic filler such as silica or a glass substrate. It is a special point that high moisture resistance reliability is obtained.
- the naphthylmethyl group or antonyl content when the content of the naphthylmethyl group or anthonylmethyl group in the aromatic nucleus of the phenol resin structure that is, the total number of phenolic hydroxyl group-containing aromatic skeletons (ph) is 100 is used.
- the total number of methyl groups is a value equal to the total number of naphthyl methylating agents or antonyl methylating agents (a2) with respect to the number of aromatic nuclei in the raw material phenol resin when producing a phenol-based resin.
- the phenolic resin (B) in the thermosetting resin composition (I) has a phenolic hydroxyl group-containing aromatic skeleton having a naphthylmethyl group or an antonylmethyl group in the aromatic nucleus (hereinafter referred to as “phenol”).
- phenol a phenolic hydroxyl group-containing aromatic skeleton having a naphthylmethyl group or an antonylmethyl group in the aromatic nucleus
- Ph1 hydroxyl group-containing aromatic skeleton
- phenolic hydroxyl group-containing aromatic a phenolic hydroxyl group-containing aromatic skeleton having no naphthylmethyl group or antonylmethyl group in the aromatic nucleus
- Ph2 Group skeleton in the resin structure, and these structural sites are alkylidene groups or aromatic hydrocarbon structure-containing methylene groups (hereinafter referred to as “methylene group nodules (X)”). ”)).
- the aromatic content in the molecular structure is increased, and excellent heat resistance and flame retardancy can be imparted to the cured product.
- the phenolic hydroxyl group-containing aromatic hydrocarbon group (Ph1) containing the group represented by the general formula (1) can have various structures, and specifically, the following P1
- An aromatic hydrocarbon group formed from phenol, naphthol represented by the structural formula of P18, and a compound having an alkyl group as a substituent on the aromatic nucleus is excellent in heat resistance and moisture resistance and solder resistance. It is preferable from the point.
- examples of the phenolic hydroxyl group-containing aromatic skeleton (Ph1) include those represented by the following structural formulas P1 to P13.
- those having two or more bonding positions with other structural sites on the naphthalene skeleton may be on the same nucleus or on different nuclei. May be.
- those having a phenol skeleton represented by the structural formula Ph1-1 are preferable from the viewpoint of low viscosity and excellent curability, heat resistance, and moisture resistance and solder resistance.
- those having a methyl group in the phenol skeleton as represented by the structural formula Ph1-4 are preferable because the effects of improving heat resistance and moisture and solder resistance are remarkable.
- the phenolic hydroxyl group-containing aromatic skeleton (Ph1) is located at the molecular end, those represented by the following structural formulas Ph1-14 to Ph1-22 can be mentioned.
- those having two or more bonding positions with other structural sites on the naphthalene skeleton may be on the same nucleus or on different nuclei. May be.
- those having a phenol skeleton represented by the structural formula Ph1-14 are preferable from the viewpoint of low viscosity and excellent curability, heat resistance, and moisture resistance and solder resistance.
- those having a methyl group in the phenol skeleton as represented by the structural formulas Ph1-15, Ph1-20, and Ph1-22 are preferable because the effects of improving heat resistance and moisture and solder resistance are remarkable.
- the phenolic hydroxyl group-containing aromatic skeleton (Ph2) having no naphthylmethyl group or antonylmethyl group in the aromatic nucleus is specifically represented by the following structural formulas Ph2-1 to Ph2-17
- An aromatic hydrocarbon group formed from phenol, naphthol, and compounds having an alkyl group as a substituent on these aromatic nuclei is preferable from the viewpoint of excellent heat resistance and moisture and solder resistance.
- those having two or more bonding positions with other structural sites on the naphthalene skeleton may be on the same nucleus or on different nuclei. May be.
- Ph2-1 a structure represented by Ph2-1 is particularly preferable in terms of excellent curability
- Ph2-4 is preferable in terms of moisture resistance and solder resistance.
- each structure is a monovalent aromatic hydrocarbon group when the structure is located at the molecular end.
- those having two or more bonding positions with other structural sites on the naphthalene skeleton may be on the same nucleus or on different nuclei. There may be.
- the methylene group nodule group (X) contained in the resin structure of the phenol resin (B) includes, for example, an methylene group, an ethylidene group, a 1-propylidene group, a 2,2-propylidene group, dimethylene as an alkylidene group.
- an methylene group an ethylidene group, a 1-propylidene group, a 2,2-propylidene group, dimethylene as an alkylidene group.
- Examples of the methylene group containing an aromatic hydrocarbon structure include those represented by the following structural formulas X1 to X8.
- a methylene group and a structure represented by the structural formulas X1, X2, and X5 are particularly preferable from the viewpoint of excellent flame retardancy in the cured product of the phenol resin (B).
- the phenolic hydroxyl group-containing aromatic skeleton (Ph1) and the phenolic hydroxyl group-containing aromatic skeleton (Ph2) have a phenolic hydroxyl group-containing fragrance via a methylene group nodule group (X). It has a resin structure bonded to the aromatic skeleton (Ph1) or the phenolic hydroxyl group-containing aromatic skeleton (Ph2), and these bond forms can take any combination.
- the molecular structure of the phenol-based resin (B) composed of each of the constituent parts is such that the phenolic hydroxyl group-containing aromatic skeleton (Ph1) is “Ph1” and the phenolic hydroxyl group-containing aromatic skeleton (Ph2) is “Ph2”.
- the methylene group nodule group (X) is represented by “X”
- the aromatic nucleus constituting the phenolic hydroxyl group-containing aromatic skeleton (Ph1) or the phenolic hydroxyl group-containing aromatic skeleton (Ph2), which is the basic skeleton of the phenolic resin (B) of the present invention is a phenyl group or an alkyl-substituted phenyl group. It is preferable that it is composed of a material having a large effect of improving moisture resistance and solder resistance.
- the naphthylmethyl group or anthonylmethyl group present in the phenolic hydroxyl group-containing aromatic skeleton (Ph1) is represented by the following structural formula (1).
- the structural formula (1) or the structural formula (2) can take an average value of 0 to 5, but is not multiplexed in the present invention because it exhibits excellent flame retardancy, n is preferably 0. Of these, a naphthylmethyl group is particularly preferred from the viewpoint of fluidity and flame retardancy.
- an alkoxy group-containing aromatic hydrocarbon group may be bonded to the aromatic nucleus via the methylene group nodule group (X).
- Examples of the hydrocarbon group include those represented by the following structural formulas A1 to A13.
- the alkoxy group-containing aromatic hydrocarbon group is represented by the structural formula A8.
- Those having a structure are excellent in the heat resistance and flame retardancy of the cured epoxy resin and can significantly reduce the dielectric loss tangent.
- the phenolic resin (B) has a melt viscosity at 150 ° C. measured by an ICI viscometer in the range of 0.1 to 50 dPa ⁇ s, particularly 0.1 to 20 dPa ⁇ s at 150 ° C. Is preferable in terms of excellent fluidity and moisture and solder resistance during molding. Furthermore, the phenolic resin (B) has a hydroxyl equivalent weight of 120 to 400 g / eq. The thing of this range is preferable from the point from which the heat resistance and flame retardance of hardened
- the hydroxyl group equivalent is particularly preferably 150 to 250 g / eq. Within this range, the balance between the moisture resistance solder resistance and flame resistance of the cured product and the curability of the composition is particularly excellent.
- the abundance ratio of the phenolic hydroxyl group-containing aromatic hydrocarbon group (Ph1) is such that the aromatic nucleus has a naphthylmethyl group or an antonylmethyl group, a phenolic hydroxyl group-containing aromatic hydrocarbon group (Ph1), and the aromatic group.
- the total number of phenolic hydroxyl group-containing aromatic hydrocarbon groups (Ph2) having no naphthylmethyl group or antonylmethyl group in the nucleus is 100
- the total number of the phenolic hydroxyl group-containing aromatic hydrocarbon groups (Ph1) is A ratio of 10 to 200 is preferable from the viewpoint of further improving the flame retardancy and moisture resistance and solder resistance of the cured product.
- a ratio of 15 to 120 is preferable because it has a high effect of improving curability, moldability, moisture resistance reliability, and flame retardancy, and a ratio in the range of 20 to 100 is preferable.
- an inorganic filler such as silica or a glass substrate
- the coefficient of thermal expansion when cured is reduced, adhesion is increased, and moisture resistance and solder resistance are dramatically improved.
- the abundance ratio is 20 to 80, moisture resistance and solder resistance are further improved.
- the phenolic resin (B) can be industrially produced by the production method described in detail below.
- the method for producing the phenolic resin (B) is a method in which a novolak resin is reacted with a naphthyl methylating agent or an antonyl methylating agent (a2) (method 1), or a phenol compound (Ph1 ′) is converted to carbonyl.
- the novolak resin used in Method 1 has a resin structure in which the above-described phenolic hydroxyl group-containing aromatic skeleton (Ph2) is bonded to the phenolic hydroxyl group-containing aromatic skeleton (Ph2) via a methylene group nodule group (X). And those having the alkoxy group-containing aromatic hydrocarbon group through the methylene nodule group (X).
- phenol novolac resins and cresols are preferable because phenolic resins having good reactivity with naphthylmethylating agents or anthonymethylating agents (a2) and excellent in moisture resistance reliability and flame retardancy can be obtained.
- Novolak resins and naphthol novolak resins are preferred.
- the naphthylmethylating agent or antonylmethylating agent (a2) used in Method 1 is 1-naphthylmethyl chloride, 2-naphthylmethyl chloride, (9-anthrylmethyl) chloride, 1-methoxymethylnaphthalene, 1 -Naphthylmethanol, 2-methoxymethylnaphthalene, 2-naphthylmethanol 9- (methoxymethyl) anthracene, 9-anthracenemethanol.
- 1-methyl chloride, 2-methyl chloride, and (9-anthrylmethyl) chloride are preferable in that they can be reacted without using a reaction catalyst and a purification step after the reaction is unnecessary.
- examples of the phenolic compound (Ph1 ′) that can be used in Method 2 include unsubstituted phenolic compounds such as phenol, resorcinol, hydroquinone, cresol, phenylphenol, ethylphenol, n-propylphenol, iso-propylphenol, monosubstituted phenolic compounds such as t-butylphenol, disubstituted phenolic compounds such as xylenol, methylpropylphenol, methylbutylphenol, methylhexylphenol, dipropylphenol, dibutylphenol, mesitol, 2,3,5-trimethylphenol, 2 , 3,6-trimethylphenol and the like, and phenolic compounds such as 1-naphthol, 2-naphthol and methylnaphthol.
- unsubstituted phenolic compounds such as phenol, resorcinol, hydroquinone, cresol, phenylphenol, e
- 1-naphthol, 2-naphthol, cresol, and phenol are particularly preferable from the viewpoint that the cured product has flame retardancy, moisture and solder resistance, and the composition has excellent fluidity.
- the carbonyl compound (X ′) is specifically, and then the carbonyl group-containing compound (a3) is specifically an aliphatic aldehyde such as formaldehyde, acetaldehyde or propionaldehyde, or a dialdehyde such as glyoxal. , Benzaldehyde, 4-methylbenzaldehyde, 3,4-dimethylbenzaldehyde, 4-biphenylaldehyde, aromatic aldehydes such as naphthylaldehyde, and ketone compounds such as benzophenone, fluorenone, and indanone.
- aliphatic aldehyde such as formaldehyde, acetaldehyde or propionaldehyde, or a dialdehyde such as glyoxal.
