WO2022123924A1 - Insulating resin composition, insulating member formed of cured product of same, and electrical device - Google Patents
Insulating resin composition, insulating member formed of cured product of same, and electrical device Download PDFInfo
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- WO2022123924A1 WO2022123924A1 PCT/JP2021/038994 JP2021038994W WO2022123924A1 WO 2022123924 A1 WO2022123924 A1 WO 2022123924A1 JP 2021038994 W JP2021038994 W JP 2021038994W WO 2022123924 A1 WO2022123924 A1 WO 2022123924A1
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- insulating
- resin
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- filler
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- 239000011342 resin composition Substances 0.000 title claims abstract description 50
- 229920005989 resin Polymers 0.000 claims abstract description 80
- 239000011347 resin Substances 0.000 claims abstract description 80
- 239000000945 filler Substances 0.000 claims abstract description 59
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 59
- 239000003822 epoxy resin Substances 0.000 claims abstract description 58
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011159 matrix material Substances 0.000 claims abstract description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 238000009413 insulation Methods 0.000 claims description 17
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract 2
- 125000006850 spacer group Chemical group 0.000 description 31
- 239000002245 particle Substances 0.000 description 24
- 239000007788 liquid Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 238000005266 casting Methods 0.000 description 13
- 238000009826 distribution Methods 0.000 description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 230000008878 coupling Effects 0.000 description 7
- 238000010168 coupling process Methods 0.000 description 7
- 238000005859 coupling reaction Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 239000004020 conductor Substances 0.000 description 6
- 239000011810 insulating material Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 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 5
- 238000002156 mixing Methods 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000011161 development Methods 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
- 230000001747 exhibiting effect Effects 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- LJBWJFWNFUKAGS-UHFFFAOYSA-N 2-[bis(2-hydroxyphenyl)methyl]phenol Chemical compound OC1=CC=CC=C1C(C=1C(=CC=CC=1)O)C1=CC=CC=C1O LJBWJFWNFUKAGS-UHFFFAOYSA-N 0.000 description 1
- KKOHCQAVIJDYAF-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O KKOHCQAVIJDYAF-UHFFFAOYSA-N 0.000 description 1
- ZPQAUEDTKNBRNG-UHFFFAOYSA-N 2-methylprop-2-enoylsilicon Chemical compound CC(=C)C([Si])=O ZPQAUEDTKNBRNG-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
- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 description 1
- JDBDDNFATWXGQZ-UHFFFAOYSA-N 5-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1=CC(C)CC2C(=O)OC(=O)C12 JDBDDNFATWXGQZ-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- VTIXMGZYGRZMAW-UHFFFAOYSA-N ditridecyl hydrogen phosphite Chemical compound CCCCCCCCCCCCCOP(O)OCCCCCCCCCCCCC VTIXMGZYGRZMAW-UHFFFAOYSA-N 0.000 description 1
- XHWQYYPUYFYELO-UHFFFAOYSA-N ditridecyl phosphite Chemical compound CCCCCCCCCCCCCOP([O-])OCCCCCCCCCCCCC XHWQYYPUYFYELO-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- RYMZZMVNJRMUDD-HGQWONQESA-N simvastatin Chemical compound C([C@H]1[C@@H](C)C=CC2=C[C@H](C)C[C@@H]([C@H]12)OC(=O)C(C)(C)CC)C[C@@H]1C[C@@H](O)CC(=O)O1 RYMZZMVNJRMUDD-HGQWONQESA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- KCNSDMPZCKLTQP-UHFFFAOYSA-N tetraphenylen-1-ol Chemical compound C12=CC=CC=C2C2=CC=CC=C2C2=CC=CC=C2C2=C1C=CC=C2O KCNSDMPZCKLTQP-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/14—Carbides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
Definitions
- the electrical device according to the embodiment of the present invention is characterized by being provided with the above-mentioned insulating member.
- An object of the present invention is an insulating resin composition capable of slightly reducing the electrical resistance (volume resistivity) of an insulating resin and suppressing the temperature dependence of the electrical resistance (volume resistivity) of the insulating resin. It is an object of the present invention to provide an insulating member and an electric device made of a cured product.
- FIG. 1 is a diagram schematically showing an insulating resin composition 4 according to an embodiment of the present invention, in which the first filler 1 and the second fillers 2a and 2b are dispersed in the matrix resin 3. It shows how it is formed.
- the epoxy resin consists of an epoxy compound having two or more epoxy groups per molecule.
- an epoxy compound any compound having two or more three-membered rings consisting of two carbon atoms and one oxygen atom in one molecule and curable can be appropriately used. It is not particularly limited.
- acid anhydride-based curing agent for example, phthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, tetrabromophthalic anhydride and the like are used. be able to.
- alumina filler spherical alumina or amorphous alumina having an average particle size of 5 to 30 ⁇ m, particularly preferably an average particle size of 15 to 25 ⁇ m can be used, or a mixture thereof can be used.
- Spherical alumina is preferable from the viewpoint of reducing the resin viscosity
- crushed alumina is preferable from the viewpoint of improving the mechanical strength of the cured resin product.
- the particle size distribution of the alumina filler is not particularly limited, but from the viewpoint of reducing the inter-particle distance, the particle size distribution is preferably broad to some extent.
- the average particle size is defined by d50
- the particle size distribution is defined by the volume distribution and the number distribution.
- LA1200 average particle size 20.0 ⁇ m
- the surface of the first filler is subjected to surface treatment such as silane coupling treatment.
- silane coupling treatment By the silane coupling treatment, the wettability with the epoxy resin can be improved.
- silane coupling agent used for the silane coupling treatment for example, epoxysilane, aminosilane, vinylsilane, methacrylsilane, mercaptosilane, methoxysilane, ethoxysilane and the like can be used. These silane coupling surface modification treatments can obtain the same effect even if they are added afterwards.
- the test method is as follows. A main electrode, an annular electrode and a counter electrode are prepared on the surface of the sample using a conductive paste, and after wiring with the measuring device, the sample is charged at a specified voltage for 60 seconds to measure the volume resistance. From the obtained volume resistance value, the volume resistivity is calculated using the following formula (1).
- the sample thickness was measured with a Mitutoyo micrometer before making the electrode. At that time, the arithmetic mean value of the thicknesses at five points in the sample to be measured was taken as the sample thickness. The sample thickness may change depending on the temperature, but the details are unknown, so all calculations were made using the measured values at room temperature.
Abstract
[Problem] To provide: an insulating resin composition which is capable of reducing the electrical resistance (volume resistivity) of an insulating resin, while being capable of suppressing the temperature dependence of the electrical resistance (volume resistivity) of the insulating resin; an insulating member; and an electrical device. [Solution] An insulating resin composition which contains (1) a matrix resin that contains an epoxy resin and a curing agent that cures the epoxy resin, (2) a first filler that is selected from the group consisting of silica and alumina, and (3) a second filler that is selected from the group consisting of Fe3O4 and B4C; an insulating member which is formed of a cured product of this insulating resin composition; and an electrical device which is provided with this insulating member.
Description
本発明の実施形態は、絶縁性樹脂組成物に関する。より具体的には、本発明の実施形態は、注型可能な絶縁性樹脂組成物、この絶縁性樹脂組成物の硬化物からなる絶縁性部材、特に、ガス絶縁開閉装置、管路気中送電装置またはその他の電気機器に使用される絶縁スペーサへの使用に最適な絶縁性部材、ならびにこの絶縁性部材を具備する電気機器に関する。
The embodiment of the present invention relates to an insulating resin composition. More specifically, an embodiment of the present invention comprises a castable insulating resin composition, an insulating member made of a cured product of the insulating resin composition, particularly a gas-insulated switchgear, and an aerial power transmission in a pipeline. The present invention relates to an insulating member that is most suitable for use in an insulating spacer used for an apparatus or other electric device, and an electric device provided with this insulating member.
近年、変電所を構成する高電圧回路の開閉装置および送電装置として、ガス絶縁開閉装置および管路気中送電装置が多く使用されている。これらのガス絶縁開閉装置および管路気中送電装置においては、その接地金属容器内に高電圧導体を絶縁支持するために絶縁スペーサが使用されている。
In recent years, gas-insulated switchgear and pipeline aerial power transmission device have been widely used as switchgear and power transmission device for high-voltage circuits constituting substations. In these gas-insulated switchgear and pipeline aerial power transmission device, an insulating spacer is used to insulate and support a high-voltage conductor in the grounded metal container.
このような絶縁スペーサとしては、エポキシ樹脂などの合成樹脂からなる絶縁スペーサ本体によって、高電圧導体が支持され、この絶縁スペーサのフランジ部には接地金属容器に絶縁スペーサを固定するための金属フランジ部が形成されている。また、接地金属容器内に封入されるＳＦ６ガスは、電界が不均一であると、その絶縁性能が低下する傾向にあるので、その対策として、高電圧導体の周りに接地シールドを一体に埋め込み、前記金属フランジ部によってその電位を確保している。また、非線形誘電率材料に着目した、絶縁スペーサ用注型樹脂に関する技術も提案されている。
As such an insulating spacer, a high voltage conductor is supported by an insulating spacer body made of a synthetic resin such as epoxy resin, and a metal flange portion for fixing the insulating spacer to a ground metal container is provided on the flange portion of the insulating spacer. Is formed. In addition, the SF 6 gas enclosed in the grounded metal container tends to deteriorate its insulation performance when the electric field is non-uniform. Therefore, as a countermeasure, a grounding shield is integrally embedded around the high voltage conductor. , The potential is secured by the metal flange portion. In addition, a technique related to a casting resin for an insulating spacer, which focuses on a non-linear dielectric constant material, has also been proposed.
以上のような構成を有する絶縁スペーサの本体部の絶縁注樹脂材料としては、化学的安定性、機械的強度などから、一般に、酸無水物を硬化剤として用いたエポキシ樹脂がベース材料として使用されている。そして、特に、ＳＦ６ガスなどを絶縁媒体とするガス絶縁開閉装置用の絶縁スペーサとしては、（１）材料コストを下げる、（２）弾性率を上げて製品の剛性を増す、（３）機械的強度を改善する、（４）線膨脹係数を下げて成形性を改善する、などの目的のために、前述のエポキシ樹脂にシリカやアルミナを充填することが一般的に行われている。
As the insulating injection resin material for the main body of the insulating spacer having the above structure, an epoxy resin using acid anhydride as a curing agent is generally used as a base material because of its chemical stability and mechanical strength. ing. In particular, as an insulating spacer for a gas-insulated switching device using SF 6 gas or the like as an insulating medium, (1) the material cost is reduced, (2) the elastic modulus is increased to increase the rigidity of the product, and (3) the machine. It is common practice to fill the above-mentioned epoxy resin with silica or alumina for the purpose of improving the target strength, (4) lowering the linear expansion coefficient and improving the moldability, and the like.
