JP4266676B2 - Electrical insulation oil - Google Patents
Electrical insulation oil Download PDFInfo
- Publication number
- JP4266676B2 JP4266676B2 JP2003062926A JP2003062926A JP4266676B2 JP 4266676 B2 JP4266676 B2 JP 4266676B2 JP 2003062926 A JP2003062926 A JP 2003062926A JP 2003062926 A JP2003062926 A JP 2003062926A JP 4266676 B2 JP4266676 B2 JP 4266676B2
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- Prior art keywords
- acid
- electrical insulating
- insulating oil
- mass
- oil
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- 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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- 238000010292 electrical insulation Methods 0.000 title 1
- 239000010735 electrical insulating oil Substances 0.000 claims description 27
- 238000002485 combustion reaction Methods 0.000 claims description 12
- -1 amine compound Chemical class 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 10
- 239000000194 fatty acid Substances 0.000 claims description 10
- 229930195729 fatty acid Natural products 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 150000004665 fatty acids Chemical class 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 239000002216 antistatic agent Substances 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- OILUAKBAMVLXGF-UHFFFAOYSA-N 3,5,5-trimethyl-hexanoic acid Chemical compound OC(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-N 0.000 claims description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 7
- 239000002199 base oil Substances 0.000 claims description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 6
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001718 carbodiimides Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 description 20
- 239000002253 acid Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000654 additive Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 3
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- WCQUXQDPAFJFHB-UHFFFAOYSA-N n,n'-bis(2-butylphenyl)methanediimine Chemical compound CCCCC1=CC=CC=C1N=C=NC1=CC=CC=C1CCCC WCQUXQDPAFJFHB-UHFFFAOYSA-N 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- KCSOBOZCMQBPFM-UHFFFAOYSA-N 4-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=C2C=CC=CC2=CC=1)C1=CC=C(C=CC=C2)C2=C1 KCSOBOZCMQBPFM-UHFFFAOYSA-N 0.000 description 1
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 1
- UUNBFTCKFYBASS-UHFFFAOYSA-N C(CCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCC Chemical compound C(CCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCC UUNBFTCKFYBASS-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 101000823778 Homo sapiens Y-box-binding protein 2 Proteins 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- ONWRHZSCWAZSHZ-UHFFFAOYSA-N n,n'-bis[2,3,4-tri(propan-2-yl)phenyl]methanediimine Chemical compound CC(C)C1=C(C(C)C)C(C(C)C)=CC=C1N=C=NC1=CC=C(C(C)C)C(C(C)C)=C1C(C)C ONWRHZSCWAZSHZ-UHFFFAOYSA-N 0.000 description 1