- Benzaldehyde 4-methylbenzaldehyde, 3,4-dimethylbenzaldehyde, 4-biphenylaldeh
- formaldehyde, benzaldehyde, 4-biphenylaldehyde, and naphthylaldehyde are preferable because the cured product obtained has excellent flame retardancy.
- the reaction between the phenol compound (Ph1 ′) and the carbonyl compound (X ′) is performed by using 0.01 to 0.9 mol of the carbonyl compound (X ′) as a catalyst with respect to 1 mol of the phenol compound (Ph1 ′). Obtained by heating in the presence.
- the polymerization catalyst used here is not particularly limited, but is preferably an acid catalyst, for example, an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid, or an organic such as methanesulfonic acid, p-toluenesulfonic acid or oxalic acid. Examples thereof include Lewis acids such as acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride.
- the amount used is preferably in the range of 0.1 to 5% by mass relative to the total mass of the charged raw materials.
- an organic solvent can be used as necessary.
- the organic solvent that can be used include, but are not limited to, methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone.
- the amount of the organic solvent used is usually 10 to 500% by mass, preferably 30 to 250% by mass, based on the total mass of the charged raw materials.
- the reaction temperature is usually 40 to 250 ° C., more preferably 100 to 200 ° C.
- the reaction time is usually 1 to 20 hours.
- an antioxidant or a reducing agent may be added to suppress it.
- the antioxidant is not particularly limited, and examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing trivalent phosphorus atoms. be able to.
- said reducing agent For example, hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, these salts, zinc, etc. are mentioned.
- the reaction mixture is neutralized or washed with water until the pH value of the reaction mixture becomes 3 to 7, preferably 4 to 7.
- a neutralization process and a water washing process in accordance with a conventional method.
- basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, triethylenetetramine, and aniline can be used as the neutralizing agent.
- a buffer such as phosphoric acid may be added in advance, or the pH may be adjusted to 3 to 7 with oxalic acid after the base side is once used.
- the naphthylmethylating agent or anthonylmethylating agent (a2) used in the method 2 is the same as in the case of the method 1, with 1-naphthylmethyl chloride, 2-naphthylmethyl chloride, (9-anthrylmethyl).
- Chloride, 1-methoxymethylnaphthalene, 1-naphthylmethanol, 2-methoxymethylnaphthalene, 2-naphthylmethanol 9- (methoxymethyl) anthracene, 9-anthracenemethanol are preferable in that they can be reacted without using a reaction catalyst and a purification step after the reaction is unnecessary.
- Reaction of the novolak resin and the naphthyl methylating agent or anthonyl methylating agent (a2) in Method 1 or the novolak resin and the naphthyl methylating agent or the anthonyl methylating agent (a2) in Method 2 The reaction can be carried out under temperature conditions of 50 ° C. to 200 ° C., preferably 70 ° C. to 180 ° C.
- the reaction catalyst is preferably an acid catalyst.
- inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid
- organic acids such as methanesulfonic acid, p-toluenesulfonic acid and oxalic acid
- boron trifluoride anhydrous aluminum chloride
- Lewis acids such as zinc chloride.
- the amount used is preferably in the range of 0.1 to 5% by mass relative to the total mass of the charged raw materials.
- the reaction time is sufficient if the naphthyl methylating agent or anthonyl methylating agent (a2) as a raw material disappears, and is generally about 1 to 50 hours.
- 1-naphthylmethyl chloride, 2-naphthylmethyl chloride, (9-anthrylmethyl) chloride is used, the generation of hydrogen chloride gas is substantially eliminated, the chloride compound as the raw material disappears, and the raw material (a2 ) Until the chlorine content is no longer detected, and depending on the reaction temperature, in the actual reaction, the reaction temperature is controlled to such an extent that hydrogen chloride gas is generated quickly and can be stably discharged out of the system.
- the temperature that can be produced is desirable, and at such a reaction temperature, the reaction time is about 1 to 25 hours.
- the melt viscosity here may be any measuring method such as ICI cone plate viscometer, B-type viscometer, E-type viscometer.
- ICI cone plate viscometer B-type viscometer
- E-type viscometer E-type viscometer
- an organic solvent can be used as necessary.
- the organic solvent that can be used include, but are not limited to, methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone.
- 1-naphthylmethyl chloride, 2-naphthylmethyl chloride, or (9-anthrylmethyl) chloride it is preferable not to use an alcoholic organic solvent because side reactions occur.
- the amount of the organic solvent used is usually 10 to 500% by mass, preferably 30 to 250% by mass, based on the total mass of the charged raw materials.
- an antioxidant or a reducing agent may be added to suppress it.
- the antioxidant is not particularly limited, and examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing trivalent phosphorus atoms. be able to.
- said reducing agent For example, hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, these salts, zinc, etc. are mentioned.
- the reaction mixture is neutralized or washed with water until the pH value of the reaction mixture becomes 3 to 7, preferably 4 to 7.
- a neutralization process and a water washing process in accordance with a conventional method.
- basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, triethylenetetramine, and aniline can be used as the neutralizing agent.
- a buffer such as phosphoric acid may be added in advance, or the pH may be adjusted to 3 to 7 with oxalic acid after the base side is once used.
- the phenolic resin (B) may be used alone, but other epoxy resin curing agents (b) may be used as long as the effects of the present invention are not impaired. May be used. Specifically, the phenolic resin (B) is used in combination with the other epoxy resin curing agent (b) in a range of 30 mass% or more, preferably 40 mass% or more with respect to the total mass of the curing agent. be able to.
- Examples of other epoxy resin curing agents (b) that can be used in combination with the phenolic resin (B) of the present invention include amine compounds, amide compounds, acid anhydride compounds, and phenolic resins (B). Examples thereof include phenolic compounds and aminotriazine-modified phenol resins (polyhydric phenol compounds in which phenol nuclei are linked with melamine, benzoguanamine, or the like).
- phenolic compounds other than phenolic resin (B) include phenol novolak resin, cresol novolak resin, phenol novolak resin, cresol novolak resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak.
- a novolak resin such as a resin; a phenol resin having a resin structure in which a methoxynaphthalene skeleton is bonded to an aromatic nucleus of the novolak resin through a methylene group; a resin structure in which a methoxyphenyl skeleton is bonded to an aromatic nucleus of the novolak resin through a methylene group Methoxy aromatic structure-containing phenolic resin such as
- n is a repeating unit and is an integer of 0 or more.
- Phenol aralkyl resin represented by The following structural formula
- Naphthol aralkyl resin represented by the following structural formula
- n is a repeating unit and is an integer of 0 or more.
- Biphenyl-modified phenolic resin represented by The following structural formula
- n is a repeating unit and is an integer of 0 or more.
- An aralkyl-type phenol resin such as a biphenyl-modified naphthol resin represented by: a phenol resin having a resin structure in which a methoxynaphthalene skeleton is bonded to an aromatic nucleus of the aralkyl-type phenol resin via a methylene group, and an aromatic nucleus of the aralkyl-type phenol resin
- phenol novolac resins cresol novolak resins, novolak resins having aromatic methylene as a nodule
- phenol Aralkyl resin naphthol aralkyl resin
- naphthol novolak resin naphthol-phenol co-condensed novolak resin
- naphthol-cresol co-condensed novolak resin biphenyl-modified phenol resin, biphenyl-modified naphthol resin, methoxy aromatic structure-containing phenol resin, aminotriazine-modified phenol resin Is preferable because of its excellent flame retardancy.
- epoxy resin (A) used in the thermosetting resin composition (I) of the present invention For example, Diglycidyloxynaphthalene, 1,1-bis (2,7-diglycidyloxynaphthyl) methane 1- (2,7-diglycidyloxynaphthyl) -1- (2′-glycidyloxynaphthyl) methane naphthalene type epoxy Resins; bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin; phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolak type epoxy resins, naphthol novolak type epoxy resins, biphenyl novolac type epoxy resins , Novolac epoxy resins such as naphthol-phenol co-condensed novolak epoxy resin, naphthol-cresol co-condensed novolac epoxy resin, and the like; An epoxy resin having a resin structure in which a
- n is a repeating unit and is an integer of 0 or more.
- n is a repeating unit and is an integer of 0 or more.
- n is a repeating unit and is an integer of 0 or more.
- a novolak-type epoxy resin having a nodule group of aromatic methylene represented by: Epoxy resin having a resin structure in which a methoxynaphthalene skeleton is bonded to the aromatic nucleus of the aralkyl epoxy resin via a methylene group, and an epoxy having a resin structure in which the methoxyphenyl skeleton is bonded to the aromatic nucleus of the aralkyl epoxy resin via a methylene group Resin; Others include tetramethylbiphenyl type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin and the like.
- these epoxy resins may be used independently and may mix 2 or more types.
- naphthalene type epoxy resin, naphthol novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, alkoxy group containing novolac type epoxy resin, or alkoxy group containing aralkyl type epoxy resin are flame retardant and dielectric. This is particularly preferable from the viewpoint of excellent characteristics.
- the epoxy resin (A) has a favorable cured product characteristic.
- the amount of active groups in the curing agent containing the phenolic resin (B) is preferably 0.7 to 1.5 equivalents with respect to a total of 1 equivalent of epoxy groups.
- a curing accelerator can be appropriately used in combination with the thermosetting resin composition (I) of the present invention.
- Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts.
- phosphorus compounds tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts.
- triphenylphosphine is used for phosphorus compounds and 1,8-diazabicyclo is used for tertiary amines.
- DBU -[5.4.0] -undecene
- thermosetting resin composition (II) of the present invention is a thermosetting resin composition containing an epoxy resin (A ′) and a curing agent (B ′) as essential components, the epoxy resin (A ') Has an epoxy resin structure in which the epoxy resin has, as a basic skeleton, a structure in which a plurality of glycidyloxy group-containing aromatic skeletons (ep) are bonded via an alkylidene group or an aromatic hydrocarbon structure-containing methylene group.
- the aromatic nucleus of the epoxy resin structure has a naphthylmethyl group or an antonylmethyl group.
- the epoxy resin (A ′) in the thermosetting resin composition (II) is obtained by epoxidizing the phenolic resin (B) constituting the thermosetting resin composition (I) with epihalohydrin. And having a basic skeleton in common with the phenolic resin (B). Therefore, as in the case of the phenolic resin (B), the aromatic nucleus of the resin itself can be enhanced and the fluidity of the resin itself can be maintained, and the affinity with inorganic fillers such as silica in the application of semiconductor sealing materials. In addition to improving the properties, the coefficient of thermal expansion when cured is lowered, and the moisture resistance reliability and flame retardancy are remarkably improved.
- such an epoxy resin (A ′) is the novel epoxy resin of the present invention.
- the abundance ratio of the naphthylmethyl group or anthonylmethyl group is such that the total number of naphthylmethyl groups or anthonylmethyl groups is 10 to 200, particularly when the total number of glycidyloxy group-containing aromatic skeletons (ep) is 100.
- the ratio is preferably from the viewpoint of further improving the balance between moisture resistance reliability and flame retardancy, and the ratio of 15 to 120 is effective in improving curability, moldability, moisture resistance reliability, and flame retardancy. It is particularly preferable because it is high.
- it is preferably in the range of 20 to 100, since it is excellent in the affinity of fillers such as silica and impregnation into glass substrates, and the effects of the present invention are remarkable, and in particular in the range of 20 to 80. Is preferred.
- the total number of naphthylmethyl groups or anthonymethyl groups means that when producing a phenol resin that is a precursor of an epoxy resin. It is a value equal to the total number of naphthyl methylating agents or antonyl methylating agents (a2) with respect to the number of aromatic nuclei in the raw material phenol resin.
