WO2022208962A1 - Magnesium oxide composition powder, resin composition, resin composition sheet, laminated substrate, and reactive resin composition - Google Patents
Magnesium oxide composition powder, resin composition, resin composition sheet, laminated substrate, and reactive resin composition Download PDFInfo
- Publication number
- WO2022208962A1 WO2022208962A1 PCT/JP2021/039907 JP2021039907W WO2022208962A1 WO 2022208962 A1 WO2022208962 A1 WO 2022208962A1 JP 2021039907 W JP2021039907 W JP 2021039907W WO 2022208962 A1 WO2022208962 A1 WO 2022208962A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- magnesium oxide
- resin composition
- powder
- composition
- resin
- Prior art date
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- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 193
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 193
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 239000000843 powder Substances 0.000 title claims abstract description 182
- 239000000203 mixture Substances 0.000 title claims abstract description 177
- 239000011342 resin composition Substances 0.000 title claims description 142
- 239000000758 substrate Substances 0.000 title claims description 25
- 239000002245 particle Substances 0.000 claims abstract description 33
- 229910021488 crystalline silicon dioxide Inorganic materials 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims description 63
- 239000010410 layer Substances 0.000 claims description 60
- 239000002184 metal Substances 0.000 claims description 55
- 239000003822 epoxy resin Substances 0.000 claims description 50
- 229920000647 polyepoxide Polymers 0.000 claims description 50
- 239000000654 additive Substances 0.000 claims description 38
- 230000000996 additive effect Effects 0.000 claims description 38
- 229920005989 resin Polymers 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 30
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 19
- 239000012044 organic layer Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 22
- 239000002253 acid Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- 239000002002 slurry Substances 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- 229910004298 SiO 2 Inorganic materials 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000011162 core material Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 description 11
- 229920002799 BoPET Polymers 0.000 description 10
- 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 10
- 238000000034 method Methods 0.000 description 10
- 238000004062 sedimentation Methods 0.000 description 10
- 229920005992 thermoplastic resin Polymers 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229920001709 polysilazane Polymers 0.000 description 9
- 229910052906 cristobalite Inorganic materials 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 229910052905 tridymite Inorganic materials 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 235000002597 Solanum melongena Nutrition 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 4
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical group ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- -1 alkoxysilanes Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- MQQXUGFEQSCYIA-OAWHIZORSA-M aluminum;(z)-4-ethoxy-4-oxobut-2-en-2-olate;propan-2-olate Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CCOC(=O)\C=C(\C)[O-] MQQXUGFEQSCYIA-OAWHIZORSA-M 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 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 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 2
- 229940082004 sodium laurate Drugs 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- HRSLYNJTMYIRHM-UHFFFAOYSA-N 2-[[4-[3,5-dimethyl-4-(oxiran-2-ylmethoxy)phenyl]-2,6-dimethylphenoxy]methyl]oxirane Chemical group CC1=CC(C=2C=C(C)C(OCC3OC3)=C(C)C=2)=CC(C)=C1OCC1CO1 HRSLYNJTMYIRHM-UHFFFAOYSA-N 0.000 description 1
- OZRVXYJWUUMVOW-UHFFFAOYSA-N 2-[[4-[4-(oxiran-2-ylmethoxy)phenyl]phenoxy]methyl]oxirane Chemical compound C1OC1COC(C=C1)=CC=C1C(C=C1)=CC=C1OCC1CO1 OZRVXYJWUUMVOW-UHFFFAOYSA-N 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
- CXXSQMDHHYTRKY-UHFFFAOYSA-N 4-amino-2,3,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1=C(O)C(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 CXXSQMDHHYTRKY-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-PZFLKRBQSA-N 4-amino-3,5-ditritiobenzoic acid Chemical compound [3H]c1cc(cc([3H])c1N)C(O)=O ALYNCZNDIQEVRV-PZFLKRBQSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
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- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- YNCDEEFMDXHURQ-UHFFFAOYSA-N aluminum;ethyl 3-oxobutanoate Chemical compound [Al].CCOC(=O)CC(C)=O YNCDEEFMDXHURQ-UHFFFAOYSA-N 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 150000002460 imidazoles Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 150000003003 phosphines Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003351 stiffener Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
Definitions
- the present invention relates to a magnesium oxide composition powder, a resin composition, a resin composition sheet, a laminated substrate and a reactive resin composition.
- Magnesium oxide (MgO) powder which has excellent thermal conductivity, is being researched, developed, and used as an inorganic filler.
- magnesium oxide powder reacts with water and changes to magnesium hydroxide, and also dissolves in acid. Therefore, by adjusting the chemical components and performing surface treatment, magnesium oxide that is imparted with water resistance and acid resistance has been developed (Patent Documents 2 to 4, Non-Patent Document 1).
- magnesium oxide powder In order to improve the water resistance and acid resistance of magnesium oxide powder, it is effective to adjust the chemical composition of magnesium oxide powder and perform surface treatment. However, when the chemical components of the magnesium oxide powder are adjusted or the surface is treated, the high thermal conductivity of the magnesium oxide powder may deteriorate. Further improvements are required to sufficiently improve water resistance and acid resistance while maintaining the high thermal conductivity of magnesium oxide powder.
- the present invention has been made in view of the above problems, and provides a magnesium oxide composition powder, a resin composition, a resin composition sheet, and a laminated substrate having high thermal conductivity and excellent water resistance and acid resistance. aim. Another object of the present invention is to provide a reactive resin composition that can produce a resin composition that has high thermal conductivity and excellent water resistance and acid resistance.
- the present inventors have found that the surface of magnesium oxide particles is coated with an oxide layer containing crystalline SiO2 or a crystalline double oxide containing Si and Al. It was found that it is possible to improve water resistance and acid resistance while maintaining the high thermal conductivity of magnesium oxide powder. And the inventors have found that by using a magnesium oxide composition powder coated with an oxide layer containing crystalline SiO2 or a crystalline double oxide containing Si and Al, the thermal conductivity is high and the water resistance is high.
- the present invention was completed by confirming that it is possible to obtain a resin composition, a resin composition sheet, a laminated substrate, and a reactive resin composition capable of producing the above-mentioned resin composition. let me That is, the present invention relates to the following inventions.
- a magnesium oxide composition powder having magnesium oxide particles and an oxide layer covering at least part of the surface of the magnesium oxide particles, wherein the oxide layer contains crystalline SiO2 .
- the oxide layer contains the crystalline SiO2 and an additive metal element other than Si, and the additive metal element is selected from the group consisting of alkali metals, alkaline earth metals, Al, Ti, and Zr.
- a magnesium oxide composition comprising magnesium oxide particles and an oxide layer covering at least part of the surface of the magnesium oxide particles, wherein the oxide layer contains a crystalline multiple oxide containing Si and Al. powder.
- the oxide layer contains the crystalline multiple oxide and an additive metal element other than Si and Al, and the additive metal element is selected from the group consisting of alkali metals, alkaline earth metals, Ti and Zr.
- a reactive resin composition comprising a reactive curable resin composition and the magnesium oxide composition powder according to [1] to [7].
- n is an integer of 2 to 40.
- the present invention it is possible to provide a magnesium oxide composition powder, a resin composition, a resin composition sheet, and a laminated substrate that have high thermal conductivity and are excellent in water resistance and acid resistance. Moreover, the present invention makes it possible to provide a reactive resin composition that has high thermal conductivity and can produce a resin composition that is excellent in water resistance and acid resistance.
- FIG. 1 is a cross-sectional view of a magnesium oxide composition powder according to one embodiment of the present invention.
- FIG. 2 is a perspective view of a resin composition sheet according to one embodiment of the present invention.
- FIG. 3 is a cross-sectional view of the resin composition sheet shown in FIG. 2 taken along line III-III.
- FIG. 4 is a perspective view of a laminated substrate according to one embodiment of the present invention. 5 is a cross-sectional view of the laminated substrate shown in FIG. 4 taken along the line VV.
- the magnesium oxide composition powder according to the embodiment of the present invention is, for example, dispersed in an organic solvent or resin as an inorganic filler for a resin composition.
- a resin composition, a resin composition sheet, and a laminated substrate according to embodiments of the present invention contain a resin and a magnesium oxide composition powder, and are used, for example, as materials for circuit boards of equipment.
- the reactive resin composition contains a reactive curable resin composition and a magnesium oxide composition powder, and for example, a resin composition is produced by curing the reactive curable resin composition.
- FIG. 1 is a cross-sectional view of a magnesium oxide composition powder according to one embodiment of the present invention.
- Magnesium oxide composition powder 10 shown in FIG. 1 has magnesium oxide particles 11 , oxide layer 12 covering magnesium oxide particles 11 , and organic layer 13 covering oxide layer 12 .
- the shape of the magnesium oxide particles 11 is not particularly limited.
- the magnesium oxide particles 11 may be spherical, oval, cylindrical, or prismatic, for example.
- the magnesium oxide particles 11 may have an average particle diameter (d50) of, for example, 1 ⁇ m or more and 50 ⁇ m or less, preferably 2 ⁇ m or more and 30 ⁇ m or less.
- the average particle size of magnesium oxide particles is a value measured by a laser diffraction scattering method.
- the magnesium oxide particles 11 may have a specific surface area, for example, in the range of 0.1 m 2 /g or more and 10 m 2 /g or less, or in the range of 0.2 m 2 /g or more and 5 m 2 /g or less. It is preferable to be in
- the oxide layer 12 comprises crystalline SiO2 .
- crystalline SiO 2 contained in the oxide layer 12 include tridymite, cristobalite and quartz.
- the oxide layer 12 may contain one of these crystalline SiO 2 alone, or may contain two or more of them.
- the inclusion of crystalline SiO 2 in the oxide layer 12 can be confirmed, for example, by the X-ray diffraction pattern of the magnesium oxide composition powder 10 .
- the oxide layer 12 is crystalline SiO 2 including.
- the oxide layer 12 may contain additional metal elements other than Si. Moreover, the oxide layer 12 may contain additional metal elements other than Si and Al. Alkaline metals (Li, Na, K, Rb, Cs, Fr), alkaline earth metals (Ca, Sr, Ba, Ra), Al, Ti, Zr can be used as the additive metal element. These additive metal elements may be contained singly or in combination of two or more. The additive metal element may be, for example, either one or both of Li and Na.
- the additive metal element in the oxide layer 12 may form an oxide, or may form a composite oxide together with Si in the oxide layer 12 .
- the oxide layer 12 may contain a composite oxide containing Si and Al.
- the oxide layer 12 may contain a crystalline multiple oxide composed of Si, Al, and O, may contain a crystalline multiple oxide composed of Si, Li, and O, or may include a crystal composed of Si, Na, and O.
- may contain a crystalline mixed oxide may contain a crystalline mixed oxide consisting of Si, K and O, may contain a crystalline mixed oxide consisting of Si, Rb and O, may contain Si, Cs, It may contain a crystalline multiple oxide made of O, may contain a crystalline multiple oxide made of Si, Ca, and O, or may contain a crystalline multiple oxide made of Si, Ti, and O, A crystalline multiple oxide composed of Si, Zr, and O may also be included.
- the content of the additive metal element in the oxide layer 12 or the content of the metal element other than Si in the oxide layer 12 may be, for example, 15 at % or less, and is in the range of 1 at % or more and 10 at % or less. is preferred.
- the content of the additive metal element is a value where the total amount of silicon (Si), the additive metal element, and oxygen (O) in the oxide layer 12 is 100 at %.
- the thickness of the oxide layer 12 may be, for example, within the range of 20 nm or more and 500 nm or less, preferably within the range of 50 nm or more and 200 nm or less, and particularly preferably within the range of 80 nm or more and 150 nm.
- the organic layer 13 preferably contains an organic material having a group having an affinity for the oxide layer 12 and a group having an affinity for the organic solvent or resin in which the magnesium oxide composition powder 10 is dispersed.
- Groups having an affinity for the oxide layer 12 include alkoxy groups, phosphonic acid groups, carboxylic acid groups, and sulfonic acid groups.
- groups having an affinity for resins include epoxy groups, vinyl groups, acrylate groups, methacrylate groups, mercapto groups, amino groups, aryl groups, and alkyl groups.
- the organic substance contained in the organic substance layer 13 may be, for example, one or both of phosphonic acid and a silane coupling agent.
- the thickness of the organic layer 13 may be, for example, within the range of 0.5 nm or more and 10 nm or less.
- the thickness of the organic layer 13 is preferably in the range of 0.5 nm or more and 5 nm or less.
- the magnesium oxide composition powder 10 according to this embodiment can be produced, for example, as follows. First, the magnesium oxide powder, the SiO 2 source, and the additive metal element compound containing the additive metal element are mixed in a solvent to obtain a raw material mixture. Next, the raw material mixed liquid is dried to obtain a dried raw material mixture. Next, the dried raw material mixture is heat-treated. Then, the obtained heat-treated product is pulverized with a mill to obtain a powder. In this production method, crystalline SiO 2 is produced by heat treatment of the raw material mixture dried product. By including the additive metal element in the dried raw material mixture, crystalline SiO 2 can be generated by heat treatment at a lower temperature than when the additive metal element is not included. The temperature of the heat treatment of the dried raw material mixture may be, for example, within the range of 700° C. or higher and 1000° C. or lower.
- the magnesium oxide composition powder 10 can also be produced as follows. First, the magnesium oxide powder and the SiO2 source are mixed to coat the surface of the magnesium oxide powder with the SiO2 source. Next, the SiO 2 source-coated magnesium oxide powder and the compound of the additional metal element are mixed to cause the additional metal element compound to adhere to the surface of the SiO 2 source-coated magnesium oxide powder. Then, the SiO 2 source-coated magnesium oxide powder to which the additive metal element compound is attached is heat-treated. Then, the obtained heat-treated product is pulverized with a mill to obtain a powder. In this production method, crystalline SiO 2 is produced by heat treatment of the SiO 2 source-coated magnesium oxide powder.
- crystalline SiO 2 can be generated by heat treatment at a lower temperature than when the additive metal element is not attached.
- the temperature of the heat treatment of the SiO 2 source-coated magnesium oxide powder may be, for example, within the range of 700° C. or higher and 1000° C. or lower.
- organic silicon compounds such as alkoxysilanes, polysilazanes, and silicone oils can be used as the SiO2 source.
- the additive metal element compound for example, carbonate, acetate, oxyacetate and organic compound can be used.
- organic compounds include ALCH (aluminum ethyl acetoacetate diisopropylate).
- the oxide layer 12 covering the magnesium oxide particles 11 contains crystalline SiO 2 or a crystalline multiple oxide containing Si and Al.
- the crystalline double oxide may or may not contain crystalline SiO2 .
- Crystalline double oxides such as crystalline SiO2 have high thermal conductivity and are chemically stable.
- the crystalline double oxide contains Al and other metal elements (for example, at least one element selected from the group consisting of alkali metals, alkaline earth metals, Ti, and Zr), chemical stability is improved. can be further enhanced. Therefore, the magnesium oxide composition powder 10 according to the present embodiment has high thermal conductivity and excellent water resistance and acid resistance.
- the magnesium oxide composition powder 10 according to the present embodiment when the oxide layer 12 contains the above-described additive metal element in an amount of 15 at% or less, the content of crystalline SiO 2 in the oxide layer 12 is becomes more likely to occur. Therefore, the thermal conductivity of the magnesium oxide composition powder 10 is higher, and the water resistance and acid resistance are further improved. Therefore, the magnesium oxide composition powder 10 of the present embodiment is suitable as an inorganic filler for circuit boards of equipment.
- the magnesium oxide composition powder 10 when the additive metal element is either one or both of Li and Na, since these metal elements have small atomic weights, the magnesium oxide composition powder 10 During production, crystalline SiO 2 is likely to be generated, and the heat treatment temperature can be set to a lower temperature. By setting the heat treatment temperature to a low temperature, the magnesium oxide powder is less likely to be sintered, so the magnesium oxide composition powder 10 has a higher uniformity in particle size, and tends to improve dispersibility in organic solvents and resins. There is Furthermore, since crystalline SiO 2 is easily generated, the amount of the additive metal element used can be reduced.
- the magnesium oxide composition powder 10 according to the present embodiment when coated with the organic layer 13, it has a high affinity for organic solvents and resins. Therefore, the magnesium oxide composition powder 10 has improved dispersibility in organic solvents and resins. Further, in the magnesium oxide composition powder 10 according to the present embodiment, when the organic layer 13 contains one or both of phosphonic acid and a silane coupling agent, these organic substances have a high affinity with the oxide layer 12. Therefore, the water resistance, acid resistance and dispersibility of the magnesium oxide composition powder 10 are further improved.
- the invention is not limited to this example.
- a part of the surface of the magnesium oxide particles 11 may be covered with the oxide layer 12 in order to bring the magnesium oxide particles 11 into direct contact with each other and improve the thermal conductivity.
- the organic layer 13 may be scattered on the surface of the magnesium oxide particles 11 .
- the organic layer 13 may not be provided on the surface of the magnesium oxide particles 11 depending on the application or the object in which the magnesium oxide composition powder 10 is dispersed.
- the resin composition of the present embodiment includes a resin and the magnesium oxide composition powder of the present embodiment described above.
- a resin for example, a cured product of a thermoplastic resin or a reaction-curable resin composition can be used.
- the thermoplastic resin for example, polystyrene and acrylic resin can be used.
- a cured product of the reaction-curable resin composition is a resin composition obtained by subjecting the reaction-curable resin composition to a curing reaction by applying energy such as heat or light from the outside.
- the cured product of the reactive curable resin composition a cured product of the reactive curable resin composition containing an epoxy resin and a curing agent can be used. The reaction-curable resin composition will be described later.
- the content of the magnesium oxide composition powder may be, for example, in the range of 10% by volume or more and 80% by volume or less, or in the range of 40% by volume or more and 80% by volume or less. It is preferably in the range of 50% by volume or more and 75% by volume or less.
- the content of the magnesium oxide composition powder is 30% by volume or more, the effect of improving the thermal conductivity of the cured product of the resin composition becomes remarkable. Further, when the content of the magnesium oxide composition powder is 80% by volume or less, sufficient moldability can be obtained when molding a resin substrate using a cured product of the resin composition.
- the resin composition of the present embodiment may contain inorganic powder other than the magnesium oxide composition powder.
- inorganic powders include boron nitride powder, alumina powder, aluminum hydroxide powder, aluminum nitride powder and silica powder. These inorganic powders may contain one type alone, or may contain two or more types.
- the content of the inorganic powder is the total amount with the magnesium oxide composition powder, and may be, for example, in the range of 20% by volume or more and 80% by volume or less, or in the range of 40% by volume or more and 80% by volume or less. more preferably in the range of 50% by volume or more and 75% by volume or less.
- the resin composition of the present embodiment may contain optional components other than the components described above, if necessary.
- Optional components include coupling agents such as silane coupling agents and titanate coupling agents, flame retardants such as halogens, plasticizers, and lubricants.
- the resin composition of the present embodiment may contain a reinforcing material.
- the stiffener may be insulating. As the insulating reinforcing material, for example, a glass cloth (glass cloth) made by knitting glass fibers into a cloth can be used.
- the resin composition of the present embodiment can be produced, for example, by mixing a thermoplastic resin and magnesium oxide composition powder.
- the resin composition of the present embodiment can also be produced by a method of mixing an uncured reactive curable resin composition and magnesium oxide composition powder and curing the resulting reactive resin composition. can.
- the resin composition of the present embodiment contains the magnesium oxide composition powder of the present embodiment described above, it has high thermal conductivity and excellent water resistance and acid resistance. Therefore, the resin composition of the present embodiment is suitable as a material for circuit boards of equipment.
- FIG. 2 is a perspective view of a resin composition sheet according to one embodiment of the present invention
- FIG. 3 is a cross-sectional view of the resin composition sheet shown in FIG. 2, taken along line III-III.
- the resin composition sheet 20 shown in FIGS. 2 and 3 contains a core material 21 and a resin composition 23 impregnated in the core material 21 and covering both sides of the core material 21 .
- the core material 21 is a glass cloth in which warp threads 21a made of glass and weft threads 21b made of glass are woven.
- the resin composition 23 includes the resin 22 and the magnesium oxide composition powder 10.
- the resin 22 for example, a cured product of a thermoplastic resin or a reaction-curable resin composition can be used.
- the resin composition 23 is the resin composition of the present embodiment described above.
- the resin composition sheet 20 using a thermoplastic resin as the resin 22 can be produced, for example, as follows. First, a raw material slurry containing a thermoplastic resin is prepared by dispersing the magnesium oxide composition powder 10 in a thermoplastic resin solution. Next, the core material 21 is impregnated with the thermoplastic resin-containing raw material slurry by a technique such as coating or immersion. Next, the solvent of the thermoplastic resin-containing raw material slurry impregnated in the core material 21 is removed by heating. The heating conditions for removing the solvent from the thermoplastic resin-containing raw material slurry can be, for example, about 60 to 150° C. for about 1 to 120 minutes, preferably about 70 to 120° C. for about 3 to 90 minutes. .
- the resin composition sheet 20 using a cured product of a reaction-curable resin composition as the resin 22 can be produced, for example, as follows. First, a raw material slurry containing a reactive resin composition is prepared by dispersing the magnesium oxide composition powder 10 in a reactive resin composition. Next, the core material 21 is impregnated with the raw material slurry containing the reactive resin composition by a technique such as coating or dipping. Next, the solvent of the raw material slurry containing the reactive resin composition impregnated in the core material 21 is removed by heating. The heating conditions for removing the solvent from the raw material slurry containing the reactive resin composition may be, for example, 60 to 150° C. for about 1 to 120 minutes, and 70 to 120° C. for about 3 to 90 minutes. is preferred.
- the reactive resin composition impregnated in the core material 21 is cured at the same time as the reactive resin composition-containing raw material slurry is heated to remove the solvent. After heating the raw material slurry containing the reactive resin composition to remove the solvent, the reactive resin composition impregnated in the core material 21 is cured under the same conditions as the heating for removing the solvent. good too.
- the resin composition sheet 20 according to this embodiment contains the resin composition of this embodiment described above, it has high thermal conductivity and is excellent in water resistance and acid resistance. Therefore, the resin composition sheet 20 of the present embodiment is suitable as a material for circuit boards of equipment.
- the resin composition sheet 20 is described using glass cloth as the core material 21 as an example, but the present invention is limited to this example. not something.
- a woven fabric or non-woven fabric using fibers other than glass fibers can be used as the core material 21, a woven fabric or non-woven fabric using fibers other than glass fibers can be used.
- fibers other than glass fibers carbon fibers, metal fibers, natural fibers and synthetic fibers can be used.
- synthetic fibers include polyester fibers and polyamide fibers. These fibers may contain only one type, or may contain two or more types.
- the resin composition sheet of the present invention may be formed only of a resin component without having a core material.
- a metal foil such as copper foil may be laminated on the surface of the resin composition sheet.
- [Laminate substrate] 4 is a perspective view of a layered substrate according to one embodiment of the present invention
- FIG. 5 is a cross-sectional view of the layered substrate shown in FIG. 4 taken along line VV.
- a laminated substrate 30 is formed by laminating and integrating a plurality of resin composition sheets 20 shown in FIGS.
- the laminated substrate 30 can be manufactured, for example, by a method of heating a plurality of resin composition sheets 20 in a superimposed state.
- the resin 22 of the resin composition sheet 20 is a cured product of a reactive resin composition
- the reactive resin composition of the resin composition sheet 20 before heating is in a semi-cured or uncured state, and the resin composition
- the reactive resin composition may be cured when the sheets 20 are superimposed and heated.
- the heating conditions for the plurality of resin composition sheets 20 can be, for example, 100 to 250° C. for about 1 to 300 minutes.
- the pressurizing condition can be, for example, about 0.1 to 10 MPa. Pressurization is not essential when heating the plurality of resin composition sheets 20 . Moreover, the heating of the plurality of resin composition sheets 20 may be performed under reduced pressure or vacuum.
- the laminated substrate 30 of the present embodiment has a high thermal conductivity because the resin composition sheets 20 are laminated. Therefore, the laminated substrate 30 of the present embodiment is suitable as a material for circuit boards of equipment.
- the laminated substrate 30 an example in which a plurality of the resin composition sheets 20 shown in FIGS. 2 and 3 are laminated has been described. At least one of them may be the resin composition sheet of the present invention.
- the laminated substrate of the present invention may be, for example, a metal-clad laminate having a metal layer on the upper surface and/or the lower surface.
- various known metal layers can be appropriately selected and used as the metal layer.
- a metal plate or metal foil made of metal such as copper, nickel, or aluminum can be used as the metal layer.
- the thickness of the metal layer is not particularly limited, and can be, for example, about 3 to 150 ⁇ m.
- a metal plate or a metal foil subjected to etching and/or perforation processing may be used.
- the reactive resin composition of the present embodiment includes a reaction-curable resin composition and the magnesium oxide composition powder of the present embodiment described above.
- a reaction-curable resin composition reacts and cures when energy such as heat or light is applied from the outside.
- reaction-curable resin composition for example, an epoxy-based resin composition containing an epoxy resin and a curing agent may be used.
- the epoxy resin composition may further contain a curing accelerator.
- epoxy resins examples include 4,4'-biphenol diglycidyl ether, 3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl, triglycidyl Known epoxy compounds such as isocyanurate (TGI), triglycidyl-p-aminophenol, novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, tetraglycidyldiaminodiphenylmethane type epoxy resin are used. A commercially available epoxy resin may be used. These epoxy resins may contain only one type, or may contain two or more types.
- a compound having a reactive group that reacts with the epoxy group of the epoxy resin can be used as the curing agent.
- reactive groups include amino groups and phenolic hydroxyl groups.
- Curing agents include, for example, p-phenylenediamine, 1,5-diaminonaphthalene, hydroquinone, 2,6-dihydroxynaphthalene, phloroglucinol, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4-amino Benzoic acid, phenolic resins, polyamidoamines can be used. Also, a compound represented by the following general formula (1) can be used. These curing agents may be contained alone or in combination of two or more.
