JP6349836B2 - Epoxy resin powder coating for varistor and varistor - Google Patents
Epoxy resin powder coating for varistor and varistor Download PDFInfo
- Publication number
- JP6349836B2 JP6349836B2 JP2014061988A JP2014061988A JP6349836B2 JP 6349836 B2 JP6349836 B2 JP 6349836B2 JP 2014061988 A JP2014061988 A JP 2014061988A JP 2014061988 A JP2014061988 A JP 2014061988A JP 6349836 B2 JP6349836 B2 JP 6349836B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- varistor
- resin powder
- powder coating
- varistors
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003822 epoxy resin Substances 0.000 title claims description 118
- 229920000647 polyepoxide Polymers 0.000 title claims description 118
- 239000000843 powder Substances 0.000 title claims description 101
- 238000000576 coating method Methods 0.000 title claims description 98
- 239000011248 coating agent Substances 0.000 title claims description 91
- 239000000463 material Substances 0.000 claims description 29
- 229910019142 PO4 Inorganic materials 0.000 claims description 20
- 239000010452 phosphate Substances 0.000 claims description 20
- 239000003063 flame retardant Substances 0.000 claims description 19
- 239000005749 Copper compound Substances 0.000 claims description 18
- 150000001880 copper compounds Chemical class 0.000 claims description 18
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000003973 paint Substances 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 10
- 229940116318 copper carbonate Drugs 0.000 claims description 6
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 6
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 5
- 238000000034 method Methods 0.000 description 17
- -1 phosphate ester Chemical class 0.000 description 13
- 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
- 238000002485 combustion reaction Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- NCEXYHBECQHGNR-UHFFFAOYSA-N chembl421 Chemical compound C1=C(O)C(C(=O)O)=CC(N=NC=2C=CC(=CC=2)S(=O)(=O)NC=2N=CC=CC=2)=C1 NCEXYHBECQHGNR-UHFFFAOYSA-N 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 1
- YAOMHRRYSRRRKP-UHFFFAOYSA-N 1,2-dichloropropyl 2,3-dichloropropyl 3,3-dichloropropyl phosphate Chemical compound ClC(Cl)CCOP(=O)(OC(Cl)C(Cl)C)OCC(Cl)CCl YAOMHRRYSRRRKP-UHFFFAOYSA-N 0.000 description 1
- RRVPPYNAZJRZFR-VYOBOKEXSA-N 1-oleoyl-2-palmitoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)O[C@@H](COP([O-])(=O)OCC[N+](C)(C)C)COC(=O)CCCCCCC\C=C/CCCCCCCC RRVPPYNAZJRZFR-VYOBOKEXSA-N 0.000 description 1
- OPASHQLYPOFCMA-UHFFFAOYSA-N 2-(9-phenylnonyl)phenol Chemical compound C(C1=CC=CC=C1)CCCCCCCCC1=C(C=CC=C1)O OPASHQLYPOFCMA-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- KTFJPMPXSYUEIP-UHFFFAOYSA-N 3-benzoylphthalic acid Chemical compound OC(=O)C1=CC=CC(C(=O)C=2C=CC=CC=2)=C1C(O)=O KTFJPMPXSYUEIP-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- SBEBTJHMGAZDPO-UHFFFAOYSA-N CC(C)(C(C=C1Br)=CC(Br)=C1O)OP(O)=O Chemical compound CC(C)(C(C=C1Br)=CC(Br)=C1O)OP(O)=O SBEBTJHMGAZDPO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical compound [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- GFHRLTVARFDWHY-UHFFFAOYSA-N OC(C(Br)=C(C(C(C1=CC=CC=C1)(C1=CC=CC=C1)OP(O)=O)=C1Br)Br)=C1Br Chemical compound OC(C(Br)=C(C(C(C1=CC=CC=C1)(C1=CC=CC=C1)OP(O)=O)=C1Br)Br)=C1Br GFHRLTVARFDWHY-UHFFFAOYSA-N 0.000 description 1
- RGMWHQPVUJXDTM-UHFFFAOYSA-N OC(C(Br)=CC(C(C1=CC=CC=C1)(C1=CC=CC=C1)OP(O)=O)=C1)=C1Br Chemical compound OC(C(Br)=CC(C(C1=CC=CC=C1)(C1=CC=CC=C1)OP(O)=O)=C1)=C1Br RGMWHQPVUJXDTM-UHFFFAOYSA-N 0.000 description 1
- WJQKYFNJUAICHO-UHFFFAOYSA-N P(=O)(OC1=C(O)C=CC(=C1)O)(OC1=CC=CC=C1)OC1=CC=CC=C1.P(=O)(OCCCCl)(OCCCCl)OCCCCCCCC Chemical compound P(=O)(OC1=C(O)C=CC(=C1)O)(OC1=CC=CC=C1)OC1=CC=CC=C1.P(=O)(OCCCCl)(OCCCCl)OCCCCCCCC WJQKYFNJUAICHO-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- WOURXYYHORRGQO-UHFFFAOYSA-N Tri(3-chloropropyl) phosphate Chemical compound ClCCCOP(=O)(OCCCCl)OCCCCl WOURXYYHORRGQO-UHFFFAOYSA-N 0.000 description 1
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 description 1
- LWZRKLRLCIITDN-UHFFFAOYSA-N [2,3-di(nonyl)phenyl] phenyl hydrogen phosphate Chemical compound CCCCCCCCCC1=CC=CC(OP(O)(=O)OC=2C=CC=CC=2)=C1CCCCCCCCC LWZRKLRLCIITDN-UHFFFAOYSA-N 0.000 description 1
- SFFTXLYPBWITRH-UHFFFAOYSA-N [2,3-di(propan-2-yl)phenyl] dihydrogen phosphate Chemical compound CC(C)C1=CC=CC(OP(O)(O)=O)=C1C(C)C SFFTXLYPBWITRH-UHFFFAOYSA-N 0.000 description 1
- BXYCHPONLSDFMX-UHFFFAOYSA-N [4-[2-[4-bis(2-methylphenoxy)phosphoryloxyphenyl]propan-2-yl]phenyl] bis(2-methylphenyl) phosphate Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=C(C(C)(C)C=2C=CC(OP(=O)(OC=3C(=CC=CC=3)C)OC=3C(=CC=CC=3)C)=CC=2)C=C1 BXYCHPONLSDFMX-UHFFFAOYSA-N 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- RAYIMXZLSRHMTK-UHFFFAOYSA-N bis(2,3-dibromopropyl) 2,3-dichloropropyl phosphate Chemical compound ClCC(Cl)COP(=O)(OCC(Br)CBr)OCC(Br)CBr RAYIMXZLSRHMTK-UHFFFAOYSA-N 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940108925 copper gluconate Drugs 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- SVOAENZIOKPANY-CVBJKYQLSA-L copper;(z)-octadec-9-enoate Chemical compound [Cu+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O SVOAENZIOKPANY-CVBJKYQLSA-L 0.000 description 1
- RSJOBNMOMQFPKQ-UHFFFAOYSA-L copper;2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)C(O)C(O)C([O-])=O RSJOBNMOMQFPKQ-UHFFFAOYSA-L 0.000 description 1
- CMRVDFLZXRTMTH-UHFFFAOYSA-L copper;2-carboxyphenolate Chemical compound [Cu+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O CMRVDFLZXRTMTH-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 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 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- WYAKJXQRALMWPB-UHFFFAOYSA-N nonyl dihydrogen phosphate Chemical compound CCCCCCCCCOP(O)(O)=O WYAKJXQRALMWPB-UHFFFAOYSA-N 0.000 description 1
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Thermistors And Varistors (AREA)
Description
本発明は、バリスタ用エポキシ樹脂粉体塗料およびバリスタに関するものである。 The present invention relates to an epoxy resin powder coating for varistors and a varistor.