- GPZRJTOZLDJPBA-UHFFFAOYSA-N n,n'-bis[2,3-di(propan-2-yl)phenyl]methanediimine Chemical compound CC(C)C1=CC=CC(N=C=NC=2C(=C(C(C)C)C=CC=2)C(C)C)=C1C(C)C GPZRJTOZLDJPBA-UHFFFAOYSA-N 0.000 description 1
- CMESPBFFDMPSIY-UHFFFAOYSA-N n,n'-diphenylmethanediimine Chemical compound C1=CC=CC=C1N=C=NC1=CC=CC=C1 CMESPBFFDMPSIY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000005472 straight-chain saturated fatty acid group Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Insulating Materials (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、難燃性、電気特性及び生分解性に優れた電気絶縁油に関する。
【０００２】
【従来の技術】
近年、変圧器等が地下街に設置されることが多くなり、難燃性に優れた電気絶縁油が多く求められるようになってきている。この難燃性電気絶縁油としては、PCB（ポリ塩化ビフエニール）の製造が禁止されて以来、シリコーン油が広く用いられている。しかし、シリコーン油は、一般に粘度が高く、伝熱性に劣り、冷却特性が不十分なため、変圧器等をコンパクト化することが困難であり、また比誘電率が小さい等の問題があった。
【０００３】
これに代わるものとして、例えば、ジペンタエリスリトールと炭素数７〜１２の脂肪酸とからなるエステル単独か、またはこれと前記以外のネオペンチルポリオールと炭素数７〜１２の脂肪酸とからなるエステルとの混合物で、引火点が２５０℃以上、流動点が−３０℃以下の電気絶縁油が提案されている（特許文献１参照）。
【０００４】
しかし、この種のポリオールエステルからなる電気絶縁油は、難燃性（燃焼点）、電気特性（誘電正接）、流動点および生分解性のうちのいずれかに問題を有し、これらをすべて満足するものはほとんど見い出されていない。
【０００５】
【特許文献１】
特公平８−８０１２号公報
【０００６】
【発明が解決しようとする課題】
本発明は、上記の性状及び性能、すなわち、燃焼点が高く（２８０℃以上）、流動点が低く（−３５℃以下）、さらに電気特性及び生分解性に優れた、すなわち、これらの特性においてバランスがとれ、実用性能に優れた電気絶縁油を提供することを目的としている。
【０００７】
【課題を解決するための手段】
本発明は、トリメチロールプロパン及び／又はペンタエリスリトールと、炭素数７〜１８の直鎖脂肪酸、３,５,５‐トリメチルヘキサン酸及び２‐エチルヘキサン酸がモル比で６０：２３：１７〜８５：１０：５からなるエステルを基油全量基準で９０質量％以上含有し、４０℃ における動粘度が２０〜４０mm2/s、生分解性が６０％以上、燃焼点が２８０℃ 以上、流動点が−３５℃以下である電気絶縁油で、好ましくは、前記絶縁油に、酸化防止剤としてフェノール系及び／又はアミン系化合物を、または加水分解抑制剤としてカルボジイミド及び／又はエポキシ化合物のいずれか１種以上を、それぞれ電気絶縁油の全質量基準で０.０５〜１質量％、もしくは帯電防止剤としてトリアゾール化合物を、電気絶縁油の全質量基準で５〜１０００質量ppm添加したことからなる電気絶縁油にかかるものである。
【０００８】
【発明の実施の形態】
本発明の電気絶縁油は、トリメチロールプロパン及び／又はペンタエリスリトールと、炭素数７〜１８の直鎖脂肪酸及び３,５,５-トリメチルヘキサン酸、或いは、さらにこれらの酸に２-エチルヘキサン酸とを混合した混合酸とのエステルを基油の主成分とするものであるが、前記炭素数７〜１８の直鎖の飽和脂肪酸としては、ヘプタン酸、カプリル酸、ペラルゴン酸、カプリン酸、ウンデカン酸、ラウリン酸、トリデカン酸、ミスチリン酸、ペンタデカン酸、パルミチン酸、ヘプタデカン酸、ステアリン酸などを挙げることができる。炭素数が６以下であると生成するエステルの引火点が低くなり、１９以上であると流動点が高くなつて好ましくない。
【０００９】
上記エステルは、トリメチロールプロパン又はペンタエリスリトールのいずれか或いは両者の混合物と、炭素数７〜１８の直鎖脂肪酸の一種以上と３,５,５-トリメチルヘキサン酸の混合物、或いはさらに、これらの酸に２-エチルヘキサン酸を混合した物を無触媒、或いは硫酸、アルキルスルホン酸などの強酸触媒や塩化スズや塩化チタンなどの金属塩化物触媒の存在下、通常の方法でエステル化することにより製造できる。また、得られたエステルは、通常のエステルを精製する場合と同様に、脱酸、水洗、脱水、脱色、ろ過などの一連の処理により精製すると良い。
【００１０】
上記エステルの製造において、炭素数７〜１８の直鎖脂肪酸と３,５,５-トリメチルヘキサン酸との混合の場合は、当該酸の全モル基準で、前記直鎖脂肪酸を７７〜９０モル％、３,５,５-トリメチルヘキサン酸を１０〜２３モル％、また、これらの酸に２-エチルヘキサン酸を混合する場合は、酸の全モル基準で前記直鎖脂肪酸を６０〜８５モル％、３,５,５-トリメチルヘキサン酸を１０〜２３モル％、２-エチルヘキサン酸を５〜１７モル％混合することで、生分解性に優れた電気絶縁油を得ることができる。
【００１１】
本発明にかかる上記エステルは、トリメチロールプロパン又はペンタエリスリトールの水酸基の一部がエステル化せずに残っている部分エステルであっても良いが、当該ポリオールの全ての水酸基がエステル化されたものであることが好ましい。
【００１２】