- n is an integer of 2-40.
- the curing agent using the compound represented by Formula (1) may contain two or more compounds in which n in Formula (1) is a different integer.
- the compound represented by formula (1) is a chain compound having a skeleton containing a mesogenic group.
- the position of the methyl group bonded to the benzene ring is not particularly limited.
- the content of the epoxy resin and the curing agent in the reactive resin composition is, for example, based on the total number of moles of reactive groups of the curing agent contained in the reactive resin composition being 1 mol,
- the total number of moles of epoxy groups in the resin is preferably in the range of 0.9 mol or more and 1.3 mol or less, and is in the range of 1.0 mol or more and 1.2 mol or less. is more preferred.
- a basic organic compound with a high boiling point can be used as the curing accelerator.
- curing accelerators include those having a boiling point of 200° C. or higher selected from tertiary amines, tertiary phosphines, 4-dimethylaminopyridine (DMAP), imidazoles, and the like.
- DMAP 4-dimethylaminopyridine
- imidazoles and the like.
- 2-ethyl-4-methylimidazole (2E4MZ) and 1-(2-cyanoethyl)-2-phenylimidazole which are imidazole-based epoxy resin curing accelerators, are particularly used as curing accelerators for ease of handling. It is preferable to use
- the content of the curing accelerator in the reactive resin composition is, for example, within the range of 0 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the epoxy resin.
- the content of the magnesium oxide composition powder may be, for example, in the range of 10% by volume or more and 80% by volume or less, or in the range of 40% by volume or more and 80% by volume or less. It is preferably within the range of 50% by volume or more and 75% by volume or less.
- the reactive resin composition of the present embodiment may contain inorganic powder other than the magnesium oxide composition powder.
- inorganic powders include boron nitride powder, alumina powder, aluminum hydroxide powder, aluminum nitride powder and silica powder. These inorganic powders may contain one type alone, or may contain two or more types.
- the content of the inorganic powder is the total amount with the magnesium oxide composition powder, and may be, for example, in the range of 20% by volume or more and 80% by volume or less, or in the range of 40% by volume or more and 80% by volume or less. more preferably in the range of 50% by volume or more and 75% by volume or less.
- the reactive resin composition of the present embodiment can be produced, for example, by mixing a reactive curable resin composition and magnesium oxide composition powder in a solvent and drying.
- solvents include ketones such as acetone and methyl ethyl ketone (MEK); alcohols such as methanol, ethanol and isopropanol; aromatic compounds such as toluene and xylene; ethers such as tetrahydrofuran (THF) and 1,3-dioxolane; Examples include esters such as ethyl acetate and ⁇ -butyrolactone, and amides such as N,N-dimethylformamide (DMF) and N-methylpyrrolidone. These solvents may be used singly or in combination of two or more.
- MEK acetone and methyl ethyl ketone
- alcohols such as methanol, ethanol and isopropanol
- aromatic compounds such as toluene and xylene
- ethers such as
- the reactive resin composition of the present embodiment includes the reaction-curable resin composition and the magnesium oxide composition powder of the present embodiment described above, curing the reaction-curable resin composition increases the thermal conductivity It is possible to produce a resin composition that has a high resistance to water and is excellent in water resistance and acid resistance.
- the produced resin composition can be used, for example, as a material for circuit boards of electronic devices.
- the reactive resin composition of the present embodiment when the reactive curable resin composition contains an epoxy resin and a curing agent, it is possible to obtain a resin composition that is chemically more stable and has excellent water resistance and acid resistance. . Furthermore, when the epoxy resin is triglycidyl isocyanurate and the curing agent is a chain compound having a skeleton containing a mesogenic group represented by the above general formula (1), the resin composition has a higher thermal conductivity. can get things. When the compound represented by the formula (1) is used as the curing agent, the rigidity is imparted to the cured product by the skeleton containing the mesogenic group of the curing agent, so the thermal conductivity of the resin composition (cured product) improves.
- Example 1 A 100 mL eggplant flask was charged with 20 g of magnesium oxide powder (average particle diameter: 10 ⁇ m, specific surface area: 0.7 m 2 /g), 42.0 g of polysilazane solution with a concentration of 5% as a SiO 2 source, and acetic acid as an additive metal element compound. 0.106 g of lithium was added and mixed with stirring for 10 minutes to obtain a raw material mixture. Next, the raw material mixture was air-dried to remove the solvent to obtain a dried raw material. Next, the raw material mixed dried material was heated at 150° C. for 1 hour and then heat-treated at 800° C. for 6 hours. The obtained heat-treated product was pulverized with a mill to obtain a magnesium oxide composition powder.
- Example 2 A magnesium oxide composition powder was obtained in the same manner as in Example 1.
- the resulting magnesium oxide composition powder and a silane coupling agent KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.
- IPA isopropyl alcohol
- the amount of the silane coupling agent added was 5% by mass with respect to the magnesium oxide composition powder.
- the solvent was then removed using a rotary evaporator, followed by drying at 120° C. for 30 minutes.
- the magnesium oxide composition powder was surface-treated with a silane coupling agent.
- Examples 3 to 5 A magnesium oxide composition powder was obtained in the same manner as in Example 1, except that the amount of the 5% polysilazane solution and the type and amount of the additive metal element compound were changed as shown in Table 1 below. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
- Example 6 A magnesium oxide composition powder was obtained in the same manner as in Example 1, except that 0.153 g of sodium carbonate was used as the additive metal element compound instead of lithium acetate.
- Example 7 A magnesium oxide composition powder was obtained in the same manner as in Example 6. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
- Example 8 A magnesium oxide composition powder was obtained in the same manner as in Example 6. The obtained magnesium oxide composition powder and phenylphosphonic acid (PPA) were put into a dioxolane solvent and stirred and mixed for 30 minutes. The amount of PPA added was 5% by mass with respect to the magnesium oxide composition powder. The solvent was then removed using a rotary evaporator and then dried at 140° C. overnight. Thus, the magnesium oxide composition powder was surface-treated with PPA.
- PPA phenylphosphonic acid
- Example 9 to 17 A magnesium oxide composition powder was obtained in the same manner as in Example 1, except that the type and amount of the additive metal element compound were changed as shown in Table 1 below. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
- Example 18 20 g of magnesium oxide powder and 42.0 g of a polysilazane solution having a concentration of 5% as a SiO 2 source were put into a 100 mL eggplant flask, and stirred and mixed for 10 minutes to obtain a mixed solution. The resulting mixture was air-dried to remove the solvent, and then heated at 150° C. for 1 hour to obtain SiO 2 source-coated magnesium oxide powder. Next, the obtained SiO 2 source-coated magnesium oxide powder and 3.360 g of an aqueous zirconium oxyacetate solution as an additive metal element compound were mixed and air-dried to remove the solvent (water). The SiO 2 source-coated magnesium oxide powder with zirconium oxyacetate attached was then heated at 150° C.
- Example 2 The obtained heat-treated product was pulverized with a mill to obtain a magnesium oxide composition powder.
- the resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
- Example 19 50 g of ethanol, 10 g of ion-exchanged water, 1 g of 28% by mass ammonia water, and 20 g of magnesium oxide powder were put into a 200 mL eggplant flask and stirred and mixed for 30 minutes. After that, TEOS (tetraethoxysilane) diluted with ethanol was added dropwise, and the mixture was further stirred and mixed for 2 hours to obtain a mixture. The resulting mixture was filtered and the solid collected was washed with ethanol, then dried at 70° C. for 1 hour and then heat-treated at 180° C. for 3 hours to obtain SiO 2 source-coated magnesium oxide powder. The resulting SiO 2 source coated magnesium oxide composition was mixed with 0.153 g of sodium carbonate.
- TEOS tetraethoxysilane
- the SiO 2 source-coated magnesium oxide powder with attached sodium carbonate was then heat-treated at 800° C. for 6 hours.
- the obtained heat-treated product was pulverized with a mill to obtain a magnesium oxide composition powder.
- the resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
- Example 20 In a 100 mL eggplant flask, 20 g of magnesium oxide powder, 3 g of silicone oil (KF-96, manufactured by Shin-Etsu Chemical Co., Ltd.) as a SiO 2 source, 0.153 g of sodium carbonate as an additive metal element compound, and 20 mL of hexane were added. , and stirred and mixed for 10 minutes to obtain a raw material mixture. The resulting raw material mixture was air-dried to remove the solvent to obtain a dried raw material. Next, the raw material mixed dried material was heated at 150° C. for 1 hour and then heat-treated at 800° C. for 6 hours. The obtained heat-treated product was pulverized with a mill to obtain a magnesium oxide composition powder. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
- silicone oil KF-96, manufactured by Shin-Etsu Chemical Co., Ltd.
- Example 21 As the magnesium oxide powder, 20 g of magnesium oxide powder having an average particle size of 3 ⁇ m and a specific surface area of 1.4 m 2 /g was used, and 84.0 g of a polysilazane solution having a concentration of 5% was used. A magnesium oxide composition powder was obtained in the same manner as in Example 1, except that 0.306 g of sodium carbonate was used instead. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
- Example 22 As the magnesium oxide powder, 20 g of magnesium oxide powder having an average particle size of 17 ⁇ m and a specific surface area of 0.5 m 2 /g was used, and 30.0 g of a polysilazane solution having a concentration of 5% was used. A magnesium oxide composition powder was obtained in the same manner as in Example 1, except that 0.110 g of sodium carbonate was used instead. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
- Example 23 A magnesium oxide composition powder was obtained in the same manner as in Example 6, except that the blending amount of the 5% polysilazane solution and the blending amount of sodium carbonate were set to the amounts shown in Table 1 below.
- Example 1 A magnesium oxide composition powder was obtained in the same manner as in Example 1, except that sodium carbonate was not used.
- Example 2 A magnesium oxide composition powder was obtained in the same manner as in Example 6, except that the blending amount of the 5% polysilazane solution and the blending amount of sodium carbonate were set to the amounts shown in Table 2 below.
- Example 3 A magnesium oxide composition powder was obtained in the same manner as in Example 21 except that sodium carbonate was not used, and the obtained magnesium oxide composition powder was surface-treated with a silane coupling agent.
- Example 4 A magnesium oxide composition powder was obtained in the same manner as in Example 22, except that sodium carbonate was not used, and the obtained magnesium oxide composition powder was surface-treated with a silane coupling agent.
- the magnesium oxide composition powders obtained in Examples 1 to 23 and Comparative Examples 1 to 4 were subjected to EDS (energy dispersive X-ray) using an atomic resolution electron microscope (JEM-ARM300F GRAND ARM, manufactured by JEOL Ltd.) analysis) performed elemental mapping. As a result, it was confirmed that the magnesium oxide composition powder was coated with an oxide layer containing SiO2 .
- EDS energy dispersive X-ray
- JEM-ARM300F GRAND ARM atomic resolution electron microscope
- the thickness, the presence or absence of crystalline SiO 2 , and the content of additive metal elements were measured by the following methods. Moreover, the presence or absence of an organic substance layer in the magnesium oxide composition powder was confirmed by the following method. Furthermore, the acid resistance (elution test), dispersibility (sedimentation test), and thermal conductivity of the magnesium oxide composition powder were measured by the following methods. The results are shown in Table 3 below. The acid resistance, dispersibility, and thermal conductivity were also measured for magnesium oxide powder (average particle size: 10 ⁇ m, specific surface area: 0.7 m 2 /g). The results are shown in Table 3 as Comparative Example 5.
- Example 30 20 g of magnesium oxide powder, and the amounts of 5% polysilazane solution, sodium laurate, and ALCH shown in Table 1 were added to a 100 ml eggplant flask and mixed with stirring for 30 minutes. The resulting mixture was air-dried to remove the solvent, dried at 150° C. for 2 hours, and heat-treated at 800° C. for 6 hours. The magnesium oxide powder after treatment is pulverized with a mill and pulverized to a particle size similar to that of the raw material, and is coated with a crystalline double oxide containing at least one of silicon, aluminum, magnesium, and sodium. A coated MgO powder was obtained.
- Example 31 A magnesium oxide composition powder obtained in the same manner as in Example 30 was surface-treated with a silane coupling agent in the same manner as in Example 2.
- Example 6 A coated MgO powder coated with a crystalline multiple oxide was obtained in the same manner as in Example 30, except that lithium carbonate was used as the additive metal element compound instead of sodium laurate.
- Presence or absence of crystalline SiO2 The presence or absence of crystalline SiO 2 was determined by detecting a diffraction peak derived from crystalline SiO 2 (tridymite, cristobalite, quartz) from an X-ray diffraction pattern measured using CuK ⁇ rays. If even one kind of diffraction peak derived from crystalline SiO 2 was detected, crystalline SiO 2 was judged to be “presence”. The X-ray diffraction pattern was measured using an X-ray diffractometer (Empyrean, manufactured by Malvern Panalytical).
- Thermal conductivity Bisphenol A type epoxy resin (JER828, manufactured by Mitsubishi Chemical Co., Ltd.) 100 parts by weight, methylhydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) 3 parts by weight, 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Kasei Kogyo Co., Ltd.) was mixed with 3 parts by mass to obtain an epoxy resin composition.
- the obtained epoxy resin composition and magnesium oxide composition powder were stirred and mixed at a volume ratio of 30:70 to obtain a reactive resin composition.
- the reactive resin composition is vacuum degassed, processed into a sheet with a thickness of 1 mm using a hand press, and then heated at 120° C. for 1 hour, 150° C. for 1 hour, and 180° C. for 1 hour to form an epoxy resin.
- a system resin composition sheet was obtained.
- the thermal conductivity of the obtained epoxy resin composition sheet is obtained by measuring the density, specific heat, and thermal diffusivity of the epoxy resin composition sheet by the methods described below, and multiplying the obtained values. Calculated. Density was determined using the Archimedes method. The specific heat was obtained using a differential scanning calorimeter (DSC) (manufactured by Hitachi High-Tech Science Co., Ltd.). The thermal diffusivity was obtained using a xenon flash thermal diffusivity measurement device (manufactured by Advance Riko Co., Ltd.).
- the magnesium oxide composition powders of Examples 1 to 23, in which the oxide layer contains crystalline SiO 2 are the magnesium oxide compositions of Comparative Examples 1 to 4, in which the oxide layer does not contain crystalline SiO 2 . It was confirmed that the thermal conductivity is higher than that of the powder. Moreover, it was confirmed that the magnesium oxide composition powders of Examples 1 to 22, in which the thickness of the oxide layer was 50 nm or more, were remarkably improved in acid resistance. Furthermore, it was confirmed that the magnesium oxide composition powders of Examples 2 to 5 and Examples 7 to 22 having organic layers had improved dispersibility.
- Example 24 Polystyrene (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., density: 1.04-1.13 g/cm 3 ) and the magnesium oxide composition powder obtained in Example 7 were mixed at a volume ratio of 45:55. Mixed using a mortar and pestle. The obtained mixture and toluene were mixed and stirred to obtain a slurry. The obtained slurry was applied on a PET film and dried at 100° C. for 5 minutes and 120° C. for 10 minutes to obtain a polystyrene composition sheet with a thickness of 100 to 150 ⁇ m. The obtained polystyrene composition sheet was peeled off from the PET film. Ten polystyrene composition sheets were laminated. A polystyrene composition sheet laminate was obtained by pressing the obtained laminate with a hand press machine at a temperature of 100° C. and a pressure of 10 MPa for 3 minutes so that the laminate had a thickness of 1 mm.
- Example 25 An acrylic resin molding material (Acrypet (registered trademark), manufactured by Mitsubishi Chemical Corporation) and the magnesium oxide composition powder obtained in Example 7 were mixed at a volume ratio of 45:55. The obtained mixture and toluene were mixed and stirred to obtain a slurry. The obtained slurry was applied on a PET film and dried at 100° C. for 5 minutes and 120° C. for 10 minutes to obtain an acrylic resin composition sheet with a thickness of 100 to 150 ⁇ m. The obtained acrylic resin composition sheet was peeled off from the PET film. Ten acrylic resin composition sheets were laminated. A methacrylic resin composition sheet laminate was obtained by pressing the resulting laminate with a hand press at a temperature of 100° C. and a pressure of 10 MPa for 3 minutes so that the laminate had a thickness of 1 mm.
- a methacrylic resin composition sheet laminate was obtained by pressing the resulting laminate with a hand press at a temperature of 100° C. and a pressure of 10 MPa for 3 minutes so that the laminate had a thickness of 1 mm.
- Example 26 Bisphenol A type epoxy resin (JER828, manufactured by Mitsubishi Chemical Corporation) and methylhydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) are added to 1 mol of the total number of moles of phenolic hydroxyl groups of methylhydroquinone. The total number of moles of epoxy groups in the resin is mixed at a ratio of 1.0 mol, and 2-ethyl-4-methylimidazole (2E4MZ) (Shikoku Kasei Kogyo Co., Ltd.) is added to 100 parts by mass of bisphenol A epoxy resin. (manufactured by the company) was added and mixed to obtain an epoxy resin composition.
- 2-ethyl-4-methylimidazole 2E4MZ
- the obtained epoxy resin composition and the magnesium oxide composition powder obtained in Example 2 were stirred and mixed in THF (tetrahydrofuran) at a volume ratio of 45:55 to obtain a slurry.
- the obtained slurry was applied on a PET film and dried at 100° C. for 5 minutes and 120° C. for 10 minutes to obtain an epoxy resin composition sheet with a thickness of 100 to 150 ⁇ m.
- the obtained epoxy resin composition sheet was peeled off from the PET film.
- Ten epoxy resin composition sheets were laminated.
- the resulting laminate was pressed using a hand press machine at a temperature of 100° C. and a pressure of 10 MPa for 3 minutes so that the thickness would be 1 mm.
- the epoxy resin composition was cured by heating at 120° C. for 1 hour, 150° C. for 1 hour, and 180° C. for 1 hour to obtain a cured epoxy resin sheet.
- Example 27 A cured epoxy resin sheet was obtained in the same manner as in Example 26, except that the magnesium oxide composition powder obtained in Example 7 was used instead of the magnesium oxide composition powder obtained in Example 2. .
- TGI Triglycidyl isocyanurate
- Mn number average molecular weight
- Mw mass average molecular weight
- the obtained epoxy resin composition and the magnesium oxide composition powder obtained in Example 2 were stirred and mixed in THF (tetrahydrofuran) at a volume ratio of 45:55 to obtain a slurry.
- the obtained slurry was applied on a PET film and dried at 100° C. for 5 minutes and 120° C. for 10 minutes to obtain an epoxy resin composition sheet with a thickness of 100 to 150 ⁇ m.
- the obtained epoxy resin composition sheet was peeled off from the PET film.
- Ten epoxy resin composition sheets were laminated.
- the obtained laminate was pressed with a hand press machine at a temperature of 100° C. and a pressure of 10 MPa for 3 minutes so as to have a thickness of 1 mm.
- the epoxy resin composition was cured by heating at 120° C. for 1 hour, 150° C. for 1 hour, and 180° C. for 1 hour to obtain an epoxy resin composition sheet.
- THF tetrahydrofuran
- Example 29 A cured epoxy resin sheet was obtained in the same manner as in Example 28, except that the magnesium oxide composition powder obtained in Example 7 was used instead of the magnesium oxide composition powder obtained in Example 2. .
- Example 32 A bisphenol A type epoxy resin, methylhydroquinone, 2-ethyl-4-methylimidazole (2E4MZ), and the magnesium oxide powder obtained in Example 31 so that the filling rate was 55 vol% were added to THF and mixed with stirring. to obtain a slurry.
- the resulting slurry was applied onto a PET film and dried at 100° C. for 5 minutes and 120° C. for 10 minutes.
- the obtained resin sheet was peeled from the PET film and laminated to form a laminate.
- the resulting laminate was pressed using a hand press machine at a temperature of 100° C. and a pressure of 10 MPa for 3 minutes so as to have a thickness of 1 mm, and then pressed at 120° C. for 1 hour, 150° C. for 1 hour, and 180° C. for 1 hour.
- a resin cured product was obtained by heating for a period of time.
- Example 33 A resin cured product was obtained in the same manner as in Example 32, except that triglycidyl isocyanurate was used as the resin instead of the bisphenol A type epoxy resin, and the compound of formula (1) was used instead of methylhydroquinone as the curing agent. Obtained.
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Abstract
This magnesium oxide composition powder includes magnesium oxide particles and an oxide layer covering at least part of the surface of the magnesium oxide particles, the oxide layer containing crystalline SiO2.
Description
本発明は、酸化マグネシウム組成物粉末、樹脂組成物、樹脂組成物シート、積層基板及び反応性樹脂組成物に関する。
本願は、２０２１年３月３０日に、日本に出願された特願２０２１－０５７８８１号に基づき優先権を主張し、それらの内容をここに援用する。 TECHNICAL FIELD The present invention relates to a magnesium oxide composition powder, a resin composition, a resin composition sheet, a laminated substrate and a reactive resin composition.
This application claims priority based on Japanese Patent Application No. 2021-057881 filed in Japan on March 30, 2021, and the contents thereof are incorporated herein.
本願は、２０２１年３月３０日に、日本に出願された特願２０２１－０５７８８１号に基づき優先権を主張し、それらの内容をここに援用する。 TECHNICAL FIELD The present invention relates to a magnesium oxide composition powder, a resin composition, a resin composition sheet, a laminated substrate and a reactive resin composition.
This application claims priority based on Japanese Patent Application No. 2021-057881 filed in Japan on March 30, 2021, and the contents thereof are incorporated herein.
自動車、産業機器等のパワーエレクトロニクスデバイス分野、発電機やモーター等の電力、電子機器分野のいずれにおいても、小型化・高出力化が進み、機器の内部から発生する熱が増大の一途をたどっている。このため、機器の内部から発生した熱をいかに効率よく機器外部に放熱させるかが重大な課題となっており、機器の回路基板等に用いられる絶縁材料には高放熱性が求められている。そこで、エポキシ樹脂などの樹脂材料に、電気絶縁性で高熱伝導率を有する無機フィラーを配合した有機／無機複合高熱伝導材料の開発が行われている（特許文献１）。
In the field of power electronics devices such as automobiles and industrial equipment, electric power such as generators and motors, and the field of electronic equipment, miniaturization and higher output are progressing, and the heat generated from the inside of the equipment is steadily increasing. there is For this reason, how to efficiently dissipate the heat generated inside the device to the outside of the device has become a serious issue, and high heat dissipation is required for the insulating materials used for the circuit boards and the like of the device. Therefore, an organic/inorganic composite high thermal conductive material is being developed in which an inorganic filler having electrical insulation and high thermal conductivity is mixed with a resin material such as epoxy resin (Patent Document 1).
無機フィラーとして熱伝導率に優れる酸化マグネシウム（ＭｇＯ）粉末が研究、開発、利用されている。しかしながら、酸化マグネシウム粉末は水と反応して水酸化マグネシウムに変化してしまうほか、酸に溶けてしまうという問題があった。そのため、化学成分の調整や表面処理を行うことで、耐水性、耐酸性を付与させた酸化マグネシウムが開発されている（特許文献２－４、非特許文献１）。
Magnesium oxide (MgO) powder, which has excellent thermal conductivity, is being researched, developed, and used as an inorganic filler. However, there is a problem that magnesium oxide powder reacts with water and changes to magnesium hydroxide, and also dissolves in acid. Therefore, by adjusting the chemical components and performing surface treatment, magnesium oxide that is imparted with water resistance and acid resistance has been developed (Patent Documents 2 to 4, Non-Patent Document 1).
酸化マグネシウム粉末の耐水性や耐酸性を向上させるために、酸化マグネシウム粉末の化学成分の調整や表面処理を行うことは有効である。しかしながら、酸化マグネシウム粉末の化学成分の調整や表面処理を行うと、酸化マグネシウム粉末が有する高い熱伝導率が低下するおそれがある。酸化マグネシウム粉末が有する高い熱伝導率を維持しつつ、耐水性や耐酸性を十分に向上させるには、さらなる改善が必要である。
In order to improve the water resistance and acid resistance of magnesium oxide powder, it is effective to adjust the chemical composition of magnesium oxide powder and perform surface treatment. However, when the chemical components of the magnesium oxide powder are adjusted or the surface is treated, the high thermal conductivity of the magnesium oxide powder may deteriorate. Further improvements are required to sufficiently improve water resistance and acid resistance while maintaining the high thermal conductivity of magnesium oxide powder.
本発明は、上記課題に鑑みてなされたものであり、熱伝導率が高く、耐水性や耐酸性に優れる酸化マグネシウム組成物粉末、樹脂組成物、樹脂組成物シート、積層基板を提供することを目的とする。また、本発明は、熱伝導率が高く、耐水性や耐酸性に優れる樹脂組成物を生成することができる反応性樹脂組成物を提供することを目的とする。
The present invention has been made in view of the above problems, and provides a magnesium oxide composition powder, a resin composition, a resin composition sheet, and a laminated substrate having high thermal conductivity and excellent water resistance and acid resistance. aim. Another object of the present invention is to provide a reactive resin composition that can produce a resin composition that has high thermal conductivity and excellent water resistance and acid resistance.
本発明者らは、上記課題を解決するために検討を重ねた結果、酸化マグネシウム粒子の表面を、結晶性ＳｉＯ２またはＳｉとＡｌを含む結晶性複酸化物を含む酸化物層で被覆することによって、酸化マグネシウム粉末が有する高い熱伝導率を維持しつつ、耐水性や耐酸性を向上させることが可能となることを見出した。そして、本発明者らは、結晶性ＳｉＯ２またはＳｉとＡｌを含む結晶性複酸化物を含む酸化物層で被覆された酸化マグネシウム組成物粉末を用いることによって、熱伝導率が高く、耐水性や耐酸性に優れる樹脂組成物、樹脂組成物シート、積層基板、及び上記の樹脂組成物を生成することができる反応性樹脂組成物を得ることが可能となることを確認して本発明を完成させた。すなわち、本発明は、以下の発明に関わる。
As a result of repeated studies to solve the above problems, the present inventors have found that the surface of magnesium oxide particles is coated with an oxide layer containing crystalline SiO2 or a crystalline double oxide containing Si and Al. It was found that it is possible to improve water resistance and acid resistance while maintaining the high thermal conductivity of magnesium oxide powder. And the inventors have found that by using a magnesium oxide composition powder coated with an oxide layer containing crystalline SiO2 or a crystalline double oxide containing Si and Al, the thermal conductivity is high and the water resistance is high. The present invention was completed by confirming that it is possible to obtain a resin composition, a resin composition sheet, a laminated substrate, and a reactive resin composition capable of producing the above-mentioned resin composition. let me That is, the present invention relates to the following inventions.