- the epoxy resin (A ′) in the thermosetting resin composition (II) has a glycidyloxy group-containing aromatic skeleton having a naphthylmethyl group or an antonylmethyl group in the aromatic nucleus (hereinafter, this structural site is referred to as “glycidyl”).
- Group skeleton (Ep2) ”) in the resin structure, and these structural sites have a resin structure that is knotted by the methylene-based knot group (X).
- examples of the glycidyloxy group-containing aromatic skeleton (Ep1) include those represented by the following structural formulas Ep1-1 to Ep1-13.
- “Gr” represents a glycidyloxy group, and among the structures listed above, those having two or more bonding positions with other structural sites on the naphthalene skeleton have their bonding positions on the same nucleus. They may be on different nuclei.
- the structure represented by the structural formula Ep1-1 is preferable in terms of low viscosity and excellent curability, heat resistance, and moisture resistance and solder resistance.
- those having a methyl group in the phenol skeleton as represented by the structural formula Ep1-4 are preferable because the effects of improving heat resistance and moisture resistance and solder resistance are remarkable.
- “Gr” represents a glycidyloxy group, and among the structures listed above, those having two or more bonding positions with other structural sites on the naphthalene skeleton have their bonding positions on the same nucleus. They may be on different nuclei.
- those having the structure of the above structural formula Ep1-14 are preferable from the viewpoint of low viscosity and excellent curability, heat resistance, and moisture resistance and solder resistance.
- those having a methyl group in the phenol skeleton as represented by the structural formulas Ep1-15, Ep1-20, and Ep1-22 are preferable because the effects of improving heat resistance and moisture and solder resistance are remarkable.
- the glycidyloxy group-containing aromatic skeleton (Ep2) having no naphthylmethyl group or antonylmethyl group in the aromatic nucleus is specifically represented by the following structural formulas Ep2-1 to Ep2-17
- An aromatic hydrocarbon group formed from phenol, naphthol, and compounds having an alkyl group as a substituent on these aromatic nuclei is preferable from the viewpoint of excellent heat resistance and moisture and solder resistance.
- “Gr” represents a glycidyloxy group, and among the structures listed above, those having two or more bonding positions with other structural sites on the naphthalene skeleton have their bonding positions on the same nucleus. They may be on different nuclei.
- Ep2-1 is preferable from the viewpoint of excellent curability
- Ep2-4 is preferable from the viewpoint of moisture resistance and solder resistance.
- the methylene nodule group (X) contained in the resin structure of the epoxy resin (A ′) is represented by X1 to X5 as in the phenolic resin in the thermosetting resin composition (I). Examples include structures.
- the epoxy resin (A ′) used in the present invention has a glycidyloxy group-containing aromatic skeleton (Ep1) and a glycidyloxy group-containing aromatic skeleton (Ep2) via a methylene nodule group (X). It has a resin structure bonded to the group skeleton (Ep1) or the glycidyloxy group-containing aromatic skeleton (Ep2), and these bond forms can take any combination.
- the molecular structure of the epoxy resin composed of such components is “Ep1” for the glycidyloxy group-containing aromatic skeleton (Ep1), “Ep2” for the glycidyloxy group-containing aromatic skeleton (Ep2), and a methylene-based nodule.
- group (X) is represented by “X”
- the aromatic nucleus constituting the glycidyloxy group-containing aromatic skeleton (Ep1) or glycidyloxy group-containing aromatic skeleton (Ep2), which is the basic skeleton of the resin structure of the epoxy resin (A ′) of the present invention is a phenyl group or an alkyl group. Those composed of substituted phenyl groups are preferred because they have a large effect of improving moisture resistance and solder resistance.
- the naphthylmethyl group or antonylmethyl group present in the glycidyloxy group-containing aromatic skeleton has the following structural formula (1):
- the structural formula (1) or the structural formula (2) can take an average value of 0 to 5, but is not multiplexed in the present invention because it exhibits excellent flame retardancy, n is preferably 0.
- the structural site bonded through the methylene group or the like (X) may contain an alkoxy group-containing aromatic hydrocarbon group, and examples thereof include those represented by the following structural formulas A1 to A13. .
- the alkoxy group-containing aromatic hydrocarbon group is represented by the structural formula A8.
- Those having a structure are excellent in the heat resistance and flame retardancy of the cured epoxy resin and can significantly reduce the dielectric loss tangent.
- the epoxy resin (A ′) has an epoxy equivalent of 180 to 500 g / eq.
- the thing of this range is preferable from the point from which the heat resistance and flame retardance of hardened
- those having a melt viscosity at 150 ° C. of 0.1 to 50 dPa ⁇ s, particularly 0.1 to 10 dPa ⁇ s, measured with an ICI viscometer have fluidity during molding and moisture resistance of the cured product. It is preferable in terms of excellent solderability.
- the epoxy equivalent is 200 to 400 g / eq. It is preferable that it is in the range from the point that the balance between the moisture resistance solder resistance and flame resistance of the cured product and the curability of the composition is particularly excellent.
- the abundance ratio of the glycidyloxy group-containing aromatic hydrocarbon group (Ep1) is the glycidyloxy group-containing aromatic hydrocarbon group (Ep1) containing the naphthylmethyl group or antonylmethyl group and the glycidyloxy group.
- the total number of the aromatic hydrocarbon groups (Ep2) is 100
- the total number of the glycidyloxy group-containing aromatic hydrocarbon groups (Ep1) is in the range of 10 to 200.
- a ratio of 15 to 120 is particularly preferred because of the high effect of improving curability, moldability, moisture resistance reliability, and flame retardancy.
- being in the range of 20 to 100 is excellent in impregnation into inorganic fillers such as silica and glass substrate in the composition, and has a low coefficient of thermal expansion when cured, resulting in adhesion. Increased moisture resistance and solder resistance has improved dramatically. In particular, when it is in the range of 20 to 80, moisture resistance and solder resistance are further improved.
- the epoxy resin (A ′) can be produced by the production method described in detail below. That is, the method for producing the epoxy resin (A ′) specifically includes a method in which the phenolic resin in the thermosetting resin composition (I) is produced by the above-described method and then reacted with epihalohydrin. It is done. Specifically, 2 to 10 mol of epihalohydrin is added to 1 mol of phenolic hydroxyl group in the phenolic resin, and 0.9 to 2.0 mol of basic catalyst is added all at once to 1 mol of phenolic hydroxyl group. Alternatively, a method of reacting at a temperature of 20 to 120 ° C. for 0.5 to 10 hours while gradually adding can be mentioned.
- the basic catalyst may be solid or an aqueous solution thereof. When an aqueous solution is used, it is continuously added and water and epihalohydrins are continuously distilled from the reaction mixture under reduced pressure or normal pressure. The solution may be taken out and further separated to remove water and the epihalohydrins are continuously returned to the reaction mixture.
- the epihalohydrin used for preparation is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, ⁇ -methylepichlorohydrin, and the like. Of these, epichlorohydrin is preferred because it is easily available industrially.
- the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides.
- alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity of the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide.
- these basic catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass or in the form of a solid.
- combination of an epoxy resin can be raised by using an organic solvent together.
- organic solvents examples include, but are not limited to, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol, methyl
- examples thereof include cellosolves such as cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, and dimethylformamide.
- ketones such as acetone and methyl ethyl ketone
- alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol, methyl
- the amount used is preferably in the range of 0.1 to 3.0% by mass with respect to the epoxy resin used.
- the generated salt is removed by filtration, washing with water, and a high-purity epoxy resin can be obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure.
- thermosetting resin composition (II) of the present invention the epoxy resin (A ′) obtained by the production method of the present invention can be used alone, but other epoxy can be used as long as the effects of the present invention are not impaired. Resin (a ′) can be used in combination.
- the ratio of the epoxy resin (A) of the present invention to the entire epoxy resin component is a ratio of 30% by mass or more, particularly a ratio of 40% by mass or more. It is preferable that
- epoxy resin (a ′) that can be used in combination with the epoxy resin (A ′) of the present invention
- various epoxy resins can be used.
- bisphenol A type epoxy resins bisphenol F type epoxy Bisphenol type epoxy resin such as resin
- phenol novolac type epoxy resin cresol novolak type epoxy resin
- a novolak-type epoxy resin such as a naphthol-cresol co-condensed novolak-type epoxy resin
- n is a repeating unit and is an integer of 0 or more.
- n is a repeating unit and is an integer of 0 or more.
- n is a repeating unit and is an integer of 0 or more.
- naphthalene type epoxy resins are flame retardant and This is particularly preferable from the viewpoint of excellent dielectric properties.
- Examples of the curing agent (B ′) used in the thermosetting resin composition (II) of the present invention include various known curing agents for epoxy resins such as amine compounds, amide compounds, acid anhydride compounds, phenols. Curing agents such as system compounds can be used.
- examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF 3 -amine complex, and guanidine derivative.
- Examples of the amide compound include dicyandiamide. And polyamide resins synthesized from dimer of linolenic acid and ethylenediamine.
- acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, and tetrahydrophthalic anhydride.
- Acid, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc., and phenolic compounds include phenol novolac resin, cresol novolac resin
- a novolak resin such as a naphthol novolak resin, a naphthol-phenol co-condensed novolak resin, a naphthol-cresol co-condensed novolak resin, or the like;
- a phenol resin containing a methoxy aromatic structure such as a phenol resin having a methoxyphenyl skeleton bonded to the aromatic nucleus of the resin via a methylene group;
- n is a repeating unit and is an integer of 0 or more.
- Phenol aralkyl resin represented by the following structural formula
- Naphthol aralkyl resin represented by the following structural formula
- n is a repeating unit and is an integer of 0 or more.
- Biphenyl modified phenolic resin represented by the following structural formula
- n is a repeating unit and is an integer of 0 or more.
- Aralkyl type phenolic resins such as biphenyl-modified naphthol resins represented by: A phenol resin having a resin structure in which a methoxynaphthalene skeleton is bonded to an aromatic nucleus of the aralkyl type phenol resin via a methylene group, and a phenol having a resin structure in which the methoxyphenyl skeleton is bonded to an aromatic nucleus of the aralkyl type phenol resin via a methylene group. Resin; following structural formula
- a novolak resin having a nodule group represented by an aromatic methylene represented by: trimethylolmethane resin examples thereof include polyphenol compounds such as tetraphenylolethane resin, dicyclopentadiene phenol addition type phenol resin, aminotriazine-modified phenol resin (polyhydric phenol compound in which phenol nuclei are linked by melamine, benzoguanamine, etc.).
- phenol novolac resins cresol novolak resins, novolak resins having aromatic methylene as a nodule
- phenol Aralkyl resin naphthol aralkyl resin
- naphthol novolak resin naphthol-phenol co-condensed novolak resin
- naphthol-cresol co-condensed novolak resin biphenyl-modified phenol resin, biphenyl-modified naphthol resin, methoxy aromatic structure-containing phenol resin, aminotriazine-modified phenol resin Is preferable because of its excellent flame retardancy.
- dihydroxyphenols such as resorcin, catechol and hydroquinone, bisphenols such as bisphenol F and bisphenol A, and dihydroxynaphthalenes such as 2,7-dihydroxynaphthalene and 1,6-dihydroxynaphthalene It is preferable to use together.
- the phenolic resin (B) used in the thermosetting resin composition (I) described above is particularly preferable since the effect of improving the heat resistance and moisture resistance and solder resistance becomes remarkable. It is preferable.
- the phenol resin is represented by the above Ph1-14, Ph1-15, Ph1-20, Ph1-22 as a phenolic hydroxyl group-containing aromatic skeleton (Ph1) having a naphthylmethyl group or an antonylmethyl group in an aromatic nucleus.