一方、機器の縮小化の目的から導体通電部の温度上昇の許容値は上昇しており、絶縁スペーサ用樹脂の耐熱性（高温クリープ特性）の改善が要求されている。耐熱性（高温クリープ特性）の改善には、樹脂のガラス転移温度を上昇させる方法が一般的に用いられるが、ガラス転移温度の上昇に伴って樹脂の脆性が大きくなり、さらに、埋め込み金属部材との線膨脹係数差に基づく熱応力が増大するため、耐クラック性が著しく低下する。これに対し、樹脂自体の耐衝撃性を向上させる方法としては、変性低分子量ポリオレフィンやポリブタジエン、シリコンゴムなどの耐衝撃性付与成分を、エポキシ樹脂に変性させること、または配合することなどの方法が存在している。しかしながら、これらの従来方法においては、絶縁スペーサなどの大型高電圧部品の構造材料用としては十分な検討がなされていないため、特に、高電圧用の注型用エポキシ樹脂においては、樹脂組成面で開発の余地が残されている。
On the other hand, for the purpose of downsizing the equipment, the permissible value of the temperature rise of the conductor current-carrying part is increasing, and improvement of the heat resistance (high temperature creep characteristic) of the resin for the insulating spacer is required. To improve heat resistance (high temperature creep characteristics), a method of increasing the glass transition temperature of the resin is generally used, but as the glass transition temperature increases, the brittleness of the resin increases, and further, with the embedded metal member. Since the thermal stress based on the difference in the linear expansion coefficient of is increased, the crack resistance is significantly reduced. On the other hand, as a method for improving the impact resistance of the resin itself, a method of modifying or blending an impact resistance-imparting component such as a modified low molecular weight polyolefin, polybutadiene, or silicon rubber into an epoxy resin is used. Existing. However, in these conventional methods, sufficient studies have not been made for structural materials of large high-voltage parts such as insulating spacers. Therefore, particularly in the case of high-voltage casting epoxy resins, the resin composition is improved. There is room for development.
このため、ＳＦ６ガスなどを絶縁媒体とするガス絶縁開閉装置や管路気中送電装置などに使用される絶縁スペーサにおいては、シリカやアルミナなどの無機充填剤を樹脂に対して高充填することにより、線膨脹係数を埋め込み金属部材の線膨脹係数に近づけて熱応力を低減し、樹脂のガラス転移温度を維持し、耐熱性（高温クリープ特性）を維持したまま耐クラック性を改善する方法が一般的に用いられている。
For this reason, in insulating spacers used in gas-insulated switching devices and pipeline aerial power transmission devices that use SF 6 gas as an insulating medium, inorganic fillers such as silica and alumina should be highly filled in the resin. By making the linear expansion coefficient close to the linear expansion coefficient of the embedded metal member, the thermal stress is reduced, the glass transition temperature of the resin is maintained, and the crack resistance is improved while maintaining the heat resistance (high temperature creep characteristics). It is commonly used.
しかしながら、以上のように、ガス絶縁開閉装置や管路気中送電装置などに使用される絶縁スペーサにおいて、アルミナなどの無機充填剤を樹脂に対して高充填した場合には、次のような問題点が指摘されている。すなわち、たとえばアルミナを配合した系では、アルミナの誘電率が大きいため、アルミナの高充填は、樹脂の誘電率を増大させ、絶縁設計上不利であった。また、アルミナの高充填は、樹脂の弾性率を上昇させるため、機械的特性面では破壊時の歪みが小さくなり、製品段階での破壊値が低下してしまうという問題点があった。さらに、アルミナの高充填は、注型時の樹脂粘度を増大させるため、ポットライフが短くなり、作業性が低下するという問題もあった。加えて、従来の樹脂は、埋め込み金属部材との接着力があまり大きくないことから、十分な接着力を確保するために、一般的に、金属部材のプライマー処理を行うことが必要であり、このことも、作業性を低下させていた。
However, as described above, when an inorganic filler such as alumina is highly filled in a resin in an insulating spacer used in a gas-insulated switchgear or an aerial power transmission device for a pipeline, the following problems occur. The point has been pointed out. That is, for example, in a system containing alumina, the dielectric constant of alumina is large, so that high filling of alumina increases the dielectric constant of the resin, which is disadvantageous in terms of insulation design. Further, since the high packing of alumina increases the elastic modulus of the resin, there is a problem that the strain at the time of fracture becomes small in terms of mechanical properties and the fracture value at the product stage decreases. Further, the high filling of alumina increases the resin viscosity at the time of casting, so that there is a problem that the pot life is shortened and the workability is lowered. In addition, since the conventional resin does not have a very large adhesive force with the embedded metal member, it is generally necessary to perform primer treatment on the metal member in order to secure sufficient adhesive force. This also reduced workability.
このように、従来の絶縁スペーサにおいては、たとえばアルミナを樹脂中に高充填することにより、耐熱性（高温クリープ特性）と耐クラック性の高いレベルでの両立を図っていたが、その反面、このような従来技術には、誘電率の増大、製品段階での機械的強度の低下、作業性の低下などの問題点が存在していた。なお、以上のような各種の問題点は、ガス絶縁開閉装置や管路気中送電装置などに使用される絶縁スペーサに限らず、同様の樹脂組成物を使用してなる各種の大型注型物や半導体封止材料などの他の電気機器や部品の絶縁材料あるいは構造材料においても、同様に存在していた。
As described above, in the conventional insulating spacer, for example, by highly filling the resin with alumina, it is possible to achieve both heat resistance (high temperature creep characteristics) and crack resistance at a high level. Such conventional techniques have problems such as an increase in dielectric constant, a decrease in mechanical strength at the product stage, and a decrease in workability. The various problems described above are not limited to the insulating spacers used in gas-insulated switchgear and aerial power transmission equipment, and various large-sized cast products using the same resin composition. It also existed in insulating materials or structural materials of other electric devices and parts such as semiconductor encapsulation materials.
さらに、従来の絶縁性樹脂では、以下のような課題を有している。
ＤＣ－ＧＩＳ(直流-ガス絶縁開閉装置)において、現行エポキシ樹脂の抵抗率が高いため、その試験に１年程度かかるという課題がある。開発のリードタイムを短縮することで、海外を中心に急速に市場が拡大すると思われるＤＣ－ＧＩＳの新型器を、いち早く市場に投入したいというニーズがあるが、現行のエポキシ樹脂では、このようなリードタイム短縮は困難である。 Further, the conventional insulating resin has the following problems.
In DC-GIS (Direct Current-Gas Insulated Switchgear), the resistivity of the current epoxy resin is high, so there is a problem that the test takes about one year. There is a need to quickly introduce a new type of DC-GIS, which is expected to rapidly expand the market mainly overseas by shortening the development lead time, but with the current epoxy resin, this is the case. It is difficult to shorten the lead time.
ＤＣ－ＧＩＳ(直流-ガス絶縁開閉装置)において、現行エポキシ樹脂の抵抗率が高いため、その試験に１年程度かかるという課題がある。開発のリードタイムを短縮することで、海外を中心に急速に市場が拡大すると思われるＤＣ－ＧＩＳの新型器を、いち早く市場に投入したいというニーズがあるが、現行のエポキシ樹脂では、このようなリードタイム短縮は困難である。 Further, the conventional insulating resin has the following problems.
In DC-GIS (Direct Current-Gas Insulated Switchgear), the resistivity of the current epoxy resin is high, so there is a problem that the test takes about one year. There is a need to quickly introduce a new type of DC-GIS, which is expected to rapidly expand the market mainly overseas by shortening the development lead time, but with the current epoxy resin, this is the case. It is difficult to shorten the lead time.
従来提案されている現行の絶縁性樹脂では、２つの課題がある。すなわち、（１）注型樹脂の電気抵抗（体積抵抗率）が高すぎるという点と、（２）注型樹脂の電気抵抗（体積抵抗率）の温度依存性が大きすぎるという点である。
The current insulating resin that has been proposed so far has two problems. That is, (1) the electric resistance (volume resistivity) of the cast resin is too high, and (2) the temperature dependence of the electric resistance (volume resistivity) of the cast resin is too large.
まず、上記（１）の課題については、単純に抵抗率を低減するだけであれば、抵抗率の低い充填剤（フィラー）を充填すればよいということになる。しかし、この場合、抵抗率は下がるが、耐電圧性能も低減させることになってしまう。また、抵抗率の低い充填剤は、主に金属系で比重が大きいために、充填剤が容易に沈殿してしまうというと問題が生じやすい。
First, regarding the problem (1) above, if the resistivity is simply reduced, a filler having a low resistivity may be filled. However, in this case, although the resistivity is lowered, the withstand voltage performance is also reduced. Further, since the filler having a low resistivity is mainly metal-based and has a large specific gravity, a problem tends to occur if the filler is easily settled.
次に、（２）の課題については、一般的な絶縁材料（絶縁性を有する材料）は、温度上昇とともに電気抵抗（体積抵抗率）が低下する。すなわち、温度上昇とともに電気が流れやすくなる。一般に、導電性とは１０－６～１０－３Ω・ｃｍ程度の体積抵抗率を、半導電性とは１０－３～１０８Ω・ｃｍ程度の体積抵抗率を、絶縁性とは１０８～１０２０Ω・ｃｍ程度の体積抵抗率を、それぞれ指す。ここでは、絶縁性（１０５～１０２０Ω・ｃｍ程度の体積抵抗率）の材料を取り扱っている。上記のように、絶縁材料が有する温度依存性は、絶縁材料の本来有する特性であり、これを制御ないし抑制することは困難であった。なお、絶縁性、半導電性、絶縁性の定義には諸説あるが、ここでは上記のような体積抵抗率として定義した。
以上のような課題を解決するため、新たな絶縁性材料が必要であった。 Next, regarding the problem of (2), the electric resistance (volume resistivity) of a general insulating material (material having an insulating property) decreases as the temperature rises. That is, electricity tends to flow as the temperature rises. Generally, conductivity is a volume resistivity of about 10 -6 to 10 -3 Ω · cm, semi-conductive is a volume resistivity of about 10 -3 to 10 8 Ω · cm, and insulation is 10 8 It refers to the volume resistivity of about 10 20 Ω · cm, respectively. Here, we are dealing with insulating materials (volume resistivity of about 105 to 10 20 Ω · cm). As described above, the temperature dependence of the insulating material is an inherent characteristic of the insulating material, and it is difficult to control or suppress it. There are various theories about the definitions of insulating property, semi-conductive property, and insulating property, but here, they are defined as the volume resistivity as described above.
In order to solve the above problems, a new insulating material was required.
以上のような課題を解決するため、新たな絶縁性材料が必要であった。 Next, regarding the problem of (2), the electric resistance (volume resistivity) of a general insulating material (material having an insulating property) decreases as the temperature rises. That is, electricity tends to flow as the temperature rises. Generally, conductivity is a volume resistivity of about 10 -6 to 10 -3 Ω · cm, semi-conductive is a volume resistivity of about 10 -3 to 10 8 Ω · cm, and insulation is 10 8 It refers to the volume resistivity of about 10 20 Ω · cm, respectively. Here, we are dealing with insulating materials (volume resistivity of about 105 to 10 20 Ω · cm). As described above, the temperature dependence of the insulating material is an inherent characteristic of the insulating material, and it is difficult to control or suppress it. There are various theories about the definitions of insulating property, semi-conductive property, and insulating property, but here, they are defined as the volume resistivity as described above.
In order to solve the above problems, a new insulating material was required.
本発明の実施形態による発明の目的は、絶縁性樹脂の電気抵抗（体積抵抗率）をわずかに低減し、かつ絶縁性樹脂の電気抵抗（体積抵抗率）の温度依存性を抑制可能な絶縁性樹脂組成物および絶縁性硬化物を提供することである。
An object of the invention according to the embodiment of the present invention is an insulating property capable of slightly reducing the electric resistance (volume resistivity) of the insulating resin and suppressing the temperature dependence of the electric resistance (volume resistivity) of the insulating resin. The present invention is to provide a resin composition and an insulating cured product.