［１］酸化マグネシウム粒子と、前記酸化マグネシウム粒子の表面の少なくとも一部を被覆する酸化物層とを有し、前記酸化物層が、結晶性ＳｉＯ２を含む酸化マグネシウム組成物粉末。
[1] A magnesium oxide composition powder having magnesium oxide particles and an oxide layer covering at least part of the surface of the magnesium oxide particles, wherein the oxide layer contains crystalline SiO2 .
［２］前記酸化物層は、前記結晶性ＳｉＯ２と、Ｓｉ以外の添加金属元素とを含み、前記添加金属元素は、アルカリ金属、アルカリ土類金属、Ａｌ、Ｔｉ、Ｚｒからなる群より選ばれる少なくとも１種であり、前記酸化物層の前記添加金属元素の含有量が１５ａｔ％以下である［１］に記載の酸化マグネシウム組成物粉末。
[2] The oxide layer contains the crystalline SiO2 and an additive metal element other than Si, and the additive metal element is selected from the group consisting of alkali metals, alkaline earth metals, Al, Ti, and Zr. The magnesium oxide composition powder according to [1], wherein the content of the additional metal element in the oxide layer is 15 at % or less.
［３］酸化マグネシウム粒子と、前記酸化マグネシウム粒子の表面の少なくとも一部を被覆する酸化物層とを有し、前記酸化物層が、ＳｉとＡｌを含む結晶性複酸化物を含む酸化マグネシウム組成物粉末。
[3] A magnesium oxide composition comprising magnesium oxide particles and an oxide layer covering at least part of the surface of the magnesium oxide particles, wherein the oxide layer contains a crystalline multiple oxide containing Si and Al. powder.
［４］前記酸化物層は、前記結晶性複酸化物と、Ｓｉ、Ａｌ以外の添加金属元素とを含み、前記添加金属元素は、アルカリ金属、アルカリ土類金属、Ｔｉ、Ｚｒからなる群より選ばれる少なくとも１種類であり、前記酸化物層のＳｉ以外の金属元素含有量が１５ａｔ％以下である［３］に記載の酸化マグネシウム組成物粉末。
[4] The oxide layer contains the crystalline multiple oxide and an additive metal element other than Si and Al, and the additive metal element is selected from the group consisting of alkali metals, alkaline earth metals, Ti and Zr. The magnesium oxide composition powder according to [3], which is at least one selected and has a metal element content other than Si in the oxide layer of 15 at % or less.
［５］前記添加金属元素が、Ｌｉ及びＮａのいずれか一方又は両方である［２］または［４］に記載の酸化マグネシウム組成物粉末。
[5] The magnesium oxide composition powder according to [2] or [4], wherein the additive metal element is one or both of Li and Na.
［６］さらに、有機物層で被覆されている［１］～［５］に記載の酸化マグネシウム組成物粉末。
[6] The magnesium oxide composition powder according to [1] to [5], which is further coated with an organic layer.
［７］前記有機物層が、ホスホン酸及びシランカップリング剤のいずれか一方又は両方を含む、［６］に記載の酸化マグネシウム組成物粉末。
[7] The magnesium oxide composition powder according to [6], wherein the organic layer contains one or both of phosphonic acid and a silane coupling agent.
［８］樹脂と、［１］～［７］に記載の酸化マグネシウム組成物粉末とを含む樹脂組成物。
[8] A resin composition containing a resin and the magnesium oxide composition powder according to [1] to [7].
［９］前記樹脂が、エポキシ樹脂と硬化剤とを含む反応硬化性樹脂組成物の硬化物である［８］に記載の樹脂組成物。
[9] The resin composition according to [8], wherein the resin is a cured product of a reaction-curable resin composition containing an epoxy resin and a curing agent.
［１０］さらに、ガラスクロスを含む［８］または［９］に記載の樹脂組成物。
[10] The resin composition according to [8] or [9], further comprising glass cloth.
［１１］［８］～［１０］に記載の樹脂組成物を含む樹脂組成物シート。
[11] A resin composition sheet containing the resin composition according to [8] to [10].
［１２］複数の樹脂基板が積層されてなり、前記複数の樹脂基板のうち、少なくとも一つが［１１］に記載の樹脂組成物シートである積層基板。
[12] A laminated substrate obtained by laminating a plurality of resin substrates, wherein at least one of the plurality of resin substrates is the resin composition sheet according to [11].
［１３］反応硬化性樹脂組成物と、［１］～［７］に記載の酸化マグネシウム組成物粉末とを含む反応性樹脂組成物。
[13] A reactive resin composition comprising a reactive curable resin composition and the magnesium oxide composition powder according to [1] to [7].
［１４］反応硬化性樹脂組成物が、エポキシ樹脂と硬化剤とを含む［１３］に記載の反応性樹脂組成物。
[14] The reactive resin composition according to [13], which contains an epoxy resin and a curing agent.
［１５］前記エポキシ樹脂がトリグリシジルイソシアヌレートであって、前記硬化剤が下記の一般式（１）で表される化合物である［１４］に記載の反応性樹脂組成物。
[15] The reactive resin composition according to [14], wherein the epoxy resin is triglycidyl isocyanurate and the curing agent is a compound represented by the following general formula (1).
（式（１）において、ｎは、２～４０の整数である。）
(In formula (1), n is an integer of 2 to 40.)
本発明によれば、熱伝導率が高く、耐水性や耐酸性に優れる酸化マグネシウム組成物粉末、樹脂組成物、樹脂組成物シート、積層基板を提供することが可能となる。また、本発明は、熱伝導率が高く、耐水性や耐酸性に優れる樹脂組成物を生成することができる反応性樹脂組成物を提供することが可能となる。
According to the present invention, it is possible to provide a magnesium oxide composition powder, a resin composition, a resin composition sheet, and a laminated substrate that have high thermal conductivity and are excellent in water resistance and acid resistance. Moreover, the present invention makes it possible to provide a reactive resin composition that has high thermal conductivity and can produce a resin composition that is excellent in water resistance and acid resistance.
以下、本発明について、図を適宜参照しながら詳細に説明する。以下の説明で用いる図面は、本発明の特徴をわかりやすくするために便宜上特徴となる部分を拡大して示している場合がある。したがって、図面に記載の各構成要素の寸法比率などは、実際とは異なっていることがある。以下の説明において例示される材料、寸法等は一例であって、本発明はそれらに限定されるものではなく、その要旨を変更しない範囲で適宜変更して実施可能である。
The present invention will be described in detail below with appropriate reference to the drawings. In the drawings used in the following description, the features of the present invention may be shown enlarged for convenience in order to make it easier to understand the features of the present invention. Therefore, the dimensional ratio of each component described in the drawings may differ from the actual one. The materials, dimensions, and the like exemplified in the following description are examples, and the present invention is not limited to them, and can be implemented with appropriate modifications without changing the gist of the invention.
本発明の実施形態に係る酸化マグネシウム組成物粉末は、例えば、樹脂組成物用の無機フィラーとして、有機溶媒や樹脂に分散されるものである。本発明の実施形態に係る樹脂組成物、樹脂組成物シート及び積層基板は、樹脂と酸化マグネシウム組成物粉末とを含み、例えば、機器の回路基板の材料として用いられるものである。反応性樹脂組成物は、反応硬化性樹脂組成物と酸化マグネシウム組成物粉末とを含み、例えば、反応硬化性樹脂組成物を硬化させることによって、樹脂組成物を生成するものである。
The magnesium oxide composition powder according to the embodiment of the present invention is, for example, dispersed in an organic solvent or resin as an inorganic filler for a resin composition. A resin composition, a resin composition sheet, and a laminated substrate according to embodiments of the present invention contain a resin and a magnesium oxide composition powder, and are used, for example, as materials for circuit boards of equipment. The reactive resin composition contains a reactive curable resin composition and a magnesium oxide composition powder, and for example, a resin composition is produced by curing the reactive curable resin composition.
［酸化マグネシウム組成物粉末］
図１は、本発明の一実施形態に係る酸化マグネシウム組成物粉末の断面図である。
図１に示す酸化マグネシウム組成物粉末１０は、酸化マグネシウム粒子１１と、酸化マグネシウム粒子１１を被覆する酸化物層１２と、酸化物層１２を被覆する有機物層１３とを有する。 [Magnesium oxide composition powder]
FIG. 1 is a cross-sectional view of a magnesium oxide composition powder according to one embodiment of the present invention.
Magnesiumoxide composition powder 10 shown in FIG. 1 has magnesium oxide particles 11 , oxide layer 12 covering magnesium oxide particles 11 , and organic layer 13 covering oxide layer 12 .
図１は、本発明の一実施形態に係る酸化マグネシウム組成物粉末の断面図である。
図１に示す酸化マグネシウム組成物粉末１０は、酸化マグネシウム粒子１１と、酸化マグネシウム粒子１１を被覆する酸化物層１２と、酸化物層１２を被覆する有機物層１３とを有する。 [Magnesium oxide composition powder]
FIG. 1 is a cross-sectional view of a magnesium oxide composition powder according to one embodiment of the present invention.
Magnesium
酸化マグネシウム粒子１１の形状は、特に制限はない。酸化マグネシウム粒子１１は、例えば、球形、楕円球形、円柱形、角柱形であってもよい。酸化マグネシウム粒子１１は、平均粒子径（ｄ５０）が、例えば、１μｍ以上５０μｍ以下の範囲内にあってもよく、２μｍ以上３０μｍ以下の範囲内にあることが好ましい。酸化マグネシウム粒子の平均粒子径は、レーザー回折散乱法によって測定された値である。また、酸化マグネシウム粒子１１は、比表面積が、例えば、０．１ｍ２／ｇ以上１０ｍ２／ｇ以下の範囲内にあってもよく、０．２ｍ２／ｇ以上５ｍ２／ｇ以下の範囲内にあることが好ましい。
The shape of the magnesium oxide particles 11 is not particularly limited. The magnesium oxide particles 11 may be spherical, oval, cylindrical, or prismatic, for example. The magnesium oxide particles 11 may have an average particle diameter (d50) of, for example, 1 μm or more and 50 μm or less, preferably 2 μm or more and 30 μm or less. The average particle size of magnesium oxide particles is a value measured by a laser diffraction scattering method. Further, the magnesium oxide particles 11 may have a specific surface area, for example, in the range of 0.1 m 2 /g or more and 10 m 2 /g or less, or in the range of 0.2 m 2 /g or more and 5 m 2 /g or less. It is preferable to be in
酸化物層１２は、結晶性ＳｉＯ２を含む。酸化物層１２に含まれる結晶性ＳｉＯ２の例としては、トリジマイト、クリストバライト、石英を挙げることができる。酸化物層１２は、これらの結晶性ＳｉＯ２のうち１種を単独で含んでいてもよいし、２種以上を含んでいてもよい。酸化物層１２が結晶性ＳｉＯ２を含むことは、例えば、酸化マグネシウム組成物粉末１０のＸ線回折パターンによって確認することができる。酸化マグネシウム組成物粉末１０のＸ線回折パターンにおいて、結晶性ＳｉＯ２に由来する回折ピークが、酸化マグネシウムのＸ線回折パターンに対して独立に検出された場合、酸化物層１２は結晶性ＳｉＯ２を含む。ＣｕＫα線を用いて測定されたＸ線回折パターンにおいて、例えば、トリジマイト由来の回折ピークは２θ＝２０度に、クリストバライト由来の回折ピークは２θ＝２２度に、石英由来の回折ピークは２θ＝２７度に検出される。
The oxide layer 12 comprises crystalline SiO2 . Examples of crystalline SiO 2 contained in the oxide layer 12 include tridymite, cristobalite and quartz. The oxide layer 12 may contain one of these crystalline SiO 2 alone, or may contain two or more of them. The inclusion of crystalline SiO 2 in the oxide layer 12 can be confirmed, for example, by the X-ray diffraction pattern of the magnesium oxide composition powder 10 . In the X-ray diffraction pattern of the magnesium oxide composition powder 10, when diffraction peaks derived from crystalline SiO 2 are detected independently with respect to the X-ray diffraction pattern of magnesium oxide, the oxide layer 12 is crystalline SiO 2 including. In the X-ray diffraction pattern measured using CuKα rays, for example, the diffraction peak derived from tridymite is at 2θ = 20 degrees, the diffraction peak derived from cristobalite is at 2θ = 22 degrees, and the diffraction peak derived from quartz is at 2θ = 27 degrees. detected at
酸化物層１２は、Ｓｉ以外の添加金属元素を含んでいてもよい。また、酸化物層１２は、Ｓｉ、Ａｌ以外の添加金属元素を含んでいてもよい。添加金属元素としては、アルカリ金属（Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｆｒ）、アルカリ土類金属（Ｃａ、Ｓｒ、Ｂａ、Ｒａ）、Ａｌ、Ｔｉ、Ｚｒを用いることができる。これらの添加金属元素は１種を単独で含有してもよいし、２種以上を含有してもよい。添加金属元素は、例えば、Ｌｉ及びＮａのいずれか一方又は両方であってもよい。酸化物層１２中の添加金属元素は、酸化物を形成していてもよいし、酸化物層１２中のＳｉと共に複酸化物を形成していてもよい。例えば、酸化物層１２中に、ＳｉとＡｌを含む複酸化物が含まれてもよい。
The oxide layer 12 may contain additional metal elements other than Si. Moreover, the oxide layer 12 may contain additional metal elements other than Si and Al. Alkaline metals (Li, Na, K, Rb, Cs, Fr), alkaline earth metals (Ca, Sr, Ba, Ra), Al, Ti, Zr can be used as the additive metal element. These additive metal elements may be contained singly or in combination of two or more. The additive metal element may be, for example, either one or both of Li and Na. The additive metal element in the oxide layer 12 may form an oxide, or may form a composite oxide together with Si in the oxide layer 12 . For example, the oxide layer 12 may contain a composite oxide containing Si and Al.
酸化物層１２は、Ｓｉ、Ａｌ、Ｏからなる結晶性複酸化物を含んでもよいし、Ｓｉ、Ｌｉ、Ｏからなる結晶性複酸化物を含んでもよいし、Ｓｉ、Ｎａ、Ｏからなる結晶性複酸化物を含んでもよいし、Ｓｉ、Ｋ、Ｏからなる結晶性複酸化物を含んでもよいし、Ｓｉ、Ｒｂ、Ｏからなる結晶性複酸化物を含んでもよいし、Ｓｉ、Ｃｓ、Ｏからなる結晶性複酸化物を含んでもよいし、Ｓｉ、Ｃａ、Ｏからなる結晶性複酸化物を含んでもよいし、Ｓｉ、Ｔｉ、Ｏからなる結晶性複酸化物を含んでもよいし、Ｓｉ、Ｚｒ、Ｏからなる結晶性複酸化物を含んでもよい。
The oxide layer 12 may contain a crystalline multiple oxide composed of Si, Al, and O, may contain a crystalline multiple oxide composed of Si, Li, and O, or may include a crystal composed of Si, Na, and O. may contain a crystalline mixed oxide, may contain a crystalline mixed oxide consisting of Si, K and O, may contain a crystalline mixed oxide consisting of Si, Rb and O, may contain Si, Cs, It may contain a crystalline multiple oxide made of O, may contain a crystalline multiple oxide made of Si, Ca, and O, or may contain a crystalline multiple oxide made of Si, Ti, and O, A crystalline multiple oxide composed of Si, Zr, and O may also be included.
酸化物層１２の添加金属元素の含有量、または酸化物層１２におけるＳｉ以外の金属元素の含有量は、例えば、１５ａｔ％以下であってもよく、１ａｔ％以上１０ａｔ％以下の範囲内にあることが好ましい。添加金属元素の含有量は、酸化物層１２のケイ素（Ｓｉ）、添加金属元素、酸素（Ｏ）の合計量を１００ａｔ％とした値である。
The content of the additive metal element in the oxide layer 12 or the content of the metal element other than Si in the oxide layer 12 may be, for example, 15 at % or less, and is in the range of 1 at % or more and 10 at % or less. is preferred. The content of the additive metal element is a value where the total amount of silicon (Si), the additive metal element, and oxygen (O) in the oxide layer 12 is 100 at %.
酸化物層１２の厚さは、例えば、２０ｎｍ以上５００ｎｍ以下の範囲内にあってもよく、５０ｎｍ以上２００ｎｍ以下の範囲内にあることが好ましく、８０ｎｍ以上１５０ｎｍの範囲内にあることが特に好ましい。
The thickness of the oxide layer 12 may be, for example, within the range of 20 nm or more and 500 nm or less, preferably within the range of 50 nm or more and 200 nm or less, and particularly preferably within the range of 80 nm or more and 150 nm.
有機物層１３は、酸化物層１２に対して親和性を有する基と、酸化マグネシウム組成物粉末１０を分散させる有機溶媒や樹脂に対して親和性を有する基とを有する有機物を含むことが好ましい。酸化物層１２に対して親和性を有する基としては、アルコキシ基、ホスホン酸基、カルボン酸基、スルホン酸基を挙げることができる。樹脂に対して親和性を有する基としては、エポキシ基、ビニル基、アクリレート基、メタクリレート基、メルカプト基、アミノ基、アリール基、アルキル基を挙げることができる。有機物層１３に含まれる有機物としては、例えば、ホスホン酸及びシランカップリング剤のいずれか一方又は両方であってもよい。
The organic layer 13 preferably contains an organic material having a group having an affinity for the oxide layer 12 and a group having an affinity for the organic solvent or resin in which the magnesium oxide composition powder 10 is dispersed. Groups having an affinity for the oxide layer 12 include alkoxy groups, phosphonic acid groups, carboxylic acid groups, and sulfonic acid groups. Examples of groups having an affinity for resins include epoxy groups, vinyl groups, acrylate groups, methacrylate groups, mercapto groups, amino groups, aryl groups, and alkyl groups. The organic substance contained in the organic substance layer 13 may be, for example, one or both of phosphonic acid and a silane coupling agent.
有機物層１３の厚さは、例えば、０．５ｎｍ以上１０ｎｍ以下の範囲内にあってもよい。有機物層１３の厚さは、０．５ｎｍ以上５ｎｍ以下の範囲内にあることが好ましい。
The thickness of the organic layer 13 may be, for example, within the range of 0.5 nm or more and 10 nm or less. The thickness of the organic layer 13 is preferably in the range of 0.5 nm or more and 5 nm or less.
本実施形態に係る酸化マグネシウム組成物粉末１０は、例えば、次のようにして製造することができる。
まず、酸化マグネシウム粉末と、ＳｉＯ２源と、上記の添加金属元素を含む添加金属元素化合物とを溶媒中で混合して、原料混合液を得る。次いで原料混合液を乾燥して、原料混合乾燥物を得る。次いで、原料混合乾燥物を加熱処理する。そして、得られた加熱処理物を、ミルで解砕して粉末とする。この製造方法では、原料混合乾燥物の加熱処理によって結晶性ＳｉＯ２が生成する。原料混合乾燥物が添加金属元素を含むことによって、添加金属元素を含まない場合と比較して低温度での加熱処理によって結晶性ＳｉＯ２を生成させることができる。原料混合乾燥物の加熱処理の温度は、例えば、７００℃以上１０００℃以下の範囲内であってもよい。 The magnesiumoxide composition powder 10 according to this embodiment can be produced, for example, as follows.
First, the magnesium oxide powder, the SiO 2 source, and the additive metal element compound containing the additive metal element are mixed in a solvent to obtain a raw material mixture. Next, the raw material mixed liquid is dried to obtain a dried raw material mixture. Next, the dried raw material mixture is heat-treated. Then, the obtained heat-treated product is pulverized with a mill to obtain a powder. In this production method, crystalline SiO 2 is produced by heat treatment of the raw material mixture dried product. By including the additive metal element in the dried raw material mixture, crystalline SiO 2 can be generated by heat treatment at a lower temperature than when the additive metal element is not included. The temperature of the heat treatment of the dried raw material mixture may be, for example, within the range of 700° C. or higher and 1000° C. or lower.
まず、酸化マグネシウム粉末と、ＳｉＯ２源と、上記の添加金属元素を含む添加金属元素化合物とを溶媒中で混合して、原料混合液を得る。次いで原料混合液を乾燥して、原料混合乾燥物を得る。次いで、原料混合乾燥物を加熱処理する。そして、得られた加熱処理物を、ミルで解砕して粉末とする。この製造方法では、原料混合乾燥物の加熱処理によって結晶性ＳｉＯ２が生成する。原料混合乾燥物が添加金属元素を含むことによって、添加金属元素を含まない場合と比較して低温度での加熱処理によって結晶性ＳｉＯ２を生成させることができる。原料混合乾燥物の加熱処理の温度は、例えば、７００℃以上１０００℃以下の範囲内であってもよい。 The magnesium
First, the magnesium oxide powder, the SiO 2 source, and the additive metal element compound containing the additive metal element are mixed in a solvent to obtain a raw material mixture. Next, the raw material mixed liquid is dried to obtain a dried raw material mixture. Next, the dried raw material mixture is heat-treated. Then, the obtained heat-treated product is pulverized with a mill to obtain a powder. In this production method, crystalline SiO 2 is produced by heat treatment of the raw material mixture dried product. By including the additive metal element in the dried raw material mixture, crystalline SiO 2 can be generated by heat treatment at a lower temperature than when the additive metal element is not included. The temperature of the heat treatment of the dried raw material mixture may be, for example, within the range of 700° C. or higher and 1000° C. or lower.
また、酸化マグネシウム組成物粉末１０は、次のようにしても製造することができる。まず、酸化マグネシウム粉末とＳｉＯ２源とを混合して、酸化マグネシウム粉末の表面をＳｉＯ２源で被覆する。次いで、ＳｉＯ２源被覆酸化マグネシウム粉末と添加金属元素の化合物とを混合して、添加金属元素化合物をＳｉＯ２源被覆酸化マグネシウム粉末の表面に付着させる。次いで、添加金属元素化合物が付着したＳｉＯ２源被覆酸化マグネシウム粉末を加熱処理する。そして、得られた加熱処理物を、ミルで解砕して粉末とする。この製造方法では、ＳｉＯ２源被覆酸化マグネシウム粉末の加熱処理によって結晶性ＳｉＯ２が生成する。ＳｉＯ２源に添加金属元素が付着していることによって、添加金属元素が付着していない場合と比較して低温度での加熱処理によって結晶性ＳｉＯ２を生成させることができる。ＳｉＯ２源被覆酸化マグネシウム粉末の加熱処理の温度は、例えば、７００℃以上１０００℃以下の範囲内であってもよい。
The magnesium oxide composition powder 10 can also be produced as follows. First, the magnesium oxide powder and the SiO2 source are mixed to coat the surface of the magnesium oxide powder with the SiO2 source. Next, the SiO 2 source-coated magnesium oxide powder and the compound of the additional metal element are mixed to cause the additional metal element compound to adhere to the surface of the SiO 2 source-coated magnesium oxide powder. Then, the SiO 2 source-coated magnesium oxide powder to which the additive metal element compound is attached is heat-treated. Then, the obtained heat-treated product is pulverized with a mill to obtain a powder. In this production method, crystalline SiO 2 is produced by heat treatment of the SiO 2 source-coated magnesium oxide powder. By attaching the additive metal element to the SiO 2 source, crystalline SiO 2 can be generated by heat treatment at a lower temperature than when the additive metal element is not attached. The temperature of the heat treatment of the SiO 2 source-coated magnesium oxide powder may be, for example, within the range of 700° C. or higher and 1000° C. or lower.
酸化マグネシウム組成物粉末１０の製造方法において、ＳｉＯ２源としては、例えば、アルコキシシラン、ポリシラザン、シリコーンオイルなどの有機ケイ素化合物を用いることができる。添加金属元素化合物としては、例えば、炭酸塩、酢酸塩、オキシ酢酸塩及び有機化合物を用いることができる。有機化合物の例としては、ＡＬＣＨ（アルミニウムエチルアセトアセテートジイソプロピレート）を挙げることができる。
In the method for producing the magnesium oxide composition powder 10, organic silicon compounds such as alkoxysilanes, polysilazanes, and silicone oils can be used as the SiO2 source. As the additive metal element compound, for example, carbonate, acetate, oxyacetate and organic compound can be used. Examples of organic compounds include ALCH (aluminum ethyl acetoacetate diisopropylate).
本実施形態に係る酸化マグネシウム組成物粉末１０は、酸化マグネシウム粒子１１を被覆する酸化物層１２が結晶性のＳｉＯ２、またはＳｉとＡｌを含む結晶性複酸化物を含む。結晶性複酸化物は、結晶性ＳｉＯ２を含んでもよいし、含まなくてもよい。結晶性ＳｉＯ２等の結晶性複酸化物は、熱伝導性が高く、化学的に安定である。結晶性複酸化物にＡｌと他の金属元素（例えば、アルカリ金属、アルカリ土類金属、Ｔｉ、Ｚｒからなる群より選ばれる少なくとも１種類の元素）を含有させた場合、化学的な安定性をさらに高めることができる。このため、本実施形態に係る酸化マグネシウム組成物粉末１０は熱伝導率が高く、耐水性や耐酸性に優れる。
In the magnesium oxide composition powder 10 according to the present embodiment, the oxide layer 12 covering the magnesium oxide particles 11 contains crystalline SiO 2 or a crystalline multiple oxide containing Si and Al. The crystalline double oxide may or may not contain crystalline SiO2 . Crystalline double oxides such as crystalline SiO2 have high thermal conductivity and are chemically stable. When the crystalline double oxide contains Al and other metal elements (for example, at least one element selected from the group consisting of alkali metals, alkaline earth metals, Ti, and Zr), chemical stability is improved. can be further enhanced. Therefore, the magnesium oxide composition powder 10 according to the present embodiment has high thermal conductivity and excellent water resistance and acid resistance.