- a phenolic hydroxyl group-containing aromatic skeleton (Ph2) having no naphthylmethyl group or anthonylmethyl group in the aromatic nucleus is represented by the above Ph2-1, Ph2-4, and the methylene nodule group (X ), A methylene group and a structure represented by the structural formulas X1, X2, and X5 are preferable from the viewpoint of excellent moisture resistance, solder resistance, and flame retardancy.
- the blending amount of the epoxy resin (A ′) and the curing agent (B ′) in the thermosetting resin composition (II) of the present invention is not particularly limited, but the properties of the resulting cured product are good. Therefore, the amount by which the active groups in the curing agent (B ′) are 0.7 to 1.5 equivalents relative to 1 equivalent in total of the epoxy groups in the epoxy resin containing the epoxy resin (A ′). It is preferable that
- a curing accelerator can be used in combination with the thermosetting resin composition (II) of the present invention as necessary.
- Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts.
- phosphorus compounds tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts.
- triphenylphosphine is used for phosphorus compounds and 1,8-diazabicyclo is used for tertiary amines.
- DBU -[5.4.0] -undecene
- thermosetting resin compositions (I) and (II) of the present invention described in detail above, the phenolic resin (B) in the thermosetting resin composition (I) or the thermosetting resin composition (II). Since the epoxy resin (A ′) has an excellent effect of imparting flame retardancy, the flame retardancy of the cured product is good even if a conventionally used flame retardant is not blended. However, in order to exert a higher degree of flame retardancy, for example, in the field of semiconductor sealing materials, it contains substantially halogen atoms in a range that does not reduce the moldability in the sealing process and the reliability of the semiconductor device. A non-halogen flame retardant (C) may be added.
- thermosetting resin composition containing such a non-halogen flame retardant (C) is substantially free of halogen atoms.
- halogen atoms may be included.
- non-halogen flame retardant (C) examples include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants. It is not limited at all, and it may be used alone, or a plurality of flame retardants of the same system may be used, or flame retardants of different systems may be used in combination.
- the phosphorus flame retardant either inorganic or organic can be used.
- the inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. .
- the red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like.
- the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of a thermosetting resin such as a phenol resin, (iii) thermosetting of a phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide
- a method of double coating with a resin may be used.
- general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phospholane compounds, organic nitrogen-containing phosphorus compounds,
- the blending amount thereof is appropriately selected according to the type of the phosphorus-based flame retardant, the other components of the thermosetting resin composition, and the desired degree of flame retardancy.
- an epoxy resin, a curing agent In 100 parts by mass of the thermosetting resin composition containing all of the non-halogen flame retardant and other fillers and additives, 0.1 to 2.0 mass when red phosphorus is used as the non-halogen flame retardant
- an organophosphorus compound it is preferably blended in the range of 0.1 to 10.0 parts by mass, particularly in the range of 0.5 to 6.0 parts by mass. It is preferable to mix with.
- the phosphorous flame retardant when using the phosphorous flame retardant, may be used in combination with hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.
- nitrogen-based flame retardant examples include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.
- triazine compound examples include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (i) guanylmelamine sulfate, melem sulfate, sulfate (Iii) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine and formguanamine and formaldehyde, (iii) (Ii) a mixture of a co-condensate of (ii) and a phenol resin such as a phenol formaldehyde condensate; (iv) a mixture of (ii) and (iii) further modified with paulownia oil, isomerized linseed oil,
- cyanuric acid compound examples include cyanuric acid and melamine cyanurate.
- the compounding amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the thermosetting resin composition, and the desired degree of flame retardancy. , Preferably in a range of 0.05 to 10 parts by mass in 100 parts by mass of the thermosetting resin composition containing all of the curing agent, non-halogen flame retardant and other fillers and additives. It is preferable to blend in the range of 0.1 to 5 parts by mass.
- a metal hydroxide, a molybdenum compound or the like may be used in combination.
- the silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.
- the amount of the silicone-based flame retardant is appropriately selected according to the type of the silicone-based flame retardant, the other components of the thermosetting resin composition, and the desired degree of flame retardancy. Further, it is preferably blended in the range of 0.05 to 20 parts by mass in 100 parts by mass of the thermosetting resin composition in which all of the curing agent, non-halogen flame retardant and other fillers and additives are blended. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.
- inorganic flame retardant examples include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.
- metal hydroxide examples include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide and the like.
- the metal oxide include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide.
- metal carbonate compound examples include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.
- the metal powder examples include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.
- boron compound examples include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.
- the low-melting-point glass include, for example, Shipley (Bokusui Brown), hydrated glass SiO 2 —MgO—H 2 O, PbO—B 2 O 3 system, ZnO—P 2 O 5 —MgO system, P 2 O 5 —B 2 O 3 —PbO—MgO system, P—Sn—O—F system, PbO—V 2 O 5 —TeO 2 system, Al 2 O 3 —H 2 O system, lead borosilicate system, etc.
- the glassy compound can be mentioned.
- the blending amount of the inorganic flame retardant is appropriately selected depending on the kind of the inorganic flame retardant, the other components of the thermosetting resin composition, and the desired degree of flame retardancy. , Preferably in the range of 0.05 to 20 parts by mass in 100 parts by mass of the thermosetting resin composition containing all of the curing agent, non-halogen flame retardant and other fillers and additives. It is preferable to blend in the range of 0.5 to 15 parts by mass.
- organometallic salt-based flame retardant examples include ferrocene, acetylacetonate metal complex, organometallic carbonyl compound, organocobalt salt compound, organosulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound or an ionic bond or Examples thereof include a coordinated compound.
- the amount of the organometallic salt-based flame retardant is appropriately selected depending on the type of organometallic salt-based flame retardant, the other components of the thermosetting resin composition, and the desired degree of flame retardancy.
- a thermosetting resin composition containing all of epoxy resin, curing agent, non-halogen flame retardant and other fillers and additives, it is blended in the range of 0.005 to 10 parts by mass. Is preferred.
- an inorganic filler can be blended as necessary.
- the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.
- fused silica When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica.
- the fused silica can be used in either a crushed shape or a spherical shape.
- the filling rate is preferably higher in consideration of flame retardancy, and particularly preferably 65% by mass or more with respect to the total amount of the thermosetting resin composition.
- electroconductive fillers such as silver powder and copper powder, can be used.
- thermosetting resin composition (I) or (II) of the present invention various compounding agents such as a silane coupling agent, a release agent, a pigment, and an emulsifier can be added as necessary.
- thermosetting resin composition (I) or (II) of the present invention can be obtained by uniformly mixing the above-described components.
- the thermosetting resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method.
- Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.
- thermosetting resin composition (I) or (II) of the present invention examples include semiconductor sealing materials, resin compositions used for laminated boards and electronic circuit boards, resin casting materials, adhesives, Examples thereof include interlayer insulating materials for build-up substrates, coating materials such as insulating paints, etc. Among them, they can be suitably used for semiconductor sealing materials.
- thermosetting resin composition (I) or (II) prepared for a semiconductor encapsulant each component containing a filler is optionally replaced with an extruder, a kneader, a roll. Or the like, and then mixed sufficiently until uniform to obtain a melt-mixed thermosetting resin composition.
- silica is usually used as the filler, but the filling rate should be in the range of 30 to 95% by mass of the filler per 100 parts by mass of the thermosetting resin composition (I) or (II).
- the composition is molded by casting or using a transfer molding machine, injection molding machine, etc., and further heated at 50 to 200 ° C. for 2 to 10 hours to form a semiconductor device as a molded product. There is a way to get it.
- thermosetting resin composition (I) or (II) of the present invention into a printed circuit board composition
- a resin composition for prepreg can be used.
- it can be used without a solvent depending on the viscosity of the thermosetting resin composition
- the organic solvent it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower such as methyl ethyl ketone, acetone, dimethylformamide, etc., and it can be used alone or as a mixed solvent of two or more kinds.
- the obtained varnish is impregnated into various reinforcing substrates such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth, and the heating temperature according to the solvent type used, preferably 50 By heating at ⁇ 170 ° C., a prepreg that is a cured product can be obtained.
- the mass ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is adjusted to 20 to 60% by mass.
- the prepreg obtained as described above is laminated by a conventional method, and a copper foil is appropriately laminated to apply a pressure of 1 to 10 MPa.
- a copper-clad laminate can be obtained by thermocompression bonding under pressure at 170 to 250 ° C. for 10 minutes to 3 hours.
- thermosetting resin composition (I) or (II) of the present invention is used as a resist ink
- a cationic polymerization catalyst is used as a curing agent for the thermosetting resin composition (II), and further a pigment. , Talc, and filler are added to obtain a resist ink composition, which is then applied to a printed circuit board by a screen printing method and then a resist ink cured product.
- thermosetting resin composition (I) or (II) of the present invention is used as a conductive paste
- fine conductive particles are dispersed in the thermosetting resin composition and used for an anisotropic conductive film.
- examples thereof include a method of forming a composition, a paste resin composition for circuit connection that is liquid at room temperature, and a method of using an anisotropic conductive adhesive.
- thermosetting resin composition (I) or (II) of the present invention for example, a circuit is formed by using the curable resin composition appropriately blended with rubber, filler or the like.
- the coated wiring board is applied using a spray coating method, a curtain coating method, or the like, and then cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness
- electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent.
- the roughening agent include an oxidizing agent, an alkali, and an organic solvent.
- Such operations are sequentially repeated as desired, and a build-up substrate can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern.
- the through-hole portion is formed after the outermost resin insulating layer is formed.
- a resin-coated copper foil obtained by semi-curing the resin composition on a copper foil is heat-pressed at 170 to 250 ° C. on a wiring board on which a circuit is formed, thereby forming a roughened surface and performing plating treatment. It is also possible to produce a build-up substrate by omitting the process.
- the method for obtaining the cured product of the present invention may be based on a general method for curing an epoxy resin composition.
- the heating temperature condition may be appropriately selected depending on the type and use of the curing agent to be combined.
- the composition obtained by the above method may be heated in a temperature range of about 20 to 250 ° C.
- a molding method a general method of an epoxy resin composition is used, and in particular, conditions specific to the thermosetting resin composition (I) or (II) of the present invention are unnecessary.
- the present invention it is possible to obtain an epoxy resin material that is safe in an environment where a high level of flame retardancy can be expressed without using a halogen-based flame retardant.
- its excellent dielectric characteristics can realize high-speed operation speed of high-frequency devices.
- the phenolic resin (B) or epoxy resin (A ′) can be easily and efficiently manufactured by the manufacturing method of the present invention, and molecular design according to the target level of performance described above is possible. It becomes.
- melt viscosity at 150 ° C., GPC measurement, NMR, and MS spectrum were measured under the following conditions.
- 103.0 g of a phenol novolac resin (“M-70G” manufactured by Showa Polymer Co., Ltd., softening point 70 ° C., hydroxyl group equivalent 103 g / eq) and 103.0 g of methyl isobutyl ketone were heated to 115 ° C. After the temperature rise, a mixed liquid of 88.8 g of methyl isobutyl ketone 18.8 g (0.50 mol) of 1-chloromethylnaphthalene was dropped in advance at 115 ° C. over 2 hours. After completion of the dropwise addition, the mixture was reacted at 120 ° C. for 1 hour and further at 150 ° C.
- a phenol resin (A-1) The softening point of the obtained phenol resin was 105 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) was 16.1 dPa ⁇ s, and the hydroxyl equivalent was 173 g / eq. Met.
- the GPC chart of the obtained phenol resin (A-1) is shown in FIG. 1, the C 13 NMR chart is shown in FIG. 2, and the MS spectrum is shown in FIG. From the above analysis, the presence of a methylnaphthyl group corresponding to the general formula (1) was confirmed. The total number of methylnaphthyl groups was 50 with respect to the total number of phenolic hydroxyl group-containing aromatic skeletons.