エポキシ樹脂粉体塗料は、従来から、電気・電子部品を絶縁外装する目的で使用されている。このようなエポキシ樹脂粉体塗料は、電気・電子部品の火災に対する安全性を確保するため、絶縁外装塗膜に高度の難燃性を有することも要求されている。このため粉体塗料の成分中には難燃性を付与する様々な化合物が配合されている。 Epoxy resin powder coatings are conventionally used for the purpose of insulating and covering electrical and electronic parts. Such an epoxy resin powder coating is also required to have a high degree of flame retardancy in the insulating exterior coating film in order to ensure the safety of electrical and electronic parts against fire. For this reason, various compounds that impart flame retardancy are blended in the components of the powder coating.
難燃性を付与する方法としては、例えば、可燃性の樹脂成分を少なくし不燃性の無機充填材、特に結晶水を含有していて燃焼時にはこれを放出することで難燃効果を発現するような、水酸化アルミニウムや水酸化マグネシウムなどの無機充填材を多く配合する方法、エポキシ樹脂を燃焼性の低いシリコーン樹脂やシアヌレート環含有樹脂で変性する方法など、さまざまな方法が提案、実施されているが、最も広く実施されているのは各種のハロゲン系難燃剤を配合する方法である(例えば、特許文献1)。 As a method for imparting flame retardancy, for example, the flame retardant resin component is reduced and the non-flammable inorganic filler, particularly crystal water, is contained and released at the time of combustion so as to exhibit the flame retardancy effect. Various methods have been proposed and implemented, such as a method of blending a large amount of inorganic fillers such as aluminum hydroxide and magnesium hydroxide, and a method of modifying an epoxy resin with a low-flammability silicone resin or a cyanurate ring-containing resin. However, the most widely practiced method is to blend various halogen-based flame retardants (for example, Patent Document 1).
本発明は、ハロゲン材を使用しなくても優れた難燃性を有するとともに、優れた耐湿性を有するバリスタ用エポキシ樹脂粉体塗料を提供するものである。また、バリスタ用エポキシ樹脂粉体塗料をバリスタの外装に使用した場合、優れた耐燃焼性、信頼性を有するバリスタを提供するものである。 The present invention provides an epoxy resin powder coating for varistors that has excellent flame retardancy and excellent moisture resistance without using a halogen material. Moreover, when the epoxy resin powder coating material for varistors is used for the exterior of a varistor, the varistor which has the outstanding combustion resistance and reliability is provided.
このような目的は、以下[1]〜[7]項に記載の本発明により達成される。
[1]バリスタの外装用に用いられるバリスタ用エポキシ樹脂粉体塗料であって、上記バリスタ用エポキシ樹脂粉体塗料が、エポキシ樹脂、硬化剤、リン酸エステル系難燃剤および銅化合物を含み、上記バリスタ用エポキシ樹脂粉体塗料で外装されたバリスタに対して、2気圧、121℃、100%RH、24時間条件のプレッシャークッカー処理前および前記処理後において、バリスタ電圧試験を行った際に1mAの電流がリークする電圧をそれぞれV01およびV1としたとき、プレッシャークッカー処理前後の電圧変化率Δ1(%)=(1−V1/V01)×100が5%以下であることを特徴とするバリスタ用エポキシ樹脂粉体塗料。
[2]上記銅化合物が、炭酸銅、シュウ酸銅からなる群より選ばれる少なくとも1種以上の銅化合物である上記[1]項に記載のバリスタ用エポキシ樹脂粉体塗料。
[3]上記銅化合物が、上記バリスタ用エポキシ樹脂粉体塗料100質量部に対して、0.1質量部以上20質量部以下である上記[1]又は[2]項に記載のバリスタ用エポキシ樹脂粉体塗料。
[4]上記リン酸エステル系難燃剤が、上記エポキシ樹脂100質量部に対して、5質量部以上100質量部以下である上記[1]から[3]項のいずれか1項に記載のバリスタ用エポキシ樹脂粉体塗料。
[5]上記バリスタ用エポキシ樹脂粉体塗料が、さらに充填剤を含有する上記[1]から[4]項のいずれか1項に記載のバリスタ用エポキシ樹脂粉体塗料。
[6]上記充填剤が、上記バリスタ用エポキシ樹脂粉体塗料100質量部に対して、40質量部以上80質量部以下である上記[5]項に記載のバリスタ用エポキシ樹脂粉体塗料。
[7]上記[1]から[6]項のいずれか1項に記載のバリスタ用エポキシ樹脂粉体塗料で外装されたことを特徴とするバリスタ。
Such an object is achieved by the present invention described in items [1] to [7] below.
[1] A varistor epoxy resin powder coating used for exterior coating of a varistor, wherein the varistor epoxy resin powder coating contains an epoxy resin, a curing agent, a phosphate ester flame retardant, and a copper compound, When a varistor voltage test was performed on a varistor covered with an epoxy resin powder coating for a varistor before and after the pressure cooker treatment under conditions of 2 atm, 121 ° C., 100% RH, 24 hours, 1 mA The voltage change rate Δ1 (%) = (1−V1 / V 0 1) × 100 before and after the pressure cooker process is 5% or less when the voltage at which the current leaks is V 0 1 and V1, respectively. Epoxy resin powder coating for varistors.
[2] The epoxy resin powder coating for a varistor according to the above [1], wherein the copper compound is at least one copper compound selected from the group consisting of copper carbonate and copper oxalate.
[3] The epoxy for varistors according to [1] or [2], wherein the copper compound is 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the epoxy resin powder coating material for varistors. Resin powder paint.
[4] The varistor according to any one of [1] to [3], wherein the phosphate ester-based flame retardant is 5 to 100 parts by mass with respect to 100 parts by mass of the epoxy resin. Epoxy resin powder paint.
[5] The epoxy resin powder coating for varistors according to any one of [1] to [4], wherein the epoxy resin powder coating for varistor further contains a filler.
[6] The epoxy resin powder coating for varistors according to [5] above, wherein the filler is 40 to 80 parts by mass with respect to 100 parts by mass of the epoxy resin powder coating for varistors.
[7] A varistor which is covered with the epoxy resin powder coating for a varistor according to any one of [1] to [6] above.
本発明によれば、優れた難燃性を有するとともに、耐湿性が向上された、バリスタ用エポキシ樹脂粉体塗料が提供される。また、本発明のバリスタ用エポキシ樹脂粉体塗料をバリスタとして使用した場合、耐燃焼性、信頼性に優れるバリスタが提供される。 According to the present invention, there is provided an epoxy resin powder coating for varistors having excellent flame retardancy and improved moisture resistance. Moreover, when the epoxy resin powder coating material for varistors of the present invention is used as a varistor, a varistor having excellent combustion resistance and reliability is provided.
本発明のバリスタ用エポキシ樹脂粉体塗料は、バリスタの外装用に用いられるバリスタ用エポキシ樹脂粉体塗料であって、前記バリスタ用エポキシ樹脂粉体塗料が、エポキシ樹脂、硬化剤、リン酸エステル系難燃剤および銅化合物を含み、上記バリスタ用エポキシ樹脂粉体塗料で外装されたバリスタに対して、2気圧、121℃、100%RH、24時間条件のプレッシャークッカー処理前および前記処理後において、バリスタ電圧試験を行った際に1mAの電流がリークする電圧をそれぞれV01およびV1としたとき、プレッシャークッカー処理前後の電圧変化率Δ1(%)=(1−V1/V01)×100が5%以下であることを特徴とする。これにより、優れた難燃性を有するとともに、耐湿性が向上された、バリスタ用エポキシ樹脂粉体塗料を得ることができる。
また、本発明のバリスタは、本発明のバリスタ用エポキシ樹脂粉体塗料で外装されたことを特徴とする。これより、加湿処理後でもバリスタ電圧が低下し難く、耐燃焼性に優れるバリスタを得ることができる。
以下に、本発明のバリスタ用エポキシ樹脂粉体塗料及びバリスタについて説明する。
The epoxy resin powder coating for a varistor of the present invention is an epoxy resin powder coating for a varistor used for the exterior of a varistor, and the epoxy resin powder coating for a varistor is an epoxy resin, a curing agent, a phosphate ester type A varistor containing a flame retardant and a copper compound and coated with the epoxy resin powder coating for a varistor before and after pressure cooker treatment under conditions of 2 atm, 121 ° C., 100% RH, 24 hours When the voltage at which a current of 1 mA leaks during the voltage test is V 0 1 and V1, respectively, the voltage change rate Δ1 (%) before and after the pressure cooker process is (1−V1 / V 0 1) × 100. It is characterized by being 5% or less. Thereby, it is possible to obtain an epoxy resin powder coating for varistors having excellent flame retardancy and improved moisture resistance.