また、本実施形態に係る酸化マグネシウム組成物粉末１０において、酸化物層１２が上記の添加金属元素を１５ａｔ％以下となる量で含む場合は、酸化物層１２内の結晶性ＳｉＯ２の含有量が多くなりやすくなる。このため、酸化マグネシウム組成物粉末１０の熱伝導率がより高く、耐水性や耐酸性がより向上する。したがって、本実施形態の酸化マグネシウム組成物粉末１０は、機器の回路基板用の無機フィラーとして好適である。
Further, in the magnesium oxide composition powder 10 according to the present embodiment, when the oxide layer 12 contains the above-described additive metal element in an amount of 15 at% or less, the content of crystalline SiO 2 in the oxide layer 12 is becomes more likely to occur. Therefore, the thermal conductivity of the magnesium oxide composition powder 10 is higher, and the water resistance and acid resistance are further improved. Therefore, the magnesium oxide composition powder 10 of the present embodiment is suitable as an inorganic filler for circuit boards of equipment.
また、本実施形態に係る酸化マグネシウム組成物粉末１０において、添加金属元素が、Ｌｉ及びＮａのいずれか一方又は両方である場合、これらの金属元素は原子量が小さいので、酸化マグネシウム組成物粉末１０の製造に際して、結晶性ＳｉＯ２が生成しやすく、加熱処理温度をより低温度とすることが可能となる。加熱処理温度を低温度とすることにより、酸化マグネシウム粉末の焼結が起こりにくくなるので、酸化マグネシウム組成物粉末１０は粒子径の均一性が高くなり、有機溶媒や樹脂に対する分散性が向上する傾向がある。さらに、結晶性ＳｉＯ２が生成しやすくなるので、添加金属元素の使用量を少なくすることができる。
Further, in the magnesium oxide composition powder 10 according to the present embodiment, when the additive metal element is either one or both of Li and Na, since these metal elements have small atomic weights, the magnesium oxide composition powder 10 During production, crystalline SiO 2 is likely to be generated, and the heat treatment temperature can be set to a lower temperature. By setting the heat treatment temperature to a low temperature, the magnesium oxide powder is less likely to be sintered, so the magnesium oxide composition powder 10 has a higher uniformity in particle size, and tends to improve dispersibility in organic solvents and resins. There is Furthermore, since crystalline SiO 2 is easily generated, the amount of the additive metal element used can be reduced.
また、本実施形態に係る酸化マグネシウム組成物粉末１０において、有機物層１３で被覆されている場合は、有機溶媒や樹脂に対する親和性が高くなる。このため、酸化マグネシウム組成物粉末１０は、有機溶媒や樹脂に対する分散性が向上する。また、本実施形態に係る酸化マグネシウム組成物粉末１０において、有機物層１３がホスホン酸及びシランカップリング剤のいずれか一方又は両方を含む場合、これらの有機物は酸化物層１２との親和性が高いので、酸化マグネシウム組成物粉末１０の耐水性、耐酸性及び分散性がより向上する。
In addition, when the magnesium oxide composition powder 10 according to the present embodiment is coated with the organic layer 13, it has a high affinity for organic solvents and resins. Therefore, the magnesium oxide composition powder 10 has improved dispersibility in organic solvents and resins. Further, in the magnesium oxide composition powder 10 according to the present embodiment, when the organic layer 13 contains one or both of phosphonic acid and a silane coupling agent, these organic substances have a high affinity with the oxide layer 12. Therefore, the water resistance, acid resistance and dispersibility of the magnesium oxide composition powder 10 are further improved.
なお、本実施形態においては、酸化マグネシウム組成物粉末１０として、図１に示すように、酸化物層１２及び有機物層１３がそれぞれ酸化マグネシウム粒子１１の全体を被覆しているものを例に挙げて説明したが、本発明は、この例に限定されるものではない。例えば、酸化マグネシウム粒子１１同士を直接接触させて熱伝導性を向上させるために、酸化マグネシウム粒子１１の表面の一部を酸化物層１２で被覆するようにしてもよい。また、有機物層１３は、酸化マグネシウム粒子１１の表面に点在させてもよい。さらに、有機物層１３は、用途もしくは酸化マグネシウム組成物粉末１０を分散させる対象物によっては、酸化マグネシウム粒子１１の表面に設けなくてもよい。
In the present embodiment, as the magnesium oxide composition powder 10, as shown in FIG. Although explained, the invention is not limited to this example. For example, a part of the surface of the magnesium oxide particles 11 may be covered with the oxide layer 12 in order to bring the magnesium oxide particles 11 into direct contact with each other and improve the thermal conductivity. Also, the organic layer 13 may be scattered on the surface of the magnesium oxide particles 11 . Furthermore, the organic layer 13 may not be provided on the surface of the magnesium oxide particles 11 depending on the application or the object in which the magnesium oxide composition powder 10 is dispersed.
［樹脂組成物］
本実施形態の樹脂組成物は、樹脂と、上述した本実施形態の酸化マグネシウム組成物粉末とを含む。樹脂としては、例えば、熱可塑性樹脂、反応硬化性樹脂組成物の硬化物を用いることができる。
熱可塑性樹脂としては、例えば、ポリスチレン、アクリル樹脂を用いることができる。 反応硬化性樹脂組成物の硬化物は、外部から熱や光などのエネルギーを付与することにより、反応硬化性樹脂組成物を硬化反応させた樹脂組成物である。反応硬化性樹脂組成物の硬化物としては、エポキシ樹脂と硬化剤とを含む反応硬化性樹脂組成物の硬化物を用いることができる。反応硬化性樹脂組成物については後述する。 [Resin composition]
The resin composition of the present embodiment includes a resin and the magnesium oxide composition powder of the present embodiment described above. As the resin, for example, a cured product of a thermoplastic resin or a reaction-curable resin composition can be used.
As the thermoplastic resin, for example, polystyrene and acrylic resin can be used. A cured product of the reaction-curable resin composition is a resin composition obtained by subjecting the reaction-curable resin composition to a curing reaction by applying energy such as heat or light from the outside. As the cured product of the reactive curable resin composition, a cured product of the reactive curable resin composition containing an epoxy resin and a curing agent can be used. The reaction-curable resin composition will be described later.
本実施形態の樹脂組成物は、樹脂と、上述した本実施形態の酸化マグネシウム組成物粉末とを含む。樹脂としては、例えば、熱可塑性樹脂、反応硬化性樹脂組成物の硬化物を用いることができる。
熱可塑性樹脂としては、例えば、ポリスチレン、アクリル樹脂を用いることができる。 反応硬化性樹脂組成物の硬化物は、外部から熱や光などのエネルギーを付与することにより、反応硬化性樹脂組成物を硬化反応させた樹脂組成物である。反応硬化性樹脂組成物の硬化物としては、エポキシ樹脂と硬化剤とを含む反応硬化性樹脂組成物の硬化物を用いることができる。反応硬化性樹脂組成物については後述する。 [Resin composition]
The resin composition of the present embodiment includes a resin and the magnesium oxide composition powder of the present embodiment described above. As the resin, for example, a cured product of a thermoplastic resin or a reaction-curable resin composition can be used.
As the thermoplastic resin, for example, polystyrene and acrylic resin can be used. A cured product of the reaction-curable resin composition is a resin composition obtained by subjecting the reaction-curable resin composition to a curing reaction by applying energy such as heat or light from the outside. As the cured product of the reactive curable resin composition, a cured product of the reactive curable resin composition containing an epoxy resin and a curing agent can be used. The reaction-curable resin composition will be described later.
本実施形態の樹脂組成物において、酸化マグネシウム組成物粉末の含有量は、例えば、１０体積％以上８０体積％以下の範囲内にあってもよく、４０体積％以上８０体積％以下の範囲内にあることが好ましく、５０体積％以上７５体積％以下の範囲内にあることがより好ましい。酸化マグネシウム組成物粉末の含有量が３０体積％以上であると、樹脂組成物の硬化物における熱伝導性向上効果が顕著となる。また、酸化マグネシウム組成物粉末の含有量が８０体積％以下であると、樹脂組成物の硬化物を用いて樹脂基板を成形する際に十分な成形加工性が得られる。
In the resin composition of the present embodiment, the content of the magnesium oxide composition powder may be, for example, in the range of 10% by volume or more and 80% by volume or less, or in the range of 40% by volume or more and 80% by volume or less. It is preferably in the range of 50% by volume or more and 75% by volume or less. When the content of the magnesium oxide composition powder is 30% by volume or more, the effect of improving the thermal conductivity of the cured product of the resin composition becomes remarkable. Further, when the content of the magnesium oxide composition powder is 80% by volume or less, sufficient moldability can be obtained when molding a resin substrate using a cured product of the resin composition.
本実施形態の樹脂組成物は、酸化マグネシウム組成物粉末以外の無機物粉末を含んでいてもよい。無機物粉末としては、窒化ホウ素粉末、アルミナ粉末、水酸化アルミニウム粉末、窒化アルミニウム粉末及びシリカ粉末等が挙げられる。こられの無機物粉末は、１種を単独で含有してもよいし、２種以上を含有してもよい。無機物粉末の含有量は、酸化マグネシウム組成物粉末との合計量で、例えば、２０体積％以上８０体積％以下の範囲内にあってもよく、４０体積％以上８０体積％以下の範囲内にあることが好ましく、５０体積％以上７５体積％以下の範囲内にあることがより好ましい。
The resin composition of the present embodiment may contain inorganic powder other than the magnesium oxide composition powder. Examples of inorganic powders include boron nitride powder, alumina powder, aluminum hydroxide powder, aluminum nitride powder and silica powder. These inorganic powders may contain one type alone, or may contain two or more types. The content of the inorganic powder is the total amount with the magnesium oxide composition powder, and may be, for example, in the range of 20% by volume or more and 80% by volume or less, or in the range of 40% by volume or more and 80% by volume or less. more preferably in the range of 50% by volume or more and 75% by volume or less.
本実施形態の樹脂組成物は、必要に応じて、上述の成分以外の任意成分を含んでいてもよい。任意成分としては、シランカップリング剤、チタネートカップリング剤等のカップリング剤、ハロゲン等の難燃剤、可塑剤、並びに滑剤等が挙げられる。また、本実施形態の樹脂組成物は、補強材を含んでいてもよい。補強材は絶縁性であってもよい。絶縁性の補強材としては、例えば、ガラス繊維を布状に編んだガラスクロス（ガラス布）を用いることができる。
The resin composition of the present embodiment may contain optional components other than the components described above, if necessary. Optional components include coupling agents such as silane coupling agents and titanate coupling agents, flame retardants such as halogens, plasticizers, and lubricants. Moreover, the resin composition of the present embodiment may contain a reinforcing material. The stiffener may be insulating. As the insulating reinforcing material, for example, a glass cloth (glass cloth) made by knitting glass fibers into a cloth can be used.
本実施形態の樹脂組成物は、例えば、熱可塑性樹脂と酸化マグネシウム組成物粉末とを混合することによって製造することができる。また、本実施形態の樹脂組成物は、未硬化の反応硬化性樹脂組成物と酸化マグネシウム組成物粉末とを混合して、得られた反応性樹脂組成物を硬化させる方法によっても製造することができる。
The resin composition of the present embodiment can be produced, for example, by mixing a thermoplastic resin and magnesium oxide composition powder. The resin composition of the present embodiment can also be produced by a method of mixing an uncured reactive curable resin composition and magnesium oxide composition powder and curing the resulting reactive resin composition. can.
本実施形態の樹脂組成物は、上述した本実施形態の酸化マグネシウム組成物粉末を含むので、熱伝導率が高く、耐水性や耐酸性に優れる。したがって、本実施形態の樹脂組成物は、機器の回路基板の材料として好適である。
Since the resin composition of the present embodiment contains the magnesium oxide composition powder of the present embodiment described above, it has high thermal conductivity and excellent water resistance and acid resistance. Therefore, the resin composition of the present embodiment is suitable as a material for circuit boards of equipment.
［樹脂組成物シート］
図２は、本発明の一実施形態に係る樹脂組成物シートの斜視図であり、図３は、図２に示す樹脂組成物シートのIII－III線断面図である。
図２及び図３に示す樹脂組成物シート２０は、芯材２１と、芯材２１に含侵されると共に芯材２１の両面を被覆する樹脂組成物２３とを含有する。芯材２１は、ガラス製の縦糸２１ａとガラス製の横糸２１ｂとを編み込んだガラスクロスとされている。 [Resin composition sheet]
2 is a perspective view of a resin composition sheet according to one embodiment of the present invention, and FIG. 3 is a cross-sectional view of the resin composition sheet shown in FIG. 2, taken along line III-III.
Theresin composition sheet 20 shown in FIGS. 2 and 3 contains a core material 21 and a resin composition 23 impregnated in the core material 21 and covering both sides of the core material 21 . The core material 21 is a glass cloth in which warp threads 21a made of glass and weft threads 21b made of glass are woven.
図２は、本発明の一実施形態に係る樹脂組成物シートの斜視図であり、図３は、図２に示す樹脂組成物シートのIII－III線断面図である。
図２及び図３に示す樹脂組成物シート２０は、芯材２１と、芯材２１に含侵されると共に芯材２１の両面を被覆する樹脂組成物２３とを含有する。芯材２１は、ガラス製の縦糸２１ａとガラス製の横糸２１ｂとを編み込んだガラスクロスとされている。 [Resin composition sheet]
2 is a perspective view of a resin composition sheet according to one embodiment of the present invention, and FIG. 3 is a cross-sectional view of the resin composition sheet shown in FIG. 2, taken along line III-III.
The
樹脂組成物２３は、樹脂２２、酸化マグネシウム組成物粉末１０とを含む。樹脂２２としては、例えば、熱可塑性樹脂、反応硬化性樹脂組成物の硬化物を用いることができる。樹脂組成物２３は、上述した本実施形態の樹脂組成物である。
The resin composition 23 includes the resin 22 and the magnesium oxide composition powder 10. As the resin 22, for example, a cured product of a thermoplastic resin or a reaction-curable resin composition can be used. The resin composition 23 is the resin composition of the present embodiment described above.
樹脂２２として熱可塑性樹脂を用いた樹脂組成物シート２０は、例えば、次のようにして製造することができる。
まず、熱可塑性樹脂溶液に酸化マグネシウム組成物粉末１０を分散した熱可塑性樹脂含有原料スラリーを用意する。次いで、芯材２１に、塗布または浸漬などの手法によって、熱可塑性樹脂含有原料スラリーを含浸させる。次いで、芯材２１に含侵させた熱可塑性樹脂含有原料スラリーの溶媒を加熱によって除去する。熱可塑性樹脂含有原料スラリーの溶媒を除去するための加熱条件は、例えば、６０～１５０℃で１～１２０分間程度とすることができ、７０～１２０℃で３～９０分間程度とすることが好ましい。 Theresin composition sheet 20 using a thermoplastic resin as the resin 22 can be produced, for example, as follows.
First, a raw material slurry containing a thermoplastic resin is prepared by dispersing the magnesiumoxide composition powder 10 in a thermoplastic resin solution. Next, the core material 21 is impregnated with the thermoplastic resin-containing raw material slurry by a technique such as coating or immersion. Next, the solvent of the thermoplastic resin-containing raw material slurry impregnated in the core material 21 is removed by heating. The heating conditions for removing the solvent from the thermoplastic resin-containing raw material slurry can be, for example, about 60 to 150° C. for about 1 to 120 minutes, preferably about 70 to 120° C. for about 3 to 90 minutes. .
まず、熱可塑性樹脂溶液に酸化マグネシウム組成物粉末１０を分散した熱可塑性樹脂含有原料スラリーを用意する。次いで、芯材２１に、塗布または浸漬などの手法によって、熱可塑性樹脂含有原料スラリーを含浸させる。次いで、芯材２１に含侵させた熱可塑性樹脂含有原料スラリーの溶媒を加熱によって除去する。熱可塑性樹脂含有原料スラリーの溶媒を除去するための加熱条件は、例えば、６０～１５０℃で１～１２０分間程度とすることができ、７０～１２０℃で３～９０分間程度とすることが好ましい。 The
First, a raw material slurry containing a thermoplastic resin is prepared by dispersing the magnesium
樹脂２２として反応硬化性樹脂組成物の硬化物を用いた樹脂組成物シート２０は、例えば、次のようにして製造することができる。
まず、反応性樹脂組成物に酸化マグネシウム組成物粉末１０を分散した反応性樹脂組成物含有原料スラリーを用意する。次いで、芯材２１に、塗布または浸漬などの手法によって、反応性樹脂組成物含有原料スラリーを含浸させる。次いで、芯材２１に含侵させた反応性樹脂組成物含有原料スラリーの溶媒を加熱によって除去する。反応性樹脂組成物含有原料スラリーの溶媒を除去するための加熱条件は、例えば、６０～１５０℃で１～１２０分間程度とすることができ、７０～１２０℃で３～９０分間程度とすることが好ましい。 Theresin composition sheet 20 using a cured product of a reaction-curable resin composition as the resin 22 can be produced, for example, as follows.
First, a raw material slurry containing a reactive resin composition is prepared by dispersing the magnesiumoxide composition powder 10 in a reactive resin composition. Next, the core material 21 is impregnated with the raw material slurry containing the reactive resin composition by a technique such as coating or dipping. Next, the solvent of the raw material slurry containing the reactive resin composition impregnated in the core material 21 is removed by heating. The heating conditions for removing the solvent from the raw material slurry containing the reactive resin composition may be, for example, 60 to 150° C. for about 1 to 120 minutes, and 70 to 120° C. for about 3 to 90 minutes. is preferred.
まず、反応性樹脂組成物に酸化マグネシウム組成物粉末１０を分散した反応性樹脂組成物含有原料スラリーを用意する。次いで、芯材２１に、塗布または浸漬などの手法によって、反応性樹脂組成物含有原料スラリーを含浸させる。次いで、芯材２１に含侵させた反応性樹脂組成物含有原料スラリーの溶媒を加熱によって除去する。反応性樹脂組成物含有原料スラリーの溶媒を除去するための加熱条件は、例えば、６０～１５０℃で１～１２０分間程度とすることができ、７０～１２０℃で３～９０分間程度とすることが好ましい。 The
First, a raw material slurry containing a reactive resin composition is prepared by dispersing the magnesium
反応性樹脂組成物含有原料スラリーの溶媒を除去するための加熱と同時に、芯材２１に含浸させた反応性樹脂組成物を硬化させる。また、反応性樹脂組成物含有原料スラリーの溶媒を除去するための加熱の後に、溶媒を除去するための加熱と同様の条件で、芯材２１に含浸させた反応性樹脂組成物を硬化させてもよい。
The reactive resin composition impregnated in the core material 21 is cured at the same time as the reactive resin composition-containing raw material slurry is heated to remove the solvent. After heating the raw material slurry containing the reactive resin composition to remove the solvent, the reactive resin composition impregnated in the core material 21 is cured under the same conditions as the heating for removing the solvent. good too.
本実施形態に係る樹脂組成物シート２０は、上述の本実施形態の樹脂組成物を含むため、熱伝導率が高く、耐水性や耐酸性に優れる。したがって、本実施形態の樹脂組成物シート２０は、機器の回路基板の材料として好適である。
Since the resin composition sheet 20 according to this embodiment contains the resin composition of this embodiment described above, it has high thermal conductivity and is excellent in water resistance and acid resistance. Therefore, the resin composition sheet 20 of the present embodiment is suitable as a material for circuit boards of equipment.
なお、本実施形態においては、樹脂組成物シート２０として、図３に示すように、芯材２１としてガラスクロスを用いたものを例に挙げて説明したが、本発明は、この例に限定されるものではない。例えば、芯材２１として、ガラス繊維以外の繊維を用いた織布または不織布を用いることができる。ガラス繊維以外の繊維としては、炭素繊維、金属繊維、天然繊維及び合成繊維を用いることができる。合成繊維の例としては、ポリエステル繊維、ポリアミド繊維を挙げることができる。これらの繊維は、１種のみ含有してもよいし、２種以上含有してもよい。
In the present embodiment, as shown in FIG. 3, the resin composition sheet 20 is described using glass cloth as the core material 21 as an example, but the present invention is limited to this example. not something. For example, as the core material 21, a woven fabric or non-woven fabric using fibers other than glass fibers can be used. As fibers other than glass fibers, carbon fibers, metal fibers, natural fibers and synthetic fibers can be used. Examples of synthetic fibers include polyester fibers and polyamide fibers. These fibers may contain only one type, or may contain two or more types.
また、本発明の樹脂組成物シートは、芯材を有さずに、樹脂成分のみで形成されているものであってもよい。さらに、樹脂組成物シートの表面上には、銅箔などの金属箔が積層されていてもよい。
In addition, the resin composition sheet of the present invention may be formed only of a resin component without having a core material. Furthermore, a metal foil such as copper foil may be laminated on the surface of the resin composition sheet.
［積層基板］
図４は、本発明の一実施形態に係る積層基板の斜視図であり、図５は、図４に示す積層基板のＶ－Ｖ線断面図である。図４および図５に示されるように、積層基板３０は、図２及び図３に示す樹脂組成物シート２０が複数積層されて一体化されている。 [Laminate substrate]
4 is a perspective view of a layered substrate according to one embodiment of the present invention, and FIG. 5 is a cross-sectional view of the layered substrate shown in FIG. 4 taken along line VV. As shown in FIGS. 4 and 5, alaminated substrate 30 is formed by laminating and integrating a plurality of resin composition sheets 20 shown in FIGS.
図４は、本発明の一実施形態に係る積層基板の斜視図であり、図５は、図４に示す積層基板のＶ－Ｖ線断面図である。図４および図５に示されるように、積層基板３０は、図２及び図３に示す樹脂組成物シート２０が複数積層されて一体化されている。 [Laminate substrate]
4 is a perspective view of a layered substrate according to one embodiment of the present invention, and FIG. 5 is a cross-sectional view of the layered substrate shown in FIG. 4 taken along line VV. As shown in FIGS. 4 and 5, a
積層基板３０は、例えば、複数枚の樹脂組成物シート２０を重ね合わせた状態で、加熱する方法により製造できる。樹脂組成物シート２０の樹脂２２が反応性樹脂組成物の硬化物である場合は、加熱する前の樹脂組成物シート２０の反応性樹脂組成物を半硬化もしくは未硬化の状態として、樹脂組成物シート２０を重ね合わせた状態で加熱する際に、反応性樹脂組成物を硬化させてもよい。複数枚の樹脂組成物シート２０の加熱条件は、例えば、１００～２５０℃で１～３００分間程度とすることができる。
The laminated substrate 30 can be manufactured, for example, by a method of heating a plurality of resin composition sheets 20 in a superimposed state. When the resin 22 of the resin composition sheet 20 is a cured product of a reactive resin composition, the reactive resin composition of the resin composition sheet 20 before heating is in a semi-cured or uncured state, and the resin composition The reactive resin composition may be cured when the sheets 20 are superimposed and heated. The heating conditions for the plurality of resin composition sheets 20 can be, for example, 100 to 250° C. for about 1 to 300 minutes.
複数枚の樹脂組成物シート２０を加熱する際には、必要に応じて加圧してもよい。加圧条件は、例えば、０．１～１０ＭＰａ程度とすることができる。複数枚の樹脂組成物シート２０を加熱する際に、加圧は必須ではない。また、複数枚の樹脂組成物シート２０の加熱は、減圧または真空下で行ってもよい。
When heating the plurality of resin composition sheets 20, pressure may be applied as necessary. The pressurizing condition can be, for example, about 0.1 to 10 MPa. Pressurization is not essential when heating the plurality of resin composition sheets 20 . Moreover, the heating of the plurality of resin composition sheets 20 may be performed under reduced pressure or vacuum.
本実施形態の積層基板３０は、樹脂組成物シート２０が積層されたものであるため、高い熱伝導率を有する。したがって、本実施形態の積層基板３０は、機器の回路基板の材料として好適である。
The laminated substrate 30 of the present embodiment has a high thermal conductivity because the resin composition sheets 20 are laminated. Therefore, the laminated substrate 30 of the present embodiment is suitable as a material for circuit boards of equipment.
本実施形態においては、積層基板３０として、図２及び図３に示す樹脂組成物シート２０が複数積層されたものを例に挙げて説明したが、本発明の積層基板は、複数の樹脂基板のうち、少なくとも一つが本発明の樹脂組成物シートであればよい。
In the present embodiment, as the laminated substrate 30, an example in which a plurality of the resin composition sheets 20 shown in FIGS. 2 and 3 are laminated has been described. At least one of them may be the resin composition sheet of the present invention.
また、本発明の積層基板は、例えば、上面および／または下面に金属層を有する金属張り積層板とされていてもよい。この場合、金属層としては、各種公知のものを適宜選択して用いることができる。具体的には、金属層として、例えば、銅、ニッケル、アルミニウム等の金属からなる金属板または金属箔などを用いることができる。金属層の厚みは、特に限定されず、例えば、３～１５０μｍ程度とすることができる。金属層として、金属板または金属箔に、エッチング及び／又は穴開け加工が施されたものを用いてもよい。
Also, the laminated substrate of the present invention may be, for example, a metal-clad laminate having a metal layer on the upper surface and/or the lower surface. In this case, various known metal layers can be appropriately selected and used as the metal layer. Specifically, for example, a metal plate or metal foil made of metal such as copper, nickel, or aluminum can be used as the metal layer. The thickness of the metal layer is not particularly limited, and can be, for example, about 3 to 150 μm. As the metal layer, a metal plate or a metal foil subjected to etching and/or perforation processing may be used.