- Example 2 [Synthesis of phenol resin (A-2)] A flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer was charged with 75.8 g (0.76 mol) of bisphenol F (“DIC-BPF” manufactured by DIC) while purging nitrogen gas. A phenol novolac resin (DIC “TD-2131” softening point 80 ° C., hydroxyl group equivalent 104 g / eq) 25.3 g (hydroxyl group 0.24 equivalent) and methyl isobutyl ketone 101.1 g were charged, and the temperature was raised to 115 ° C.
- DIC-BPF bisphenol F
- a mixture of 99.6 g of methyl isobutyl ketone 19.6 g (0.56 mol) of chloromethylnaphthalene was dropped in advance at 115 ° C. over 2 hours. Thereafter, the same operation as in Example 1 was carried out to obtain a phenol resin (A-2).
- the resulting phenol resin had a softening point of 75 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 0.7 dPa ⁇ s, and a hydroxyl group equivalent of 180 g / eq. Met.
- a GPC chart of the resulting phenol resin (A-2) is shown in FIG. The total number of methylnaphthyl groups was 56 with respect to the total number of phenolic hydroxyl group-containing aromatic skeletons.
- Example 3 [Synthesis of phenol resin (A-3)] A flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer was subjected to nitrogen gas purge, while 100.0 g (1.00 mol) of bisphenol F (DIC, purity 99%) and methyl were added. 100.0 g of isobutyl ketone was charged and the temperature was raised to 115 ° C. After raising the temperature, a mixture of 126.1 g of methyl isobutyl ketone and 126.1 g (0.71 mol) of 1-chloromethylnaphthalene was added dropwise at 115 ° C. over 2 hours.
- A-3 Synthesis of phenol resin (A-3)
- Example 2 Thereafter, the same operation as in Example 1 was carried out to obtain a phenol resin (A-3).
- the obtained phenol resin had a softening point of 72 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 0.5 dPa ⁇ s, and a hydroxyl group equivalent of 200 g / eq. Met.
- a GPC chart of the resulting phenol resin (A-3) is shown in FIG. The total number of methylnaphthyl groups was 71 with respect to 100 total phenolic hydroxyl group-containing aromatic skeletons.
- Example 4 [Synthesis of phenol resin (A-4)] A flask equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer was purged with nitrogen gas, and 59.0 g of the phenol resin (A-3) obtained in Example 3 and bisphenol F (made by DIC, purity 99.0) were obtained. %) 41.0 g was charged, and heated and mixed at 120 ° C. for 1 hour to obtain a phenol resin (A-4). The softening point of the obtained phenol resin was 57 ° C.
- melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) was 0.2 dPa ⁇ s, and the hydroxyl equivalent was 142 g / eq. Met.
- a GPC chart of the obtained phenol resin is shown in FIG. Further, the total number of methylnaphthyl groups was 30 with respect to the total number 100 of phenolic hydroxyl group-containing aromatic skeletons.
- Example 5 [Synthesis of phenol resin (A-5)] A flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer was purged with nitrogen gas, and 35.0 g of the phenol resin (A-3) obtained in Example 3 and bisphenol F ( 65.0 g of a DIC product, purity 99.0%) was charged, and the mixture was superheated at 120 ° C. for 1 hour to obtain a phenol resin (A-5). The resulting phenol resin had a softening point of 52 ° C.
- the obtained phenol resin A-6 had a softening point of 91 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 3.1 dPa ⁇ s, and a hydroxyl group equivalent of 174 g / eq. Met.
- the obtained phenol resin A-7 had a hydroxyl group equivalent of 114 g / eq.
- the softening point was 102 ° C. (B & R method), and the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) was 20.1 dPa ⁇ s.
- Example 6 [Synthesis of Epoxy Resin (E-1)] A flask equipped with a thermometer, a dropping funnel, a condenser tube, and a stirrer was purged with nitrogen gas while 173 g (1 equivalent of hydroxyl group) of the phenol resin (A-1) obtained in Example 1 and 463 g of epichlorohydrin (5. 0 mol), 139 g of n-butanol and 2 g of tetraethylbenzylammonium chloride were charged and dissolved.
- the resulting epoxy resin had a softening point of 83 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometry method, measurement temperature: 150 ° C.) of 5.1 dPa ⁇ s, and an epoxy equivalent of 260 g / eq. Met.
- the GPC chart of the resulting epoxy resin (E-1) is shown in FIG. 8, the C 13 NMR chart is shown in FIG. 9, and the MS spectrum is shown in FIG. From the above analysis, the presence of a methylnaphthyl group corresponding to the general formula (1) was confirmed.
- the total number of methylnaphthyl groups was 50 with respect to the total number 100 of glycidyl group-containing aromatic hydrocarbon groups.
- Example 7 Synthesis of Epoxy Resin (E-2)
- the epoxidation reaction was performed in the same manner as in Example 6 except that the phenol resin (A-1) in Example 6 was changed to 180 g (1 equivalent of hydroxyl group) of the phenol resin (A-2) obtained in Example 2. And an epoxy resin (E-2) was obtained.
- the resulting epoxy resin had a softening point of 56 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 0.5 dPa ⁇ s, and an epoxy equivalent of 268 g / eq. Met.
- a GPC chart of the resulting epoxy resin (E-2) is shown in FIG. The total number of methyl naphthyl groups was 56 with respect to the total number of glycidyl group-containing aromatic hydrocarbon groups.
- Example 8 Synthesis of Epoxy Resin (E-3)
- the epoxidation reaction was performed in the same manner as in Example 6 except that the phenol resin (A-1) in Example 6 was changed to 200 g (1 equivalent of hydroxyl group) of the phenol resin (A-3) obtained in Example 3. And an epoxy resin (E-3) was obtained.
- the resulting epoxy resin had a softening point of 56 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometry method, measurement temperature: 150 ° C.) of 0.4 dPa ⁇ s, and an epoxy equivalent of 291 g / eq. Met.
- a GPC chart of the resulting epoxy resin (E-3) is shown in FIG. The total number of methylnaphthyl groups was 71 with respect to the total number of glycidyl group-containing aromatic hydrocarbon groups.
- Example 9 [Synthesis of Epoxy Resin (E-4)]
- the epoxidation reaction was the same as in Example 6 except that the phenol resin (A-1) in Example 6 was changed to 142 g (1 equivalent of hydroxyl group) of the phenol resin (A-4) obtained in Example 4. And an epoxy resin (E-4) was obtained.
- the resulting epoxy resin has a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 0.1 dPa ⁇ s, and an epoxy equivalent of 225 g / eq. Met.
- a GPC chart of the resulting epoxy resin (E-4) is shown in FIG. The total number of methylnaphthyl groups was 30 with respect to the total number 100 of glycidyl group-containing aromatic hydrocarbon groups.
- Example 10 Synthesis of Epoxy Resin (E-5)
- the epoxidation reaction was performed in the same manner as in Example 6 except that the phenol resin (A-1) in Example 6 was changed to 121 g (1 equivalent of hydroxyl group) of the phenol resin (A-5) obtained in Example 5. And an epoxy resin (E-5) was obtained.
- the epoxy equivalent of the obtained epoxy resin is 201 g / eq. Met.
- a GPC chart of the resulting epoxy resin (E-5) is shown in FIG.
- the total number of methylnaphthyl groups was 15 with respect to the total number 100 of glycidyl group-containing aromatic hydrocarbon groups.
- the azeotropic epichlorohydrin was returned to the system through a Dean-Stark water separator, and water was removed out of the system.
- the end point of the reaction was defined as the point at which the distillation of water ceased after completion of the dropwise addition of the aqueous sodium hydroxide solution.
- by-product inorganic salts and the like were filtered off, and excess epichlorohydrin was distilled off from the filtrate under reduced pressure to obtain an epoxy resin (E-6).
- the resulting epoxy resin had a softening point of 78 ° C.
- the resulting epoxy resin had a softening point of 62 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometry method, measurement temperature: 150 ° C.) of 1.2 dPa ⁇ s, and an epoxy equivalent of 175 g / eq. Met.
- the resulting epoxy resin has a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 0.8 dPa ⁇ s, and an epoxy equivalent of 250 g / eq. Met.
- epoxy resin As the epoxy resin, the above (E-1) to (E-8) and “YX-4000H” (tetramethylbiphenol type epoxy resin, epoxy equivalent: 195 g / eq) manufactured by Japan Epoxy Resin Co., Ltd., Nippon Kayaku Co., Ltd. “NC-3000” (biphenyl novolac type epoxy resin, epoxy equivalent: 274 g / eq) manufactured by Nippon Kayaku Co., Ltd.
- NC-2000L phenol aralkyl type epoxy resin, epoxy equivalent: 236 g / eq
- DIC Corporation “N-655-EXP-S” orthocresol novolac type epoxy resin, epoxy equivalent: 200 g / eq) manufactured by (N-1) to (A-7) as a phenol resin
- TD- manufactured by DIC Corporation 2131 "(phenol novolac resin, hydroxyl group equivalent: 104 g / eq), Mitsui Chemicals, Inc.
- the pulverized composition obtained was formed into a disk shape of ⁇ 50 mm ⁇ 3 (t) mm in a transfer molding machine at a pressure of 70 kg / cm 2, a ram speed of 5 cm / second, a temperature of 175 ° C., and a time of 180 seconds.
- a product formed into a rectangle having a width of 12.7 mm, a length of 127 mm, and a thickness of 1.6 mm was further cured at 180 ° C. for 5 hours.
- the physical properties of the cured product are as follows. Using the cured product obtained by the transfer molding, a test piece is prepared by the following method, and the heat resistance, linear expansion coefficient, adhesion, moisture resistance, solder resistance, and flame resistance are determined by the following method.
- the adhesiveness is a copper foil (manufactured by Furukawa Circuit Foil Co., Ltd., 35 ⁇ m thick, using the Shine surface of GTS-MP treated as an adhesive surface with the resin composition) on one side of the mold. Then, a test piece was prepared from what was formed into a rectangle having a width of 12.7 mm, a length of 127 mm, and a thickness of 1.6 mm and further cured at 180 ° C. for 5 hours.
- thermomechanical analysis was performed in a compression mode using a thermomechanical analyzer (TMA: “SS-6100” manufactured by Seiko Instruments Inc.). (Measurement weight: 30 mN, temperature increase rate: twice at 3 ° C./min, measurement temperature range: ⁇ 50 ° C. to 250 ° C.)
- TMA thermomechanical analyzer
- the linear expansion coefficient at 50 ° C. in the second measurement was evaluated.
- ⁇ Adhesion> The cured product was used as a test piece having a width of 10 mm, and the peel strength was measured at a speed of 50 mm / min.