したがって、本発明の実施形態による絶縁性樹脂組成物は、
エポキシ樹脂、および前記エポキシ樹脂を硬化させる硬化剤を含むマトリックス樹脂と、
シリカおよびアルミナからなる群から選ばれた第一の充填剤と、
Ｆｅ３Ｏ４およびＢ４Ｃからなるから群から選ばれた第二の充填剤と、を含有してなること、を特徴とする。 Therefore, the insulating resin composition according to the embodiment of the present invention is
An epoxy resin and a matrix resin containing a curing agent that cures the epoxy resin,
A first filler selected from the group consisting of silica and alumina,
It is characterized by containing a second filler selected from the group consisting of Fe 3 O 4 and B 4 C.
エポキシ樹脂、および前記エポキシ樹脂を硬化させる硬化剤を含むマトリックス樹脂と、
シリカおよびアルミナからなる群から選ばれた第一の充填剤と、
Ｆｅ３Ｏ４およびＢ４Ｃからなるから群から選ばれた第二の充填剤と、を含有してなること、を特徴とする。 Therefore, the insulating resin composition according to the embodiment of the present invention is
An epoxy resin and a matrix resin containing a curing agent that cures the epoxy resin,
A first filler selected from the group consisting of silica and alumina,
It is characterized by containing a second filler selected from the group consisting of Fe 3 O 4 and B 4 C.
そして、本発明の実施形態による絶縁性部材は、上記の絶縁性樹脂組成物の硬化物からなること、を特徴とする。
The insulating member according to the embodiment of the present invention is characterized by being made of a cured product of the above-mentioned insulating resin composition.
そして、本発明の実施形態による絶縁スぺーサは、上記の絶縁性樹脂組成物の硬化物からなること、を特徴とする。
The insulating spacer according to the embodiment of the present invention is characterized by being composed of a cured product of the above-mentioned insulating resin composition.
そして、本発明の実施形態による電気機器は、上記の絶縁性部材を具備してなること、を特徴とする。
The electrical device according to the embodiment of the present invention is characterized by being provided with the above-mentioned insulating member.
本発明の目的は、絶縁性樹脂の電気抵抗（体積抵抗率）をわずかに低減し、かつ絶縁性樹脂の電気抵抗（体積抵抗率）の温度依存性を抑制可能な絶縁性樹脂組成物、この硬化物からなる絶縁性部材および電気機器を提供することである。
An object of the present invention is an insulating resin composition capable of slightly reducing the electrical resistance (volume resistivity) of an insulating resin and suppressing the temperature dependence of the electrical resistance (volume resistivity) of the insulating resin. It is an object of the present invention to provide an insulating member and an electric device made of a cured product.
本発明の実施形態においては、第一の充填剤（シリカ、アルミナ）に加えて、第二の充填剤としてＢ４Ｃおよび／またはＦｅ３Ｏ４を配合することにより、抵抗率の低減と、抵抗率の温度依存性の低減を達成することができる。
In the embodiment of the present invention, the resistivity is reduced and the resistivity is reduced by blending B 4 C and / or Fe 3 O 4 as the second filler in addition to the first filler (silica, alumina). A reduction in the temperature dependence of resistivity can be achieved.
〔基本構成〕
本発明の実施形態による絶縁性樹脂組成物は、
エポキシ樹脂、および前記エポキシ樹脂を硬化させる硬化剤を含むマトリックス樹脂と、
シリカおよびアルミナからなる群から選ばれた第一の充填剤と、
Ｆｅ３Ｏ４およびＢ４Ｃからなるから群から選ばれた第二の充填剤と、を含有してなること、を特徴とする。 [Basic configuration]
The insulating resin composition according to the embodiment of the present invention is
An epoxy resin and a matrix resin containing a curing agent that cures the epoxy resin,
A first filler selected from the group consisting of silica and alumina,
It is characterized by containing a second filler selected from the group consisting of Fe 3 O 4 and B 4 C.
本発明の実施形態による絶縁性樹脂組成物は、
エポキシ樹脂、および前記エポキシ樹脂を硬化させる硬化剤を含むマトリックス樹脂と、
シリカおよびアルミナからなる群から選ばれた第一の充填剤と、
Ｆｅ３Ｏ４およびＢ４Ｃからなるから群から選ばれた第二の充填剤と、を含有してなること、を特徴とする。 [Basic configuration]
The insulating resin composition according to the embodiment of the present invention is
An epoxy resin and a matrix resin containing a curing agent that cures the epoxy resin,
A first filler selected from the group consisting of silica and alumina,
It is characterized by containing a second filler selected from the group consisting of Fe 3 O 4 and B 4 C.
ここで、「絶縁性」とは、「経済産業省（МＥＴＩ）の電気用品安全法、電気用品安全法令・解釈・規定等の「通達」記載の、「別表第十一 電気用品に使用される絶縁物の使用温度の上限値」のｐ．１「第１章 電気用品に使用される絶縁物の使用温度の上限値」における「１ 電気用品に使用される電気絶縁物又は熱絶縁物（電源電線等に使用されるものを除く。）」の（１）適用範囲等のロ によって規定される、体積抵抗率が１０８以上Ω・ｃｍであること」をいう。
参考ＵＲＬ：https://www.meti.go.jp/policy/consumer/seian/denan/act.html Here, "insulation" is used in "Appendix 11 Electrical Appliance and Material" described in "Notice" of the Electrical Appliance and Material Safety Law of the Ministry of Economy, Trade and Industry (МETI), Electrical Appliance and Material Safety Laws, Interpretations, Regulations, etc. "Upper limit of operating temperature of insulator" p. 1 "1 Electrical insulation or thermal insulation used for electrical appliances (excluding those used for power wires, etc.)" in "Chapter 1 Upper limit of operating temperature of insulators used for electrical appliances" (1) The volume resistance is 108 or more and Ω · cm, which is defined by (b) such as the applicable range. "
Reference URL: https://www.meti.go.jp/policy/consumer/seian/denan/act.html
参考ＵＲＬ：https://www.meti.go.jp/policy/consumer/seian/denan/act.html Here, "insulation" is used in "Appendix 11 Electrical Appliance and Material" described in "Notice" of the Electrical Appliance and Material Safety Law of the Ministry of Economy, Trade and Industry (МETI), Electrical Appliance and Material Safety Laws, Interpretations, Regulations, etc. "Upper limit of operating temperature of insulator" p. 1 "1 Electrical insulation or thermal insulation used for electrical appliances (excluding those used for power wires, etc.)" in "
Reference URL: https://www.meti.go.jp/policy/consumer/seian/denan/act.html
図１は、本発明の実施形態による絶縁性樹脂組成物４を模式的に示す図であって、第一の充填剤１と第二の充填剤２ａ、２ｂとがマトリックス樹脂３中に分散を形成している様子を示している。
FIG. 1 is a diagram schematically showing an insulating resin composition 4 according to an embodiment of the present invention, in which the first filler 1 and the second fillers 2a and 2b are dispersed in the matrix resin 3. It shows how it is formed.
＜マトリックス樹脂＞
本発明に係る実施の形態の絶縁性樹脂組成物は、エポキシ樹脂およびこのエポキシ樹脂を硬化させる硬化剤からなるマトリックス樹脂を備える。そして、このマトリックス樹脂に分散して配合される第一の充填剤（シリカまたはアルミナ、あるいはこれらの混合物）、第二の充填剤（注型樹脂の電気抵抗を制御する充填剤）を含有している。なお、この注型樹脂は、硬化剤を含有しているが、注型樹脂として使用される際には、硬化していない、粘性液状の状態を維持している。 <Matrix resin>
The insulating resin composition of the embodiment according to the present invention comprises a matrix resin composed of an epoxy resin and a curing agent that cures the epoxy resin. Then, it contains a first filler (silica or alumina, or a mixture thereof) and a second filler (a filler that controls the electric resistance of the casting resin) that are dispersed and blended in the matrix resin. There is. Although this casting resin contains a curing agent, when it is used as a casting resin, it is not cured and maintains a viscous liquid state.
本発明に係る実施の形態の絶縁性樹脂組成物は、エポキシ樹脂およびこのエポキシ樹脂を硬化させる硬化剤からなるマトリックス樹脂を備える。そして、このマトリックス樹脂に分散して配合される第一の充填剤（シリカまたはアルミナ、あるいはこれらの混合物）、第二の充填剤（注型樹脂の電気抵抗を制御する充填剤）を含有している。なお、この注型樹脂は、硬化剤を含有しているが、注型樹脂として使用される際には、硬化していない、粘性液状の状態を維持している。 <Matrix resin>
The insulating resin composition of the embodiment according to the present invention comprises a matrix resin composed of an epoxy resin and a curing agent that cures the epoxy resin. Then, it contains a first filler (silica or alumina, or a mixture thereof) and a second filler (a filler that controls the electric resistance of the casting resin) that are dispersed and blended in the matrix resin. There is. Although this casting resin contains a curing agent, when it is used as a casting resin, it is not cured and maintains a viscous liquid state.
エポキシ樹脂は、１分子当たり２個以上のエポキシ基を有するエポキシ化合物からなるものである。このようなエポキシ化合物としては、炭素原子２個と酸素原子１個とからなる三員環を１分子中に２個以上持ち、硬化可能な化合物であれば適宜に使用可能であり、その種類は特に限定されるものではない。
The epoxy resin consists of an epoxy compound having two or more epoxy groups per molecule. As such an epoxy compound, any compound having two or more three-membered rings consisting of two carbon atoms and one oxygen atom in one molecule and curable can be appropriately used. It is not particularly limited.
エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、臭素化ビスフェノールＡ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＡＦ型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、フルオレン型エポキシ樹脂、ノボラック型エポキシ樹脂、フェノール－ノボラック型エポキシ樹脂、オルソクレゾール－ノボラック型エポキシ樹脂、トリス（ヒドロキシフェニル）メタン型エポキシ樹脂、テトラフェニロールエタン型エポキシ樹脂等のグリシジルエーテル型エポキシ樹脂、エピクロルヒドリンとガルボン酸との縮合によって得られるグリジジルエステル型エポキシ樹脂、トリグリシジルイソシアネートやエピクロルヒドリンとヒダントイン類との反応によって得られるヒダントイン型エポキシ樹脂のような複素環式エポキシ樹脂等が挙げられる。また、ビスフェノールＡ型のエポキシ樹脂を単独で使用してもよいし、２種以上混合して使用してもよい。特に好ましいエポキシ樹脂としては、たとえば、エポミックＲ１４０Ｐ（三井化学株式会社製商品名）を挙げることができる。
Examples of the epoxy resin include bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, and biphenyl type epoxy resin. Glycidyl such as naphthalene type epoxy resin, fluorene type epoxy resin, novolak type epoxy resin, phenol-novolak type epoxy resin, orthocresol-novolak type epoxy resin, tris (hydroxyphenyl) methane type epoxy resin, tetraphenylol ethane type epoxy resin, etc. Ether-type epoxy resins, glycidyl ester-type epoxy resins obtained by condensing epichlorhydrin and galbon acid, heterocyclic epoxy resins such as triglycidyl isocyanate and hydridein-type epoxy resins obtained by the reaction of epichlorohydrin with hydranthins, etc. Can be mentioned. Further, the bisphenol A type epoxy resin may be used alone, or two or more kinds may be mixed and used. As a particularly preferable epoxy resin, for example, Epomic R140P (trade name manufactured by Mitsui Chemicals, Inc.) can be mentioned.