The varistor of the present invention is characterized in that it is covered with the epoxy resin powder coating material for varistors of the present invention. Accordingly, it is possible to obtain a varistor that is less likely to decrease the varistor voltage even after the humidification process and has excellent combustion resistance.
Below, the epoxy resin powder coating material and varistor for varistors of this invention are demonstrated.
まず、本発明のバリスタ用エポキシ樹脂粉体塗料について説明する。
本発明のバリスタ用エポキシ樹脂粉体塗料は、バリスタの外装用に用いられるバリスタ用エポキシ樹脂粉体塗料であって、前記バリスタ用エポキシ樹脂粉体塗料が、エポキシ樹脂、硬化剤、リン酸エステル系難燃剤および銅化合物を含み、上記バリスタ用エポキシ樹脂粉体塗料で外装されたバリスタに対して、2気圧、121℃、100%RH、24時間条件のプレッシャークッカー処理前および前記処理後において、バリスタ電圧試験を行った際に1mAの電流がリークする電圧をそれぞれV01およびV1としたとき、プレッシャークッカー処理前後の電圧変化率Δ1(%)=(1−V1/V01)×100が5%以下であることを特徴とする。これにより、優れた難燃性を有するとともに、耐湿性が向上された、バリスタ用エポキシ樹脂粉体塗料を得ることができる。
First, the epoxy resin powder coating material for varistors of the present invention will be described.
The epoxy resin powder coating for a varistor of the present invention is an epoxy resin powder coating for a varistor used for the exterior of a varistor, and the epoxy resin powder coating for a varistor is an epoxy resin, a curing agent, a phosphate ester type A varistor containing a flame retardant and a copper compound and coated with the epoxy resin powder coating for a varistor before and after pressure cooker treatment under conditions of 2 atm, 121 ° C., 100% RH, 24 hours When the voltage at which a current of 1 mA leaks during the voltage test is V 0 1 and V1, respectively, the voltage change rate Δ1 (%) before and after the pressure cooker process is (1−V1 / V 0 1) × 100. It is characterized by being 5% or less. Thereby, it is possible to obtain an epoxy resin powder coating for varistors having excellent flame retardancy and improved moisture resistance.
本発明で用いられるエポキシ樹脂は、分子中に少なくとも1個のエポキシ基を有し、かつ、非ハロゲン化エポキシ樹脂であり、一般のエポキシ樹脂粉体塗料に適用される室温下で固形のものであれば使用することができる。このようなエポキシ樹脂としては、例えば、ビスフェノールA型、ビスフェノールF型、ビスフェノールS型、フェノールノボラック型、クレゾールノボラック型、ビフェニル型、ナフタレン型、芳香族アミン型などが挙げられるが、これらに限定されるものではない。なお、これらは単独で用いても、複数を組み合わせて用いてもよい。特に低コスト、溶融時の粘度、耐熱性という観点から、ビスフェノールA型エポキシ樹脂、クレゾールノボラック型が好適に用いられる。 The epoxy resin used in the present invention has at least one epoxy group in the molecule, is a non-halogenated epoxy resin, and is solid at room temperature applied to general epoxy resin powder coatings. Can be used if present. Examples of such epoxy resins include, but are not limited to, bisphenol A type, bisphenol F type, bisphenol S type, phenol novolac type, cresol novolac type, biphenyl type, naphthalene type, and aromatic amine type. It is not something. These may be used alone or in combination. In particular, bisphenol A type epoxy resin and cresol novolac type are preferably used from the viewpoints of low cost, viscosity at melting, and heat resistance.
本発明で用いられる硬化剤は、バリスタ用エポキシ樹脂粉体塗料が適用される目的に応じて種々のものを単独または複数を組み合わせ使用することができる。例えば、ジアミノジフェニルメタンやアニリン樹脂などの芳香族アミン、脂肪族アミンと脂肪族ジカルボン酸との縮合物、ジシアンジアミド及びその誘導体、各種イミダゾールやイミダゾリン化合物、アジピン酸、セバチン酸、フタル酸、マレイン酸、トリメリット酸、ベンゾフェノンジカルボン酸、ピロメリット酸などのポリジカルボン酸またはその酸無水物、アジピン酸やフタル酸などのジヒドラジッド、フェノール、クレゾール、キシレノール、ビスフェノールAなどとアルデヒドとの縮合物であるノボラック類、カルボン酸アミド、メチロール化メラミン類、ブロック型イソシアヌレート類等が挙げられる。これらの中でも、酸無水物系の硬化剤が、得られる粉体塗料の硬化特性を向上させることから好ましい。 As the curing agent used in the present invention, various kinds of curing agents can be used alone or in combination depending on the purpose to which the epoxy resin powder coating for varistor is applied. For example, aromatic amines such as diaminodiphenylmethane and aniline resins, condensates of aliphatic amines and aliphatic dicarboxylic acids, dicyandiamide and its derivatives, various imidazoles and imidazoline compounds, adipic acid, sebacic acid, phthalic acid, maleic acid, Polydicarboxylic acids such as merit acid, benzophenone dicarboxylic acid, pyromellitic acid or anhydrides thereof, dihydrazides such as adipic acid or phthalic acid, phenols, cresols, xylenol, bisphenol A and the like novolaks that are condensates of aldehydes, Examples thereof include carboxylic acid amides, methylolated melamines, and block type isocyanurates. Among these, an acid anhydride-based curing agent is preferable because it improves the curing characteristics of the obtained powder coating material.
エポキシ樹脂に対する硬化剤の割合は、使用するエポキシ樹脂及び硬化剤の種類により調整することができる。好ましくは、硬化剤の官能基(数)が、エポキシ樹脂のエポキシ基(数)に対して、0.6モル当量以上1.2モル当量以下、さらに好ましくは0.9モル当量以上1.1モル当量以下の範囲で使用される。上記範囲であると、良好な硬化特性が得ることができる。なお、これらの硬化剤に対して必要により3級アミン類、イミダゾール類などの硬化促進剤を使用してもよく、なかでも有機リン化合物の使用はさらに難燃性を高めるために望ましい。 The ratio of the curing agent to the epoxy resin can be adjusted depending on the type of the epoxy resin and the curing agent used. Preferably, the functional group (number) of the curing agent is 0.6 mole equivalent to 1.2 mole equivalent, more preferably 0.9 mole equivalent to 1.1 mole equivalent to the epoxy group (number) of the epoxy resin. It is used in the range of the molar equivalent or less. When it is in the above range, good curing characteristics can be obtained. If necessary, curing accelerators such as tertiary amines and imidazoles may be used for these curing agents. Among them, the use of an organic phosphorus compound is desirable for further improving the flame retardancy.