- NC-2000L phenol aralkyl type epoxy resin (“NC-2000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 236 g / eq)
- NC-3000 biphenyl novolac type epoxy resin (“NC-3000” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 274 g / eq)
- YX-4000H Tetramethylbiphenol type epoxy resin (“YX-4000H” manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent: 195 g / eq)
- N-655-EXP-S Cresol novolac type epoxy resin (“Epiclon N-655-EXP-S”, epoxy equivalent: 200 g / eq)
- MEH-7851SS Biphenyl novolak resin (“MEH-7851SS” manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent: 200 g / eq)
- XLC-3L phenol aralky
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Abstract
Description
更に近年、環境調和の観点からハロゲン系難燃剤排除の動きがより一層高まり、ハロゲンフリー系で高度な難燃性を発現するエポキシ樹脂及びフェノール樹脂(硬化剤)が求められている。
本発明の熱硬化性樹脂組成物(I)は、先ず、エポキシ樹脂(A)及びフェノール系樹脂(B)を必須成分とする熱硬化性樹脂組成物であって、前記フェノール系樹脂(B)が、複数のフェノール性水酸基含有芳香族骨格(ph)がアルキリデン基又は芳香族炭化水素構造含有メチレン基を介して結合した構造を基本骨格とするフェノール樹脂構造を有しており、かつ、該フェノール樹脂構造の芳香核にナフチルメチル基又はアントニルメチル基を有することを特徴とするものである。
本発明では、これらのなかでも、低粘度で、硬化性、耐熱性、耐湿耐半田性に優れる点では前記構造式Ph1-14のフェノール骨格を有するものが好ましい。また、前記構造式Ph1-15、Ph1-20、Ph1-22に代表されるようにフェノール骨格にメチル基を有するものは、耐熱性と耐湿耐半田性の改善効果が顕著なものとなり好ましい。
で表されるように多重化した構造を有するものであってもよい。ここで、上記構造式(1)又は構造式(2)は、その平均が0~5の値を採りうるが、本発明では優れた難燃性を発現する点から多重化していないもの、即ちnが0のものが好ましい。また、これらのなかでも特に流動性、難燃性の点からナフチルメチル基であることが好ましい。
これらの中ででも反応触媒を使用せずに反応でき、反応後の精製工程が不要となる点で、1-メチルクロリド、2-メチルクロリド、(9-アントリルメチル)クロリドが好ましい。
この時、発生する塩化水素ガスは、速やかに系外に放出し、アルカリ水などにより中和、無害化することが望ましい。
ここでいう溶融粘度とは、ICIコーンプレート粘度計やB型粘度計、E型粘度計等、いずれの測定方法でも構わない。
この様にして得られた反応生成物には、未反応フェノール化合物が多量に残存しており、蒸留、水洗等任意の方法で未反応フェノールを除去することにより本発明のフェノール系樹脂(B)が得られる。
(式中、nは繰り返し単位であり、0以上の整数である。)
で表されるビフェニル変性ナフトール樹脂等のアラルキル型フェノール樹脂;前記アラルキル型フェノール樹脂の芳香核にメトキシナフタレン骨格がメチレン基を介して結合した樹脂構造のフェノール樹脂、前記アラルキル型フェノール樹脂の芳香核にメトキシフェニル骨格がメチレン基を介して結合した樹脂構造のフェノール樹脂;下記構造式
(式中、Xは、フェニル基、ビフェニル基を表し、nは繰り返し単位であり、0以上の整数である。)で表される芳香族メチレンを結節基とするノボラック樹脂;トリメチロールメタン樹脂、テトラフェニロールエタン樹脂、ジシクロペンタジエンフェノール付加型フェノール樹脂が挙げられる。
例えば、
ジグリシジルオキシナフタレン、1,1-ビス(2,7-ジグリシジルオキシナフチル)メタン1-(2,7-ジグリシジルオキシナフチル)-1-(2’-グリシジルオキシナフチル)メタン等のナフタレン型エポキシ樹脂;ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂等のビスフェノール型エポキシ樹脂;フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールAノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、ナフトール-フェノール共縮ノボラック型エポキシ樹脂、ナフトール-クレゾール共縮ノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂;前記ノボラック型エポキシ樹脂の芳香核にメトキシナフタレン骨格がメチレン基を介して結合した樹脂構造のエポキシ樹脂、前記ノボラック型エポキシ樹脂の芳香核にメトキシフェニル骨格がメチレン基を介して結合した樹脂構造のエポキシ樹脂;下記構造式B1
(式中、Xは、フェニル基、ビフェニル基を表し、nは繰り返し単位であり、0以上の整数である。)
で表される芳香族メチレンを結節基とするノボラック型エポキシ樹脂;
前記アラルキル型エポキシ樹脂の芳香核にメトキシナフタレン骨格がメチレン基を介して結合した樹脂構造のエポキシ樹脂、前記アラルキル型エポキシ樹脂の芳香核にメトキシフェニル骨格がメチレン基を介して結合した樹脂構造のエポキシ樹脂;その他テトラメチルビフェニル型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂、ジシクロペンタジエン-フェノール付加反応型エポキシ樹脂等が挙げられる。またこれらのエポキシ樹脂は単独で用いてもよく、2種以上を混合してもよい。これらのなかでも、ナフタレン型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ビフェニル型エポキシ樹脂、アルコキシ基含有ノボラック型エポキシ樹脂、又はアルコキシ基含有アラルキル型エポキシ樹脂が、難燃性や誘電特性に優れる点から特に好ましい。
ここで、「Gr」は、グリシジルオキシ基を表し、また、上掲した構造のうちナフタレン骨格上に他の構造部位との結合位置を二つ以上有するものは、それらの結合位置は同一核上であってもよいし、或いは、それぞれ異核上にあってもよい。
ここで、「Gr」は、グリシジルオキシ基を表し、また、上掲した構造のうちナフタレン骨格上に他の構造部位との結合位置を二つ以上有するものは、それらの結合位置は同一核上であってもよいし、或いは、それぞれ異核上にあってもよい。
ここで、「Gr」は、グリシジルオキシ基を表し、また、上掲した構造のうちナフタレン骨格上に他の構造部位との結合位置を二つ以上有するものは、それらの結合位置は同一核上であってもよいし、或いは、それぞれ異核上にあってもよい。
で表されるように多重化した構造を有するものであってもよい。ここで、上記構造式(1)又は構造式(2)は、その平均が0~5の値を採りうるが、本発明では優れた難燃性を発現する点から多重化していないもの、即ちnが0のものが好ましい。
(式中、Xは、フェニル基、ビフェニル基を表し、nは繰り返し単位であり、0以上の整数である。)
で表される芳香族メチレンを結節基とするノボラック型エポキシ樹脂;前記アラルキル型エポキシ樹脂の芳香核にメトキシナフタレン骨格がメチレン基を介して結合した樹脂構造のエポキシ樹脂、前記アラルキル型エポキシ樹脂の芳香核にメトキシフェニル骨格がメチレン基を介して結合した樹脂構造のエポキシ樹脂;その他テトラメチルビフェニル型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂、
ジシクロペンタジエン-フェノール付加反応型エポキシ樹脂等が挙げられる。またこれらのエポキシ樹脂は単独で用いてもよく、2種以上を混合してもよい。
(式中、nは繰り返し単位であり、0以上の整数である。)
で表されるビフェニル変性ナフトール樹脂等のアラルキル型フェノール樹脂;
前記アラルキル型フェノール樹脂の芳香核にメトキシナフタレン骨格がメチレン基を介して結合した樹脂構造のフェノール樹脂、前記アラルキル型フェノール樹脂の芳香核にメトキシフェニル骨格がメチレン基を介して結合した樹脂構造のフェノール樹脂;下記構造式
(式中、Xは、フェニル基、ビフェニル基を表し、nは繰り返し単位であり、0以上の整数である。)で表される芳香族メチレンを結節基とするノボラック樹脂;トリメチロールメタン樹脂、テトラフェニロールエタン樹脂、ジシクロペンタジエンフェノール付加型フェノール樹脂、アミノトリアジン変性フェノール樹脂(メラミンやベンゾグアナミンなどでフェノール核が連結された多価フェノール化合物)等の多価フェノール化合物が挙げられる。
芳香核にナフチルメチル基又はアントニルメチル基を有しないフェノール性水酸基含有芳香族骨格(Ph2)として前記Ph2-1、Ph2-4で表されるものであり、かつ、前記メチレン系結節基(X)として、メチレン基、前記構造式X1、X2、X5で表される構造のものであることが耐湿耐半田性及び難燃性に優れる点から好ましい。
1)150℃における溶融粘度:ASTM D4287に準拠
2)軟化点測定法:JIS K7234
3)GPC:
・装置:東ソー株式会社製 HLC-8220 GPC、カラム:東ソー株式会社製 TSK-GEL G2000HXL+G2000HXL+G3000HXL+G4000HXL
・溶媒:テトラヒドロフラン
・流速:1ml/min
・検出器:RI
4)NMR:日本電子株式会社製 NMR GSX270
5)MS :日本電子株式会社製 二重収束型質量分析装置 AX505H(FD505H)
温度計、冷却管、分留管、窒素ガス導入管、撹拌器を取り付けたフラスコに、窒素ガスパージを施しながら、下記構造式
で表されるフェノールノボラック樹脂(昭和高分子製「M-70G」軟化点70℃、水酸基当量103g/eq)103.0g、メチルイソブチルケトン103.0gを仕込み、115℃まで昇温した。昇温後、予めメチルイソブチルケトン88.8g1-クロロメチルナフタレン88.8g(0.50モル)の混合液を、115℃で2時間かけて滴下した。滴下終了後、120℃で1時間、更に150℃で3時間反応させフェノール樹脂(A-1)161gを得た。得られたフェノール樹脂の軟化点は105℃(B&R法)、溶融粘度(測定法:ICI粘度計法、測定温度:150℃)は16.1dPa・s、水酸基当量は173g/eq.であった。
得られたフェノール樹脂(A-1)のGPCチャートを図1に、C13 NMRチャートを図2に、MSスペクトルを図3に示す。上記分析により、前記一般式(1)に該当するメチルナフチル基の存在を確認した。また、フェノール性水酸基含有芳香族骨格の総数100に対してメチルナフチル基の総数は50の割合であった。
温度計、冷却管、分留管、窒素ガス導入管、撹拌器を取り付けたフラスコに、窒素ガスパージを施しながら、ビスフェノールF(DIC製「DIC-BPF」)75.8g(0.76モル)とフェノールノボラック樹脂(DIC製「TD-2131」軟化点80℃、水酸基当量104g/eq)25.3g(水酸基0.24当量)、メチルイソブチルケトン101.1gを仕込み、115℃まで昇温した。昇温後、予めメチルイソブチルケトン99.6g1-クロロメチルナフタレン99.6g(0.56モル)の混合液を、115℃で2時間かけて滴下した。その後の操作は実施例1と同様にしてフェノール樹脂(A-2)を得た。得られたフェノール樹脂の軟化点は75℃(B&R法)、溶融粘度(測定法:ICI粘度計法、測定温度:150℃)は0.7dPa・s、水酸基当量は180g/eq.であった。
得られたフェノール樹脂(A-2)のGPCチャートを図4に示す。また、フェノール性水酸基含有芳香族骨格の総数100に対してメチルナフチル基の総数は56の割合であった。
温度計、冷却管、分留管、窒素ガス導入管、撹拌器を取り付けたフラスコに、窒素ガスパージを施しながら、ビスフェノールF(DIC製、純度99%)100.0g(1.00モル)とメチルイソブチルケトン100.0gを仕込み、115℃まで昇温した。昇温後、予めメチルイソブチルケトン126.1gと1-クロロメチルナフタレン126.1g(0.71モル)の混合液を、115℃で2時間かけて滴下した。その後の操作は実施例1と同様にしてフェノール樹脂(A-3)を得た。得られたフェノール樹脂の軟化点は72℃(B&R法)、溶融粘度(測定法:ICI粘度計法、測定温度:150℃)は0.5dPa・s、水酸基当量は200g/eq.であった。得られたフェノール樹脂(A-3)のGPCチャートを図5に示す。また、フェノール性水酸基含有芳香族骨格の総数100に対してメチルナフチル基の総数は71の割合であった。