また、樹脂の耐熱性を向上させるために、必要に応じて、脂環式のエポキシ樹脂を適量配合することもできる。脂環式のエポキシ樹脂としては、たとえば、ＣＹ１７９（ハンツマン株式会社製商品名）、Ｅ１７１（ジャパンエポキシレジン株式会社製商品名）、セロキサイド２０２１Ｐ（株式会社ダイセル製商品名）などを用いることができる。
Further, in order to improve the heat resistance of the resin, an alicyclic epoxy resin can be blended in an appropriate amount, if necessary. As the alicyclic epoxy resin, for example, CY179 (trade name manufactured by Huntsman Co., Ltd.), E171 (trade name manufactured by Japan Epoxy Resin Co., Ltd.), Serokiside 2021P (trade name manufactured by Daicel Co., Ltd.) and the like can be used.
エポキシ樹脂を硬化させる硬化剤は、エポキシ樹脂と化学反応してエポキシ樹脂を硬化させるものである。この硬化剤は、エポキシ樹脂を硬化させるものであれば適宜に使用可能であり、その種類は特に限定されるものではない。このような硬化剤としては、例えば、アミン系硬化剤、酸無水物系硬化剤などを使用することができる。アミン系硬化剤としては、例えば、エチレンジアミン、ポリアミドアミンなどを使用することができる。酸無水物系硬化剤としては、例えば、無水フタル酸、ヘキサヒドロ無水フタル酸、４－メチルヘキサヒドロ無水フタル酸、テトラヒドロ無水フタル酸、４－メチルテトラヒドロ無水フタル酸、テトラブロモ無水フタル酸などを使用することができる。
The curing agent that cures the epoxy resin is one that chemically reacts with the epoxy resin to cure the epoxy resin. This curing agent can be appropriately used as long as it cures the epoxy resin, and the type thereof is not particularly limited. As such a curing agent, for example, an amine-based curing agent, an acid anhydride-based curing agent, or the like can be used. As the amine-based curing agent, for example, ethylenediamine, polyamide amine and the like can be used. As the acid anhydride-based curing agent, for example, phthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, tetrabromophthalic anhydride and the like are used. be able to.
硬化剤の含有量は、マトリックス樹脂１００質量部に対して、好ましくは６０～９０質量部、特に好ましくは７０～８０質量部、である。
The content of the curing agent is preferably 60 to 90 parts by mass, particularly preferably 70 to 80 parts by mass with respect to 100 parts by mass of the matrix resin.
本発明の実施形態の絶縁性樹脂組成物のマトリックス樹脂は、エポキシ樹脂に加えて、エポキシ樹脂以外の樹脂成分を含むことができる。そのようなエポキシ樹脂以外の樹脂成分としては、アクリル樹脂を挙げることができる。アクリル樹脂の含有量は、好ましくは０．１～１０質量部、好ましくは１～５質量部、である（エポキシ樹脂とアクリル樹脂との合計量を１質量部とする）。このようなアクリル樹脂を含む場合、主に粘度低減という点で好ましい。
The matrix resin of the insulating resin composition according to the embodiment of the present invention may contain a resin component other than the epoxy resin in addition to the epoxy resin. As a resin component other than such an epoxy resin, an acrylic resin can be mentioned. The content of the acrylic resin is preferably 0.1 to 10 parts by mass, preferably 1 to 5 parts by mass (the total amount of the epoxy resin and the acrylic resin is 1 part by mass). When such an acrylic resin is contained, it is preferable mainly in terms of reducing the viscosity.
そして、前記マトリックス樹脂は、必要に応じて他の成分を含むことができる。そのような他の成分としては、例えば、消泡剤、分散剤、沈降防止剤等を挙げることができる。
Then, the matrix resin can contain other components as needed. Examples of such other components include defoaming agents, dispersants, anti-sedimenting agents and the like. It was
消泡剤の好ましい具体例としては、例えばＴＳＡ７２０（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製商品名）、ＫＰ－３３０（信越化学工業株式会社製商品名）、を挙げることができる。消泡剤を用いる場合、その含有量は、好ましくは０．０００１～０．０１質量部、特に好ましくは０．０００５～０．００１質量部、である（マトリックス樹脂の全量を１質量部とする）。
Preferred specific examples of the defoaming agent include, for example, TSA720 (trade name manufactured by Momentive Performance Materials Japan GK) and KP-330 (trade name manufactured by Shin-Etsu Chemical Co., Ltd.). When a defoaming agent is used, its content is preferably 0.0001 to 0.01 parts by mass, particularly preferably 0.0005 to 0.001 parts by mass (the total amount of the matrix resin is 1 part by mass). ).
分散剤の好ましい具体例としては、例えばホモゲノール Ｌ－１８、ホモゲノール Ｌ－９５、ホモゲノール Ｌ－１００、ホモゲノール Ｌ－１８２０（いずれも花王株式会社製商品名）、を挙げることができる。分散剤を用いる場合、その含有量は、好ましくは０．００５～０．１質量部、特に好ましくは０．０１～０．０５質量部、である（マトリックス樹脂の全量を１質量部とする）。
Preferred specific examples of the dispersant include, for example, Homogenol L-18, Homogenol L-95, Homogenol L-100, and Homogenol L-1820 (all of which are trade names manufactured by Kao Corporation). When a dispersant is used, its content is preferably 0.005 to 0.1 parts by mass, particularly preferably 0.01 to 0.05 parts by mass (the total amount of the matrix resin is 1 part by mass). ..
沈降防止剤の好ましい具体例としては、例えばＡＥＲＯＳＩＬ ２００、ＡＥＲＯＸＩＤＥ Ａｌｕ Ｃ（いずれも日本アエロジル株式会社製商品名）、を挙げることができる。沈降防止剤を用いる場合、その含有量は、好ましくは０．００５～０．１質量部、特に好ましくは０．０１～０．０５質量部、である（マトリックス樹脂の全量を１質量部とする）。
Preferred specific examples of the anti-precipitation agent include, for example, AEROSIL 200 and AEROXIDE Alu C (both are trade names manufactured by Nippon Aerosil Co., Ltd.). When an anti-settling agent is used, its content is preferably 0.005 to 0.1 parts by mass, particularly preferably 0.01 to 0.05 parts by mass (the total amount of the matrix resin is 1 part by mass). ).
＜第一の充填剤＞
本発明の実施形態による絶縁性樹脂組成物では、第一の充填剤として、シリカおよびアルミナからなる群から選ばれた充填剤を採用している。 <First filler>
In the insulating resin composition according to the embodiment of the present invention, a filler selected from the group consisting of silica and alumina is adopted as the first filler.
本発明の実施形態による絶縁性樹脂組成物では、第一の充填剤として、シリカおよびアルミナからなる群から選ばれた充填剤を採用している。 <First filler>
In the insulating resin composition according to the embodiment of the present invention, a filler selected from the group consisting of silica and alumina is adopted as the first filler.
このシリカ充填剤としては、好ましくは平均粒径５～３０μｍ、特に好ましくは平均粒径１０～２０μｍ、の球形状シリカもしくは不定形シリカを用いることができ、またこれらの混在物を用いることができる。樹脂粘度の低減という観点からは球形状シリカが好ましく、また、樹脂硬化物の機械強度向上という観点からは破砕状の不定形シリカが好ましい。シリカ充填剤の粒度分布は、特に限定されないが、粒子間距離の低減という観点からは、粒度分布はある程度ブロードな分布をもつことが好ましい。ここで、平均粒径とは、ｄ５０で規定されるものであり、粒度分布は、体積分布および個数分布で規定されるものである。
As the silica filler, spherical silica or amorphous silica having an average particle size of 5 to 30 μm, particularly preferably an average particle size of 10 to 20 μm can be used, or a mixture thereof can be used. .. Spherical silica is preferable from the viewpoint of reducing the resin viscosity, and crushed amorphous silica is preferable from the viewpoint of improving the mechanical strength of the cured resin product. The particle size distribution of the silica filler is not particularly limited, but from the viewpoint of reducing the distance between particles, it is preferable that the particle size distribution has a broad distribution to some extent. Here, the average particle size is defined by d50, and the particle size distribution is defined by the volume distribution and the number distribution.
特に好ましいシリカ充填剤の具体例としては、ＦＵＭＩＴＥＣ社製ＲＦ２５（平均粒径１７．５μｍ）、Ｆ１１５（平均粒径１４．０μｍ）、ＤＥＮＫＡ製ＦＢ４８（平均粒径１３．３μｍ）などを挙げることができる。
Specific examples of particularly preferable silica fillers include RF25 (average particle size 17.5 μm) manufactured by FUMITEC, F115 (average particle size 14.0 μm), FB48 (average particle size 13.3 μm) manufactured by DENKA, and the like. can.
アルミナ充填剤としては、好ましくは平均粒径５～３０μｍ、特に好ましくは平均粒径１５～２５μｍ、の球形状アルミナもしくは不定形アルミナを用いることができ、またこれらの混在物を用いることができる。樹脂粘度の低減という観点からは球形状アルミナが好ましく、また、樹脂硬化物の機械強度向上という観点からは破砕状アルミナが好ましい。アルミナ充填剤の粒度分布は、特に限定されないが、粒子間距離の低減という観点からは、粒度分布は、ある程度ブロードな分布をもつことが好ましい。ここで、平均粒径とは、ｄ５０で規定されるものであり、粒度分布は、体積分布および個数分布で規定されるものである。好ましいアルミナ充填剤としては、太平洋ランダム社製ＬＡ１２００（平均粒径２０．０μｍ）などを用いることができる。
As the alumina filler, spherical alumina or amorphous alumina having an average particle size of 5 to 30 μm, particularly preferably an average particle size of 15 to 25 μm can be used, or a mixture thereof can be used. Spherical alumina is preferable from the viewpoint of reducing the resin viscosity, and crushed alumina is preferable from the viewpoint of improving the mechanical strength of the cured resin product. The particle size distribution of the alumina filler is not particularly limited, but from the viewpoint of reducing the inter-particle distance, the particle size distribution is preferably broad to some extent. Here, the average particle size is defined by d50, and the particle size distribution is defined by the volume distribution and the number distribution. As a preferable alumina filler, LA1200 (average particle size 20.0 μm) manufactured by Pacific Random Co., Ltd. can be used.
第一の充填剤（シリカ）の表面は、シランカップリング処理などの表面処理が施されていることが好ましい。シランカップリング処理することで、エポキシ樹脂とのぬれ性を向上させることができる。シランカップリング処理に使用するシランカップリング剤としては、例えば、エポキシシラン、アミノシラン、ビニルシラン、メタクリルシラン、メルカプトシラン、メトキシシラン、エトキシシランなどを使用することができる。これらのシランカップリング表面改質処理は、後添加しても同様の効果を得ることができる。
It is preferable that the surface of the first filler (silica) is subjected to surface treatment such as silane coupling treatment. By the silane coupling treatment, the wettability with the epoxy resin can be improved. As the silane coupling agent used for the silane coupling treatment, for example, epoxysilane, aminosilane, vinylsilane, methacrylsilane, mercaptosilane, methoxysilane, ethoxysilane and the like can be used. These silane coupling surface modification treatments can obtain the same effect even if they are added afterwards.