［反応性樹脂組成物］
本実施形態の反応性樹脂組成物は、反応硬化性樹脂組成物と、上述した本実施形態の酸化マグネシウム組成物粉末とを含む。反応硬化性樹脂組成物は、外部から熱や光などのエネルギーを付与することにより、反応して硬化するものである。 [Reactive resin composition]
The reactive resin composition of the present embodiment includes a reaction-curable resin composition and the magnesium oxide composition powder of the present embodiment described above. A reaction-curable resin composition reacts and cures when energy such as heat or light is applied from the outside.
本実施形態の反応性樹脂組成物は、反応硬化性樹脂組成物と、上述した本実施形態の酸化マグネシウム組成物粉末とを含む。反応硬化性樹脂組成物は、外部から熱や光などのエネルギーを付与することにより、反応して硬化するものである。 [Reactive resin composition]
The reactive resin composition of the present embodiment includes a reaction-curable resin composition and the magnesium oxide composition powder of the present embodiment described above. A reaction-curable resin composition reacts and cures when energy such as heat or light is applied from the outside.
反応硬化性樹脂組成物としては、例えば、エポキシ樹脂と硬化剤とを含むエポキシ系樹脂組成物を用いてもよい。エポキシ系樹脂組成物は、さらに硬化促進剤を含んでいてもよい。
As the reaction-curable resin composition, for example, an epoxy-based resin composition containing an epoxy resin and a curing agent may be used. The epoxy resin composition may further contain a curing accelerator.
エポキシ樹脂としては、例えば、４，４’－ビフェノールジグリシジルエーテル、３，３’，５，５’－テトラメチル－４，４’－ビス（グリシジルオキシ）－１，１’－ビフェニル、トリグリシジルイソシアヌレート（ＴＧＩ）、トリグリシジル－ｐ－アミノフェノール、ノボラック型エポキシ樹脂、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、ナフタレン型エポキシ樹脂、テトラグリシジルジアミノジフェニルメタン型エポキシ樹脂など公知のエポキシ化合物を用いることができ、市販のエポキシ樹脂を用いてもよい。これらのエポキシ樹脂は、１種のみ含有してもよいし、２種以上含有してもよい。
Examples of epoxy resins include 4,4'-biphenol diglycidyl ether, 3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl, triglycidyl Known epoxy compounds such as isocyanurate (TGI), triglycidyl-p-aminophenol, novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, tetraglycidyldiaminodiphenylmethane type epoxy resin are used. A commercially available epoxy resin may be used. These epoxy resins may contain only one type, or may contain two or more types.
硬化剤としては、エポキシ樹脂のエポキシ基と反応する反応基を有する化合物を用いることができる。反応基の例としては、アミノ基、フェノール性水酸基を挙げることができる。硬化剤としては、例えば、ｐ－フェニレンジアミン、１，５－ジアミノナフタレン、ヒドロキノン、２，６－ジヒドロキシナフタレン、フロログルシノール、４－ヒドロキシ安息香酸、６－ヒドロキシ－２－ナフトエ酸、４－アミノ安息香酸、フェノール樹脂、ポリアミドアミンを用いることができる。また、下記の一般式（１）で表される化合物を用いることができる。これらの硬化剤は、１種のみ含有してもよいし、２種以上含有してもよい。
A compound having a reactive group that reacts with the epoxy group of the epoxy resin can be used as the curing agent. Examples of reactive groups include amino groups and phenolic hydroxyl groups. Curing agents include, for example, p-phenylenediamine, 1,5-diaminonaphthalene, hydroquinone, 2,6-dihydroxynaphthalene, phloroglucinol, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4-amino Benzoic acid, phenolic resins, polyamidoamines can be used. Also, a compound represented by the following general formula (1) can be used. These curing agents may be contained alone or in combination of two or more.
式（１）において、ｎは、２～４０の整数である。なお、式（１）で表される化合物を用いた硬化剤は、式（１）のｎが互いに異なる整数である化合物を２種以上含んでいてもよい。
In formula (1), n is an integer of 2-40. The curing agent using the compound represented by Formula (1) may contain two or more compounds in which n in Formula (1) is a different integer.
式（１）で表される化合物は、メソゲン基を含む骨格を有する鎖状化合物である。式（１）で表される化合物に含まれる１つのメチル基で置換されたパラフェニレン基において、ベンゼン環に結合しているメチル基の位置は特に限定されない。
The compound represented by formula (1) is a chain compound having a skeleton containing a mesogenic group. In the paraphenylene group substituted with one methyl group contained in the compound represented by formula (1), the position of the methyl group bonded to the benzene ring is not particularly limited.
反応性樹脂組成物のエポキシ樹脂と硬化剤との含有量は、例えば、反応性樹脂組成物に含まれる硬化剤の反応基の合計モル数を１モルとして、反応性樹脂組成物に含まれるエポキシ樹脂のエポキシ基の合計モル数が０．９モル以上１．３モル以下の範囲内となる割合であることが好ましく、１．０モル以上１．２モル以下の範囲内となる割合であることがより好ましい。
The content of the epoxy resin and the curing agent in the reactive resin composition is, for example, based on the total number of moles of reactive groups of the curing agent contained in the reactive resin composition being 1 mol, The total number of moles of epoxy groups in the resin is preferably in the range of 0.9 mol or more and 1.3 mol or less, and is in the range of 1.0 mol or more and 1.2 mol or less. is more preferred.
硬化促進剤としては、高沸点の塩基性の有機化合物を用いることができる。具体的には、硬化促進剤として、３級アミン類、３級ホスフィン類、４－ジメチルアミノピリジン（ＤＭＡＰ）、イミダゾール類などから選ばれる沸点が２００℃以上のものなどが挙げられる。これらの中でも特に、取り扱いのしやすさから硬化促進剤として、イミダゾール系エポキシ樹脂硬化促進剤である２－エチル－４－メチルイミダゾール（２Ｅ４ＭＺ）、１－（２－シアノエチル）－２－フェニルイミダゾールを用いることが好ましい。反応性樹脂組成物の硬化促進剤の含有量は、エポキシ樹脂１００質量部に対して、例えば、０質量部以上５質量部以下の範囲内である。
A basic organic compound with a high boiling point can be used as the curing accelerator. Specific examples of curing accelerators include those having a boiling point of 200° C. or higher selected from tertiary amines, tertiary phosphines, 4-dimethylaminopyridine (DMAP), imidazoles, and the like. Among these, 2-ethyl-4-methylimidazole (2E4MZ) and 1-(2-cyanoethyl)-2-phenylimidazole, which are imidazole-based epoxy resin curing accelerators, are particularly used as curing accelerators for ease of handling. It is preferable to use The content of the curing accelerator in the reactive resin composition is, for example, within the range of 0 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the epoxy resin.
本実施形態の反応性樹脂組成物において、酸化マグネシウム組成物粉末の含有量は、例えば、１０体積％以上８０体積％以下の範囲内にあってもよく、４０体積％以上８０体積％以下の範囲内にあることが好ましく、５０体積％以上７５体積％以下の範囲内にあることがより好ましい。
In the reactive resin composition of the present embodiment, the content of the magnesium oxide composition powder may be, for example, in the range of 10% by volume or more and 80% by volume or less, or in the range of 40% by volume or more and 80% by volume or less. It is preferably within the range of 50% by volume or more and 75% by volume or less.
本実施形態の反応性樹脂組成物は、酸化マグネシウム組成物粉末以外の無機物粉末を含んでいてもよい。無機物粉末としては、窒化ホウ素粉末、アルミナ粉末、水酸化アルミニウム粉末、窒化アルミニウム粉末及びシリカ粉末等が挙げられる。こられの無機物粉末は、１種を単独で含有してもよいし、２種以上を含有してもよい。無機物粉末の含有量は、酸化マグネシウム組成物粉末との合計量で、例えば、２０体積％以上８０体積％以下の範囲内にあってもよく、４０体積％以上８０体積％以下の範囲内にあることが好ましく、５０体積％以上７５体積％以下の範囲内にあることがより好ましい。
The reactive resin composition of the present embodiment may contain inorganic powder other than the magnesium oxide composition powder. Examples of inorganic powders include boron nitride powder, alumina powder, aluminum hydroxide powder, aluminum nitride powder and silica powder. These inorganic powders may contain one type alone, or may contain two or more types. The content of the inorganic powder is the total amount with the magnesium oxide composition powder, and may be, for example, in the range of 20% by volume or more and 80% by volume or less, or in the range of 40% by volume or more and 80% by volume or less. more preferably in the range of 50% by volume or more and 75% by volume or less.
本実施形態の反応性樹脂組成物は、例えば、反応硬化性樹脂組成物と、酸化マグネシウム組成物粉末とを溶媒中で混合し、乾燥することによって製造することができる。溶媒としては、アセトン、メチルエチルケトン（ＭＥＫ）等のケトン類、メタノール、エタノール、イソプロパノール等のアルコール類、トルエン、キシレン等の芳香族化合物類、テトラヒドロフラン（ＴＨＦ）、１，３－ジオキソラン等のエーテル類、酢酸エチル、γ－ブチロラクトン等のエステル類、Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）、Ｎ－メチルピロリドン等のアミド類などが挙げられる。これらの溶媒は、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
The reactive resin composition of the present embodiment can be produced, for example, by mixing a reactive curable resin composition and magnesium oxide composition powder in a solvent and drying. Examples of solvents include ketones such as acetone and methyl ethyl ketone (MEK); alcohols such as methanol, ethanol and isopropanol; aromatic compounds such as toluene and xylene; ethers such as tetrahydrofuran (THF) and 1,3-dioxolane; Examples include esters such as ethyl acetate and γ-butyrolactone, and amides such as N,N-dimethylformamide (DMF) and N-methylpyrrolidone. These solvents may be used singly or in combination of two or more.
本実施形態の反応性樹脂組成物は、反応硬化性樹脂組成物と、上述した本実施形態の酸化マグネシウム組成物粉末とを含むので、反応硬化性樹脂組成物を硬化させることによって、熱伝導率が高く、耐水性や耐酸性に優れる樹脂組成物を生成することができる。生成した樹脂組成物は、例えば、電子機器の回路基板の材料として利用することができる。
Since the reactive resin composition of the present embodiment includes the reaction-curable resin composition and the magnesium oxide composition powder of the present embodiment described above, curing the reaction-curable resin composition increases the thermal conductivity It is possible to produce a resin composition that has a high resistance to water and is excellent in water resistance and acid resistance. The produced resin composition can be used, for example, as a material for circuit boards of electronic devices.
本実施形態の反応性樹脂組成物において、反応硬化性樹脂組成物が、エポキシ樹脂と硬化剤とを含む場合は、化学的により安定で耐水性や耐酸性に優れる樹脂組成物を得ることができる。さらに、エポキシ樹脂がトリグリシジルイソシアヌレートであって、硬化剤が上記の一般式（１）で表されるメソゲン基を含む骨格を有する鎖状化合物である場合は、より熱伝導率が高い樹脂組成物を得ることができる。硬化剤として、式（１）で表される化合物を用いた場合、硬化剤のメソゲン基を含む骨格によって、硬化物に剛直性が付与されるため、樹脂組成物（硬化物）の熱伝導性が向上する。
In the reactive resin composition of the present embodiment, when the reactive curable resin composition contains an epoxy resin and a curing agent, it is possible to obtain a resin composition that is chemically more stable and has excellent water resistance and acid resistance. . Furthermore, when the epoxy resin is triglycidyl isocyanurate and the curing agent is a chain compound having a skeleton containing a mesogenic group represented by the above general formula (1), the resin composition has a higher thermal conductivity. can get things. When the compound represented by the formula (1) is used as the curing agent, the rigidity is imparted to the cured product by the skeleton containing the mesogenic group of the curing agent, so the thermal conductivity of the resin composition (cured product) improves.
以上、本発明の実施形態について図面を参照して詳述したが、各実施形態における各構成及びそれらの組み合わせ等は一例であり、本発明の趣旨から逸脱しない範囲内で、構成の付加、省略、置換、及びその他の変更が可能である。
As described above, the embodiments of the present invention have been described in detail with reference to the drawings. , substitutions, and other modifications are possible.
次に、本発明を実施例により具体的に説明するが、本発明は以下の実施例に限定されるものではない。
EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples.
［実施例１］
１００ｍＬのナスフラスコに、酸化マグネシウム粉末（平均粒子径：１０μｍ、比表面積：０．７ｍ２／ｇ）２０ｇと、ＳｉＯ２源として濃度５％のポリシラザン溶液４２．０ｇと、添加金属元素化合物として酢酸リチウム０．１０６ｇとを投入し、１０分間攪拌混合して原料混合液を得た。次いで、原料混合液を風乾し、溶媒を除去して原料乾燥物を得た。次いで、原料混合乾燥物を、１５０℃で１時間加熱した後、８００℃で６時間加熱処理した。得られた加熱処理物をミルで解砕して、酸化マグネシウム組成物粉末を得た。 [Example 1]
A 100 mL eggplant flask was charged with 20 g of magnesium oxide powder (average particle diameter: 10 μm, specific surface area: 0.7 m 2 /g), 42.0 g of polysilazane solution with a concentration of 5% as a SiO 2 source, and acetic acid as an additive metal element compound. 0.106 g of lithium was added and mixed with stirring for 10 minutes to obtain a raw material mixture. Next, the raw material mixture was air-dried to remove the solvent to obtain a dried raw material. Next, the raw material mixed dried material was heated at 150° C. for 1 hour and then heat-treated at 800° C. for 6 hours. The obtained heat-treated product was pulverized with a mill to obtain a magnesium oxide composition powder.
１００ｍＬのナスフラスコに、酸化マグネシウム粉末（平均粒子径：１０μｍ、比表面積：０．７ｍ２／ｇ）２０ｇと、ＳｉＯ２源として濃度５％のポリシラザン溶液４２．０ｇと、添加金属元素化合物として酢酸リチウム０．１０６ｇとを投入し、１０分間攪拌混合して原料混合液を得た。次いで、原料混合液を風乾し、溶媒を除去して原料乾燥物を得た。次いで、原料混合乾燥物を、１５０℃で１時間加熱した後、８００℃で６時間加熱処理した。得られた加熱処理物をミルで解砕して、酸化マグネシウム組成物粉末を得た。 [Example 1]
A 100 mL eggplant flask was charged with 20 g of magnesium oxide powder (average particle diameter: 10 μm, specific surface area: 0.7 m 2 /g), 42.0 g of polysilazane solution with a concentration of 5% as a SiO 2 source, and acetic acid as an additive metal element compound. 0.106 g of lithium was added and mixed with stirring for 10 minutes to obtain a raw material mixture. Next, the raw material mixture was air-dried to remove the solvent to obtain a dried raw material. Next, the raw material mixed dried material was heated at 150° C. for 1 hour and then heat-treated at 800° C. for 6 hours. The obtained heat-treated product was pulverized with a mill to obtain a magnesium oxide composition powder.
［実施例２］
実施例１と同様にして酸化マグネシウム組成物粉末を得た。得られた酸化マグネシウム組成物粉末とシランカップリング剤（ＫＢＭ－４０３、信越化学工業株式会社製）とを、イソプロピルアルコール（ＩＰＡ）水溶液溶媒（ＩＰＡ／水＝９／１（体積比））に投入し、一晩攪拌混合した。シランカップリング剤の添加量は、酸化マグネシウム組成物粉末に対して５質量％とした。その後、ロータリーエバポレーターを用いて溶媒を除去し、次いで１２０℃で３０分間乾燥した。こうして、酸化マグネシウム組成物粉末をシランカップリング剤で表面処理した。 [Example 2]
A magnesium oxide composition powder was obtained in the same manner as in Example 1. The resulting magnesium oxide composition powder and a silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) were added to an isopropyl alcohol (IPA) aqueous solution solvent (IPA/water = 9/1 (volume ratio)). and mixed with stirring overnight. The amount of the silane coupling agent added was 5% by mass with respect to the magnesium oxide composition powder. The solvent was then removed using a rotary evaporator, followed by drying at 120° C. for 30 minutes. Thus, the magnesium oxide composition powder was surface-treated with a silane coupling agent.
実施例１と同様にして酸化マグネシウム組成物粉末を得た。得られた酸化マグネシウム組成物粉末とシランカップリング剤（ＫＢＭ－４０３、信越化学工業株式会社製）とを、イソプロピルアルコール（ＩＰＡ）水溶液溶媒（ＩＰＡ／水＝９／１（体積比））に投入し、一晩攪拌混合した。シランカップリング剤の添加量は、酸化マグネシウム組成物粉末に対して５質量％とした。その後、ロータリーエバポレーターを用いて溶媒を除去し、次いで１２０℃で３０分間乾燥した。こうして、酸化マグネシウム組成物粉末をシランカップリング剤で表面処理した。 [Example 2]
A magnesium oxide composition powder was obtained in the same manner as in Example 1. The resulting magnesium oxide composition powder and a silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) were added to an isopropyl alcohol (IPA) aqueous solution solvent (IPA/water = 9/1 (volume ratio)). and mixed with stirring overnight. The amount of the silane coupling agent added was 5% by mass with respect to the magnesium oxide composition powder. The solvent was then removed using a rotary evaporator, followed by drying at 120° C. for 30 minutes. Thus, the magnesium oxide composition powder was surface-treated with a silane coupling agent.
［実施例３～５］
５％ポリシラザン溶液の配合量、及び添加金属元素化合物の種類と配合量を、下記の表１に示すように変えたこと以外は、実施例１と同様にして酸化マグネシウム組成物粉末を得た。得られた酸化マグネシウム組成物粉末を、実施例２と同様にして、シランカップリング剤で表面処理した。 [Examples 3 to 5]
A magnesium oxide composition powder was obtained in the same manner as in Example 1, except that the amount of the 5% polysilazane solution and the type and amount of the additive metal element compound were changed as shown in Table 1 below. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
５％ポリシラザン溶液の配合量、及び添加金属元素化合物の種類と配合量を、下記の表１に示すように変えたこと以外は、実施例１と同様にして酸化マグネシウム組成物粉末を得た。得られた酸化マグネシウム組成物粉末を、実施例２と同様にして、シランカップリング剤で表面処理した。 [Examples 3 to 5]
A magnesium oxide composition powder was obtained in the same manner as in Example 1, except that the amount of the 5% polysilazane solution and the type and amount of the additive metal element compound were changed as shown in Table 1 below. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
［実施例６］
添加金属元素化合物として、酢酸リチウムの代わりに炭酸ナトリウム０．１５３ｇを用いたこと以外は、実施例１と同様にして酸化マグネシウム組成物粉末を得た。 [Example 6]
A magnesium oxide composition powder was obtained in the same manner as in Example 1, except that 0.153 g of sodium carbonate was used as the additive metal element compound instead of lithium acetate.
添加金属元素化合物として、酢酸リチウムの代わりに炭酸ナトリウム０．１５３ｇを用いたこと以外は、実施例１と同様にして酸化マグネシウム組成物粉末を得た。 [Example 6]
A magnesium oxide composition powder was obtained in the same manner as in Example 1, except that 0.153 g of sodium carbonate was used as the additive metal element compound instead of lithium acetate.
［実施例７］
実施例６と同様にして酸化マグネシウム組成物粉末を得た。得られた酸化マグネシウム組成物粉末を実施例２と同様にして、シランカップリング剤で表面処理した。 [Example 7]
A magnesium oxide composition powder was obtained in the same manner as in Example 6. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
実施例６と同様にして酸化マグネシウム組成物粉末を得た。得られた酸化マグネシウム組成物粉末を実施例２と同様にして、シランカップリング剤で表面処理した。 [Example 7]
A magnesium oxide composition powder was obtained in the same manner as in Example 6. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
［実施例８］
実施例６と同様にして酸化マグネシウム組成物粉末を得た。得られた酸化マグネシウム組成物粉末と、フェニルホスホン酸（ＰＰＡ）とをジオキソラン溶媒に投入し、３０分間攪拌混合した。ＰＰＡの添加量は、酸化マグネシウム組成物粉末に対して５質量％とした。その後、ロータリーエバポレーターを用いて溶媒を除去し、次いで１４０℃で一晩乾燥した。こうして、酸化マグネシウム組成物粉末をＰＰＡで表面処理した。 [Example 8]
A magnesium oxide composition powder was obtained in the same manner as in Example 6. The obtained magnesium oxide composition powder and phenylphosphonic acid (PPA) were put into a dioxolane solvent and stirred and mixed for 30 minutes. The amount of PPA added was 5% by mass with respect to the magnesium oxide composition powder. The solvent was then removed using a rotary evaporator and then dried at 140° C. overnight. Thus, the magnesium oxide composition powder was surface-treated with PPA.
実施例６と同様にして酸化マグネシウム組成物粉末を得た。得られた酸化マグネシウム組成物粉末と、フェニルホスホン酸（ＰＰＡ）とをジオキソラン溶媒に投入し、３０分間攪拌混合した。ＰＰＡの添加量は、酸化マグネシウム組成物粉末に対して５質量％とした。その後、ロータリーエバポレーターを用いて溶媒を除去し、次いで１４０℃で一晩乾燥した。こうして、酸化マグネシウム組成物粉末をＰＰＡで表面処理した。 [Example 8]
A magnesium oxide composition powder was obtained in the same manner as in Example 6. The obtained magnesium oxide composition powder and phenylphosphonic acid (PPA) were put into a dioxolane solvent and stirred and mixed for 30 minutes. The amount of PPA added was 5% by mass with respect to the magnesium oxide composition powder. The solvent was then removed using a rotary evaporator and then dried at 140° C. overnight. Thus, the magnesium oxide composition powder was surface-treated with PPA.