エポキシ樹脂と硬化剤との合計量は、バリスタ用エポキシ樹脂粉体塗料100質量部に対して、好ましくは、10質量部以上80質量部以下であり、さらに好ましくは20質量部以上50質量部以下である。配合量が上記下限値以上の場合、塗膜の平滑性が低下し難く、一方、上記上限値以下の場合、塗装後の硬化工程である焼成時にタレやトガリといった外観不良を起こし難い。 The total amount of the epoxy resin and the curing agent is preferably 10 parts by mass or more and 80 parts by mass or less, more preferably 20 parts by mass or more and 50 parts by mass or less, with respect to 100 parts by mass of the epoxy resin powder coating material for varistors. It is. When the blending amount is not less than the above lower limit value, the smoothness of the coating film is hardly lowered. On the other hand, when the blending amount is not more than the above upper limit value, it is difficult to cause appearance defects such as sagging or toggling during firing, which is a curing step after coating.
リン酸エステル系難燃剤は、難燃性を向上するのに添加されるものであり、難燃剤として一般的に用いられる有機リン酸エステルであればいずれも用いることができる。リン酸エステル化合物の具体例としては、トリフェニルホスフェート、トリスノニルフェニルホスフェート、レゾルシノールビス(ジフェニルホスフェート)、レゾルシノールビス[ジ(2,6−ジメチルフェニル)ホスフェート]、2,2−ビス{4−[ビス(フェノキシ)ホスホリルオキシ]フェニル}プロパン、2,2−ビス{4−[ビス(メチルフェノキシ)ホスホリルオキシ]フェニル}プロパン等が挙げられるがこれらに制限されることはない。さらに上記以外にリン酸エステル化合物としては、特に限定されないが、例えば、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリオクチルホスフェート、トリブトキシエチルホスフェート、トリクレジルホスフェート、クレジルフェニルホスフェート、オクチルジフェニルホスフェート、ジイソプロピルフェニルホスフェートなどのリン酸エステル化合物、ジフェニル−4−ヒドロキシ−2,3,5,6−テトラブロモベンジルホスフォネート、ジメチル−4−ヒドロキシ−3,5−ジブロモベンジルホスフォネート、ジフェニル−4−ヒドロキシ−3,5−ジブロモベンジルホスフォネート、トリス(クロロエチル)ホスフェート、トリス(ジクロロプロピル)ホスフェート、トリス(クロロプロピル)ホスフェート、ビス(2、3−ジブロモプロピル)−2、3−ジクロロプロピルホスフェート、トリス(2,3−ジブロモプロピル)ホスフェート、ビス(クロロプロピル)モノオクチルホスフェートハイドロキノニルジフェニルホスフェート、フェニルノニルフェニルハイドロキノニルホスフェート、及びフェニルジノニルフェニルホスフェートなどのモノリン酸エステル化合物、芳香族縮合型リン酸エステルなどが挙げられる。リン酸エステル系難燃剤は、1種単独で用いても、2種以上を併用してもよい。 The phosphate ester flame retardant is added to improve flame retardancy, and any organic phosphate ester generally used as a flame retardant can be used. Specific examples of the phosphate compound include triphenyl phosphate, trisnonylphenyl phosphate, resorcinol bis (diphenyl phosphate), resorcinol bis [di (2,6-dimethylphenyl) phosphate], 2,2-bis {4- [ Examples thereof include, but are not limited to, bis (phenoxy) phosphoryloxy] phenyl} propane, 2,2-bis {4- [bis (methylphenoxy) phosphoryloxy] phenyl} propane, and the like. In addition to the above, the phosphate ester compound is not particularly limited, but for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, Phosphate ester compounds such as diisopropylphenyl phosphate, diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzyl phosphonate, dimethyl-4-hydroxy-3,5-dibromobenzyl phosphonate, diphenyl-4 -Hydroxy-3,5-dibromobenzyl phosphonate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) Phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, tris (2,3-dibromopropyl) phosphate, bis (chloropropyl) monooctyl phosphate hydroquinonyl diphenyl phosphate, phenylnonylphenyl hydroxide Examples thereof include monophosphate ester compounds such as nonyl phosphate and phenyl dinonylphenyl phosphate, and aromatic condensed phosphate esters. Phosphoric ester flame retardants may be used alone or in combination of two or more.
これらのなかでも、本発明で用いられるリン酸エステル系難燃剤は、十分な難燃性を付与するためにはリン含有量が高く室温において固形のものが望ましく、例えば、トリフェニルホスフェートや芳香族縮合型リン酸エステルが好適に用いられる。 Among these, the phosphate ester flame retardant used in the present invention preferably has a high phosphorus content and is solid at room temperature in order to impart sufficient flame retardancy, for example, triphenyl phosphate or aromatics. Condensed phosphate esters are preferably used.
リン酸エステル系難燃剤の配合量は、エポキシ樹脂100質量部に対して、5質量部以上100質量部以下であり、好ましくは20質量部以上70質量部以下、さらに好ましくは40質量部以上60質量部以下である。これにより、バリスタ用エポキシ樹脂粉体塗料の難燃性を向上させることができる。特に、20質量部以上70質量部以下とすることにより、バリスタ用エポキシ樹脂粉体塗料をバリスタの外装に使用した場合、バリスタの耐燃焼性を優れたものとすることができる。さらに、40質量部以上60質量部以下とすることにより、難燃性と硬化物特性のバランスに優れたバリスタを得ることができる。 The amount of the phosphate ester flame retardant is 5 parts by mass or more and 100 parts by mass or less, preferably 20 parts by mass or more and 70 parts by mass or less, more preferably 40 parts by mass or more and 60 parts by mass with respect to 100 parts by mass of the epoxy resin. It is below mass parts. Thereby, the flame retardance of the epoxy resin powder coating material for varistors can be improved. In particular, when the epoxy resin powder coating material for varistors is used for the exterior of the varistor, the varistor can have excellent combustion resistance by being 20 parts by mass or more and 70 parts by mass or less. Furthermore, the varistor excellent in the balance of a flame retardance and hardened | cured material characteristic can be obtained by setting it as 40 to 60 mass parts.
本発明において用いられる銅化合物は、耐湿性を向上するのに添加されるものである。銅化合物は、ハロゲン化合物を除くものであればよく、シュウ酸銅、ステアリン酸銅、ギ酸銅、酒石酸銅、オレイン酸銅、酢酸銅、グルコン酸銅、サリチル酸銅などの有機銅化合物や、炭酸銅、塩化銅、臭化銅、ヨウ化銅、リン酸銅、ハイドロタルサイト、スチヒタイト、パイロライト等の天然鉱物などの無機銅化合物を用いることができる。特に、エポキシ樹脂との相溶性やバリスタ用エポキシ樹脂粉体塗料の成形性、さらに耐湿性の向上という観点から、炭酸銅、シュウ酸銅が好適に用いられる。 The copper compound used in the present invention is added to improve moisture resistance. The copper compound only needs to exclude halogen compounds, such as copper oxalate, copper stearate, copper formate, copper tartrate, copper oleate, copper acetate, copper gluconate, copper salicylate, and copper carbonate. Inorganic copper compounds such as natural minerals such as copper chloride, copper bromide, copper iodide, copper phosphate, hydrotalcite, stichite, and pyrolite can be used. In particular, from the viewpoints of compatibility with the epoxy resin, moldability of the epoxy resin powder coating material for varistors, and improvement of moisture resistance, copper carbonate and copper oxalate are preferably used.