また、第一の充填剤の表面は、チタネートカップリング処理することで、エポキシ樹脂とのぬれ性を向上させることもできる。チタネートカップリング処理に使用するチタネートカップリング剤としては、イソプロピルトリイソステアロイルタイト、イソプロピルトリドデシルベンゼンスルホニルチタネート、イソプロピル－トリス（ジオクチルピロホスフェート）チタネート、テトライソプロピル－ビス（ジオクチルホスファイト）チタネート、テトラオクチル－ビス（ジトリデシルホスファイト）チタネート、テトラ（２，２－ジアリロキシメチル－１－ブチル）－ビス（ジトリデシル）ホスファイトチタネート、ビス（ジオクチルピロホスフェート）オキシアセテートチタネートなどが挙げられる。これらのチタネートカップリング表面改質処理は、後添加しても同様の効果を得ることができる。
Further, the surface of the first filler can be treated with a titanate coupling to improve the wettability with the epoxy resin. The titanate coupling agent used for the titanate coupling treatment includes isopropyltriisostearoyltite, isopropyltridodecylbenzenesulfonyl titanate, isopropyl-tris (dioctylpyrophosphate) titanate, tetraisopropyl-bis (dioctylphosphite) titanate, and tetraoctyl. -Bis (ditridecylphosphite) titanate, tetra (2,2-dialyloximethyl-1-butyl) -bis (ditridecyl) phosphite titanate, bis (dioctylpyrrophosphate) oxyacetate titanate and the like can be mentioned. These titanate coupling surface modification treatments can obtain the same effect even if they are added afterwards.
第一の充填剤の含有量は、前記マトリックス樹脂１質量部に対して、好ましくは０．１～２．５質量部、特に好ましくは１．５～２．０質量部、である。第一の充填剤の含有量が０．１質量部未満の場合は、樹脂硬化物の強度が維持できないという懸念があり、一方、２．５質量部超過の場合、樹脂粘度上昇により注型不可となることがある。
The content of the first filler is preferably 0.1 to 2.5 parts by mass, and particularly preferably 1.5 to 2.0 parts by mass with respect to 1 part by mass of the matrix resin. If the content of the first filler is less than 0.1 parts by mass, there is a concern that the strength of the cured resin may not be maintained, while if it exceeds 2.5 parts by mass, casting is not possible due to an increase in resin viscosity. May become.
＜第二の充填剤＞
本発明の実施形態による絶縁性樹脂組成物では、第二の充填剤として、Ｆｅ３Ｏ４およびＢ４Ｃからなるから群から選ばれた充填剤を採用している。 <Second filler>
In the insulating resin composition according to the embodiment of the present invention, a filler selected from the group consisting of Fe 3 O 4 and B 4 C is adopted as the second filler.
本発明の実施形態による絶縁性樹脂組成物では、第二の充填剤として、Ｆｅ３Ｏ４およびＢ４Ｃからなるから群から選ばれた充填剤を採用している。 <Second filler>
In the insulating resin composition according to the embodiment of the present invention, a filler selected from the group consisting of Fe 3 O 4 and B 4 C is adopted as the second filler.
Ｆｅ３Ｏ４について、以下に説明する。
Ｆｅ３Ｏ４は黒色の粉体である（比重：約５．２ｇ／ｃｍ３）。粒径は、Ｆｅ３Ｏ４充填剤単体で絶縁抵抗特性を発現させつつ、塗装などの作業性を確保するために、０．１μｍ～１０μｍであることが好ましい。この範囲のうちでも、絶縁抵抗特性が良好となる、０．５μｍ～５μｍの粒径がさらに好ましい。なお、粒径は、ＳＥＭ（走査型電子顕微鏡）による樹脂硬化物の観察などによって測定される。Ｆｅ３Ｏ４の含有量は、絶縁抵抗材料における導電パスの形成および塗装などの作業性を確保するために、マトリックス樹脂１質量部に対して０．１０～０．７０質量部含有されることが好ましい。 Fe 3 O 4 will be described below.
Fe 3 O 4 is a black powder (specific gravity: about 5.2 g / cm 3 ). The particle size is preferably 0.1 μm to 10 μm in order to ensure workability such as painting while exhibiting insulation resistance characteristics with the Fe 3 O 4 filler alone. Even within this range, a particle size of 0.5 μm to 5 μm, which has good insulation resistance characteristics, is more preferable. The particle size is measured by observing the cured resin product with an SEM (scanning electron microscope). The content of Fe 3 O 4 is 0.10 to 0.70 parts by mass with respect to 1 part by mass of the matrix resin in order to ensure workability such as formation of a conductive path and coating in the insulating resistance material. Is preferable.
Ｆｅ３Ｏ４は黒色の粉体である（比重：約５．２ｇ／ｃｍ３）。粒径は、Ｆｅ３Ｏ４充填剤単体で絶縁抵抗特性を発現させつつ、塗装などの作業性を確保するために、０．１μｍ～１０μｍであることが好ましい。この範囲のうちでも、絶縁抵抗特性が良好となる、０．５μｍ～５μｍの粒径がさらに好ましい。なお、粒径は、ＳＥＭ（走査型電子顕微鏡）による樹脂硬化物の観察などによって測定される。Ｆｅ３Ｏ４の含有量は、絶縁抵抗材料における導電パスの形成および塗装などの作業性を確保するために、マトリックス樹脂１質量部に対して０．１０～０．７０質量部含有されることが好ましい。 Fe 3 O 4 will be described below.
Fe 3 O 4 is a black powder (specific gravity: about 5.2 g / cm 3 ). The particle size is preferably 0.1 μm to 10 μm in order to ensure workability such as painting while exhibiting insulation resistance characteristics with the Fe 3 O 4 filler alone. Even within this range, a particle size of 0.5 μm to 5 μm, which has good insulation resistance characteristics, is more preferable. The particle size is measured by observing the cured resin product with an SEM (scanning electron microscope). The content of Fe 3 O 4 is 0.10 to 0.70 parts by mass with respect to 1 part by mass of the matrix resin in order to ensure workability such as formation of a conductive path and coating in the insulating resistance material. Is preferable.
Ｂ４Ｃについて、以下に説明する。
Ｂ４Ｃは黒色の粉体である（比重：約２．５ｇ／ｃｍ３）。粒径は、Ｂ４Ｃ充填剤単体で絶縁抵抗特性を発現させつつ、塗装などの作業性を確保するために、２．５μｍ～１２．０μｍであることが好ましい。この範囲のうちでも、絶縁抵抗特性が良好となる、３．０μｍ～１０．０μｍの粒径がさらに好ましい。なお、粒径は、ＳＥＭ（走査型電子顕微鏡）による樹脂硬化物の観察などによって測定される。Ｂ４Ｃの含有量は、絶縁抵抗材料における導電パスの形成および塗装などの作業性を確保するために、マトリックス樹脂１質量部に対して０．１０～０．７０質量部含有されることが好ましい。 B 4 C will be described below.
B 4 C is a black powder (specific gravity: about 2.5 g / cm 3 ). The particle size is preferably 2.5 μm to 12.0 μm in order to ensure workability such as painting while exhibiting insulation resistance characteristics with the B4 C filler alone. Even within this range, a particle size of 3.0 μm to 10.0 μm, which has good insulation resistance characteristics, is more preferable. The particle size is measured by observing the cured resin product with an SEM (scanning electron microscope). The content of B 4 C may be 0.10 to 0.70 parts by mass with respect to 1 part by mass of the matrix resin in order to ensure workability such as formation of a conductive path and coating in the insulating resistance material. preferable.
Ｂ４Ｃは黒色の粉体である（比重：約２．５ｇ／ｃｍ３）。粒径は、Ｂ４Ｃ充填剤単体で絶縁抵抗特性を発現させつつ、塗装などの作業性を確保するために、２．５μｍ～１２．０μｍであることが好ましい。この範囲のうちでも、絶縁抵抗特性が良好となる、３．０μｍ～１０．０μｍの粒径がさらに好ましい。なお、粒径は、ＳＥＭ（走査型電子顕微鏡）による樹脂硬化物の観察などによって測定される。Ｂ４Ｃの含有量は、絶縁抵抗材料における導電パスの形成および塗装などの作業性を確保するために、マトリックス樹脂１質量部に対して０．１０～０．７０質量部含有されることが好ましい。 B 4 C will be described below.
B 4 C is a black powder (specific gravity: about 2.5 g / cm 3 ). The particle size is preferably 2.5 μm to 12.0 μm in order to ensure workability such as painting while exhibiting insulation resistance characteristics with the B4 C filler alone. Even within this range, a particle size of 3.0 μm to 10.0 μm, which has good insulation resistance characteristics, is more preferable. The particle size is measured by observing the cured resin product with an SEM (scanning electron microscope). The content of B 4 C may be 0.10 to 0.70 parts by mass with respect to 1 part by mass of the matrix resin in order to ensure workability such as formation of a conductive path and coating in the insulating resistance material. preferable.
第二の充填剤として、Ｆｅ３Ｏ４およびＢ４Ｃの両方を用いる場合には、体積抵抗率の詳細なる制御という相乗的効果を得ることができる。この場合、Ｆｅ３Ｏ４の含有量は、前記マトリックス樹脂１質量部に対して０．１０～０．７０質量部であり、前記Ｂ４Ｃの含有量は、前記マトリックス樹脂１質量部に対して０．１～１質量部であることが好ましい。特に、Ｆｅ３Ｏ４の含有量は、前記マトリックス樹脂１質量部に対して０．１０～０．６０質量部であり、前記Ｂ４Ｃの含有量は、前記マトリックス樹脂１質量部に対して０．１０～０．５０質量部であることが好ましい。
When both Fe 3 O 4 and B 4 C are used as the second filler, the synergistic effect of detailed control of volume resistivity can be obtained. In this case, the content of Fe 3 O 4 is 0.10 to 0.70 parts by mass with respect to 1 part by mass of the matrix resin, and the content of B 4 C is with respect to 1 part by mass of the matrix resin. It is preferably 0.1 to 1 part by mass. In particular, the content of Fe 3 O 4 is 0.10 to 0.60 parts by mass with respect to 1 part by mass of the matrix resin, and the content of B 4 C is with respect to 1 part by mass of the matrix resin. It is preferably 0.10 to 0.50 parts by mass.
〔絶縁性部材〕
本発明の実施形態による絶縁性部材は、上記の絶縁性樹脂組成物の硬化物からなること、を特徴とするものである。
下記は、絶縁性部材の好ましい一つの具体例である絶縁性スペーサについて詳述するものである。
絶縁性樹脂組成物の硬化は、第一の充填剤および第二の充填剤が分散したエポキシ樹脂を含むマトリックス樹脂を、エポキシ樹脂を硬化させる硬化剤と共に、絶縁スペーサ成形用の型内でエポキシ樹脂樹脂組成物の硬化条件に付すことによって行うことができる。 [Insulating member]
The insulating member according to the embodiment of the present invention is characterized by being made of a cured product of the above-mentioned insulating resin composition.
The following details an insulating spacer, which is a preferred specific example of the insulating member.
Curing of the insulating resin composition is performed by using a matrix resin containing an epoxy resin in which a first filler and a second filler are dispersed, together with a curing agent for curing the epoxy resin, and an epoxy resin in a mold for forming an insulating spacer. This can be done by subjecting the resin composition to curing conditions.
本発明の実施形態による絶縁性部材は、上記の絶縁性樹脂組成物の硬化物からなること、を特徴とするものである。
下記は、絶縁性部材の好ましい一つの具体例である絶縁性スペーサについて詳述するものである。
絶縁性樹脂組成物の硬化は、第一の充填剤および第二の充填剤が分散したエポキシ樹脂を含むマトリックス樹脂を、エポキシ樹脂を硬化させる硬化剤と共に、絶縁スペーサ成形用の型内でエポキシ樹脂樹脂組成物の硬化条件に付すことによって行うことができる。 [Insulating member]
The insulating member according to the embodiment of the present invention is characterized by being made of a cured product of the above-mentioned insulating resin composition.