［実施例９～１７］
添加金属元素化合物の種類と配合量を、下記の表１に示すように変えたこと以外は、実施例１と同様にして酸化マグネシウム組成物粉末を得た。得られた酸化マグネシウム組成物粉末を、実施例２と同様にして、シランカップリング剤で表面処理した。 [Examples 9 to 17]
A magnesium oxide composition powder was obtained in the same manner as in Example 1, except that the type and amount of the additive metal element compound were changed as shown in Table 1 below. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
添加金属元素化合物の種類と配合量を、下記の表１に示すように変えたこと以外は、実施例１と同様にして酸化マグネシウム組成物粉末を得た。得られた酸化マグネシウム組成物粉末を、実施例２と同様にして、シランカップリング剤で表面処理した。 [Examples 9 to 17]
A magnesium oxide composition powder was obtained in the same manner as in Example 1, except that the type and amount of the additive metal element compound were changed as shown in Table 1 below. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
［実施例１８］
１００ｍＬのナスフラスコに、酸化マグネシウム粉末２０ｇと、ＳｉＯ２源として濃度５％のポリシラザン溶液４２．０ｇとを投入し、１０分間攪拌混合して混合液を得た。得られた混合液を風乾して溶媒を除去し、次いで１５０℃で１時間加熱してＳｉＯ２源被覆酸化マグネシウム粉末を得た。次いで、得られたＳｉＯ２源被覆酸化マグネシウム粉末と、添加金属元素化合物としてオキシ酢酸ジルコニウム水溶液３．３６０ｇとを混合し、風乾して、溶媒（水）を除去した。次いで、オキシ酢酸ジルコニウムが付着したＳｉＯ２源被覆酸化マグネシウム粉末を、１５０℃で１時間加熱した後、８００℃で６時間加熱処理した。得られた加熱処理物をミルで解砕して、酸化マグネシウム組成物粉末を得た。得られた酸化マグネシウム組成物粉末を、実施例２と同様にして、シランカップリング剤で表面処理した。 [Example 18]
20 g of magnesium oxide powder and 42.0 g of a polysilazane solution having a concentration of 5% as a SiO 2 source were put into a 100 mL eggplant flask, and stirred and mixed for 10 minutes to obtain a mixed solution. The resulting mixture was air-dried to remove the solvent, and then heated at 150° C. for 1 hour to obtain SiO 2 source-coated magnesium oxide powder. Next, the obtained SiO 2 source-coated magnesium oxide powder and 3.360 g of an aqueous zirconium oxyacetate solution as an additive metal element compound were mixed and air-dried to remove the solvent (water). The SiO 2 source-coated magnesium oxide powder with zirconium oxyacetate attached was then heated at 150° C. for 1 hour and then heat-treated at 800° C. for 6 hours. The obtained heat-treated product was pulverized with a mill to obtain a magnesium oxide composition powder. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
１００ｍＬのナスフラスコに、酸化マグネシウム粉末２０ｇと、ＳｉＯ２源として濃度５％のポリシラザン溶液４２．０ｇとを投入し、１０分間攪拌混合して混合液を得た。得られた混合液を風乾して溶媒を除去し、次いで１５０℃で１時間加熱してＳｉＯ２源被覆酸化マグネシウム粉末を得た。次いで、得られたＳｉＯ２源被覆酸化マグネシウム粉末と、添加金属元素化合物としてオキシ酢酸ジルコニウム水溶液３．３６０ｇとを混合し、風乾して、溶媒（水）を除去した。次いで、オキシ酢酸ジルコニウムが付着したＳｉＯ２源被覆酸化マグネシウム粉末を、１５０℃で１時間加熱した後、８００℃で６時間加熱処理した。得られた加熱処理物をミルで解砕して、酸化マグネシウム組成物粉末を得た。得られた酸化マグネシウム組成物粉末を、実施例２と同様にして、シランカップリング剤で表面処理した。 [Example 18]
20 g of magnesium oxide powder and 42.0 g of a polysilazane solution having a concentration of 5% as a SiO 2 source were put into a 100 mL eggplant flask, and stirred and mixed for 10 minutes to obtain a mixed solution. The resulting mixture was air-dried to remove the solvent, and then heated at 150° C. for 1 hour to obtain SiO 2 source-coated magnesium oxide powder. Next, the obtained SiO 2 source-coated magnesium oxide powder and 3.360 g of an aqueous zirconium oxyacetate solution as an additive metal element compound were mixed and air-dried to remove the solvent (water). The SiO 2 source-coated magnesium oxide powder with zirconium oxyacetate attached was then heated at 150° C. for 1 hour and then heat-treated at 800° C. for 6 hours. The obtained heat-treated product was pulverized with a mill to obtain a magnesium oxide composition powder. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
［実施例１９］
２００ｍＬのナスフラスコに、エタノール５０ｇと、イオン交換水１０ｇと、２８質量％アンモニア水１ｇと、酸化マグネシウム粉末２０ｇとを投入し、３０分間攪拌混合した。その後、エタノールで希釈したＴＥＯＳ（テトラエトキシシラン）を滴下し、さらに２時間攪拌混合して混合物を得た。得られた混合物をろ過して回収した固形物を、エタノールで洗浄し、次いで７０℃で１時間乾燥した後、１８０℃で３時間加熱処理して、ＳｉＯ２源被覆酸化マグネシウム粉末を得た。得られたＳｉＯ２源被覆酸化マグネシウム組成物と、炭酸ナトリウム０．１５３ｇとを混合した。次いで、炭酸ナトリウムが付着したＳｉＯ２源被覆酸化マグネシウム粉末を、８００℃で６時間加熱処理した。得られた加熱処理物をミルで解砕して、酸化マグネシウム組成物粉末を得た。得られた酸化マグネシウム組成物粉末を、実施例２と同様にして、シランカップリング剤で表面処理した。 [Example 19]
50 g of ethanol, 10 g of ion-exchanged water, 1 g of 28% by mass ammonia water, and 20 g of magnesium oxide powder were put into a 200 mL eggplant flask and stirred and mixed for 30 minutes. After that, TEOS (tetraethoxysilane) diluted with ethanol was added dropwise, and the mixture was further stirred and mixed for 2 hours to obtain a mixture. The resulting mixture was filtered and the solid collected was washed with ethanol, then dried at 70° C. for 1 hour and then heat-treated at 180° C. for 3 hours to obtain SiO 2 source-coated magnesium oxide powder. The resulting SiO 2 source coated magnesium oxide composition was mixed with 0.153 g of sodium carbonate. The SiO 2 source-coated magnesium oxide powder with attached sodium carbonate was then heat-treated at 800° C. for 6 hours. The obtained heat-treated product was pulverized with a mill to obtain a magnesium oxide composition powder. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
２００ｍＬのナスフラスコに、エタノール５０ｇと、イオン交換水１０ｇと、２８質量％アンモニア水１ｇと、酸化マグネシウム粉末２０ｇとを投入し、３０分間攪拌混合した。その後、エタノールで希釈したＴＥＯＳ（テトラエトキシシラン）を滴下し、さらに２時間攪拌混合して混合物を得た。得られた混合物をろ過して回収した固形物を、エタノールで洗浄し、次いで７０℃で１時間乾燥した後、１８０℃で３時間加熱処理して、ＳｉＯ２源被覆酸化マグネシウム粉末を得た。得られたＳｉＯ２源被覆酸化マグネシウム組成物と、炭酸ナトリウム０．１５３ｇとを混合した。次いで、炭酸ナトリウムが付着したＳｉＯ２源被覆酸化マグネシウム粉末を、８００℃で６時間加熱処理した。得られた加熱処理物をミルで解砕して、酸化マグネシウム組成物粉末を得た。得られた酸化マグネシウム組成物粉末を、実施例２と同様にして、シランカップリング剤で表面処理した。 [Example 19]
50 g of ethanol, 10 g of ion-exchanged water, 1 g of 28% by mass ammonia water, and 20 g of magnesium oxide powder were put into a 200 mL eggplant flask and stirred and mixed for 30 minutes. After that, TEOS (tetraethoxysilane) diluted with ethanol was added dropwise, and the mixture was further stirred and mixed for 2 hours to obtain a mixture. The resulting mixture was filtered and the solid collected was washed with ethanol, then dried at 70° C. for 1 hour and then heat-treated at 180° C. for 3 hours to obtain SiO 2 source-coated magnesium oxide powder. The resulting SiO 2 source coated magnesium oxide composition was mixed with 0.153 g of sodium carbonate. The SiO 2 source-coated magnesium oxide powder with attached sodium carbonate was then heat-treated at 800° C. for 6 hours. The obtained heat-treated product was pulverized with a mill to obtain a magnesium oxide composition powder. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
［実施例２０］
１００ｍＬのナスフラスコに、酸化マグネシウム粉末２０ｇと、ＳｉＯ２源としてシリコーンオイル（ＫＦ－９６、信越化学工業株式会社製）３ｇ、添加金属元素化合物として炭酸ナトリウム０．１５３ｇと、ヘキサン２０ｍＬとを投入し、１０分間攪拌混合して原料混合物を得た。得られた原料混合物を風乾して、溶媒を除去して原料乾燥物を得た。次いで、原料混合乾燥物を、１５０℃で１時間加熱した後、８００℃で６時間加熱処理した。得られた加熱処理物をミルで解砕して、酸化マグネシウム組成物粉末を得た。得られた酸化マグネシウム組成物粉末を、実施例２と同様にして、シランカップリング剤で表面処理した。 [Example 20]
In a 100 mL eggplant flask, 20 g of magnesium oxide powder, 3 g of silicone oil (KF-96, manufactured by Shin-Etsu Chemical Co., Ltd.) as a SiO 2 source, 0.153 g of sodium carbonate as an additive metal element compound, and 20 mL of hexane were added. , and stirred and mixed for 10 minutes to obtain a raw material mixture. The resulting raw material mixture was air-dried to remove the solvent to obtain a dried raw material. Next, the raw material mixed dried material was heated at 150° C. for 1 hour and then heat-treated at 800° C. for 6 hours. The obtained heat-treated product was pulverized with a mill to obtain a magnesium oxide composition powder. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
１００ｍＬのナスフラスコに、酸化マグネシウム粉末２０ｇと、ＳｉＯ２源としてシリコーンオイル（ＫＦ－９６、信越化学工業株式会社製）３ｇ、添加金属元素化合物として炭酸ナトリウム０．１５３ｇと、ヘキサン２０ｍＬとを投入し、１０分間攪拌混合して原料混合物を得た。得られた原料混合物を風乾して、溶媒を除去して原料乾燥物を得た。次いで、原料混合乾燥物を、１５０℃で１時間加熱した後、８００℃で６時間加熱処理した。得られた加熱処理物をミルで解砕して、酸化マグネシウム組成物粉末を得た。得られた酸化マグネシウム組成物粉末を、実施例２と同様にして、シランカップリング剤で表面処理した。 [Example 20]
In a 100 mL eggplant flask, 20 g of magnesium oxide powder, 3 g of silicone oil (KF-96, manufactured by Shin-Etsu Chemical Co., Ltd.) as a SiO 2 source, 0.153 g of sodium carbonate as an additive metal element compound, and 20 mL of hexane were added. , and stirred and mixed for 10 minutes to obtain a raw material mixture. The resulting raw material mixture was air-dried to remove the solvent to obtain a dried raw material. Next, the raw material mixed dried material was heated at 150° C. for 1 hour and then heat-treated at 800° C. for 6 hours. The obtained heat-treated product was pulverized with a mill to obtain a magnesium oxide composition powder. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
［実施例２１］
酸化マグネシウム粉末として、平均粒子径が３μｍで、比表面積が１．４ｍ２／ｇの酸化マグネシウム粉末を２０ｇ用い、濃度５％のポリシラザン溶液を８４．０ｇ用い、添加金属元素化合物として、酢酸リチウムの代わりに炭酸ナトリウム０．３０６ｇを用いたこと以外は、実施例１と同様にして酸化マグネシウム組成物粉末を得た。得られた酸化マグネシウム組成物粉末を、実施例２と同様にして、シランカップリング剤で表面処理した。 [Example 21]
As the magnesium oxide powder, 20 g of magnesium oxide powder having an average particle size of 3 μm and a specific surface area of 1.4 m 2 /g was used, and 84.0 g of a polysilazane solution having a concentration of 5% was used. A magnesium oxide composition powder was obtained in the same manner as in Example 1, except that 0.306 g of sodium carbonate was used instead. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
酸化マグネシウム粉末として、平均粒子径が３μｍで、比表面積が１．４ｍ２／ｇの酸化マグネシウム粉末を２０ｇ用い、濃度５％のポリシラザン溶液を８４．０ｇ用い、添加金属元素化合物として、酢酸リチウムの代わりに炭酸ナトリウム０．３０６ｇを用いたこと以外は、実施例１と同様にして酸化マグネシウム組成物粉末を得た。得られた酸化マグネシウム組成物粉末を、実施例２と同様にして、シランカップリング剤で表面処理した。 [Example 21]
As the magnesium oxide powder, 20 g of magnesium oxide powder having an average particle size of 3 μm and a specific surface area of 1.4 m 2 /g was used, and 84.0 g of a polysilazane solution having a concentration of 5% was used. A magnesium oxide composition powder was obtained in the same manner as in Example 1, except that 0.306 g of sodium carbonate was used instead. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
［実施例２２］
酸化マグネシウム粉末として、平均粒子径が１７μｍで、比表面積が０．５ｍ２／ｇの酸化マグネシウム粉末を２０ｇ用い、濃度５％のポリシラザン溶液を３０．０ｇ用い、添加金属元素化合物として、酢酸リチウムの代わりに炭酸ナトリウム０．１１０ｇを用いたこと以外は、実施例１と同様にして酸化マグネシウム組成物粉末を得た。得られた酸化マグネシウム組成物粉末を、実施例２と同様にして、シランカップリング剤で表面処理した。 [Example 22]
As the magnesium oxide powder, 20 g of magnesium oxide powder having an average particle size of 17 μm and a specific surface area of 0.5 m 2 /g was used, and 30.0 g of a polysilazane solution having a concentration of 5% was used. A magnesium oxide composition powder was obtained in the same manner as in Example 1, except that 0.110 g of sodium carbonate was used instead. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
酸化マグネシウム粉末として、平均粒子径が１７μｍで、比表面積が０．５ｍ２／ｇの酸化マグネシウム粉末を２０ｇ用い、濃度５％のポリシラザン溶液を３０．０ｇ用い、添加金属元素化合物として、酢酸リチウムの代わりに炭酸ナトリウム０．１１０ｇを用いたこと以外は、実施例１と同様にして酸化マグネシウム組成物粉末を得た。得られた酸化マグネシウム組成物粉末を、実施例２と同様にして、シランカップリング剤で表面処理した。 [Example 22]
As the magnesium oxide powder, 20 g of magnesium oxide powder having an average particle size of 17 μm and a specific surface area of 0.5 m 2 /g was used, and 30.0 g of a polysilazane solution having a concentration of 5% was used. A magnesium oxide composition powder was obtained in the same manner as in Example 1, except that 0.110 g of sodium carbonate was used instead. The resulting magnesium oxide composition powder was surface-treated with a silane coupling agent in the same manner as in Example 2.
［実施例２３］
５％ポリシラザン溶液の配合量と、炭酸ナトリウムの配合量を、下記の表１に示す量としたこと以外は、実施例６と同様にして酸化マグネシウム組成物粉末を得た。 [Example 23]
A magnesium oxide composition powder was obtained in the same manner as in Example 6, except that the blending amount of the 5% polysilazane solution and the blending amount of sodium carbonate were set to the amounts shown in Table 1 below.
５％ポリシラザン溶液の配合量と、炭酸ナトリウムの配合量を、下記の表１に示す量としたこと以外は、実施例６と同様にして酸化マグネシウム組成物粉末を得た。 [Example 23]
A magnesium oxide composition powder was obtained in the same manner as in Example 6, except that the blending amount of the 5% polysilazane solution and the blending amount of sodium carbonate were set to the amounts shown in Table 1 below.
［比較例１］
炭酸ナトリウムを用いなかったこと以外は、実施例１と同様にして酸化マグネシウム組成物粉末を得た。 [Comparative Example 1]
A magnesium oxide composition powder was obtained in the same manner as in Example 1, except that sodium carbonate was not used.
炭酸ナトリウムを用いなかったこと以外は、実施例１と同様にして酸化マグネシウム組成物粉末を得た。 [Comparative Example 1]
A magnesium oxide composition powder was obtained in the same manner as in Example 1, except that sodium carbonate was not used.
［比較例２］
５％ポリシラザン溶液の配合量と、炭酸ナトリウムの配合量を、下記の表２に示す量としたこと以外は、実施例６と同様にして酸化マグネシウム組成物粉末を得た。 [Comparative Example 2]
A magnesium oxide composition powder was obtained in the same manner as in Example 6, except that the blending amount of the 5% polysilazane solution and the blending amount of sodium carbonate were set to the amounts shown in Table 2 below.
５％ポリシラザン溶液の配合量と、炭酸ナトリウムの配合量を、下記の表２に示す量としたこと以外は、実施例６と同様にして酸化マグネシウム組成物粉末を得た。 [Comparative Example 2]
A magnesium oxide composition powder was obtained in the same manner as in Example 6, except that the blending amount of the 5% polysilazane solution and the blending amount of sodium carbonate were set to the amounts shown in Table 2 below.
［比較例３］
炭酸ナトリウムを用いなかったこと以外は、実施例２１と同様にして酸化マグネシウム組成物粉末を得て、得られた酸化マグネシウム組成物粉末をシランカップリング剤で表面処理した。 [Comparative Example 3]
A magnesium oxide composition powder was obtained in the same manner as in Example 21 except that sodium carbonate was not used, and the obtained magnesium oxide composition powder was surface-treated with a silane coupling agent.
炭酸ナトリウムを用いなかったこと以外は、実施例２１と同様にして酸化マグネシウム組成物粉末を得て、得られた酸化マグネシウム組成物粉末をシランカップリング剤で表面処理した。 [Comparative Example 3]
A magnesium oxide composition powder was obtained in the same manner as in Example 21 except that sodium carbonate was not used, and the obtained magnesium oxide composition powder was surface-treated with a silane coupling agent.
［比較例４］
炭酸ナトリウムを用いなかったこと以外は、実施例２２と同様にして酸化マグネシウム組成物粉末を得て、得られた酸化マグネシウム組成物粉末をシランカップリング剤で表面処理した。
[Comparative Example 4]
A magnesium oxide composition powder was obtained in the same manner as in Example 22, except that sodium carbonate was not used, and the obtained magnesium oxide composition powder was surface-treated with a silane coupling agent.
炭酸ナトリウムを用いなかったこと以外は、実施例２２と同様にして酸化マグネシウム組成物粉末を得て、得られた酸化マグネシウム組成物粉末をシランカップリング剤で表面処理した。
[Comparative Example 4]
A magnesium oxide composition powder was obtained in the same manner as in Example 22, except that sodium carbonate was not used, and the obtained magnesium oxide composition powder was surface-treated with a silane coupling agent.
［評価］
実施例１～２３、比較例１～４で得られた酸化マグネシウム組成物粉末を、原子分解能電子顕微鏡（ＪＥＭ－ＡＲＭ３００Ｆ ＧＲＡＮＤ ＡＲＭ、日本電子株式会社製）を用いて、ＥＤＳ（エネルギー分散型Ｘ線分析）により元素マッピングを行った。その結果、酸化マグネシウム組成物粉末は、ＳｉＯ２を含む酸化物層で被覆されていることが確認された。 [evaluation]
The magnesium oxide composition powders obtained in Examples 1 to 23 and Comparative Examples 1 to 4 were subjected to EDS (energy dispersive X-ray) using an atomic resolution electron microscope (JEM-ARM300F GRAND ARM, manufactured by JEOL Ltd.) analysis) performed elemental mapping. As a result, it was confirmed that the magnesium oxide composition powder was coated with an oxide layer containing SiO2 .
実施例１～２３、比較例１～４で得られた酸化マグネシウム組成物粉末を、原子分解能電子顕微鏡（ＪＥＭ－ＡＲＭ３００Ｆ ＧＲＡＮＤ ＡＲＭ、日本電子株式会社製）を用いて、ＥＤＳ（エネルギー分散型Ｘ線分析）により元素マッピングを行った。その結果、酸化マグネシウム組成物粉末は、ＳｉＯ２を含む酸化物層で被覆されていることが確認された。 [evaluation]
The magnesium oxide composition powders obtained in Examples 1 to 23 and Comparative Examples 1 to 4 were subjected to EDS (energy dispersive X-ray) using an atomic resolution electron microscope (JEM-ARM300F GRAND ARM, manufactured by JEOL Ltd.) analysis) performed elemental mapping. As a result, it was confirmed that the magnesium oxide composition powder was coated with an oxide layer containing SiO2 .
実施例１～２３、比較例１～４で得られた酸化マグネシウム組成物粉末の酸化物層について、厚さ、結晶性ＳｉＯ２の有無、添加金属元素の含有量を下記の方法により測定した。また、酸化マグネシウム組成物粉末の有機物層の有無を、下記の方法により確認した。さらに、酸化マグネシウム組成物粉末の耐酸性（溶出試験）、分散性（沈降試験）、熱伝導率を下記の方法より測定した。その結果を、下記の表３に示す。なお、耐酸性、分散性、熱伝導率は、酸化マグネシウム粉末（平均粒子径：１０μｍ、比表面積：０．７ｍ２／ｇ）についても測定した。その結果を、比較例５として表３に示す。
For the oxide layers of the magnesium oxide composition powders obtained in Examples 1 to 23 and Comparative Examples 1 to 4, the thickness, the presence or absence of crystalline SiO 2 , and the content of additive metal elements were measured by the following methods. Moreover, the presence or absence of an organic substance layer in the magnesium oxide composition powder was confirmed by the following method. Furthermore, the acid resistance (elution test), dispersibility (sedimentation test), and thermal conductivity of the magnesium oxide composition powder were measured by the following methods. The results are shown in Table 3 below. The acid resistance, dispersibility, and thermal conductivity were also measured for magnesium oxide powder (average particle size: 10 μm, specific surface area: 0.7 m 2 /g). The results are shown in Table 3 as Comparative Example 5.
［実施例３０］
酸化マグネシウム粉末２０ｇと、表１に記載の量の５％ポリシラザン溶液、ラウリン酸ナトリウム、およびＡＬＣＨを１００ｍｌナスフラスコへ添加し、３０分間の攪拌混合を行った。得られた混合物を風乾して溶媒を飛ばした後に、１５０℃で２時間乾燥させ、８００℃で６時間の加熱処理を行った。処理後の酸化マグネシウム粉末をミルで解砕して原料と同程度の粒径に粉砕することで、ケイ素、アルミニウム、マグネシウム、およびナトリウムのうち少なくとも一つを含む結晶性複酸化物によって被覆された被覆ＭｇＯ粉末を得た。 [Example 30]
20 g of magnesium oxide powder, and the amounts of 5% polysilazane solution, sodium laurate, and ALCH shown in Table 1 were added to a 100 ml eggplant flask and mixed with stirring for 30 minutes. The resulting mixture was air-dried to remove the solvent, dried at 150° C. for 2 hours, and heat-treated at 800° C. for 6 hours. The magnesium oxide powder after treatment is pulverized with a mill and pulverized to a particle size similar to that of the raw material, and is coated with a crystalline double oxide containing at least one of silicon, aluminum, magnesium, and sodium. A coated MgO powder was obtained.
酸化マグネシウム粉末２０ｇと、表１に記載の量の５％ポリシラザン溶液、ラウリン酸ナトリウム、およびＡＬＣＨを１００ｍｌナスフラスコへ添加し、３０分間の攪拌混合を行った。得られた混合物を風乾して溶媒を飛ばした後に、１５０℃で２時間乾燥させ、８００℃で６時間の加熱処理を行った。処理後の酸化マグネシウム粉末をミルで解砕して原料と同程度の粒径に粉砕することで、ケイ素、アルミニウム、マグネシウム、およびナトリウムのうち少なくとも一つを含む結晶性複酸化物によって被覆された被覆ＭｇＯ粉末を得た。 [Example 30]
20 g of magnesium oxide powder, and the amounts of 5% polysilazane solution, sodium laurate, and ALCH shown in Table 1 were added to a 100 ml eggplant flask and mixed with stirring for 30 minutes. The resulting mixture was air-dried to remove the solvent, dried at 150° C. for 2 hours, and heat-treated at 800° C. for 6 hours. The magnesium oxide powder after treatment is pulverized with a mill and pulverized to a particle size similar to that of the raw material, and is coated with a crystalline double oxide containing at least one of silicon, aluminum, magnesium, and sodium. A coated MgO powder was obtained.
［実施例３１］
実施例３０と同様にして得た酸化マグネシウム組成物粉末を、実施例２と同様にシランカップリング剤で表面処理した。 [Example 31]
A magnesium oxide composition powder obtained in the same manner as in Example 30 was surface-treated with a silane coupling agent in the same manner as in Example 2.
実施例３０と同様にして得た酸化マグネシウム組成物粉末を、実施例２と同様にシランカップリング剤で表面処理した。 [Example 31]
A magnesium oxide composition powder obtained in the same manner as in Example 30 was surface-treated with a silane coupling agent in the same manner as in Example 2.
［比較例６］
添加金属元素化合物として、ラウリン酸ナトリウムの代わりに炭酸リチウムを用いたこと以外は、実施例３０と同様にして、結晶性複酸化物によって被覆された被覆ＭｇＯ粉末を得た。 [Comparative Example 6]
A coated MgO powder coated with a crystalline multiple oxide was obtained in the same manner as in Example 30, except that lithium carbonate was used as the additive metal element compound instead of sodium laurate.
添加金属元素化合物として、ラウリン酸ナトリウムの代わりに炭酸リチウムを用いたこと以外は、実施例３０と同様にして、結晶性複酸化物によって被覆された被覆ＭｇＯ粉末を得た。 [Comparative Example 6]
A coated MgO powder coated with a crystalline multiple oxide was obtained in the same manner as in Example 30, except that lithium carbonate was used as the additive metal element compound instead of sodium laurate.
（酸化物層の厚さ）
酸化マグネシウム組成物粉末に対して、ＥＤＳを用いて、Ｍｇ及びＳｉの元素マッピングを行った。Ｏ（酸素）は、検出しないように設定した。取得された元素マップ像のＭｇとＳｉのＸ線強度プロファイルにおいて、ＳｉのＸ線強度がＭｇのＸ線強度よりも大きい範囲を酸化物層として、その厚さを計測した。酸化物層の厚さは、３個の粒子について行った。表３に記載した値は、その平均値である。 (thickness of oxide layer)
Elemental mapping of Mg and Si was performed on the magnesium oxide composition powder using EDS. O (oxygen) was set not to be detected. In the X-ray intensity profiles of Mg and Si in the acquired elemental map image, the thickness of the oxide layer was measured in the range where the X-ray intensity of Si was greater than the X-ray intensity of Mg. The thickness of the oxide layer was carried out on three particles. The values listed in Table 3 are the average values.
酸化マグネシウム組成物粉末に対して、ＥＤＳを用いて、Ｍｇ及びＳｉの元素マッピングを行った。Ｏ（酸素）は、検出しないように設定した。取得された元素マップ像のＭｇとＳｉのＸ線強度プロファイルにおいて、ＳｉのＸ線強度がＭｇのＸ線強度よりも大きい範囲を酸化物層として、その厚さを計測した。酸化物層の厚さは、３個の粒子について行った。表３に記載した値は、その平均値である。 (thickness of oxide layer)
Elemental mapping of Mg and Si was performed on the magnesium oxide composition powder using EDS. O (oxygen) was set not to be detected. In the X-ray intensity profiles of Mg and Si in the acquired elemental map image, the thickness of the oxide layer was measured in the range where the X-ray intensity of Si was greater than the X-ray intensity of Mg. The thickness of the oxide layer was carried out on three particles. The values listed in Table 3 are the average values.
（結晶性ＳｉＯ２の有無）
結晶性ＳｉＯ２の有無は、ＣｕＫα線を用いて測定されたＸ線回折パターンから結晶性ＳｉＯ２（トリジマイト、クリストバライト、石英）に由来する回折ピークが検出されるか否かによって判定した。結晶性ＳｉＯ２に由来する回折ピークが１種でも検出された場合は、結晶性ＳｉＯ２を「有」とした。Ｘ線回折パターンは、Ｘ線回折装置（Ｅｍｐｙｒｅａｎ、Ｍａｌｖｅｒｎ Ｐａｎａｌｙｔｉｃａｌ社製）を用いて測定した。 (Presence or absence of crystalline SiO2 )
The presence or absence of crystalline SiO 2 was determined by detecting a diffraction peak derived from crystalline SiO 2 (tridymite, cristobalite, quartz) from an X-ray diffraction pattern measured using CuKα rays. If even one kind of diffraction peak derived from crystalline SiO 2 was detected, crystalline SiO 2 was judged to be “presence”. The X-ray diffraction pattern was measured using an X-ray diffractometer (Empyrean, manufactured by Malvern Panalytical).
結晶性ＳｉＯ２の有無は、ＣｕＫα線を用いて測定されたＸ線回折パターンから結晶性ＳｉＯ２（トリジマイト、クリストバライト、石英）に由来する回折ピークが検出されるか否かによって判定した。結晶性ＳｉＯ２に由来する回折ピークが１種でも検出された場合は、結晶性ＳｉＯ２を「有」とした。Ｘ線回折パターンは、Ｘ線回折装置（Ｅｍｐｙｒｅａｎ、Ｍａｌｖｅｒｎ Ｐａｎａｌｙｔｉｃａｌ社製）を用いて測定した。 (Presence or absence of crystalline SiO2 )
The presence or absence of crystalline SiO 2 was determined by detecting a diffraction peak derived from crystalline SiO 2 (tridymite, cristobalite, quartz) from an X-ray diffraction pattern measured using CuKα rays. If even one kind of diffraction peak derived from crystalline SiO 2 was detected, crystalline SiO 2 was judged to be “presence”. The X-ray diffraction pattern was measured using an X-ray diffractometer (Empyrean, manufactured by Malvern Panalytical).