銅化合物の配合量は、上記バリスタ用エポキシ樹脂粉体塗料100質量部に対して、0.1質量部以上20質量部以下であり、さらに好ましくは3質量部以上10質量部以下である。0.1質量部よりも多いと銅化合物による耐湿改善効果に優れ、20質量部よりも少ないと硬化性が良好となり、優れた特性を持った硬化物が得ることができる。さらに、3質量部以上10質量部以下とすることにより、バリスタ用エポキシ樹脂粉体塗料をバリスタとして使用した時にプレッシャークッカー(PCT)処理後のバリスタの電圧変化率が低下し難く、耐湿性に優れたものとなり、かつバリスタ用エポキシ樹脂粉体塗料の硬化度がばらつき難く、バリスタ用エポキシ樹脂粉体塗料の硬化性が優れたものとなる。 The compounding quantity of a copper compound is 0.1 to 20 mass parts with respect to 100 mass parts of said epoxy resin powder coating materials for varistors, More preferably, it is 3 to 10 mass parts. When the amount is more than 0.1 parts by mass, the effect of improving the moisture resistance by the copper compound is excellent. When the amount is less than 20 parts by mass, the curability becomes good, and a cured product having excellent characteristics can be obtained. Furthermore, when the epoxy resin powder coating for varistors is used as a varistor, the voltage change rate of the varistor after the pressure cooker (PCT) treatment is hardly lowered and the moisture resistance is excellent by setting the amount to 3 parts by mass or more and 10 parts by mass or less. In addition, the degree of cure of the epoxy resin powder coating for varistors is unlikely to vary, and the curability of the epoxy resin powder coating for varistors is excellent.
本発明のバリスタ用エポキシ樹脂粉体塗料は、さらに充填剤を含むことができる。充填剤を含むことにより、硬化物の強度が向上や溶融時の粘度を最適な範囲に調整することができる。充填材としては、炭酸カルシウム、硫酸カルシウム、硫酸バリウム、水酸化アルミニウム、水酸化マグネシウム、酸化アルミニウム、結晶又は溶融シリカ、表面処理シリカ、タルク、カオリン、クレー、マイカ、ドロマイト、ウォラストナイト、ガラス繊維、ガラスビーズ、ジルコン、チタン化合物、モリブデン化合物等が挙げられる。これらは単独で用いても、複数組み合わせて用いてもよい。特に、低コスト、入手のしやすさという観点から、水酸化アルミニウム、結晶または溶融シリカが好適に用いられる。 The epoxy resin powder coating material for varistors of the present invention can further contain a filler. By containing the filler, the strength of the cured product can be improved and the viscosity at the time of melting can be adjusted to an optimum range. Fillers include calcium carbonate, calcium sulfate, barium sulfate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, crystalline or fused silica, surface treated silica, talc, kaolin, clay, mica, dolomite, wollastonite, glass fiber , Glass beads, zircon, titanium compounds, molybdenum compounds and the like. These may be used alone or in combination. In particular, aluminum hydroxide, crystal, or fused silica is preferably used from the viewpoint of low cost and availability.
充填材の配合量は、バリスタ用エポキシ樹脂粉体塗料100質量部に対して、好ましくは、40質量部以上80質量部以下であり、さらに好ましくは、50質量部以上70質量部以下である。配合量が上記下限値よりも大きいと焼成時にタレやトガリといった外観上の不具合を起こし難く、塗膜の機械的強度も十分となる場合がある。一方、上記上限値よりも小さいと塗膜の平滑性が低下し難い。 The blending amount of the filler is preferably 40 parts by mass or more and 80 parts by mass or less, and more preferably 50 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the epoxy resin powder coating material for varistors. When the blending amount is larger than the above lower limit value, it is difficult to cause appearance problems such as sagging or toggling during firing, and the mechanical strength of the coating film may be sufficient. On the other hand, if it is smaller than the above upper limit value, the smoothness of the coating film is hardly lowered.
また、充填材の粒径としては特に限定されないが、通常、平均粒径として2μm以上50μm以下、さらに好ましくは5μm以上30μm以下のものが用いられる。これにより、粉体塗料に良好な流動性が付与され塗装性がより向上し、さらには塗膜の機械的強度についても最適なものとすることができる。 The particle diameter of the filler is not particularly limited, but usually an average particle diameter of 2 to 50 μm, more preferably 5 to 30 μm is used. Thereby, favorable fluidity | liquidity is provided to a powder coating material, coating property improves more, and also it can be made optimal about the mechanical strength of a coating film.
本発明のバリスタ用エポキシ樹脂粉体塗料は、バリスタ用エポキシ樹脂粉体塗料で外装されたバリスタに対して、2気圧、121℃、100%RH、24時間条件のプレッシャークッカー処理前および前記処理後において、バリスタ電圧試験を行った際に1mAの電流がリークする電圧をそれぞれV01およびV1としたとき、プレッシャークッカー処理前後の電圧変化率Δ1(%)=(1−V1/V01)×100が5%以下であることを特徴とする。PCT処理前後の電圧変化率Δ1が5%以下であり、さらに好ましくは2%以下とすることにより、バリスタの信頼性がより優れたものとなる。また、PCT処理において、2気圧、121℃、100%RH、2時間条件で行うことができるが、上記条件(2気圧、121℃、100%RH、24時間)の方が、環境負荷が大きく、他の電子部品(セラミックコンデンサ等)と比較して基準電圧以下では高い絶縁性が必要なので、より信頼性が求められるバリスタの性能を指標する処理条件としてはより好適に使用することができる。 The epoxy resin powder paint for varistors of the present invention is a varistor covered with an epoxy resin powder paint for varistors before and after pressure cooker treatment under conditions of 2 atm, 121 ° C., 100% RH, 24 hours. , The voltage change rate Δ1 (%) before and after the pressure cooker process is (1−V1 / V 0 1), where V 0 1 and V1 are voltages at which a current of 1 mA leaks when the varistor voltage test is performed, respectively. X100 is 5% or less. When the voltage change rate Δ1 before and after the PCT treatment is 5% or less, and more preferably 2% or less, the reliability of the varistor is further improved. In addition, the PCT treatment can be performed under conditions of 2 atm, 121 ° C., 100% RH and 2 hours, but the above conditions (2 atm, 121 ° C., 100% RH, 24 hours) have a larger environmental load. As compared with other electronic components (ceramic capacitors or the like), high insulation is required at a reference voltage or lower, so that it can be used more suitably as a processing condition for indicating the performance of a varistor that requires more reliability.
さらにバリスタ電圧試験について1mAの電流がリークする電圧を測定する代わりに、10μAおよび1μAの電流がリークする電圧を測定することもできる。10μAおよび1μAの電流がリークする電圧を測定する場合は、1mAの電流がリークする電圧と比べて、PCT処理前後で電圧変化率が増大しやすく、より厳しい評価となる。10μAの電流がリークする電圧を測定する場合は、PCT処理前後の電圧変化率Δ2が30%以下であり、さらに20%以下とすることが好ましい。1μAの電流がリークする電圧を測定する場合は、PCT処理前後の電圧変化率Δ3が70%以下であり、さらに50%以下とすることが好ましい。この数値条件を満たす場合、バリスタ用エポキシ樹脂粉体塗料の耐湿性に優れ、バリスタ用エポキシ樹脂粉体塗料をバリスタと使用した場合、バリスタの信頼性が優れるものとなる。 Further, instead of measuring the voltage at which a current of 1 mA leaks in the varistor voltage test, the voltage at which a current of 10 μA and 1 μA leaks can also be measured. When measuring the voltage at which a current of 10 μA and 1 μA leaks, the voltage change rate is likely to increase before and after the PCT process as compared with the voltage at which a current of 1 mA leaks, and the evaluation becomes more severe. When measuring the voltage at which a current of 10 μA leaks, the voltage change rate Δ2 before and after the PCT treatment is 30% or less, and preferably 20% or less. When measuring a voltage at which a current of 1 μA leaks, the voltage change rate Δ3 before and after the PCT process is 70% or less, and preferably 50% or less. When this numerical condition is satisfied, the moisture resistance of the varistor epoxy resin powder coating is excellent, and when the varistor epoxy resin powder coating is used with a varistor, the reliability of the varistor is excellent.