The following details an insulating spacer, which is a preferred specific example of the insulating member.
Curing of the insulating resin composition is performed by using a matrix resin containing an epoxy resin in which a first filler and a second filler are dispersed, together with a curing agent for curing the epoxy resin, and an epoxy resin in a mold for forming an insulating spacer. This can be done by subjecting the resin composition to curing conditions.
この絶縁性樹脂組成物の硬化は、目的とする絶縁スペーサが得られるように、絶縁性樹脂組成物を所定温度に加熱し、所定時間保持することによって行うことができる。例えば、第一の充填剤および第二の充填剤等を含んでなるエポキシ樹脂と硬化剤を、例えば８０～１００℃の温度条件下で混合を行なって、絶縁性樹脂組成物を調製し、この樹脂組成物を例えば８０～１００℃の温度にまで予熱してあった絶縁スペーサ成形用の金型内に注型し、この金型内で所定の温度および時間保持することによって、目的とする絶縁性部材を製造することができる。金型内における絶縁性樹脂組成物の硬化は、連続的に行うことができるし、また段階的に行うこともできる。好ましくは、例えば、金型内に絶縁性樹脂組成物を注型した後、好ましく９０～１２０℃の温度で、好ましくは１２０～２４０分間（２～４時間）保持することからなる第一段目の加熱を行った後、引き続き、好ましくは１４０～１７０℃の温度で、好ましくは７８０～１０８０分間（１３～１８時間）保持することからなる第二段目の加熱を行なって、絶縁性樹脂組成物の硬化物を製造することができる。
Curing of this insulating resin composition can be performed by heating the insulating resin composition to a predetermined temperature and holding it for a predetermined time so that the desired insulating spacer can be obtained. For example, an epoxy resin containing a first filler, a second filler, and the like and a curing agent are mixed, for example, under a temperature condition of 80 to 100 ° C. to prepare an insulating resin composition. The resin composition is cast into a mold for forming an insulating spacer that has been preheated to a temperature of, for example, 80 to 100 ° C., and the resin composition is maintained at a predetermined temperature and time in the mold to provide the desired insulation. It is possible to manufacture a sex member. Curing of the insulating resin composition in the mold can be performed continuously or stepwise. Preferably, for example, the first stage comprising casting the insulating resin composition into a mold and then holding the insulating resin composition at a temperature of preferably 90 to 120 ° C. for preferably 120 to 240 minutes (2 to 4 hours). After the heating of the above, the insulating resin composition is subsequently subjected to the second stage heating consisting of holding at a temperature of preferably 140 to 170 ° C., preferably for 780 to 1080 minutes (13 to 18 hours). It is possible to produce a cured product of an object.
なお、絶縁スペーサ成形用の型内部には、必要に応じて、例えば絶縁スペーサの機能や性能ないし設置性等を向上させるような部材を、絶縁性樹脂組成物の注型の前に予め配置しておき、絶縁性樹脂組成物の注型ならびに硬化の際に、これら部材と絶縁スペーサとの接合を行うことができる。そのような部材の典型例としては、絶縁スペーサと金属容器１３（詳細後記）と電界差を緩和する導電性のリング状部材を挙げることができる。また、金型から取り出された絶縁性樹脂の硬化物に対しては、必要に応じて、寸法や材質特性等の検査ないし評価を行い、必要に応じて、例えば切削や研磨、塗装、表面特性の向上処理等を行うことができる。従って、本発明の実施形態による絶縁スペーサは、絶縁性樹脂の硬化物のみからなるもののみに限定されず、上記のような部材を具備するものや、樹脂硬化物に対して適当な後処理等がなされた、絶縁性樹脂組成物の硬化物からなるものを包含する。
If necessary, a member for improving the function, performance, installability, etc. of the insulating spacer is arranged in advance inside the mold for forming the insulating spacer before the casting of the insulating resin composition. In addition, these members can be joined to the insulating spacer at the time of casting and curing of the insulating resin composition. Typical examples of such a member include an insulating spacer, a metal container 13 (details will be described later), and a conductive ring-shaped member that reduces an electric field difference. In addition, the cured product of the insulating resin taken out from the mold is inspected or evaluated for dimensions and material characteristics as necessary, and if necessary, for example, cutting, polishing, painting, and surface characteristics. Can be improved. Therefore, the insulating spacer according to the embodiment of the present invention is not limited to the one made of only the cured product of the insulating resin, the one provided with the above-mentioned members, the appropriate post-treatment for the cured resin product, and the like. Includes those made of a cured product of an insulating resin composition.
なお、型内に注入する前の、注型用の絶縁性樹脂組成物の調製は、「硬化剤を含まない予備混合物」（Ａ液）と、「硬化剤を含む予備混合物」（Ｂ液）とを、混合することによって行うことができる。好ましくは、例えば、「第一の充填剤および第二の充填剤が分散したエポキシ樹脂を含む予備混合物」（Ａ液）と、「硬化剤、第一の充填剤および第二の充填剤が分散した予備混合物」（Ｂ液）とを、混合することによって、注型用の絶縁性樹脂組成物の調製を行うことができる。
Before pouring into the mold, the insulating resin composition for casting was prepared by "premixture without curing agent" (liquid A) and "premixture containing curing agent" (liquid B). And can be done by mixing. Preferably, for example, "a premixture containing an epoxy resin in which a first filler and a second filler are dispersed" (Liquid A) and "a curing agent, a first filler and a second filler are dispersed". The insulating resin composition for casting can be prepared by mixing the "preliminary mixture" (Liquid B).
なお、「上記以外の成分（例えば、消泡剤、分散剤、沈降防止剤、その他）」を配合する場合には、これらの各成分は、上記の（Ａ液）、（Ｂ液）のどちらか片方に予め混合しておくことができ、あるいは、好ましくは、上記の（Ａ液）および（Ｂ液）の両方に予め混合しておくことができる。
When "components other than the above (for example, antifoaming agent, dispersant, anti-sedimentant, etc.)" are blended, each of these components should be either (Liquid A) or (Liquid B) described above. It can be premixed with one of them, or preferably with both (Liquid A) and (Liquid B) described above.
〔電気機器〕
本発明の実施形態による電気機器は、上記の絶縁性部材を具備してなること、を特徴とする。 [Electrical equipment]
The electric device according to the embodiment of the present invention is characterized by comprising the above-mentioned insulating member.
本発明の実施形態による電気機器は、上記の絶縁性部材を具備してなること、を特徴とする。 [Electrical equipment]
The electric device according to the embodiment of the present invention is characterized by comprising the above-mentioned insulating member.
図２は、本発明の実施形態による電気機器の好ましい一つの具体例として、本発明の実施形態による絶縁スペーサを具備してなる密閉型絶縁装置１０を示す断面図である。
図２に示される密閉型絶縁装置では、高電圧導体１１ａ、１１ｂが、例えばＳＦ６のような絶縁ガス１２が封入された金属容器１３の内部に、コーン状の絶縁スペーサ（本発明の実施形態による絶縁スペーサ）１４によって支持されている。この絶縁スペーサ１４は、金属容器１３のフランジ１５ａ、１５ｂの間に挟持されており、絶縁ガス１２を金属容器１３の内部に封入している。 FIG. 2 is a cross-sectional view showing a closedtype insulating device 10 provided with an insulating spacer according to the embodiment of the present invention, as a preferred specific example of the electric device according to the embodiment of the present invention.
In the closed-type insulating device shown in FIG. 2, the high- voltage conductors 11a and 11b have a cone-shaped insulating spacer (embodiment of the present invention) inside a metal container 13 in which an insulating gas 12 such as SF 6 is sealed. Insulated spacer) 14 is supported by. The insulating spacer 14 is sandwiched between the flanges 15a and 15b of the metal container 13, and the insulating gas 12 is enclosed inside the metal container 13.
図２に示される密閉型絶縁装置では、高電圧導体１１ａ、１１ｂが、例えばＳＦ６のような絶縁ガス１２が封入された金属容器１３の内部に、コーン状の絶縁スペーサ（本発明の実施形態による絶縁スペーサ）１４によって支持されている。この絶縁スペーサ１４は、金属容器１３のフランジ１５ａ、１５ｂの間に挟持されており、絶縁ガス１２を金属容器１３の内部に封入している。 FIG. 2 is a cross-sectional view showing a closed
In the closed-type insulating device shown in FIG. 2, the high-
＜実施例１＞
下記の（Ａ液）および（Ｂ液）を、それぞれ調製した。 <Example 1>
The following (Liquid A) and (Liquid B) were prepared, respectively.
下記の（Ａ液）および（Ｂ液）を、それぞれ調製した。 <Example 1>
The following (Liquid A) and (Liquid B) were prepared, respectively.
（Ａ液）
エポキシ樹脂（エポミックＲ１４０Ｐ：３５質量部＋セロキサイド２０２１Ｐ：１５質量部で、合わせて）５０質量部、第一の充填剤（溶融シリカ）（ＦＵＭＩＴＥＣ社製ＲＦ２５）１００質量部、第二の充填剤（Ｆｅ３Ｏ４）（キシダ化学株式会社製）１８質量部を、自転公転式ミキサーによって攪拌混合して、（Ａ液）を調製した。 (Liquid A)
Epoxy resin (Epomic R140P: 35 parts by mass + seroxide 2021P: 15 parts by mass, total) 50 parts by mass, first filler (molten silica) (RF25 manufactured by FUMITEC) 100 parts by mass, second filler ( 18 parts by mass of Fe 3 O 4 ) (manufactured by Kishida Chemical Co., Ltd.) was stirred and mixed with a rotating and revolving mixer to prepare (Liquid A).
エポキシ樹脂（エポミックＲ１４０Ｐ：３５質量部＋セロキサイド２０２１Ｐ：１５質量部で、合わせて）５０質量部、第一の充填剤（溶融シリカ）（ＦＵＭＩＴＥＣ社製ＲＦ２５）１００質量部、第二の充填剤（Ｆｅ３Ｏ４）（キシダ化学株式会社製）１８質量部を、自転公転式ミキサーによって攪拌混合して、（Ａ液）を調製した。 (Liquid A)
Epoxy resin (Epomic R140P: 35 parts by mass + seroxide 2021P: 15 parts by mass, total) 50 parts by mass, first filler (molten silica) (RF25 manufactured by FUMITEC) 100 parts by mass, second filler ( 18 parts by mass of Fe 3 O 4 ) (manufactured by Kishida Chemical Co., Ltd.) was stirred and mixed with a rotating and revolving mixer to prepare (Liquid A).
（Ｂ液）
硬化剤（リカシッドＭＨ－７００、新日本理化株式会社製商品名）３８質量部、第一の充填剤（溶融シリカ）（ＦＵＭＩＴＥＣ社製ＲＦ２５）６２質量部および第二の充填剤（Ｆｅ３Ｏ４）（キシダ化学株式会社製）１４質量部を、自転公転式ミキサーによって攪拌混合して、（Ｂ液）を調製した。 (Liquid B)
Hardener (Ricacid MH-700, trade name manufactured by Shin Nihon Rika Co., Ltd.) 38 parts by mass, first filler (molten silica) (RF25 manufactured by FUMITEC) 62 parts by mass, and second filler (Fe 3 O 4 ) ) (Manufactured by Kishida Chemical Co., Ltd.) 14 parts by mass was stirred and mixed with a rotating and revolving mixer to prepare (Liquid B).