（添加金属元素の含有量）
試料０．１ｇを秤量し、これに８ｍＬの硝酸水溶液（硝酸／水＝２／１（体積比））と２ｍＬのフッ酸とを加え、マイクロウェーブ試料分解装置（Ｍｕｌｔｉｗａｖｅ３０００、Ａｎｔｏｎ Ｐａａｒ社製）を用いて、２００℃で３０分間加熱処理して溶解させた。得られた溶液に、純水を加えて２０ｇに定容した後、ＩＣＰ－ＡＥＳ（ＩＣＰＳ－８１００ＣＬ、島津製作所社製）を用いて検量線法によって、マグネシウムと添加金属元素の含有量を定量した。 (Content of additive metal element)
0.1 g of sample was weighed, 8 mL of nitric acid aqueous solution (nitric acid/water = 2/1 (volume ratio)) and 2 mL of hydrofluoric acid were added thereto, and a microwave sample decomposition device (Multiwave 3000, manufactured by Anton Paar) was used. was used and heat-treated at 200° C. for 30 minutes to dissolve. Pure water was added to the obtained solution to adjust the volume to 20 g, and then the contents of magnesium and added metal elements were quantified by the calibration curve method using ICP-AES (ICPS-8100CL, manufactured by Shimadzu Corporation). .
試料０．１ｇを秤量し、これに８ｍＬの硝酸水溶液（硝酸／水＝２／１（体積比））と２ｍＬのフッ酸とを加え、マイクロウェーブ試料分解装置（Ｍｕｌｔｉｗａｖｅ３０００、Ａｎｔｏｎ Ｐａａｒ社製）を用いて、２００℃で３０分間加熱処理して溶解させた。得られた溶液に、純水を加えて２０ｇに定容した後、ＩＣＰ－ＡＥＳ（ＩＣＰＳ－８１００ＣＬ、島津製作所社製）を用いて検量線法によって、マグネシウムと添加金属元素の含有量を定量した。 (Content of additive metal element)
0.1 g of sample was weighed, 8 mL of nitric acid aqueous solution (nitric acid/water = 2/1 (volume ratio)) and 2 mL of hydrofluoric acid were added thereto, and a microwave sample decomposition device (Multiwave 3000, manufactured by Anton Paar) was used. was used and heat-treated at 200° C. for 30 minutes to dissolve. Pure water was added to the obtained solution to adjust the volume to 20 g, and then the contents of magnesium and added metal elements were quantified by the calibration curve method using ICP-AES (ICPS-8100CL, manufactured by Shimadzu Corporation). .
（有機物層の有無）
酸化マグネシウム組成物粉末の表面の赤外吸収スペクトルを測定した。赤外吸収スペクトルの測定は、ＦＴ－ＩＲ（Ｎｉｃｏｌｅｔ ｉＳ５０、サーモフィッシャー社製）を用い、拡散反射法により行った。赤外吸収スペクトルからシランカップリング剤もしくはホスホン酸に起因するピークが検出された場合は、有機物層を「有」とした。 (Presence or absence of organic layer)
An infrared absorption spectrum of the surface of the magnesium oxide composition powder was measured. The infrared absorption spectrum was measured by a diffuse reflection method using FT-IR (Nicolet iS50, manufactured by Thermo Fisher). When a peak attributed to the silane coupling agent or phosphonic acid was detected from the infrared absorption spectrum, the organic layer was evaluated as "present".
酸化マグネシウム組成物粉末の表面の赤外吸収スペクトルを測定した。赤外吸収スペクトルの測定は、ＦＴ－ＩＲ（Ｎｉｃｏｌｅｔ ｉＳ５０、サーモフィッシャー社製）を用い、拡散反射法により行った。赤外吸収スペクトルからシランカップリング剤もしくはホスホン酸に起因するピークが検出された場合は、有機物層を「有」とした。 (Presence or absence of organic layer)
An infrared absorption spectrum of the surface of the magnesium oxide composition powder was measured. The infrared absorption spectrum was measured by a diffuse reflection method using FT-IR (Nicolet iS50, manufactured by Thermo Fisher). When a peak attributed to the silane coupling agent or phosphonic acid was detected from the infrared absorption spectrum, the organic layer was evaluated as "present".
（耐酸性（溶出試験））
ｐＨを５に調製した硫酸水溶液１０ｍＬに、酸化マグネシウム組成物粉末を０．５ｇ添加し、１０分攪拌を行った。攪拌後の硫酸水溶液のｐＨをｐＨメーターで測定して、その値を酸化マグネシウム組成物粉末の酸性溶液に対する溶出性とした。ｐＨが低いことは、酸化マグネシウムが酸に溶出しにくいこと、すなわち耐酸性に優れることを表す。 (Acid resistance (elution test))
0.5 g of magnesium oxide composition powder was added to 10 mL of an aqueous sulfuric acid solution adjusted to pH 5, and the mixture was stirred for 10 minutes. The pH of the sulfuric acid aqueous solution after stirring was measured with a pH meter, and the value was defined as the dissolution property of the magnesium oxide composition powder in an acidic solution. A low pH indicates that magnesium oxide is less likely to dissolve in an acid, that is, it has excellent acid resistance.
ｐＨを５に調製した硫酸水溶液１０ｍＬに、酸化マグネシウム組成物粉末を０．５ｇ添加し、１０分攪拌を行った。攪拌後の硫酸水溶液のｐＨをｐＨメーターで測定して、その値を酸化マグネシウム組成物粉末の酸性溶液に対する溶出性とした。ｐＨが低いことは、酸化マグネシウムが酸に溶出しにくいこと、すなわち耐酸性に優れることを表す。 (Acid resistance (elution test))
0.5 g of magnesium oxide composition powder was added to 10 mL of an aqueous sulfuric acid solution adjusted to pH 5, and the mixture was stirred for 10 minutes. The pH of the sulfuric acid aqueous solution after stirring was measured with a pH meter, and the value was defined as the dissolution property of the magnesium oxide composition powder in an acidic solution. A low pH indicates that magnesium oxide is less likely to dissolve in an acid, that is, it has excellent acid resistance.
（分散性（沈降試験））
沈降管として、２０ｍＬの（有栓）メスシリンダーを用いた。この沈降管に、酸化マグネシウム組成物粉末を０．５ｇ、ジオキソランを２０ｍＬ量り取り、攪拌しながら１０分間超音波分散処理を行った。次いで、沈降管を栓で封止した後、沈降管を水平な面に静置させたと同時に時間の計測を開始し、静置５分後の気液界面から完全に澄明な液相と懸濁が認められる液相との界面までの距離を目視での沈降距離として測定した。沈降距離の測定に際して、界面の読み取りを容易とするために黒色背景の前に沈降管を設置した。沈降距離が大きいほど分散性に優れることを表す。 (Dispersibility (sedimentation test))
A 20 mL (stoppered) graduated cylinder was used as a sedimentation tube. 0.5 g of the magnesium oxide composition powder and 20 mL of dioxolane were weighed into this sedimentation tube and subjected to ultrasonic dispersion treatment for 10 minutes while stirring. Next, after sealing the sedimentation tube with a stopper, the sedimentation tube was allowed to stand still on a horizontal surface, and at the same time, time measurement was started. The distance to the interface with the liquid phase at which the is observed was measured as the visual sedimentation distance. When measuring sedimentation distances, the sedimentation tube was placed in front of a black background to facilitate reading of the interface. A larger sedimentation distance indicates better dispersibility.
沈降管として、２０ｍＬの（有栓）メスシリンダーを用いた。この沈降管に、酸化マグネシウム組成物粉末を０．５ｇ、ジオキソランを２０ｍＬ量り取り、攪拌しながら１０分間超音波分散処理を行った。次いで、沈降管を栓で封止した後、沈降管を水平な面に静置させたと同時に時間の計測を開始し、静置５分後の気液界面から完全に澄明な液相と懸濁が認められる液相との界面までの距離を目視での沈降距離として測定した。沈降距離の測定に際して、界面の読み取りを容易とするために黒色背景の前に沈降管を設置した。沈降距離が大きいほど分散性に優れることを表す。 (Dispersibility (sedimentation test))
A 20 mL (stoppered) graduated cylinder was used as a sedimentation tube. 0.5 g of the magnesium oxide composition powder and 20 mL of dioxolane were weighed into this sedimentation tube and subjected to ultrasonic dispersion treatment for 10 minutes while stirring. Next, after sealing the sedimentation tube with a stopper, the sedimentation tube was allowed to stand still on a horizontal surface, and at the same time, time measurement was started. The distance to the interface with the liquid phase at which the is observed was measured as the visual sedimentation distance. When measuring sedimentation distances, the sedimentation tube was placed in front of a black background to facilitate reading of the interface. A larger sedimentation distance indicates better dispersibility.
（熱伝導率）
ビスフェノールＡ型エポキシ樹脂（ＪＥＲ８２８、三菱ケミカル株式会社製）１００質量部に対して、メチルヒドロキノン（東京化成工業株式会社製）３質量部と、２－エチル－４－メチルイミダゾール（２Ｅ４ＭＺ、四国化成工業株式会社製）３質量部とを混合してエポキシ系樹脂組成物を得た。得られたエポキシ系樹脂組成物と、酸化マグネシウム組成物粉末とを体積比で３０：７０の割合で攪拌混合して、反応性樹脂組成物を得た。次いで、反応性樹脂組成物を真空脱気し、ハンドプレス機で厚さ１ｍｍのシート状に加工した後、１２０℃で１時間、１５０℃で１時間、１８０℃で１時間加熱することでエポキシ系樹脂組成物シートを得た。 (Thermal conductivity)
Bisphenol A type epoxy resin (JER828, manufactured by Mitsubishi Chemical Co., Ltd.) 100 parts by weight, methylhydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) 3 parts by weight, 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Kasei Kogyo Co., Ltd.) was mixed with 3 parts by mass to obtain an epoxy resin composition. The obtained epoxy resin composition and magnesium oxide composition powder were stirred and mixed at a volume ratio of 30:70 to obtain a reactive resin composition. Next, the reactive resin composition is vacuum degassed, processed into a sheet with a thickness of 1 mm using a hand press, and then heated at 120° C. for 1 hour, 150° C. for 1 hour, and 180° C. for 1 hour to form an epoxy resin. A system resin composition sheet was obtained.
ビスフェノールＡ型エポキシ樹脂（ＪＥＲ８２８、三菱ケミカル株式会社製）１００質量部に対して、メチルヒドロキノン（東京化成工業株式会社製）３質量部と、２－エチル－４－メチルイミダゾール（２Ｅ４ＭＺ、四国化成工業株式会社製）３質量部とを混合してエポキシ系樹脂組成物を得た。得られたエポキシ系樹脂組成物と、酸化マグネシウム組成物粉末とを体積比で３０：７０の割合で攪拌混合して、反応性樹脂組成物を得た。次いで、反応性樹脂組成物を真空脱気し、ハンドプレス機で厚さ１ｍｍのシート状に加工した後、１２０℃で１時間、１５０℃で１時間、１８０℃で１時間加熱することでエポキシ系樹脂組成物シートを得た。 (Thermal conductivity)
Bisphenol A type epoxy resin (JER828, manufactured by Mitsubishi Chemical Co., Ltd.) 100 parts by weight, methylhydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) 3 parts by weight, 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Kasei Kogyo Co., Ltd.) was mixed with 3 parts by mass to obtain an epoxy resin composition. The obtained epoxy resin composition and magnesium oxide composition powder were stirred and mixed at a volume ratio of 30:70 to obtain a reactive resin composition. Next, the reactive resin composition is vacuum degassed, processed into a sheet with a thickness of 1 mm using a hand press, and then heated at 120° C. for 1 hour, 150° C. for 1 hour, and 180° C. for 1 hour to form an epoxy resin. A system resin composition sheet was obtained.
得られたエポキシ系樹脂組成物シートの熱伝導率は、エポキシ系樹脂組成物シートの密度と、比熱と、熱拡散率とを以下に示す方法によりそれぞれ測定し、得られた値を乗じることにより算出した。
密度は、アルキメデス法を用いて求めた。
比熱は、示差走査熱量計（ＤＳＣ）（株式会社日立ハイテクサイエンス社製）を用いて求めた。
熱拡散率は、キセノンフラッシュ熱拡散率測定装置（アドバンス理工株式会社製）を用いて求めた。 The thermal conductivity of the obtained epoxy resin composition sheet is obtained by measuring the density, specific heat, and thermal diffusivity of the epoxy resin composition sheet by the methods described below, and multiplying the obtained values. Calculated.
Density was determined using the Archimedes method.
The specific heat was obtained using a differential scanning calorimeter (DSC) (manufactured by Hitachi High-Tech Science Co., Ltd.).
The thermal diffusivity was obtained using a xenon flash thermal diffusivity measurement device (manufactured by Advance Riko Co., Ltd.).
密度は、アルキメデス法を用いて求めた。
比熱は、示差走査熱量計（ＤＳＣ）（株式会社日立ハイテクサイエンス社製）を用いて求めた。
熱拡散率は、キセノンフラッシュ熱拡散率測定装置（アドバンス理工株式会社製）を用いて求めた。 The thermal conductivity of the obtained epoxy resin composition sheet is obtained by measuring the density, specific heat, and thermal diffusivity of the epoxy resin composition sheet by the methods described below, and multiplying the obtained values. Calculated.
Density was determined using the Archimedes method.
The specific heat was obtained using a differential scanning calorimeter (DSC) (manufactured by Hitachi High-Tech Science Co., Ltd.).
The thermal diffusivity was obtained using a xenon flash thermal diffusivity measurement device (manufactured by Advance Riko Co., Ltd.).
表３の結果から、酸化物層が結晶性ＳｉＯ２を含む実施例１～２３の酸化マグネシウム組成物粉末は、酸化物層が結晶性ＳｉＯ２を含まない比較例１～４の酸化マグネシウム組成物粉末と比較して熱伝導率が高いことが確認された。また、酸化物層の厚さが５０ｎｍ以上である実施例１～２２の酸化マグネシウム組成物粉末は、耐酸性が顕著に向上することが確認された。さらに、有機物層を有する実施例２～５及び実施例７～２２の酸化マグネシウム組成物粉末は分散性が向上することが確認された。
From the results in Table 3, the magnesium oxide composition powders of Examples 1 to 23, in which the oxide layer contains crystalline SiO 2 , are the magnesium oxide compositions of Comparative Examples 1 to 4, in which the oxide layer does not contain crystalline SiO 2 . It was confirmed that the thermal conductivity is higher than that of the powder. Moreover, it was confirmed that the magnesium oxide composition powders of Examples 1 to 22, in which the thickness of the oxide layer was 50 nm or more, were remarkably improved in acid resistance. Furthermore, it was confirmed that the magnesium oxide composition powders of Examples 2 to 5 and Examples 7 to 22 having organic layers had improved dispersibility.
［実施例２４］
ポリスチレン（富士フイルム和光純薬株式会社製、密度：１．０４－１．１３ｇ／ｃｍ３）と、実施例７で得られた酸化マグネシウム組成物粉末とを、体積比で４５：５５の割合で乳鉢と乳棒を用いて混合した。得られた混合物とトルエンとを混合して、攪拌混合してスラリーを得た。得られたスラリーをＰＥＴフィルム上に塗布し、１００℃で５分、１２０℃で１０分間乾燥して、厚さ１００～１５０μｍのポリスチレン組成物シートを得た。得られたポリスチレン組成物シートをＰＥＴフィルムから剥離した。ポリスチレン組成物シート１０枚を積層した。得られた積層体を厚さが１ｍｍになるように、ハンドプレス機を用いて温度１００℃、圧力１０ＭＰａ、３分間プレスすることにより、ポリスチレン組成物シート積層体を得た。 [Example 24]
Polystyrene (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., density: 1.04-1.13 g/cm 3 ) and the magnesium oxide composition powder obtained in Example 7 were mixed at a volume ratio of 45:55. Mixed using a mortar and pestle. The obtained mixture and toluene were mixed and stirred to obtain a slurry. The obtained slurry was applied on a PET film and dried at 100° C. for 5 minutes and 120° C. for 10 minutes to obtain a polystyrene composition sheet with a thickness of 100 to 150 μm. The obtained polystyrene composition sheet was peeled off from the PET film. Ten polystyrene composition sheets were laminated. A polystyrene composition sheet laminate was obtained by pressing the obtained laminate with a hand press machine at a temperature of 100° C. and a pressure of 10 MPa for 3 minutes so that the laminate had a thickness of 1 mm.
ポリスチレン（富士フイルム和光純薬株式会社製、密度：１．０４－１．１３ｇ／ｃｍ３）と、実施例７で得られた酸化マグネシウム組成物粉末とを、体積比で４５：５５の割合で乳鉢と乳棒を用いて混合した。得られた混合物とトルエンとを混合して、攪拌混合してスラリーを得た。得られたスラリーをＰＥＴフィルム上に塗布し、１００℃で５分、１２０℃で１０分間乾燥して、厚さ１００～１５０μｍのポリスチレン組成物シートを得た。得られたポリスチレン組成物シートをＰＥＴフィルムから剥離した。ポリスチレン組成物シート１０枚を積層した。得られた積層体を厚さが１ｍｍになるように、ハンドプレス機を用いて温度１００℃、圧力１０ＭＰａ、３分間プレスすることにより、ポリスチレン組成物シート積層体を得た。 [Example 24]
Polystyrene (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., density: 1.04-1.13 g/cm 3 ) and the magnesium oxide composition powder obtained in Example 7 were mixed at a volume ratio of 45:55. Mixed using a mortar and pestle. The obtained mixture and toluene were mixed and stirred to obtain a slurry. The obtained slurry was applied on a PET film and dried at 100° C. for 5 minutes and 120° C. for 10 minutes to obtain a polystyrene composition sheet with a thickness of 100 to 150 μm. The obtained polystyrene composition sheet was peeled off from the PET film. Ten polystyrene composition sheets were laminated. A polystyrene composition sheet laminate was obtained by pressing the obtained laminate with a hand press machine at a temperature of 100° C. and a pressure of 10 MPa for 3 minutes so that the laminate had a thickness of 1 mm.
［実施例２５］
アクリル樹脂成形材料（アクリペット（登録商標）、三菱ケミカル株式会社製）と、実施例７で得られた酸化マグネシウム組成物粉末とを、体積比で４５：５５の割合で混合した。得られた混合物とトルエンとを混合して、攪拌混合してスラリーを得た。得られたスラリーをＰＥＴフィルム上に塗布し、１００℃で５分、１２０℃で１０分間乾燥して、厚さ１００～１５０μｍのアクリル樹脂組成物シートを得た。得られたアクリル樹脂組成物シートをＰＥＴフィルムから剥離した。アクリル樹脂組成物シート１０枚を積層した。得られた積層体を厚さが１ｍｍになるように、ハンドプレス機を用いて温度１００℃、圧力１０ＭＰａ、３分間プレスすることにより、メタクリル樹脂組成物シート積層体を得た。 [Example 25]
An acrylic resin molding material (Acrypet (registered trademark), manufactured by Mitsubishi Chemical Corporation) and the magnesium oxide composition powder obtained in Example 7 were mixed at a volume ratio of 45:55. The obtained mixture and toluene were mixed and stirred to obtain a slurry. The obtained slurry was applied on a PET film and dried at 100° C. for 5 minutes and 120° C. for 10 minutes to obtain an acrylic resin composition sheet with a thickness of 100 to 150 μm. The obtained acrylic resin composition sheet was peeled off from the PET film. Ten acrylic resin composition sheets were laminated. A methacrylic resin composition sheet laminate was obtained by pressing the resulting laminate with a hand press at a temperature of 100° C. and a pressure of 10 MPa for 3 minutes so that the laminate had a thickness of 1 mm.
アクリル樹脂成形材料（アクリペット（登録商標）、三菱ケミカル株式会社製）と、実施例７で得られた酸化マグネシウム組成物粉末とを、体積比で４５：５５の割合で混合した。得られた混合物とトルエンとを混合して、攪拌混合してスラリーを得た。得られたスラリーをＰＥＴフィルム上に塗布し、１００℃で５分、１２０℃で１０分間乾燥して、厚さ１００～１５０μｍのアクリル樹脂組成物シートを得た。得られたアクリル樹脂組成物シートをＰＥＴフィルムから剥離した。アクリル樹脂組成物シート１０枚を積層した。得られた積層体を厚さが１ｍｍになるように、ハンドプレス機を用いて温度１００℃、圧力１０ＭＰａ、３分間プレスすることにより、メタクリル樹脂組成物シート積層体を得た。 [Example 25]
An acrylic resin molding material (Acrypet (registered trademark), manufactured by Mitsubishi Chemical Corporation) and the magnesium oxide composition powder obtained in Example 7 were mixed at a volume ratio of 45:55. The obtained mixture and toluene were mixed and stirred to obtain a slurry. The obtained slurry was applied on a PET film and dried at 100° C. for 5 minutes and 120° C. for 10 minutes to obtain an acrylic resin composition sheet with a thickness of 100 to 150 μm. The obtained acrylic resin composition sheet was peeled off from the PET film. Ten acrylic resin composition sheets were laminated. A methacrylic resin composition sheet laminate was obtained by pressing the resulting laminate with a hand press at a temperature of 100° C. and a pressure of 10 MPa for 3 minutes so that the laminate had a thickness of 1 mm.
［実施例２６］
ビスフェノールＡ型エポキシ樹脂（ＪＥＲ８２８、三菱ケミカル株式会社製）と、メチルヒドロキノン（東京化成工業株式会社製）とを、メチルヒドロキノンのフェノール性水酸基の合計モル数を１モルに対して、ビスフェノールＡ型エポキシ樹脂のエポキシ基の合計モル数が１．０モルとなる割合で混合し、さらに、ビスフェノールＡ型エポキシ樹脂１００質量部に対して、２－エチル－４－メチルイミダゾール（２Ｅ４ＭＺ）（四国化成工業株式会社製）３質量部を加えて、混合してエポキシ系樹脂組成物を得た。得られたエポキシ系樹脂組成物と、実施例２で得られた酸化マグネシウム組成物粉末とを、体積比で４５：５５の割合で、ＴＨＦ（テトラヒドロフラン）中で攪拌混合してスラリーを得た。得られたスラリーをＰＥＴフィルム上に塗布し、１００℃で５分、１２０℃で１０分間乾燥して、厚さ１００～１５０μｍのエポキシ系樹脂組成物シートを得た。得られたエポキシ系樹脂組成物シートをＰＥＴフィルムから剥離した。エポキシ系樹脂組成物シート１０枚を積層した。得られた積層体を厚さが１ｍｍになるように、ハンドプレス機を用いて温度１００℃、圧力１０ＭＰａ、３分間プレスした。次いで１２０℃で１時間、１５０℃で１時間、１８０℃で１時間加熱して、エポキシ系樹脂組成物を硬化させて、エポキシ樹脂硬化物シートを得た。 [Example 26]
Bisphenol A type epoxy resin (JER828, manufactured by Mitsubishi Chemical Corporation) and methylhydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) are added to 1 mol of the total number of moles of phenolic hydroxyl groups of methylhydroquinone. The total number of moles of epoxy groups in the resin is mixed at a ratio of 1.0 mol, and 2-ethyl-4-methylimidazole (2E4MZ) (Shikoku Kasei Kogyo Co., Ltd.) is added to 100 parts by mass of bisphenol A epoxy resin. (manufactured by the company) was added and mixed to obtain an epoxy resin composition. The obtained epoxy resin composition and the magnesium oxide composition powder obtained in Example 2 were stirred and mixed in THF (tetrahydrofuran) at a volume ratio of 45:55 to obtain a slurry. The obtained slurry was applied on a PET film and dried at 100° C. for 5 minutes and 120° C. for 10 minutes to obtain an epoxy resin composition sheet with a thickness of 100 to 150 μm. The obtained epoxy resin composition sheet was peeled off from the PET film. Ten epoxy resin composition sheets were laminated. The resulting laminate was pressed using a hand press machine at a temperature of 100° C. and a pressure of 10 MPa for 3 minutes so that the thickness would be 1 mm. Then, the epoxy resin composition was cured by heating at 120° C. for 1 hour, 150° C. for 1 hour, and 180° C. for 1 hour to obtain a cured epoxy resin sheet.
ビスフェノールＡ型エポキシ樹脂（ＪＥＲ８２８、三菱ケミカル株式会社製）と、メチルヒドロキノン（東京化成工業株式会社製）とを、メチルヒドロキノンのフェノール性水酸基の合計モル数を１モルに対して、ビスフェノールＡ型エポキシ樹脂のエポキシ基の合計モル数が１．０モルとなる割合で混合し、さらに、ビスフェノールＡ型エポキシ樹脂１００質量部に対して、２－エチル－４－メチルイミダゾール（２Ｅ４ＭＺ）（四国化成工業株式会社製）３質量部を加えて、混合してエポキシ系樹脂組成物を得た。得られたエポキシ系樹脂組成物と、実施例２で得られた酸化マグネシウム組成物粉末とを、体積比で４５：５５の割合で、ＴＨＦ（テトラヒドロフラン）中で攪拌混合してスラリーを得た。得られたスラリーをＰＥＴフィルム上に塗布し、１００℃で５分、１２０℃で１０分間乾燥して、厚さ１００～１５０μｍのエポキシ系樹脂組成物シートを得た。得られたエポキシ系樹脂組成物シートをＰＥＴフィルムから剥離した。エポキシ系樹脂組成物シート１０枚を積層した。得られた積層体を厚さが１ｍｍになるように、ハンドプレス機を用いて温度１００℃、圧力１０ＭＰａ、３分間プレスした。次いで１２０℃で１時間、１５０℃で１時間、１８０℃で１時間加熱して、エポキシ系樹脂組成物を硬化させて、エポキシ樹脂硬化物シートを得た。 [Example 26]
Bisphenol A type epoxy resin (JER828, manufactured by Mitsubishi Chemical Corporation) and methylhydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) are added to 1 mol of the total number of moles of phenolic hydroxyl groups of methylhydroquinone. The total number of moles of epoxy groups in the resin is mixed at a ratio of 1.0 mol, and 2-ethyl-4-methylimidazole (2E4MZ) (Shikoku Kasei Kogyo Co., Ltd.) is added to 100 parts by mass of bisphenol A epoxy resin. (manufactured by the company) was added and mixed to obtain an epoxy resin composition. The obtained epoxy resin composition and the magnesium oxide composition powder obtained in Example 2 were stirred and mixed in THF (tetrahydrofuran) at a volume ratio of 45:55 to obtain a slurry. The obtained slurry was applied on a PET film and dried at 100° C. for 5 minutes and 120° C. for 10 minutes to obtain an epoxy resin composition sheet with a thickness of 100 to 150 μm. The obtained epoxy resin composition sheet was peeled off from the PET film. Ten epoxy resin composition sheets were laminated. The resulting laminate was pressed using a hand press machine at a temperature of 100° C. and a pressure of 10 MPa for 3 minutes so that the thickness would be 1 mm. Then, the epoxy resin composition was cured by heating at 120° C. for 1 hour, 150° C. for 1 hour, and 180° C. for 1 hour to obtain a cured epoxy resin sheet.