ここで試験に使用するバリスタ用エポキシ樹脂粉体塗料を用いたバリスタとは、外装されていない半導体セラミック(例えば、直径9.5mm×厚み3.5mm)にバリスタ用エポキシ樹脂粉体塗料を膜厚300〜3000μmとなるように外装したバリスタである。PCT処理に用いる装置は、上述の条件となる環境を作れるものであればよく、例えば、飽和型プレッシャークッカー処理装置(平山製作所社製、PC-362M)などが挙げられる。電圧変化率を測定する装置は、例えば、定電流電源装置(岩田高電圧研究所社製、AS508B)などが挙げられる。電圧を測定する際、常温、50%RH雰囲気下で行い、電圧引加による発熱の影響を避けるため、できるだけ速やかに処理する。 Here, the varistor using the epoxy resin powder coating for varistor used in the test is a film thickness of the epoxy resin powder coating for varistor on a semiconductor ceramic (for example, diameter 9.5 mm × thickness 3.5 mm) which is not packaged. The varistor is packaged to have a thickness of 300 to 3000 μm. The apparatus used for the PCT process may be any apparatus that can create an environment that satisfies the above-described conditions. Examples thereof include a saturated pressure cooker processing apparatus (PC-362M manufactured by Hirayama Seisakusho Co., Ltd.). Examples of the device for measuring the voltage change rate include a constant current power supply device (AS508B, manufactured by Iwata High Voltage Research Institute). When measuring the voltage, it is performed at room temperature and in an atmosphere of 50% RH, and is processed as quickly as possible in order to avoid the influence of heat generation due to voltage application.
本発明のバリスタ用エポキシ樹脂粉体塗料は、以上に説明した成分のほか、必要に応じて、顔料、レベリング剤、カップリング剤、消泡剤などの添加剤を配合することができる。また、難燃性を高めるためにシリコーン樹脂、メラミン樹脂などのシアヌレート環骨格を有する樹脂、あるいはホウ酸亜鉛、膨張性黒鉛などの非ハロゲンの難燃性助剤を使用することもできる。 The epoxy resin powder coating material for varistors of the present invention can contain additives such as pigments, leveling agents, coupling agents, and antifoaming agents, if necessary, in addition to the components described above. In order to enhance the flame retardancy, a resin having a cyanurate ring skeleton such as a silicone resin or a melamine resin, or a non-halogen flame retardant aid such as zinc borate or expandable graphite may be used.
本発明において粉体塗料を製造する方法は特に限定されるものではなく、一般的な方法を用いることができる。一例としては、所定の組成比に配合した原料成分をミキサーによって十分に均一混合した後、エクストルーダーや二軸混練機などで溶融混合し、ついで粉砕機により適当な粒度に粉砕、分級して得ることができる。 In the present invention, the method for producing the powder coating material is not particularly limited, and a general method can be used. As an example, the raw material components blended in a predetermined composition ratio are sufficiently uniformly mixed with a mixer, then melt mixed with an extruder or a twin-screw kneader, and then pulverized and classified to an appropriate particle size with a pulverizer. be able to.
次に、本発明のバリスタについて説明する。
本発明のバリスタは、本発明のバリスタ用エポキシ樹脂粉体塗料で外装されたことを特徴とする。これより、加湿処理後でもバリスタ電圧が低下し難く、耐燃焼性に優れるバリスタを得ることができる。外装する前のバリスタは、非直線性抵抗特性を持つ半導体セラミックスを2枚の電極ではさんだ構造をしているタイプのものを使用することができる。半導体セラミックスは、酸化亜鉛、チタン酸ストロンチウム、炭化珪素などを使用することができる。バリスタ用エポキシ樹脂粉体塗料で外装する箇所は、非直線性抵抗特性を持つ半導体セラミックスと接するように外周全体を覆うものであればよく、例えば、非直線性抵抗特性を持つ半導体セラミックスをはさんだ2枚の電極の一部を覆ってもよい。外装の厚みは、特に限定されないが、300μm以上3000μm以下が好ましく、500μm以上2000μm以下がさらに好ましい。この範囲の場合、優れた耐湿性を有したバリスタが得られ、また、塗装装置の小型化することができ、バリスタのコストを下げることができる。
Next, the varistor of the present invention will be described.
The varistor of the present invention is characterized in that it is covered with the epoxy resin powder paint for varistors of the present invention. Accordingly, it is possible to obtain a varistor that is less likely to decrease the varistor voltage even after the humidification process and has excellent combustion resistance. A varistor having a structure in which a semiconductor ceramic having non-linear resistance characteristics is sandwiched between two electrodes can be used as a varistor before packaging. As the semiconductor ceramic, zinc oxide, strontium titanate, silicon carbide, or the like can be used. The part to be covered with the epoxy resin powder coating for varistors only needs to cover the entire outer periphery so as to be in contact with semiconductor ceramics having non-linear resistance characteristics, for example, sandwiching semiconductor ceramics having non-linear resistance characteristics. A part of the two electrodes may be covered. The thickness of the exterior is not particularly limited, but is preferably 300 μm or more and 3000 μm or less, and more preferably 500 μm or more and 2000 μm or less. In this range, a varistor having excellent moisture resistance can be obtained, the size of the coating apparatus can be reduced, and the cost of the varistor can be reduced.
エポキシ樹脂粉体塗料によるバリスタの外装方法は、特に限定はないが、外装のないバリスタを準備し、塗装装置を用いて、バリスタの封止箇所にバリスタ用エポキシ樹脂粉体塗料を塗装し、加熱することによりバリスタ用エポキシ樹脂粉体塗料を硬化させ、バリスタを作製する方法が挙げられる。塗装装置は、バリスタ用エポキシ樹脂粉体塗料の付着性が良く、操作が簡易という観点から、流動浸漬タイプの装置が好適に使用される。 There are no particular restrictions on how to coat the varistor with the epoxy resin powder paint, but a varistor without an exterior is prepared, and the epoxy resin powder paint for the varistor is applied to the sealed part of the varistor using a coating device and heated. Thus, there is a method of curing the varistor epoxy resin powder coating material to produce the varistor. As the coating apparatus, a fluid immersion type apparatus is preferably used from the viewpoint of good adhesion of the epoxy resin powder coating material for varistors and easy operation.
以下、本発明を実施例により詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.
実施例及び比較例において用いた原材料は以下の通りである。
1.エポキシ樹脂
・ビスフェノールA型エポキシ樹脂:ジャパンエポキシレジン三菱化学社製・「エピコート1003」(エポキシ当量720)
2.硬化剤
・TMA:トリメリット酸無水物
3.硬化促進剤
・TPP:トリフェニルホスフィン
4.充填材
・水酸化アルミニウム:日本軽金属製・BF083(平均粒径10μm)
5.顔料
・カーボンブラック
6.リン酸エステル系難燃剤
・リン酸エステル系難燃剤:大八化学製・PX−200
7.銅化合物
・炭酸銅
・シュウ酸銅
8.その他 金属化合物
・シュウ酸マグネシウム
The raw materials used in Examples and Comparative Examples are as follows.