温度計、窒素ガス導入管、撹拌器を取り付けたフラスコに、窒素ガスパージを施しながら、実施例3で得られたフェノール樹脂(A-3)59.0gとビスフェノールF(DIC製、純度99.0%)41.0gを仕込み、120℃で1時間過熱混合しフェノール樹脂(A-4)を得た。得られたフェノール樹脂の軟化点は57℃(B&R法)、溶融粘度(測定法:ICI粘度計法、測定温度:150℃)は0.2dPa・s、水酸基当量は142g/eq.であった。得られたフェノール樹脂のGPCチャートを図6に示す。また、フェノール性水酸基含有芳香族骨格の総数100に対してメチルナフチル基の総数は30の割合であった。
温度計、冷却管、分留管、窒素ガス導入管、撹拌器を取り付けたフラスコに、窒素ガスパージを施しながら、実施例3で得られたフェノール樹脂(A-3)35.0gとビスフェノールF(DIC製、純度99.0%)65.0gを仕込み、120℃で1時間過熱混合しフェノール樹脂(A-5)を得た。得られたフェノール樹脂の軟化点は52℃(B&R法)、溶融粘度(測定法:ICI粘度計法、測定温度:150℃)は0.1dPa・s、水酸基当量は121g/eq.であった。得られたフェノール樹脂(A-5)のGPCチャートを図7に示す。また、フェノール性水酸基含有芳香族骨格の総数100に対してメチルナフチル基の総数は15の割合であった。
温度計、冷却管、分留管、窒素ガス導入管、撹拌器を取り付けたフラスコに、窒素ガスパージを施しながら、軟化点86℃のフェノールノボラック樹脂208gとp-トルエンスルホン酸0.5gを仕込み140℃に昇温した。これに、p-メチルベンジルメチルエーテル136g(1モル)を5時間かけて滴下した。途中、生成するメタノールは系外へ留去させ、同温度で更に5時間熟成を行って反応を終了した。この後、アスピレーターの減圧下で脱気しフェノール樹脂を得た。得られたフェノール樹脂A-6の軟化点は91℃(B&R法)、溶融粘度(測定法:ICI粘度計法、測定温度:150℃)は3.1dPa・s、水酸基当量は174g/eq.であった。
温度計、冷却管、分留管、窒素ガス導入管、撹拌器を取り付けたフラスコに、窒素ガスパージを施しながら、1,6-ナフタレンジオール192g、ジクロロメチルナフタレン(1,5-ジクロロメチル体95.6%、その他のジクロロメチル体3.0%、モノクロロメチル体1.4%)81g及びトルエン550gを量り採り、攪拌しながら徐々に昇温溶解させ、約116℃で還流させながらそのまま2時間反応させた。その後、トルエンを留去しながら180℃まで昇温し、そのまま1時間反応させた。反応後、減圧留去により溶媒を除去してフェノール樹脂を得た。得られたフェノール樹脂A-7の水酸基当量は114g/eq.、軟化点は102℃(B&R法)、溶融粘度(測定法:ICI粘度計法、測定温度:150℃)は20.1dPa・sであった。
温度計、滴下ロート、冷却管、撹拌機を取り付けたフラスコに、窒素ガスパージを施しながら、実施例1で得られたフェノール樹脂(A-1)を173g(水酸基1当量)、エピクロルヒドリン463g(5.0モル)、n-ブタノール139g、テトラエチルベンジルアンモニウムクロライド2gを仕込み溶解させた。65℃に昇温した後、共沸する圧力まで減圧して、49%水酸化ナトリウム水溶液90g(1.1モル)を5時間かけて滴下した。その後、同条件で0.5時間撹拌を続けた。この間、共沸によって留出してきた留出分をディーンスタークトラップで分離し、水層を除去し、油層を反応系内に戻しながら、反応を行った。その後、未反応のエピクロルヒドリンを減圧蒸留によって留去させた。それで得られた粗エポキシ樹脂にメチルイソブチルケトン590gとn-ブタノール177gとを加え溶解した。更にこの溶液に10%水酸化ナトリウム水溶液10gを添加して80℃で2時間反応させた後に洗浄液のPHが中性となるまで水150gで水洗を3回繰り返した。次いで共沸によって系内を脱水し、精密濾過を経た後に、溶媒を減圧下で留去してエポキシ樹脂(E-1)218gを得た。得られたエポキシ樹脂の軟化点は83℃(B&R法)、溶融粘度(測定法:ICI粘度計法、測定温度:150℃)は5.1dPa・s、エポキシ当量は260g/eq.であった。
エポキシ化反応は、実施例6においてフェノール樹脂(A-1)を、実施例2で得られたフェノール樹脂(A-2)180g(水酸基1当量)に変更した以外は実施例6と同様にして行い、エポキシ樹脂(E-2)を得た。得られたエポキシ樹脂の軟化点は56℃(B&R法)、溶融粘度(測定法:ICI粘度計法、測定温度:150℃)は0.5dPa・s、エポキシ当量は268g/eq.であった。得られたエポキシ樹脂(E-2)のGPCチャートを図11に示す。また、グリシジル基含有芳香族炭化水素基の総数100に対してメチルナフチル基の総数は56の割合であった。
エポキシ化反応は、実施例6においてフェノール樹脂(A-1)を、実施例3で得られたフェノール樹脂(A-3)200g(水酸基1当量)に変更した以外は実施例6と同様にして行い、エポキシ樹脂(E-3)を得た。得られたエポキシ樹脂の軟化点は56℃(B&R法)、溶融粘度(測定法:ICI粘度計法、測定温度:150℃)は0.4dPa・s、エポキシ当量は291g/eq.であった。得られたエポキシ樹脂(E-3)のGPCチャートを図12に示す。また、グリシジル基含有芳香族炭化水素基の総数100に対してメチルナフチル基の総数は71の割合であった。
エポキシ化反応は、実施例6においてフェノール樹脂(A-1)を、実施例4で得られたフェノール樹脂(A-4)142g(水酸基1当量)に変更した以外は実施例6と同様にして行い、エポキシ樹脂(E-4)を得た。得られたエポキシ樹脂の溶融粘度(測定法:ICI粘度計法、測定温度:150℃)は0.1dPa・s、エポキシ当量は225g/eq.であった。得られたエポキシ樹脂(E-4)のGPCチャートを図13に示す。また、グリシジル基含有芳香族炭化水素基の総数100に対してメチルナフチル基の総数は30の割合であった。
エポキシ化反応は、実施例6においてフェノール樹脂(A-1)を、実施例5で得られたフェノール樹脂(A-5)121g(水酸基1当量)に変更した以外は実施例6と同様にして行い、エポキシ樹脂(E-5)を得た。得られたエポキシ樹脂のエポキシ当量は201g/eq.であった。得られたエポキシ樹脂(E-5)のGPCチャートを図14に示す。また、グリシジル基含有芳香族炭化水素基の総数100に対してメチルナフチル基の総数は15の割合であった。
温度計、冷却管、分留管、窒素ガス導入管、撹拌器を取り付けたフラスコに、窒素ガスパージを施しながら、比較例1で得られたフェノール樹脂(A-3)を152g、エピクロルヒドリン555g(6モル)を仕込み115℃まで加熱昇温した。これに、40%苛性ソーダ水溶液105g(1.05モル)を4時間で滴下した。滴下中、反応温度は100℃以上に保ち、共沸されてくるエピクロルヒドリンはディーンスターク水分離器を通じて系内に戻し、水は系外へ除去した。苛性ソーダ水溶液の滴下終了後、水の留出がなくなった時点を反応の終点とした。反応終了後、副生した無機塩等を濾別し、濾液より過剰のエピクロルヒドリンを減圧留去することによりエポキシ樹脂(E-6)を得た。得られたエポキシ樹脂の軟化点は78℃(B&R法)、溶融粘度(測定法:ICI粘度計法、測定温度:150℃)は2.3dPa・s、エポキシ当量は251g/eq.であった。
温度計、冷却管、分留管、窒素ガス導入管、撹拌器を取り付けたフラスコに、窒素ガスパージを施しながら、比較例2で得えられたフェノール樹脂(A-4)を100g、エピクロルヒドリン812.1g及びジグライム162.4gを仕込み、減圧下(約100mmHg)、60℃にて48%水酸化ナトリウム水溶液71gを4時間かけて滴下した。この間、生成する水はエピクロルヒドリンとの共沸により系外に除き、留出したエピクロルヒドリンは系内に戻した。滴下終了後、更に1時間反応を継続した。その後、エピクロルヒドリン及びジグライムを減圧留去し、メチルイソブチルケトン348.1gに溶解した後、濾過により生成した塩を除いた。その後、48%水酸化ナトリウム水溶液21gを加え、80℃で2時間反応させた。反応後、濾過、水洗を行った後、溶媒であるメチルイソブチルケトンを減圧留去しエポキシ樹脂(E-7)を得た。得られたエポキシ樹脂の軟化点は62℃(B&R法)、溶融粘度(測定法:ICI粘度計法、測定温度:150℃)は1.2dPa・s、エポキシ当量は175g/eq.であった。
温度計、冷却管、分留管、窒素ガス導入管、撹拌器を取り付けたフラスコに、o-クレゾール432.4g(4.00モル)と2-メトキシナフタレン158.2g(1.00モル)と41質量%ホルムアルデヒド水溶液179.3g(ホルムアルデヒド2.45モル)を仕込み、シュウ酸9.0gを加えて、100℃まで昇温し100℃で3時間反応させた。ついで、水を分留管で捕集しながら41質量%ホルムアルデヒド水溶液73.2g(ホルムアルデヒド1.00モル)を1時間かけて滴下した。滴下終了後、150℃まで1時間で昇温し、更に150℃で2時間反応させた。反応終了後、更にメチルイソブチルケトン1500gを加え、分液ロートに移し水洗した。次いで洗浄水が中性を示すまで水洗後、有機層から未反応のo-クレゾールと2-メトキシナフタレン、及びメチルイソブチルケトンを加熱減圧下に除去しフェノール樹脂を得た。得られたフェノール樹脂の水酸基当量は164g/eq.であった。
無機充填材として球状シリカ(電気化学株式会社製「FB-560」)、シランカップリング剤としてγ-グリシドキシトリエトキシキシシラン(信越化学工業株式会社製「KBM-403」)、カルナウバワックス(株式会社セラリカ野田製「PEARL WAX No.1-P」)、カーボンブラックを用いて表1~2に示した組成で配合し、2本ロールを用いて90℃の温度で5分間溶融混練して目的の組成物を作成した。得られた組成物を粉砕したものを、トランスファー成形機にて、圧力70kg/cm2、ラム速度5cm/秒、温度175℃、時間180秒でφ50mm×3(t)mmの円板状に成形したもの、または幅12.7mm、長さ127mm、厚み1.6mmの長方形に成形したものを180℃で5時間さらに硬化せしめた。硬化物の物性は、前記トランスファー成形により得られた硬化物を用い下記の方法で試験片を作成し、耐熱性、線膨張係数、密着性、耐湿耐半田性、難燃性を下記の方法で測定し結果を表1~2に示した。尚、密着性は前記トランスファー成形する際、金型の片面に銅箔(古河サーキットホイル株式会社製。厚さ35μm、GTS-MP処理したもののシャイン面を樹脂組成物との接着面として使用)をおいて、幅12.7mm、長さ127mm、厚み1.6mmの長方形に成形したものを180℃で5時間さらに硬化せしめたものから試験片を作成した。
エポキシ樹脂組成物0.15gを175℃に加熱したキュアプレート(サーモ・エレクトリック社製)上に載せ、ストップウォッチで計時を開始する。棒の先端にて試料を均一に攪拌し、糸状に試料が切れてプレートに残るようになった時、ストップウォッチを止める。この試料が切れてプレートに残るようになるまでの時間をゲルタイムとした。
<耐熱性>
ガラス転移温度:粘弾性測定装置(レオメトリック社製 固体粘弾性測定装置「RSAII」、二重カレンチレバー法;周波数1Hz、昇温速度3℃/分)を用いて測定した。
<線膨張係数>
硬化物を幅約5mm長さ約5mmの試験片とし、熱機械分析装置(TMA:セイコーインスツルメント社製「SS-6100」)を用いて、圧縮モードで熱機械分析を行った。(測定架重:30mN、昇温速度:3℃/分で2回、測定温度範囲:-50℃から250℃)2回目の測定における、50℃における線膨張係数を評価した。
<密着性>
硬化物を幅10mmの試験片とし、50mm/minの速度でピール強度を測定した。
<耐湿耐半田性>
前記φ50mm×3(t)mmの円板状の試験片を用い85℃/85%RHの雰囲気下168時間放置し、吸湿処理を行った後、これを260℃のハンダ浴に10秒間浸漬させた際、クラックの発生の有無を調べた。
○:クラックの発生なし
×:クラック発生
<難燃性>
幅12.7mm、長さ127mm、厚み1.6mmの評価用試験片を用いUL-94試験法に準拠し、厚さ1.6mmの試験片5本を用いて、燃焼試験を行った。
*1:試験片5本の合計燃焼時間(秒)
*2:1回の接炎における最大燃焼時間(秒)
表中の略号は以下の通りである。