［実施例２７］
実施例２で得られた酸化マグネシウム組成物粉末の代わりに、実施例７で得られた酸化マグネシウム組成物粉末を用いたこと以外は、実施例２６と同様にしてエポキシ樹脂硬化物シートを得た。 [Example 27]
A cured epoxy resin sheet was obtained in the same manner as in Example 26, except that the magnesium oxide composition powder obtained in Example 7 was used instead of the magnesium oxide composition powder obtained in Example 2. .
実施例２で得られた酸化マグネシウム組成物粉末の代わりに、実施例７で得られた酸化マグネシウム組成物粉末を用いたこと以外は、実施例２６と同様にしてエポキシ樹脂硬化物シートを得た。 [Example 27]
A cured epoxy resin sheet was obtained in the same manner as in Example 26, except that the magnesium oxide composition powder obtained in Example 7 was used instead of the magnesium oxide composition powder obtained in Example 2. .
［実施例２８］
トリグリシジルイソシアヌレート（ＴＧＩ）（日産化学株式会社製）と、上記の一般式（１）の化合物（数平均分子量（Ｍｎ）＝２５００、質量平均分子量（Мｗ）＝５８００）とを、一般式（１）の化合物１００質量部に対して、ＴＧＩが１５質量部となる割合で混合し、さらに、ＴＧＩ１００質量部に対して、２Ｅ４ＭＺ（四国化成工業株式会社製）３質量部を加えて、混合してエポキシ系樹脂組成物を得た。得られたエポキシ系樹脂組成物と、実施例２で得られた酸化マグネシウム組成物粉末とを、体積比で４５：５５の割合で、ＴＨＦ（テトラヒドロフラン）中で攪拌混合してスラリーを得た。得られたスラリーをＰＥＴフィルム上に塗布し、１００℃で５分、１２０℃で１０分間乾燥して、厚さ１００～１５０μｍのエポキシ系樹脂組成物シートを得た。得られたエポキシ系樹脂組成物シートをＰＥＴフィルムから剥離した。エポキシ系樹脂組成物シート１０枚を積層した。得られた積層体を厚さが１ｍｍになるように、ハンドプレス機を用いて温度１００℃、圧力１０ＭＰａ、３分間プレスした。次いで１２０℃で１時間、１５０℃で１時間、１８０℃で１時間加熱して、エポキシ系樹脂組成物を硬化させて、エポキシ系樹脂組成物シートを得た。 [Example 28]
Triglycidyl isocyanurate (TGI) (manufactured by Nissan Chemical Co., Ltd.) and the compound of the general formula (1) (number average molecular weight (Mn) = 2500, mass average molecular weight (Mw) = 5800), the general formula ( 1) To 100 parts by mass of the compound of 1), TGI is mixed at a ratio of 15 parts by mass, and 3 parts by mass of 2E4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.) is added to 100 parts by mass of TGI and mixed. to obtain an epoxy resin composition. The obtained epoxy resin composition and the magnesium oxide composition powder obtained in Example 2 were stirred and mixed in THF (tetrahydrofuran) at a volume ratio of 45:55 to obtain a slurry. The obtained slurry was applied on a PET film and dried at 100° C. for 5 minutes and 120° C. for 10 minutes to obtain an epoxy resin composition sheet with a thickness of 100 to 150 μm. The obtained epoxy resin composition sheet was peeled off from the PET film. Ten epoxy resin composition sheets were laminated. The obtained laminate was pressed with a hand press machine at a temperature of 100° C. and a pressure of 10 MPa for 3 minutes so as to have a thickness of 1 mm. Then, the epoxy resin composition was cured by heating at 120° C. for 1 hour, 150° C. for 1 hour, and 180° C. for 1 hour to obtain an epoxy resin composition sheet.
トリグリシジルイソシアヌレート（ＴＧＩ）（日産化学株式会社製）と、上記の一般式（１）の化合物（数平均分子量（Ｍｎ）＝２５００、質量平均分子量（Мｗ）＝５８００）とを、一般式（１）の化合物１００質量部に対して、ＴＧＩが１５質量部となる割合で混合し、さらに、ＴＧＩ１００質量部に対して、２Ｅ４ＭＺ（四国化成工業株式会社製）３質量部を加えて、混合してエポキシ系樹脂組成物を得た。得られたエポキシ系樹脂組成物と、実施例２で得られた酸化マグネシウム組成物粉末とを、体積比で４５：５５の割合で、ＴＨＦ（テトラヒドロフラン）中で攪拌混合してスラリーを得た。得られたスラリーをＰＥＴフィルム上に塗布し、１００℃で５分、１２０℃で１０分間乾燥して、厚さ１００～１５０μｍのエポキシ系樹脂組成物シートを得た。得られたエポキシ系樹脂組成物シートをＰＥＴフィルムから剥離した。エポキシ系樹脂組成物シート１０枚を積層した。得られた積層体を厚さが１ｍｍになるように、ハンドプレス機を用いて温度１００℃、圧力１０ＭＰａ、３分間プレスした。次いで１２０℃で１時間、１５０℃で１時間、１８０℃で１時間加熱して、エポキシ系樹脂組成物を硬化させて、エポキシ系樹脂組成物シートを得た。 [Example 28]
Triglycidyl isocyanurate (TGI) (manufactured by Nissan Chemical Co., Ltd.) and the compound of the general formula (1) (number average molecular weight (Mn) = 2500, mass average molecular weight (Mw) = 5800), the general formula ( 1) To 100 parts by mass of the compound of 1), TGI is mixed at a ratio of 15 parts by mass, and 3 parts by mass of 2E4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.) is added to 100 parts by mass of TGI and mixed. to obtain an epoxy resin composition. The obtained epoxy resin composition and the magnesium oxide composition powder obtained in Example 2 were stirred and mixed in THF (tetrahydrofuran) at a volume ratio of 45:55 to obtain a slurry. The obtained slurry was applied on a PET film and dried at 100° C. for 5 minutes and 120° C. for 10 minutes to obtain an epoxy resin composition sheet with a thickness of 100 to 150 μm. The obtained epoxy resin composition sheet was peeled off from the PET film. Ten epoxy resin composition sheets were laminated. The obtained laminate was pressed with a hand press machine at a temperature of 100° C. and a pressure of 10 MPa for 3 minutes so as to have a thickness of 1 mm. Then, the epoxy resin composition was cured by heating at 120° C. for 1 hour, 150° C. for 1 hour, and 180° C. for 1 hour to obtain an epoxy resin composition sheet.
なお、一般式（１）の化合物（Мｎ＝２５００、Мｗ＝５８００）は、次のようにして合成した。
メチルヒドロキノン０．４０５モルと、α、α‘－ジクロロ－ｐ－キシレン０．３４５モルとを、３口フラスコに量りとり、テトラヒドロフラン（ＴＨＦ）１Ｌに溶解させて混合溶液を得た。混合溶液を窒素気流中でリフラックス（還流）させて、混合溶液中の溶存酸素を除去した。次いで、混合溶液に、α、α‘－ジクロロ－ｐ－キシレンの２倍の物質量（モル数）の水酸化ナトリウムを含む水酸化ナトリウム５０％水溶液を加え、１２時間リフラックス状態を保ち反応させた後、室温まで放冷した。反応終了後、得られた反応溶液に塩酸を加えて、反応溶液をｐＨ４～６に調整した。その後、反応液に水を注いで３０分間撹拌し、生成した沈殿物をろ過で回収した。回収した沈殿物をメチルエチルケトン（МＥＫ）１Ｌで洗浄、ろ過して不溶分を回収し、１２時間以上真空乾燥し、一般式（１）の化合物を得た。 The compound of general formula (1) (Mn=2500, Mw=5800) was synthesized as follows.
0.405 mol of methylhydroquinone and 0.345 mol of α,α'-dichloro-p-xylene were weighed into a three-necked flask and dissolved in 1 L of tetrahydrofuran (THF) to obtain a mixed solution. The mixed solution was refluxed in a nitrogen stream to remove dissolved oxygen in the mixed solution. Next, to the mixed solution, a 50% aqueous solution of sodium hydroxide containing twice the amount (number of moles) of sodium hydroxide as that of α,α'-dichloro-p-xylene was added, and the mixture was allowed to react while maintaining the reflux state for 12 hours. After that, it was allowed to cool to room temperature. After completion of the reaction, hydrochloric acid was added to the obtained reaction solution to adjust the reaction solution to pH 4-6. After that, water was poured into the reaction solution, the mixture was stirred for 30 minutes, and the formed precipitate was collected by filtration. The collected precipitate was washed with 1 L of methyl ethyl ketone (МEK), filtered to collect insoluble matter, and vacuum-dried for 12 hours or more to obtain the compound of general formula (1).
メチルヒドロキノン０．４０５モルと、α、α‘－ジクロロ－ｐ－キシレン０．３４５モルとを、３口フラスコに量りとり、テトラヒドロフラン（ＴＨＦ）１Ｌに溶解させて混合溶液を得た。混合溶液を窒素気流中でリフラックス（還流）させて、混合溶液中の溶存酸素を除去した。次いで、混合溶液に、α、α‘－ジクロロ－ｐ－キシレンの２倍の物質量（モル数）の水酸化ナトリウムを含む水酸化ナトリウム５０％水溶液を加え、１２時間リフラックス状態を保ち反応させた後、室温まで放冷した。反応終了後、得られた反応溶液に塩酸を加えて、反応溶液をｐＨ４～６に調整した。その後、反応液に水を注いで３０分間撹拌し、生成した沈殿物をろ過で回収した。回収した沈殿物をメチルエチルケトン（МＥＫ）１Ｌで洗浄、ろ過して不溶分を回収し、１２時間以上真空乾燥し、一般式（１）の化合物を得た。 The compound of general formula (1) (Mn=2500, Mw=5800) was synthesized as follows.
0.405 mol of methylhydroquinone and 0.345 mol of α,α'-dichloro-p-xylene were weighed into a three-necked flask and dissolved in 1 L of tetrahydrofuran (THF) to obtain a mixed solution. The mixed solution was refluxed in a nitrogen stream to remove dissolved oxygen in the mixed solution. Next, to the mixed solution, a 50% aqueous solution of sodium hydroxide containing twice the amount (number of moles) of sodium hydroxide as that of α,α'-dichloro-p-xylene was added, and the mixture was allowed to react while maintaining the reflux state for 12 hours. After that, it was allowed to cool to room temperature. After completion of the reaction, hydrochloric acid was added to the obtained reaction solution to adjust the reaction solution to pH 4-6. After that, water was poured into the reaction solution, the mixture was stirred for 30 minutes, and the formed precipitate was collected by filtration. The collected precipitate was washed with 1 L of methyl ethyl ketone (МEK), filtered to collect insoluble matter, and vacuum-dried for 12 hours or more to obtain the compound of general formula (1).
［実施例２９］
実施例２で得られた酸化マグネシウム組成物粉末の代わりに、実施例７で得られた酸化マグネシウム組成物粉末を用いたこと以外は、実施例２８と同様にしてエポキシ樹脂硬化物シートを得た。 [Example 29]
A cured epoxy resin sheet was obtained in the same manner as in Example 28, except that the magnesium oxide composition powder obtained in Example 7 was used instead of the magnesium oxide composition powder obtained in Example 2. .
実施例２で得られた酸化マグネシウム組成物粉末の代わりに、実施例７で得られた酸化マグネシウム組成物粉末を用いたこと以外は、実施例２８と同様にしてエポキシ樹脂硬化物シートを得た。 [Example 29]
A cured epoxy resin sheet was obtained in the same manner as in Example 28, except that the magnesium oxide composition powder obtained in Example 7 was used instead of the magnesium oxide composition powder obtained in Example 2. .
［実施例３２］
ビスフェノールＡ型エポキシ樹脂、メチルヒドロキノン、２－エチル－４－メチルイミダゾール（２Ｅ４ＭＺ）と、充填率が５５ｖｏｌ％になるように実施例３１で得られた酸化マグネシウム粉末を、ＴＨＦに添加し、攪拌混合を行いスラリーを得た。得られたスラリーをＰＥＴフィルム上に塗布し、１００℃で５分、１２０℃で１０分乾燥させた。得られた樹脂シートをＰＥＴフィルムから剥離して積層し、積層体とした。得られた積層体を厚さが１ｍｍになるように、ハンドプレス機を用いて温度１００℃、圧力１０ＭＰａ、３分間プレスし、その後１２０℃で１時間、１５０℃で１時間、１８０℃で１時間加熱することで樹脂硬化物を得た。 [Example 32]
A bisphenol A type epoxy resin, methylhydroquinone, 2-ethyl-4-methylimidazole (2E4MZ), and the magnesium oxide powder obtained in Example 31 so that the filling rate was 55 vol% were added to THF and mixed with stirring. to obtain a slurry. The resulting slurry was applied onto a PET film and dried at 100° C. for 5 minutes and 120° C. for 10 minutes. The obtained resin sheet was peeled from the PET film and laminated to form a laminate. The resulting laminate was pressed using a hand press machine at a temperature of 100° C. and a pressure of 10 MPa for 3 minutes so as to have a thickness of 1 mm, and then pressed at 120° C. for 1 hour, 150° C. for 1 hour, and 180° C. for 1 hour. A resin cured product was obtained by heating for a period of time.
ビスフェノールＡ型エポキシ樹脂、メチルヒドロキノン、２－エチル－４－メチルイミダゾール（２Ｅ４ＭＺ）と、充填率が５５ｖｏｌ％になるように実施例３１で得られた酸化マグネシウム粉末を、ＴＨＦに添加し、攪拌混合を行いスラリーを得た。得られたスラリーをＰＥＴフィルム上に塗布し、１００℃で５分、１２０℃で１０分乾燥させた。得られた樹脂シートをＰＥＴフィルムから剥離して積層し、積層体とした。得られた積層体を厚さが１ｍｍになるように、ハンドプレス機を用いて温度１００℃、圧力１０ＭＰａ、３分間プレスし、その後１２０℃で１時間、１５０℃で１時間、１８０℃で１時間加熱することで樹脂硬化物を得た。 [Example 32]
A bisphenol A type epoxy resin, methylhydroquinone, 2-ethyl-4-methylimidazole (2E4MZ), and the magnesium oxide powder obtained in Example 31 so that the filling rate was 55 vol% were added to THF and mixed with stirring. to obtain a slurry. The resulting slurry was applied onto a PET film and dried at 100° C. for 5 minutes and 120° C. for 10 minutes. The obtained resin sheet was peeled from the PET film and laminated to form a laminate. The resulting laminate was pressed using a hand press machine at a temperature of 100° C. and a pressure of 10 MPa for 3 minutes so as to have a thickness of 1 mm, and then pressed at 120° C. for 1 hour, 150° C. for 1 hour, and 180° C. for 1 hour. A resin cured product was obtained by heating for a period of time.
［実施例３３］
樹脂としてビスフェノールＡ型エポキシ樹脂の代わりにトリグリシジルイソシアヌレートを用い、硬化剤としてメチルヒドロキノンの代わりに式（１）の化合物を用いたこと以外は、実施例３２と同様にして、樹脂硬化物を得た。 [Example 33]
A resin cured product was obtained in the same manner as in Example 32, except that triglycidyl isocyanurate was used as the resin instead of the bisphenol A type epoxy resin, and the compound of formula (1) was used instead of methylhydroquinone as the curing agent. Obtained.
樹脂としてビスフェノールＡ型エポキシ樹脂の代わりにトリグリシジルイソシアヌレートを用い、硬化剤としてメチルヒドロキノンの代わりに式（１）の化合物を用いたこと以外は、実施例３２と同様にして、樹脂硬化物を得た。 [Example 33]
A resin cured product was obtained in the same manner as in Example 32, except that triglycidyl isocyanurate was used as the resin instead of the bisphenol A type epoxy resin, and the compound of formula (1) was used instead of methylhydroquinone as the curing agent. Obtained.
［評価］
実施例２４～２９で得られた積層体の熱伝導率を測定した。熱伝導率は、積層の密度と、比熱と、熱拡散率とを上記の方法によりそれぞれ測定し、得られた値を乗じることにより算出した。その結果を、下記の表４に示す。 [evaluation]
The thermal conductivity of the laminates obtained in Examples 24-29 was measured. The thermal conductivity was calculated by measuring the laminate density, specific heat, and thermal diffusivity by the above methods and multiplying the obtained values. The results are shown in Table 4 below.
実施例２４～２９で得られた積層体の熱伝導率を測定した。熱伝導率は、積層の密度と、比熱と、熱拡散率とを上記の方法によりそれぞれ測定し、得られた値を乗じることにより算出した。その結果を、下記の表４に示す。 [evaluation]
The thermal conductivity of the laminates obtained in Examples 24-29 was measured. The thermal conductivity was calculated by measuring the laminate density, specific heat, and thermal diffusivity by the above methods and multiplying the obtained values. The results are shown in Table 4 below.
表４の結果から、酸化物層が結晶性ＳｉＯ２を含む酸化マグネシウム組成物粉末を用いた樹脂組成物は高い熱伝導率を有することが確認された。特に、ＴＧＩと上記の一般式（１）で表される化合物とを含むエポキシ系樹脂組成物の硬化物は高い熱伝導率を有することが確認された。
From the results in Table 4, it was confirmed that the resin composition using the magnesium oxide composition powder whose oxide layer contains crystalline SiO 2 has high thermal conductivity. In particular, it was confirmed that the cured product of the epoxy resin composition containing TGI and the compound represented by the general formula (1) has high thermal conductivity.
１０…酸化マグネシウム組成物粉末、１１…酸化マグネシウム粒子、１２…酸化物層、１３…有機物層、２０…樹脂組成物シート、２１…芯材、２１ａ…縦糸、２１ｂ…横糸、２２…樹脂、２３…樹脂組成物、３０…積層基板
DESCRIPTION OF SYMBOLS 10... Magnesium oxide composition powder, 11... Magnesium oxide particles, 12... Oxide layer, 13... Organic layer, 20... Resin composition sheet, 21... Core material, 21a... Warp, 21b... Weft, 22... Resin, 23 ... Resin composition, 30 ... Laminated substrate
Claims (15)
- 酸化マグネシウム粒子と、前記酸化マグネシウム粒子の表面の少なくとも一部を被覆する酸化物層とを有し、前記酸化物層が、結晶性ＳｉＯ２を含む酸化マグネシウム組成物粉末。 A magnesium oxide composition powder comprising magnesium oxide particles and an oxide layer covering at least part of the surface of said magnesium oxide particles, said oxide layer containing crystalline SiO2 .
- 前記酸化物層は、前記結晶性ＳｉＯ２と、Ｓｉ以外の添加金属元素とを含み、前記添加金属元素は、アルカリ金属、アルカリ土類金属、Ａｌ、Ｔｉ、Ｚｒからなる群より選ばれる少なくとも１種であり、前記酸化物層の前記添加金属元素の含有量が１５ａｔ％以下である請求項１に記載の酸化マグネシウム組成物粉末。 The oxide layer contains the crystalline SiO2 and an additive metal element other than Si, and the additive metal element is at least one selected from the group consisting of alkali metals, alkaline earth metals, Al, Ti, and Zr. 2. The magnesium oxide composition powder according to claim 1, wherein the content of said additive metal element in said oxide layer is 15 at % or less.
- 酸化マグネシウム粒子と、前記酸化マグネシウム粒子の表面の少なくとも一部を被覆する酸化物層とを有し、前記酸化物層が、ＳｉとＡｌを含む結晶性複酸化物を含む酸化マグネシウム組成物粉末。 A magnesium oxide composition powder having magnesium oxide particles and an oxide layer covering at least part of the surface of the magnesium oxide particles, wherein the oxide layer contains a crystalline composite oxide containing Si and Al.
- 前記酸化物層は、前記結晶性複酸化物と、Ｓｉ、Ａｌ以外の添加金属元素とを含み、前記添加金属元素は、アルカリ金属、アルカリ土類金属、Ｔｉ、Ｚｒからなる群より選ばれる少なくとも１種類であり、前記酸化物層のＳｉ以外の金属元素含有量が１５ａｔ％以下である請求項３に記載の酸化マグネシウム組成物粉末。 The oxide layer contains the crystalline multiple oxide and an additive metal element other than Si and Al, and the additive metal element is at least selected from the group consisting of alkali metals, alkaline earth metals, Ti and Zr. 4. The magnesium oxide composition powder according to claim 3, wherein there is one type and the content of metal elements other than Si in the oxide layer is 15 at % or less.
- 前記添加金属元素が、Ｌｉ及びＮａのいずれか一方又は両方である請求項２または４のいずれかに記載の酸化マグネシウム組成物粉末。 The magnesium oxide composition powder according to any one of claims 2 and 4, wherein the additive metal element is either one or both of Li and Na.
- さらに、有機物層で被覆されている請求項１～請求項５のいずれか１項に記載の酸化マグネシウム組成物粉末。 The magnesium oxide composition powder according to any one of claims 1 to 5, which is further coated with an organic layer.
- 前記有機物層が、ホスホン酸及びシランカップリング剤のいずれか一方又は両方を含む、請求項６に記載の酸化マグネシウム組成物粉末。 The magnesium oxide composition powder according to claim 6, wherein the organic layer contains one or both of phosphonic acid and a silane coupling agent.
- 樹脂と、請求項１～請求項７のいずれか１項に記載の酸化マグネシウム組成物粉末とを含む樹脂組成物。 A resin composition containing a resin and the magnesium oxide composition powder according to any one of claims 1 to 7.
- 前記樹脂が、エポキシ樹脂と硬化剤とを含む反応硬化性樹脂組成物の硬化物である請求項８に記載の樹脂組成物。 The resin composition according to claim 8, wherein the resin is a cured product of a reaction-curable resin composition containing an epoxy resin and a curing agent.
- さらに、ガラスクロスを含む請求項８または請求項９に記載の樹脂組成物。 The resin composition according to claim 8 or 9, further comprising glass cloth.
- 請求項８～請求項１０のいずれか１項に記載の樹脂組成物を含む樹脂組成物シート。 A resin composition sheet containing the resin composition according to any one of claims 8 to 10.
- 複数の樹脂基板が積層されてなり、前記複数の樹脂基板のうち、少なくとも一つが請求項１１に記載の樹脂組成物シートである積層基板。 A laminated substrate formed by laminating a plurality of resin substrates, wherein at least one of the plurality of resin substrates is the resin composition sheet according to claim 11.
- 反応硬化性樹脂組成物と、請求項１～請求項７のいずれか１項に記載の酸化マグネシウム組成物粉末とを含む反応性樹脂組成物。 A reactive resin composition comprising a reactive curable resin composition and the magnesium oxide composition powder according to any one of claims 1 to 7.
- 反応硬化性樹脂組成物が、エポキシ樹脂と硬化剤とを含む請求項１３に記載の反応性樹脂組成物。 The reactive resin composition according to claim 13, wherein the reactive curable resin composition contains an epoxy resin and a curing agent.
- 前記エポキシ樹脂がトリグリシジルイソシアヌレートであって、前記硬化剤が下記の一般式（１）で表される化合物である請求項１４に記載の反応性樹脂組成物。
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| JPS63307107A (en) * | 1987-06-09 | 1988-12-14 | Asahi Glass Co Ltd | Highly heat conductive magnesia based powder |
| WO2005033214A1 (en) * | 2003-10-03 | 2005-04-14 | Tateho Chemical Industries Co., Ltd. | Coated magnesium oxide powder exhibiting high flowability, and resin composition comprising the powder |
| JP2012116715A (en) * | 2010-12-02 | 2012-06-21 | Shin Kobe Electric Mach Co Ltd | Method for producing magnesium oxide powder, method for producing thermosetting resin composition, and method for producing prepreg and laminate |
| JP2012212791A (en) * | 2011-03-31 | 2012-11-01 | Tdk Corp | Magnetic sheet |
| JP2017122029A (en) * | 2016-01-07 | 2017-07-13 | 協和化学工業株式会社 | Magnesium hydroxide particle having slow growth late and low aspect ratio method for producing the same |
| WO2020203444A1 (en) * | 2019-03-29 | 2020-10-08 | Tdk株式会社 | Compound, resin composition and polymerization product |
-
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- 2021-10-28 WO PCT/JP2021/039907 patent/WO2022208962A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63307107A (en) * | 1987-06-09 | 1988-12-14 | Asahi Glass Co Ltd | Highly heat conductive magnesia based powder |
| WO2005033214A1 (en) * | 2003-10-03 | 2005-04-14 | Tateho Chemical Industries Co., Ltd. | Coated magnesium oxide powder exhibiting high flowability, and resin composition comprising the powder |
| JP2012116715A (en) * | 2010-12-02 | 2012-06-21 | Shin Kobe Electric Mach Co Ltd | Method for producing magnesium oxide powder, method for producing thermosetting resin composition, and method for producing prepreg and laminate |
| JP2012212791A (en) * | 2011-03-31 | 2012-11-01 | Tdk Corp | Magnetic sheet |
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| WO2020203444A1 (en) * | 2019-03-29 | 2020-10-08 | Tdk株式会社 | Compound, resin composition and polymerization product |
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