1. Epoxy resin / bisphenol A type epoxy resin: Japan Epoxy Resin Mitsubishi Chemical Co., Ltd. “Epicoat 1003” (epoxy equivalent 720)
2. 2. Curing agent / TMA: trimellitic anhydride 3. Curing accelerator, TPP: Triphenylphosphine Filler / Aluminum hydroxide: Nippon Light Metal / BF083 (average particle size 10 μm)
5. 5. Pigment / carbon black Phosphate ester flame retardant / Phosphate ester flame retardant: PX-200, manufactured by Daihachi Chemical
7). 7. Copper compound, copper carbonate, copper oxalate Other metal compounds / magnesium oxalate
(実施例1)
(1)バリスタ用エポキシ樹脂粉体塗料の作製
ビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン三菱化学社製・「エピコート1003」)28質量部、トリメリット酸無水物4.4質量部、トリフェニルホスフィン0.1質量部、水酸化アルミニウム(日本軽金属製・「BF083」(平均粒径10μm))57質量部、リン酸エステル系難燃剤13質量部、炭酸銅0.1質量部をミキサーにより混合し、80℃条件下で溶融混練した後、粉砕機により粉砕して、平均粒度が40〜60μmのバリスタ用エポキシ樹脂粉体塗料1を得た。
(2)バリスタの作製
流動浸漬塗装装置(OPPC社製、0S型)を用いて、上述により作製したバリスタ用エポキシ樹脂粉体塗料1(1000g)を用いて外装されていない半導体セラミック(直径9.5mm×高さ3.5mm)に膜厚300μmとなるように塗装し、150℃の条件下でバリスタ用エポキシ樹脂粉体塗料を30分硬化させ、バリスタ1を作製した。
Example 1
(1) Preparation of Epoxy Resin Powder Coating for Varistor 28 parts by mass of bisphenol A type epoxy resin (Japan Epoxy Resin Mitsubishi Chemical Co., Ltd. “Epicoat 1003”), 4.4 parts by mass of trimellitic anhydride, triphenylphosphine 0 .1 part by mass, 57 parts by mass of aluminum hydroxide (Nippon Light Metal Co., Ltd., “BF083” (average particle size 10 μm)), 13 parts by mass of a phosphate ester flame retardant, and 0.1 parts by mass of copper carbonate were mixed with a mixer, After melt-kneading under 80 degreeC conditions, it grind | pulverized with the grinder and the epoxy resin powder coating material 1 for varistors with an average particle diameter of 40-60 micrometers was obtained.
(2) Production of varistor Semiconductor ceramic (diameter: 9.g) with fluidized dip coater (OPPC, model 0S), which is produced by using varistor epoxy resin powder coating 1 (1000 g) produced as described above. 5 mm × height 3.5 mm) so as to have a film thickness of 300 μm, and the epoxy resin powder coating material for varistors was cured for 30 minutes under the condition of 150 ° C. to produce varistor 1.
(実施例2〜7、および比較例1〜4)
表1に記載の配合種類および配合量(質量部)に従い、バリスタ用エポキシ樹脂粉体塗料を作製した以外は、実施例1と同様にバリスタ用エポキシ樹脂粉体塗料及びバリスタを作製した。
また、各実施例及び比較例により得られたバリスタ用エポキシ樹脂粉体塗料およびバリスタについて、次の各評価を行った。評価結果を表1に示す。
(Examples 2-7 and Comparative Examples 1-4)
A varistor epoxy resin powder coating and a varistor were prepared in the same manner as in Example 1 except that a varistor epoxy resin powder coating was prepared according to the blending types and blending amounts (parts by mass) shown in Table 1.
The following evaluations were made on the epoxy resin powder coating for varistors and the varistors obtained in the examples and comparative examples. The evaluation results are shown in Table 1.
(評価方法)
上述の各評価について、評価方法を以下に示す。
(Evaluation method)
An evaluation method is shown below for each of the above evaluations.
(1)ゲル化時間
得られたバリスタ用エポキシ樹脂粉体塗料に対して、JIS C 2161に準拠して、165℃の熱盤を用いてゲル化するまでの時間(秒)を測定した。ゲル化時間が80秒より長く、且つ80秒に近いゲル化時間である方が、優れた成形性を有していると判断される。
(1) Gelation time Based on JIS C 2161, the time (seconds) until gelation was measured with respect to the obtained epoxy resin powder coating material for varistors using a 165 ° C. hot platen. A gelation time longer than 80 seconds and a gelation time close to 80 seconds is judged to have excellent moldability.
(2)難燃性
加熱可能なハンドプレス装置を用いて得られたバリスタ用エポキシ樹脂粉体塗料を120℃で溶融させ、150℃で乾燥機にて硬化し、長さ125mm×幅13mm×厚み0.8mmの試験板を作製し、UL94垂直法に準拠して測定した。試験の結果が接炎後の燃焼時間の最大値が3秒以下である場合は◎、10秒以下である場合は○、10秒より長い場合は×と記載した。難燃性試験の結果が◎である場合は、特に優れた難燃性を有するバリスタ用エポキシ樹脂粉体塗料であると判断される。
(2) Flame retardance The epoxy resin powder coating for varistors obtained using a heatable hand press device is melted at 120 ° C. and cured in a dryer at 150 ° C., and the length is 125 mm × width 13 mm × thickness. A 0.8 mm test plate was prepared and measured according to the UL94 vertical method. When the test result shows that the maximum value of the burning time after flame contact is 3 seconds or less, ◎ is shown when it is 10 seconds or less, and ○ is shown when it is longer than 10 seconds. When the result of the flame retardancy test is ◎, it is judged that the epoxy resin powder coating material for varistors has particularly excellent flame retardancy.
(3)プレッシャークッカー(PCT)処理前後におけるバリスタ電圧変化率(%)
得られたバリスタに対して、バリスタ電圧試験を行い、1mA、10μAおよび1μAの電流がリークする電圧V01、V02およびV03をそれぞれ測定した。電圧測定後、2気圧、121℃、100%RHの条件で24時間プレッシャークッカー(PCT)処理を実施し、PCT処理後バリスタを取り出し、再度バリスタ電圧試験を行い、PCT処理後における1mA、10μAおよび1μAの電流がリークする電圧V1、V2およびV3をそれぞれ測定した。以下の式により、PCT処理前後のバリスタ電圧変化率を算出した。
1mAリーク電圧変化率Δ1(%)= (1−V1/V01)×100
10μAリーク電圧変化率Δ2(%)= (1−V2/V02)×100
1μAリーク電圧変化率Δ3(%)= (1−V3/V03)×100
1mA、10μAおよび1μAリーク電圧PCT前後のバリスタ電圧変化率の値が低いほど、優れた耐湿性を有するバリスタ用エポキシ樹脂粉体塗料であると判断される。
PCT処理を行う装置は、飽和型プレッシャークッカー処理装置(平山製作所社製、PC-362M)を用い、電圧変化率を測定する装置は、定電流電源装置(岩田高電圧研究所社製、AS508B)を用いた。
(3) Rate of change of varistor voltage before and after pressure cooker (PCT) treatment (%)
The obtained varistor was subjected to a varistor voltage test, and voltages V 0 1, V 0 2 and V 0 3 at which currents of 1 mA, 10 μA and 1 μA leaked were measured, respectively. After voltage measurement, pressure cooker (PCT) treatment was performed for 24 hours under the conditions of 2 atm, 121 ° C., and 100% RH. After the PCT treatment, the varistor was taken out, the varistor voltage test was performed again, and after the PCT treatment, 1 mA, 10 μA and Voltages V1, V2 and V3 at which a current of 1 μA leaks were measured, respectively. The rate of change of varistor voltage before and after the PCT treatment was calculated from the following equation.
1 mA leakage voltage change rate Δ1 (%) = (1−V1 / V 0 1) × 100
10 μA leakage voltage change rate Δ2 (%) = (1−V2 / V 0 2) × 100
1 μA leakage voltage change rate Δ3 (%) = (1−V3 / V 0 3) × 100
The lower the value of the varistor voltage change rate before and after the 1 mA, 10 μA, and 1 μA leakage voltage PCT, it is judged that the epoxy resin powder coating for varistors has better moisture resistance.
The apparatus for performing the PCT treatment is a saturated pressure cooker treatment apparatus (made by Hirayama Seisakusho, PC-362M), and the apparatus for measuring the voltage change rate is a constant current power supply (made by Iwata High Voltage Research Institute, AS508B). Was used.