NC-2000L:フェノールアラルキル型エポキシ樹脂(日本化薬株式会社製「NC-2000L」、エポキシ当量:236g/eq)
NC-3000:ビフェニルノボラック型エポキシ樹脂(日本化薬株式会社製「NC-3000」、エポキシ当量:274g/eq)
YX-4000H:テトラメチルビフェノール型エポキシ樹脂(ジャパンエポキシレジン株式会社製「YX-4000H」、エポキシ当量:195g/eq)
N-655-EXP-S:クレゾールノボラック型エポキシ樹脂(「エピクロンN-655-EXP-S」、エポキシ当量:200g/eq)
MEH-7851SS:ビフェニルノボラック樹脂(明和化成株式会社製「MEH-7851SS」、水酸基当量:200g/eq)
XLC-3L:フェノールアラルキル樹脂(三井化学株式会社製「XLC-3L」、水酸基当量172g/eq)
TD-2131:フェノールノボラック型フェノール樹脂(DIC(株)製「TD-2131」、水酸基当量:104g/eq)
TPP:トリフェニルホスフィン
Claims (16)
- エポキシ樹脂(A)及びフェノール系樹脂(B)を必須成分とする熱硬化性樹脂組成物であって、前記フェノール系樹脂(B)が、複数のフェノール性水酸基含有芳香族骨格(ph)がアルキリデン基又は芳香族炭化水素構造含有メチレン基を介して結合した構造を基本骨格とするフェノール樹脂構造を有しており、かつ、該フェノール樹脂構造の芳香核にナフチルメチル基又はアントニルメチル基を有するフェノール系樹脂であることを特徴とする熱硬化性樹脂組成物。
- 前記フェノール系樹脂(B)が、フェノール性水酸基含有芳香族骨格(ph)の総数を100とした場合、ナフチルメチル基又はアントニルメチル基の総数が10~200となる割合で含むものである請求項1記載の熱硬化性樹脂組成物。
- 前記フェノール系樹脂(B)が、ICI粘度計で測定した150℃における溶融粘度が0.1~100dPa・sのものである請求項1記載の熱硬化性樹脂組成物。
- 請求項1、2、又は3記載の前記エポキシ樹脂(A)及び前記フェノール系樹脂(B)に加え、更に無機質充填材を組成物中70~95質量%となる割合で含有することを特徴とする半導体封止材料。
- 請求項1~3の何れか一つの熱硬化性樹脂組成物を硬化反応させてなることを特徴とする硬化物。
- 複数のフェノール性水酸基含有芳香族骨格(ph)がアルキリデン基又は芳香族炭化水素構造含有メチレン基を介して結合した構造を基本骨格として有するフェノール樹脂構造を有しており、かつ、該フェノール樹脂構造の芳香核にナフチルメチル基又はアントニルメチル基を有することを特徴とするフェノール系樹脂。
- フェノール性水酸基含有芳香族骨格(ph)の総数を100とした場合、ナフチルメチル基又はアントニルメチル基の総数が10~200となる割合で含む請求項6記載のフェノール系樹脂。
- ICI粘度計で測定した150℃における溶融粘度が0.1~100dPa・sのものである請求項6又は7記載のフェノール系樹脂。
- エポキシ樹脂(A’)及び硬化剤(B’)を必須成分とする熱硬化性樹脂組成物であって、前記エポキシ樹脂(A’)が、複数のグリシジルオキシ基含有芳香族骨格(ep)がアルキリデン基又は芳香族炭化水素構造含有メチレン基を介して結合した構造を基本骨格として有するエポキシ樹脂構造を有しており、かつ、該エポキシ樹脂構造の芳香核にナフチルメチル基又はアントニルメチル基を有するものであることを特徴とする熱硬化性樹脂組成物。
- 前記エポキシ樹脂(A’)が、グリシジルオキシ基含有芳香族骨格(ph)の総数を100とした場合、ナフチルメチル基又はアントニルメチル基の総数が10~200となる割合で含むものである請求項9記載の熱硬化性樹脂組成物。
- 前記エポキシ樹脂(A’)が、ICI粘度計で測定した150℃における溶融粘度が0.1~100dPa・sのものである請求項9又は10記載の熱硬化性樹脂組成物。
- 前記エポキシ樹脂(A’)及び前記硬化剤(B’)に加え、更に無機質充填材を組成物中70~95質量%となる割合で含有することを特徴とする半導体封止材料。
- 請求項9~10の何れか一つの熱硬化性樹脂組成物を硬化反応させてなることを特徴とする硬化物。
- 複数のグリシジルオキシ基含有芳香族骨格(ep)がアルキリデン基又は芳香族炭化水素構造含有メチレン基を介して結合した構造を基本骨格として有するエポキシ樹脂構造を有しており、かつ、該エポキシ樹脂構造の芳香核にナフチルメチル基又はアントニルメチル基を有することを特徴とするエポキシ樹脂。
- グリシジルオキシ基含有芳香族骨格(ph)の総数を100とした場合、ナフチルメチル基又はアントニルメチル基の総数を10~200となる割合で含むものである請求項14記載のエポキシ樹脂。
- 前記エポキシ樹脂が、ICI粘度計で測定した150℃における溶融粘度が0.1~100dPa・sのものである請求項14又は15記載のエポキシ樹脂。
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CN201180037503.0A CN103052667B (zh) | 2010-07-30 | 2011-07-19 | 固化性树脂组合物、其固化物、酚醛系树脂、环氧树脂、和半导体封装材料 |
US13/812,972 US20130184377A1 (en) | 2010-07-30 | 2011-07-19 | Curable resin composition, cured product thereof, phenol resin, epoxy resin, and semiconductor encapsulating material |
KR1020137001282A KR20130133747A (ko) | 2010-07-30 | 2011-07-19 | 경화성 수지 조성물, 그 경화물, 페놀계 수지, 에폭시 수지, 및 반도체 봉지 재료 |
EP11812307.4A EP2599812A4 (en) | 2010-07-30 | 2011-07-19 | CURABLE RESIN COMPOSITION, CURED PRODUCT OBTAINED THEREFROM, PHENOLIC RESIN, EPOXY RESIN, AND SEMICONDUCTOR SEALING MATERIAL |
SG2013006895A SG187238A1 (en) | 2010-07-30 | 2011-07-19 | Curing resin composition, cured product thereof, phenolic resin, epoxy resin, and semiconductor sealing material |
JP2012507518A JP5013234B2 (ja) | 2010-07-30 | 2011-07-19 | 硬化性樹脂組成物、その硬化物、フェノール系樹脂、エポキシ樹脂、及び半導体封止材料 |
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JP (1) | JP5013234B2 (ja) |
KR (1) | KR20130133747A (ja) |
CN (1) | CN103052667B (ja) |
MY (1) | MY156448A (ja) |
SG (1) | SG187238A1 (ja) |
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Cited By (6)
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JP2012077120A (ja) * | 2010-09-30 | 2012-04-19 | Dic Corp | 硬化性樹脂組成物、その硬化物、フェノール樹脂、エポキシ樹脂、及び半導体封止材 |
JP2013001863A (ja) * | 2011-06-20 | 2013-01-07 | Dic Corp | 硬化性樹脂組成物、その硬化物、フェノール樹脂、エポキシ樹脂、及び半導体封止材料 |
JP2013006954A (ja) * | 2011-06-24 | 2013-01-10 | Dic Corp | シアネート樹脂およびそれを含有する硬化性樹脂組成物 |
WO2013167733A1 (en) | 2012-05-09 | 2013-11-14 | Ion Beam Applications S.A. | Method for compensating the deviation of a hadron beam produced by a hadron-therapy installation |
JP2014037474A (ja) * | 2012-08-14 | 2014-02-27 | Dic Corp | 硬化性樹脂組成物、硬化物、及びプリント配線基板 |
WO2014073557A1 (ja) * | 2012-11-12 | 2014-05-15 | Dic株式会社 | フェノール性水酸基含有樹脂、エポキシ樹脂、硬化性樹脂組成物、その硬化物、及び半導体封止材料 |
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KR101480178B1 (ko) * | 2011-12-20 | 2015-01-09 | 제일모직주식회사 | 반도체 소자 밀봉용 에폭시 수지 조성물 및 이를 사용하여 밀봉된 반도체 소자 |
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JP2012077120A (ja) * | 2010-09-30 | 2012-04-19 | Dic Corp | 硬化性樹脂組成物、その硬化物、フェノール樹脂、エポキシ樹脂、及び半導体封止材 |
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JP2014037474A (ja) * | 2012-08-14 | 2014-02-27 | Dic Corp | 硬化性樹脂組成物、硬化物、及びプリント配線基板 |
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JP5614520B1 (ja) * | 2012-11-12 | 2014-10-29 | Dic株式会社 | フェノール性水酸基含有樹脂、エポキシ樹脂、硬化性樹脂組成物、その硬化物、及び半導体封止材料 |
KR20150084768A (ko) * | 2012-11-12 | 2015-07-22 | 디아이씨 가부시끼가이샤 | 페놀성 수산기 함유 수지, 에폭시 수지, 경화성 수지 조성물, 그 경화물, 및 반도체 봉지 재료 |
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US9580634B2 (en) | 2012-11-12 | 2017-02-28 | Dic Corporation | Phenolic-hydroxyl-containing resin, epoxy resin, curable resin composition, substance obtained by curing same, and semiconductor sealant |
KR102020854B1 (ko) | 2012-11-12 | 2019-09-16 | 디아이씨 가부시끼가이샤 | 페놀성 수산기 함유 수지, 에폭시 수지, 경화성 수지 조성물, 그 경화물, 및 반도체 봉지 재료 |
Also Published As
Publication number | Publication date |
---|---|
EP2599812A1 (en) | 2013-06-05 |
CN103052667A (zh) | 2013-04-17 |
JPWO2012014715A1 (ja) | 2013-09-12 |
SG187238A1 (en) | 2013-03-28 |
CN103052667B (zh) | 2014-03-26 |
MY156448A (en) | 2016-02-26 |
US20130184377A1 (en) | 2013-07-18 |
EP2599812A4 (en) | 2015-03-18 |
KR20130133747A (ko) | 2013-12-09 |
TWI472559B (zh) | 2015-02-11 |
JP5013234B2 (ja) | 2012-08-29 |
TW201224008A (en) | 2012-06-16 |
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