硬化剤（リカシッドＭＨ－７００、新日本理化株式会社製商品名）３８質量部、第一の充填剤（溶融シリカ）（ＦＵＭＩＴＥＣ社製ＲＦ２５）６２質量部および第二の充填剤（Ｆｅ３Ｏ４）（キシダ化学株式会社製）１４質量部を、自転公転式ミキサーによって攪拌混合して、（Ｂ液）を調製した。 (Liquid B)
Hardener (Ricacid MH-700, trade name manufactured by Shin Nihon Rika Co., Ltd.) 38 parts by mass, first filler (molten silica) (RF25 manufactured by FUMITEC) 62 parts by mass, and second filler (Fe 3 O 4 ) ) (Manufactured by Kishida Chemical Co., Ltd.) 14 parts by mass was stirred and mixed with a rotating and revolving mixer to prepare (Liquid B).
上記の（Ａ液）と（Ｂ液）とを配合し、自転公転式ミキサーによって撹拌した後、真空チャンバー等を用いて脱気・脱泡して、本発明の実施形態による絶縁性樹脂組成物を製造した。
この絶縁性樹脂組成物を、型内に注型し、一次硬化条件として、温度１００℃で、１８０分保持し、次いで二次硬化条件として、温度１５０℃で、９００分保持することからなる硬化条件に付して、電気特性評価用の試料１を得た。 The above-mentioned (solution A) and (solution B) are mixed, stirred by a rotating and revolving mixer, and then degassed and defoamed using a vacuum chamber or the like to form an insulating resin composition according to an embodiment of the present invention. Manufactured.
This insulating resin composition is cast into a mold and held at a temperature of 100 ° C. for 180 minutes as a primary curing condition, and then held at a temperature of 150 ° C. for 900 minutes as a secondary curing condition. Under the conditions, asample 1 for evaluation of electrical characteristics was obtained.
この絶縁性樹脂組成物を、型内に注型し、一次硬化条件として、温度１００℃で、１８０分保持し、次いで二次硬化条件として、温度１５０℃で、９００分保持することからなる硬化条件に付して、電気特性評価用の試料１を得た。 The above-mentioned (solution A) and (solution B) are mixed, stirred by a rotating and revolving mixer, and then degassed and defoamed using a vacuum chamber or the like to form an insulating resin composition according to an embodiment of the present invention. Manufactured.
This insulating resin composition is cast into a mold and held at a temperature of 100 ° C. for 180 minutes as a primary curing condition, and then held at a temperature of 150 ° C. for 900 minutes as a secondary curing condition. Under the conditions, a
ここで、実器向けの絶縁スペーサを製造する際には、上記の手法を参照しつつ、撹拌方法に真空撹拌機、同心二軸ミキサー、三本ロールミキサーといった多量の樹脂向けの撹拌方法を用いて撹拌のうえ、適切な金型に注型することができる。
Here, when manufacturing an insulating spacer for an actual device, a stirring method for a large amount of resin such as a vacuum stirrer, a concentric twin-screw mixer, and a three-roll mixer is used as a stirring method while referring to the above method. After stirring, it can be cast into an appropriate mold.
電気特性の評価
電気特性の評価は、下記のようにして行った。
電気特性の評価するために、平板の試験片を用いて、電気特性を測定した。電気特性としては、体積抵抗率の測定を行った。詳細は下記の通りである。 Evaluation of electrical characteristics The evaluation of electrical characteristics was performed as follows.
In order to evaluate the electrical characteristics, the electrical characteristics were measured using a flat plate test piece. As for the electrical characteristics, the volume resistivity was measured. The details are as follows.
電気特性の評価は、下記のようにして行った。
電気特性の評価するために、平板の試験片を用いて、電気特性を測定した。電気特性としては、体積抵抗率の測定を行った。詳細は下記の通りである。 Evaluation of electrical characteristics The evaluation of electrical characteristics was performed as follows.
In order to evaluate the electrical characteristics, the electrical characteristics were measured using a flat plate test piece. As for the electrical characteristics, the volume resistivity was measured. The details are as follows.
試験規格は、ＡＳＴＭ ０２５７ Ｂ法に準拠した。測定装置は、超高抵抗絶縁計Ｒ８３４０Ａ（エーディーシー製）を使用し、測定試料の測定時の温度を一定に保つチャンバーにはＴＲ４３Ｃ（アドバンテスト製）を用いた。試料片寸法は、約５５ｍｍ×５５ｍｍ×３ｍｍｔである。電極の形状は、主電極φ２５．４ｍｍの環状電極、裏面は外径φ５０ｍｍの対電極とした。電極の材質は、導電性ペースト（銀ペーストを用いた）。印加電圧は５００Ｖの１分値を採用した。試料の前処理としては、室温で９０ｈ（湿度：６０％）にて一定とした。試験温度は室温（２０℃）および８０℃とした。なお、導電性ペーストによる電極作製前に、試料を溶剤（エタノール）拭き、きれいな面とした上で、より平滑な面側に主電極を形成した。
The test standard complied with ASTM 0257 B method. As the measuring device, an ultra-high resistance insulation meter R8340A (manufactured by ADC) was used, and TR43C (manufactured by Advantest) was used for the chamber that keeps the temperature of the measured sample constant at the time of measurement. The sample piece size is about 55 mm × 55 mm × 3 mmt. The shape of the electrode was an annular electrode with a main electrode of φ25.4 mm, and the back surface was a counter electrode with an outer diameter of φ50 mm. The material of the electrode is conductive paste (silver paste was used). As the applied voltage, a 1-minute value of 500 V was adopted. As the pretreatment of the sample, it was kept constant at room temperature for 90 hours (humidity: 60%). The test temperatures were room temperature (20 ° C.) and 80 ° C. Before preparing the electrode with the conductive paste, the sample was wiped with a solvent (ethanol) to make a clean surface, and then the main electrode was formed on the smoother surface side.
試験方法は、下記の通りである。
試料表面に導電性ペーストを用いて主電極、環状電極および対電極を作製し、測定機器と配線後、規定電圧で６０秒間充電して体積抵抗を測定する。得られた体積抵抗値から、下記の式（１）を用いて体積抵抗率を算出する。試料厚さはミツトヨ製マイクロメータにより電極作製前に測定した。その際、被測定試料内５ヶ所の厚さの相加平均値を試料厚さとした。なお、試料厚さは温度により変化することが考えられるが、その詳細は不明なため、すべて室温での測定値を用いて計算した。
The test method is as follows.
A main electrode, an annular electrode and a counter electrode are prepared on the surface of the sample using a conductive paste, and after wiring with the measuring device, the sample is charged at a specified voltage for 60 seconds to measure the volume resistance. From the obtained volume resistance value, the volume resistivity is calculated using the following formula (1). The sample thickness was measured with a Mitutoyo micrometer before making the electrode. At that time, the arithmetic mean value of the thicknesses at five points in the sample to be measured was taken as the sample thickness. The sample thickness may change depending on the temperature, but the details are unknown, so all calculations were made using the measured values at room temperature.
試料表面に導電性ペーストを用いて主電極、環状電極および対電極を作製し、測定機器と配線後、規定電圧で６０秒間充電して体積抵抗を測定する。得られた体積抵抗値から、下記の式（１）を用いて体積抵抗率を算出する。試料厚さはミツトヨ製マイクロメータにより電極作製前に測定した。その際、被測定試料内５ヶ所の厚さの相加平均値を試料厚さとした。なお、試料厚さは温度により変化することが考えられるが、その詳細は不明なため、すべて室温での測定値を用いて計算した。
A main electrode, an annular electrode and a counter electrode are prepared on the surface of the sample using a conductive paste, and after wiring with the measuring device, the sample is charged at a specified voltage for 60 seconds to measure the volume resistance. From the obtained volume resistance value, the volume resistivity is calculated using the following formula (1). The sample thickness was measured with a Mitutoyo micrometer before making the electrode. At that time, the arithmetic mean value of the thicknesses at five points in the sample to be measured was taken as the sample thickness. The sample thickness may change depending on the temperature, but the details are unknown, so all calculations were made using the measured values at room temperature.
ここで、ρｖは、体積抵抗率[Ω・ｃｍ]を、
ｄは、主電極の直径[＝２．５４ｃｍ]を、
ｔは、試験片の厚さ[ｃｍ]を、
Ｒｖは、体積抵抗[Ω]を、
πは、円周率[３．１４]を、示す。
評価結果は、表１に示される通りである。
表１より、試料３、試料５、および試料７で、抵抗率の低減と、抵抗率の温度依存性の低減が確認された。
次いで、電気特性として、体積抵抗率（２４時間）の測定を行った。詳細は下記の通りである。
試験片は、前記のエポキシ樹脂硬化物（約４０～５０ｍｍ×３ｍｍｔ）を使用した。φ３０ｍｍの主電極、φ３２ｍｍのガード電極を、アルミニウム真球蒸着により形成した。微小電流計Ｋｅｉｔｈｌｅｒ ６５１７Ａを用いて漏れ電流を測定し、体積抵抗率（誘電率）を評価した。印加電圧：ＤＣ３０Ｖ（印加電界：０．１ｋＶ／ｍｍ）を、２４時間印加した。大気圧空気雰囲気下、恒温恒湿漕内で測定を行った。
試験結果は、表１に示される通りである。 Here, ρv is the volume resistivity [Ω · cm],
d is the diameter of the main electrode [= 2.54 cm].
t is the thickness [cm] of the test piece,
Rv is the volume resistance [Ω],
π indicates the pi [3.14].
The evaluation results are as shown in Table 1.
From Table 1, it was confirmed that the resistivity was reduced and the temperature dependence of the resistivity was reduced inSample 3, Sample 5, and Sample 7.
Next, the volume resistivity (24 hours) was measured as an electrical characteristic. The details are as follows.
As the test piece, the cured epoxy resin (about 40 to 50 mm × 3 mmt) was used. A main electrode having a diameter of 30 mm and a guard electrode having a diameter of 32 mm were formed by thin-film aluminum sphere deposition. The leakage current was measured using a micro ammeter Keithler 6517A, and the volume resistivity (dielectric constant) was evaluated. Applied voltage: DC30V (applied electric field: 0.1 kV / mm) was applied for 24 hours. The measurement was performed in a constant temperature and humidity chamber under an atmospheric pressure air atmosphere.
The test results are as shown in Table 1.
ｄは、主電極の直径[＝２．５４ｃｍ]を、
ｔは、試験片の厚さ[ｃｍ]を、
Ｒｖは、体積抵抗[Ω]を、
πは、円周率[３．１４]を、示す。
評価結果は、表１に示される通りである。
表１より、試料３、試料５、および試料７で、抵抗率の低減と、抵抗率の温度依存性の低減が確認された。
次いで、電気特性として、体積抵抗率（２４時間）の測定を行った。詳細は下記の通りである。
試験片は、前記のエポキシ樹脂硬化物（約４０～５０ｍｍ×３ｍｍｔ）を使用した。φ３０ｍｍの主電極、φ３２ｍｍのガード電極を、アルミニウム真球蒸着により形成した。微小電流計Ｋｅｉｔｈｌｅｒ ６５１７Ａを用いて漏れ電流を測定し、体積抵抗率（誘電率）を評価した。印加電圧：ＤＣ３０Ｖ（印加電界：０．１ｋＶ／ｍｍ）を、２４時間印加した。大気圧空気雰囲気下、恒温恒湿漕内で測定を行った。
試験結果は、表１に示される通りである。 Here, ρv is the volume resistivity [Ω · cm],
d is the diameter of the main electrode [= 2.54 cm].
t is the thickness [cm] of the test piece,
Rv is the volume resistance [Ω],
π indicates the pi [3.14].