(4)信頼性
バリスタの外装樹脂の信頼性評価のため、加熱可能なハンドプレス装置を用いて得られたバリスタ用エポキシ樹脂粉体塗料を120℃で溶融させ、150℃で乾燥機にて硬化し、長さ100mm×幅100mm×厚み1mmの試験板を作製し、試験片を85℃85%の条件で1000時間加湿処理した後、JIS C2161に準拠した方法で体積抵抗率を測定した。1013Ω・cm以上のものを○、1013Ω・cm未満のものを×と判定した。○であれば、バリスタの信頼性が優れると判断される。
(4) Reliability To evaluate the reliability of varistor exterior resin, melt the epoxy resin powder coating for varistors obtained using a heatable hand press device at 120 ° C and cure at 150 ° C with a dryer. Then, a test plate having a length of 100 mm × width of 100 mm × thickness of 1 mm was prepared, and the test piece was humidified for 1000 hours under the condition of 85 ° C. and 85%, and then volume resistivity was measured by a method based on JIS C2161. A sample having a density of 10 13 Ω · cm or more was evaluated as ◯, and a sample having a value less than 10 13 Ω · cm was evaluated as x. If it is ○, it is judged that the reliability of the varistor is excellent.
(5)バリスタの耐燃焼性
得られたバリスタに対して、電圧電源装置を用いて電圧を引加し、バリスタを過電圧破壊させ、発熱・発火してから、消火するまでの時間を測定した。過電圧破壊時の発火から消火までの時間が短いほど、耐燃焼性に優れたバリスタであると判断される。
(5) Combustion resistance of varistor A voltage was applied to the obtained varistor using a voltage power supply device to cause overvoltage breakdown of the varistor, and the time from heat generation / ignition to fire extinguishing was measured. As the time from ignition to extinguishing at the time of overvoltage breakdown is shorter, it is judged that the varistor has better combustion resistance.
表1に記載されている評価結果より、以下のことが分かる。 From the evaluation results described in Table 1, the following can be understood.
難燃性評価において、実施例1〜7で得られた本発明のエポキシ樹脂粉体塗料は、リン酸エステル系難燃剤を含有しない比較例3、4のエポキシ樹脂粉体塗料と比較して、優れた難燃性を持つことがわかった。 In the flame retardancy evaluation, the epoxy resin powder coatings of the present invention obtained in Examples 1 to 7 are compared with the epoxy resin powder coatings of Comparative Examples 3 and 4 that do not contain a phosphate ester flame retardant, It was found to have excellent flame retardancy.
プレッシャークッカー(PCT)前後のバリスタ電圧変化率において、実施例1〜7で得られた本発明のエポキシ樹脂粉体塗装を用いたバリスタは、プレッシャークッカー(PCT)前後のバリスタ電圧変化率Δ1の値が低く、優れた耐湿性を有していることがわかった。
一方、銅化合物を含まない比較例1、銅化合物ではなくマグネシウム化合物を含有する比較例2により得られたエポキシ樹脂粉体塗装を用いたバリスタは、プレッシャークッカー(PCT)前後のバリスタ電圧変化率Δ1の値が高く、またプレッシャークッカー後に初期値から大きく増加し、実施例1〜7で得られた本発明のバリスタと比較して、耐湿性に優れないことがわかった。
In the varistor voltage change rate before and after the pressure cooker (PCT), the varistor using the epoxy resin powder coating of the present invention obtained in Examples 1 to 7 is the value of the varistor voltage change rate Δ1 before and after the pressure cooker (PCT). Was found to have low moisture and excellent moisture resistance.
On the other hand, the varistor using the epoxy resin powder coating obtained in Comparative Example 1 containing no copper compound and Comparative Example 2 containing a magnesium compound instead of a copper compound has a varistor voltage change rate Δ1 before and after the pressure cooker (PCT). This value was high and increased greatly from the initial value after the pressure cooker, and it was found that the moisture resistance was not excellent as compared with the varistors of the present invention obtained in Examples 1-7.
特に、実施例3〜6で得られた本発明のエポキシ樹脂粉体塗装を用いたバリスタは、プレッシャークッカー(PCT)前後のバリスタ電圧変化率Δ2の値およびΔ3の値が低く、さらに優れた耐湿性を有していることがわかった。 In particular, the varistor using the epoxy resin powder coating of the present invention obtained in Examples 3 to 6 has a low varistor voltage change rate Δ2 value and Δ3 value before and after pressure cooker (PCT), and further excellent moisture resistance. It was found to have sex.
信頼性評価において、実施例1〜7で得られた本発明のエポキシ樹脂粉体塗料を用いたバリスタは、プレッシャークッカー処理前後の電圧変化率Δ1の値が5%以下でない比較例1,2のエポキシ樹脂粉体塗料を用いたバリスタと比較して、信頼性に優れたバリスタであることがわかった。 In the reliability evaluation, the varistors using the epoxy resin powder coatings of the present invention obtained in Examples 1 to 7 are those of Comparative Examples 1 and 2 in which the voltage change rate Δ1 before and after the pressure cooker treatment is not less than 5%. Compared to varistors using epoxy resin powder coatings, the varistors were found to be more reliable.
バリスタの耐燃焼性評価において、実施例1〜7で得られた本発明のエポキシ樹脂粉体塗料を用いたバリスタは、リン酸エステル系難燃剤を含有しない比較例3、4のエポキシ樹脂粉体塗料を用いたバリスタと比較して、耐燃焼性に優れたバリスタであることがわかった。 The varistors using the epoxy resin powder coatings of the present invention obtained in Examples 1 to 7 in the evaluation of the flame resistance of varistors were the epoxy resin powders of Comparative Examples 3 and 4 that did not contain a phosphate ester flame retardant. It was found that the varistor is superior in combustion resistance compared to a varistor using a paint.
本発明は、ハロゲン材を使用しなくても優れた難燃性を有するとともに、優れた耐湿性を有するバリスタ用エポキシ樹脂粉体塗料を提供するものであり、また、バリスタ用エポキシ樹脂粉体塗料をバリスタの外装に使用した場合、優れた耐燃焼性を有するバリスタを提供するものであるため、工業的なバリスタの製造に好適に用いることができる。 The present invention provides an epoxy resin powder coating material for varistors that has excellent flame resistance and excellent moisture resistance without using a halogen material, and also has an epoxy resin powder coating material for varistors. Is used for the exterior of a varistor, it provides a varistor having excellent combustion resistance, and can therefore be suitably used for industrial varistor production.
Claims (7)
前記バリスタ用エポキシ樹脂粉体塗料が、エポキシ樹脂、硬化剤、リン酸エステル系難燃剤および銅化合物を含み、
前記バリスタ用エポキシ樹脂粉体塗料で膜厚300μmに外装されたバリスタに対して、2気圧、121℃ 、100%RH、24時間条件のプレッシャークッカー処理前および前記処理後において、バリスタ電圧試験を行った際に1mAの電流がリークする電圧をそれぞれV01およびV1としたとき、プレッシャークッカー処理前後の電圧変化率Δ1(%)=(1−V1/V01)×100が5%以下であることを特徴とするバリスタ用エポキシ樹脂粉体塗料。 An epoxy resin powder coating for a varistor used for the exterior of a varistor,
The epoxy resin powder coating for varistor includes an epoxy resin, a curing agent, a phosphate ester flame retardant, and a copper compound,
A varistor voltage test was performed on the varistor coated with the epoxy resin powder coating for varistors to a film thickness of 300 μm before and after the pressure cooker treatment at 2 atm, 121 ° C., 100% RH, 24 hours. when a 1mA current has a voltage from leaking and V 0 1 and V1 respectively during the voltage change rate before and after the pressure cooker treatment Δ1 (%) = (1- V1 / V 0 1) × 100 5% or less Epoxy resin powder coating for varistors, characterized in that
前記バリスタ用エポキシ樹脂粉体塗料が、請求項1から6のいずれか1項に記載のバリスタ用エポキシ樹脂粉体塗料である、バリスタ。A varistor, wherein the epoxy resin powder coating for varistor is the epoxy resin powder coating for varistor according to any one of claims 1 to 6.
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