The evaluation results are as shown in Table 1.
From Table 1, it was confirmed that the resistivity was reduced and the temperature dependence of the resistivity was reduced in
Next, the volume resistivity (24 hours) was measured as an electrical characteristic. The details are as follows.
As the test piece, the cured epoxy resin (about 40 to 50 mm × 3 mmt) was used. A main electrode having a diameter of 30 mm and a guard electrode having a diameter of 32 mm were formed by thin-film aluminum sphere deposition. The leakage current was measured using a micro ammeter Keithler 6517A, and the volume resistivity (dielectric constant) was evaluated. Applied voltage: DC30V (applied electric field: 0.1 kV / mm) was applied for 24 hours. The measurement was performed in a constant temperature and humidity chamber under an atmospheric pressure air atmosphere.
The test results are as shown in Table 1.
＜実施例２＞
実施例１における、第一の充填剤および第二の充填剤の種類および量を、表１に示されるように変更した以外は実施例１を同様にして、試料２～１６を得た。
なお、試料２～１３において用いられた溶融シリカは、前記ＦＵＭＩＴＥＣ社製ＲＦ２５のものであり、試料１５、１６において用いられたアルミナは、前記太平洋ランダム社製ＬＡ１２００のものであり、試料２～４、１０～１２、１５においてで用いられたＦｅ３Ｏ４は、キシダ化学株式会社のものであり、試料５～１２、１６において用いられたＢ４Ｃは、ケー・イー・アイ株式会社のものである。
各試料について、実施例１と同様に電気特性を評価した。評価結果は、表１に示される通りである。
<Example 2>
Samples 2 to 16 were obtained in the same manner as in Example 1 except that the types and amounts of the first filler and the second filler in Example 1 were changed as shown in Table 1.
The molten silica used in Samples 2 to 13 is from RF25 manufactured by FUMITEC, and the alumina used in Samples 15 and 16 is from LA1200 manufactured by Pacific Random Co., Ltd., and Samples 2 to 4 are used. Fe 3 O 4 used in 10 to 12 and 15 is from Kishida Chemical Co., Ltd., and B 4 C used in samples 5 to 12 and 16 is from KEI Co., Ltd. Is.
The electrical characteristics of each sample were evaluated in the same manner as in Example 1. The evaluation results are as shown in Table 1.
実施例１における、第一の充填剤および第二の充填剤の種類および量を、表１に示されるように変更した以外は実施例１を同様にして、試料２～１６を得た。
なお、試料２～１３において用いられた溶融シリカは、前記ＦＵＭＩＴＥＣ社製ＲＦ２５のものであり、試料１５、１６において用いられたアルミナは、前記太平洋ランダム社製ＬＡ１２００のものであり、試料２～４、１０～１２、１５においてで用いられたＦｅ３Ｏ４は、キシダ化学株式会社のものであり、試料５～１２、１６において用いられたＢ４Ｃは、ケー・イー・アイ株式会社のものである。
各試料について、実施例１と同様に電気特性を評価した。評価結果は、表１に示される通りである。
Samples 2 to 16 were obtained in the same manner as in Example 1 except that the types and amounts of the first filler and the second filler in Example 1 were changed as shown in Table 1.
The molten silica used in Samples 2 to 13 is from RF25 manufactured by FUMITEC, and the alumina used in Samples 15 and 16 is from LA1200 manufactured by Pacific Random Co., Ltd., and Samples 2 to 4 are used. Fe 3 O 4 used in 10 to 12 and 15 is from Kishida Chemical Co., Ltd., and B 4 C used in samples 5 to 12 and 16 is from KEI Co., Ltd. Is.
The electrical characteristics of each sample were evaluated in the same manner as in Example 1. The evaluation results are as shown in Table 1.
特に、表１において評価「〇」と示した試料（すなわち、試料１、試料２、試料６～試料８、試料１０～試料１２、試料１５、試料１６）において、本発明の目的である、注型樹脂の電気抵抗（体積抵抗率）をわずかに低減し、かつ電気抵抗（体積抵抗率）の温度依存性を抑制可能な絶縁性樹脂組成物を提供できる。
なお、表１における含有量（質量部）は、樹脂１に対しての配合量として示した。 In particular, in the samples shown as “○” in Table 1 (that is,sample 1, sample 2, sample 6 to sample 8, sample 10 to sample 12, sample 15, sample 16), which is the object of the present invention, Note. It is possible to provide an insulating resin composition capable of slightly reducing the electric resistance (volume resistance) of the mold resin and suppressing the temperature dependence of the electric resistance (volume resistance).
The content (parts by mass) in Table 1 is shown as the blending amount with respect to theresin 1.
なお、表１における含有量（質量部）は、樹脂１に対しての配合量として示した。 In particular, in the samples shown as “○” in Table 1 (that is,
The content (parts by mass) in Table 1 is shown as the blending amount with respect to the
以上説明した実施形態によれば、注型樹脂として優れた電気特性を得ることが可能となる。
なお、本発明では、いくつかの実施形態を説明したが、これらの実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これら新規な実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。 According to the embodiment described above, it is possible to obtain excellent electrical characteristics as a casting resin.
Although some embodiments have been described in the present invention, these embodiments are presented as examples and are not intended to limit the scope of the invention. These novel embodiments can be implemented in various other embodiments, and various omissions, replacements, and changes can be made without departing from the gist of the invention.
なお、本発明では、いくつかの実施形態を説明したが、これらの実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これら新規な実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。 According to the embodiment described above, it is possible to obtain excellent electrical characteristics as a casting resin.
Although some embodiments have been described in the present invention, these embodiments are presented as examples and are not intended to limit the scope of the invention. These novel embodiments can be implemented in various other embodiments, and various omissions, replacements, and changes can be made without departing from the gist of the invention.
１：第一の充填剤、２ａ、２ｂ：第二の充填剤、３：マトリックス樹脂、４：絶縁性樹脂、１０：密閉型絶縁装置、１１ａ、１１ｂ：高電圧導体、１２：絶縁ガス、１３：金属容器、１４：絶縁スペーサ、１５ａ、１５ｂ：フランジ
1: First filler, 2a, 2b: Second filler, 3: Matrix resin, 4: Insulation resin, 10: Sealed insulation device, 11a, 11b: High voltage conductor, 12: Insulation gas, 13 : Metal container, 14: Insulation spacer, 15a, 15b: Flange
Claims (11)
- エポキシ樹脂、および前記エポキシ樹脂を硬化させる硬化剤を含むマトリックス樹脂と、
シリカおよびアルミナからなる群から選ばれた第一の充填剤と、
Ｆｅ３Ｏ４およびＢ４Ｃからなる群から選ばれた第二の充填剤と、を含有してなることを特徴とする、絶縁性樹脂組成物。 An epoxy resin and a matrix resin containing a curing agent that cures the epoxy resin,
A first filler selected from the group consisting of silica and alumina,
An insulating resin composition comprising a second filler selected from the group consisting of Fe 3 O 4 and B 4 C. - 前記第一の充填剤の含有量は、前記マトリックス樹脂１質量部に対して０．１～２質量部である、請求項１に記載の絶縁性樹脂組成物。 The insulating resin composition according to claim 1, wherein the content of the first filler is 0.1 to 2 parts by mass with respect to 1 part by mass of the matrix resin.
- 前記第二の充填剤はＦｅ３Ｏ４であって、その含有量は、前記マトリックス樹脂１質量部に対して０．１０～０．７０質量部である、請求項１または２に記載の絶縁性樹脂組成物。 The insulation according to claim 1 or 2, wherein the second filler is Fe 3 O 4 , and the content thereof is 0.10 to 0.70 parts by mass with respect to 1 part by mass of the matrix resin. Sex resin composition.
- 前記第二の充填剤はＢ４Ｃであって、その含有量は、前記マトリックス樹脂１質量部に対して０．１０～０．７０質量部である、請求項１または２に記載の絶縁性樹脂組成物。 The insulating property according to claim 1 or 2, wherein the second filler is B 4 C, and the content thereof is 0.10 to 0.70 parts by mass with respect to 1 part by mass of the matrix resin. Resin composition.
- 前記第二の充填剤としてＦｅ３Ｏ４およびＢ４Ｃの両方を含み、前記Ｆｅ３Ｏ４の含有量は、前記マトリックス樹脂１質量部に対して０．１０～０．７０質量部であり、前記Ｂ４Ｃの含有量は、前記マトリックス樹脂１質量部に対して０．１０～０．７０質量部である、請求項１に記載の絶縁性樹脂組成物。 Both Fe 3 O 4 and B 4 C are contained as the second filler, and the content of the Fe 3 O 4 is 0.10 to 0.70 parts by mass with respect to 1 part by mass of the matrix resin. The insulating resin composition according to claim 1, wherein the content of B 4 C is 0.10 to 0.70 parts by mass with respect to 1 part by mass of the matrix resin.
- 前記マトリックス樹脂は、アクリル樹脂を含むものである、請求項１～５のいずれか１項に記載の絶縁性樹脂組成物。 The insulating resin composition according to any one of claims 1 to 5, wherein the matrix resin contains an acrylic resin.
- 前記マトリックス樹脂は、消泡剤を含むものである、請求項１～６のいずれか１項に記載の絶縁性樹脂組成物。 The insulating resin composition according to any one of claims 1 to 6, wherein the matrix resin contains a defoaming agent.
- 前記マトリックス樹脂は、分散剤を含むものである、請求項１～７のいずれか１項に記載の絶縁性樹脂組成物。 The insulating resin composition according to any one of claims 1 to 7, wherein the matrix resin contains a dispersant.
- 前記マトリックス樹脂は、沈降防止剤を含むものである、請求項１～８のいずれか１項に記載の絶縁性樹脂組成物。 The insulating resin composition according to any one of claims 1 to 8, wherein the matrix resin contains a settling inhibitor.
- 請求項１～９のいずれか１項に記載の絶縁性樹脂組成物の硬化物からなることを特徴とする、絶縁性部材。 An insulating member comprising a cured product of the insulating resin composition according to any one of claims 1 to 9.
- 請求項１０に記載の絶縁性部材を具備してなることを特徴とする、電気機器。 An electrical device comprising the insulating member according to claim 10.
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| CN109627555A (en) * | 2018-12-25 | 2019-04-16 | 安徽辰源电气有限公司 | A kind of potent high temperature-resistant cable sheath and preparation method thereof |
| CN111944467A (en) * | 2019-05-16 | 2020-11-17 | 三河市镭目机电科技有限公司 | Nuclear-grade epoxy pouring sealant, preparation method and application |
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- 2020-12-07 JP JP2020202963A patent/JP2022090522A/en active Pending
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- 2021-10-21 WO PCT/JP2021/038994 patent/WO2022123924A1/en active Application Filing
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| JP2017128621A (en) * | 2016-01-18 | 2017-07-27 | 株式会社日立産機システム | Mold resin material for high voltage equipment and method for manufacturing high voltage equipment |
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| CN111944467A (en) * | 2019-05-16 | 2020-11-17 | 三河市镭目机电科技有限公司 | Nuclear-grade epoxy pouring sealant, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115214138A (en) * | 2022-07-20 | 2022-10-21 | 西安理工大学 | Preparation method of gradient insulator made of nano zinc oxide modified epoxy resin material |
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| JP2022090522A (en) | 2022-06-17 |
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