上記エステルは基油の主成分として含まれておれば良いが、特には、動粘度、燃焼点、流動点、生分解性及び電気特性等の要求性能全てをより確実にバランスよく満たすという点から、上記エステルは基油全量基準で５０質量％以上含有させることが好ましく、８０質量％以上含有させることがより好ましく、９０質量％以上含有させることがさらに好ましく、エステル１００質量％が最も好ましい。
【００１３】
本発明の電気絶縁油の基油としては、上記エステルに加えて、鉱油、オレフィン重合体、アルキルベンゼン等の炭化水素系油や、ポリグリコール、ポリビニルエーテル、ケトン、ポリフェニルエーテル、シリコーン、ポリシロキサン、パーフルオロエーテル、上記エステル以外のエステルやエーテル等の酸素含有合成油を用いても良い。
【００１４】
本発明の電気絶縁油は、４０℃における動粘度が２０〜４０mm2/sの範囲にあることが必要で、２０mm2/s未満では、燃焼点や引火点が低下し、また４０mm2/sを超えると、変圧器内での絶縁油の循環が不十分となり、冷却が不完全となって加熱の原因となる。
【００１５】
また、本発明の電気絶縁油は、自然環境に及ぼす影響を小さいものとするために、生分解性が６０％以上を有するものであることが必要である。なお、この生分解性は、ASTM D5864に規定された方法により測定されるものである。
【００１６】
さらに、本発明の電気絶縁油は、燃焼点が２８０℃以上ないと十分な難燃性を発揮することができず、特には、燃焼点が３００℃以上であることが好ましい。また流動点が−３５℃以下でないと、寒冷地等での使用に耐えることができない。
【００１７】
また、本発明の電気絶縁油は、良好な安定性を確保するため、全酸価が０.１mgKOH/g以下であることが好ましく、優れた電気特性を確保するためには、JIS C2101による誘電正接（８０℃）が５％以下、JIS C2101による絶縁破壊電圧が３０KV以上であるものが好ましい。
【００１８】
本発明の電気絶縁油には、上記エステルを主成分とする基油に、酸化防止剤、金属不活性剤、加水分解抑制剤及び帯電防止剤のうち一種以上を各１質量パ−セント以下添加することが好ましく、前記酸化防止剤であるフェノ−ル系やアミン系化合物としては、ジ-tert-ブチル-p-クレゾール、４,４’-メチレン-ビス-（２,６-ジ-tert-ブチルフェノール）、ビスフェノールＡ、フェニル-α-ナフチルアミン、Ｎ,Ｎ-ジ（２-ナフチル）-p-フェニレンジアミン、ジオクチルジフェニルアミン等を例示することができる。
【００１９】
帯電防止剤であるトリアゾ−ル化合物としては、ベンゾトリアゾール、ベンゾトリアゾール誘導剤、チアジアゾール等を挙げることができ、さらに、加水分解抑制剤であるカルボジイミドとしては、ジフェニルカルボジイミドや、ジトリルカルボジイミド、ビス（イソプロピルフェニル）カルボジイミド、ビス（ジイソプロピルフェニル）カルボジイミド、ビス（トリイソプロピルフェニル）カルボジイミド、ビス（ブチルフェニル）カルボジイミド等のビス（アルキルフェニル）カルボジイミド等を、またエポキシ化合物としては、フェニルグリシジルエーテル、フェニルグリシジルエステル、炭素数５〜１８のアルキルグリシジルエーテル、同アルキルグリシジルエステル等を挙げることができる。
【００２０】
これらの酸化防止剤、加水分解抑制剤及び帯電防止剤は、個々の要求性能に応じ、一種以上を添加すれば良い。添加量は、電気絶縁油の全質量基準で、各添加剤で、１質量％以下とすべきである。１質量％を超えると、劣化時のスラッジ生成や着色が生じる。特には、酸化防止剤及び加水分解抑制剤については、０.０５〜１質量％、帯電防止剤については、５〜１０００ppm添加することが好ましい。
【００２１】
また、上記添加剤以外に、ジチオリン酸亜鉛等の摩耗防止剤、硫黄化合物等の極圧剤、粘度指数向上剤、流動点降下剤、清浄分散剤等の添加剤を単独で、または複数種類組み合わせて添加することもできる。これらの添加剤の添加量は特に制限されないが、電気絶縁油全量基準で、好ましくは１質量％以下である。
【００２２】
【実施例】
以下、実施例に基づいて、本発明をさらに詳細に説明する。なお、本発明は、以下の実施例によって何ら制限されるものではない。
【００２３】
アルコールとしてペンタエリスリトール（PE）及びトリメチロールプロパン（TMP）を用い、カルボン酸を表１に示したように組み合わせて（モル比）エステル調製して、供試油とした。
【００２４】
【表１】
上記供試油について、それぞれの物性を測定して、実用性能を評価した。物性測定及び性能評価試験は、次の方法で行った。これらの結果を表２に示した。
(1) 動粘度：JIS K 2283に規定された方法により、４０℃で測定した。
(2) 生分解性：ASTM D 5864に規定された方法で測定した。
(3) 流動点： JIS K 2269に規定された方法で測定した。
(4) 燃焼点：JIS K 2265に規定された方法で測定した。
(5) 全酸価：JIS K 2514に規定された方法で測定した。
(6) 絶縁破壊電圧： JIS C2101に規定された方法で測定した。
(7) 誘電正接：JIS C2101に規定された方法により、８０℃で測定した。
【００２６】
【表２】
上記実施例２の供試油に、酸化防止剤として、2,6-ジ-t-ブチル-p-クレゾール（DBPC）又はフェニル-α-ナフチルアミン（PNA）、帯電防止剤として、ベンゾトリアゾール（BTA）、加水分解抑制剤として、ビス（ブチルフェニル）カルボジイミド（BBPC）又はフェニルグリシジルエーテル（PGE）を全供試油質量基準で表３に示した量、それぞれ添加した。
【００２８】
これについて、酸化安定度試験（JIS C 2101に規定された方法により、１２０℃、７５時間で）を行った。この結果を、表３に示した。
【００２９】
【表３】
表２から、実施例１〜５の供試油は、動粘度、生分解性、低温流動性、燃焼性、熱安定性が良く、電気絶縁油の性能としてバランスがとれている。
これに対して、比較例１は動粘度及び燃焼点が低く、比較例２は流動点が高過ぎて、比較例３は動粘度及び流動点が高く、しかも生分解性が低く、比較例４は流動点が高く、しかも生分解性及び燃焼点が低く、比較例５は流動点が高く、比較例６は生分解性及び燃焼点が低く、しかも動粘度が高く、比較例７は生分解性及び燃焼点が低く、しかも流動点が高いなど、いずれも電気絶縁油として劣っている。
【００３１】
また、実施例６〜１１の酸化防止剤、帯電防止剤或いは加水分解抑制剤等を添加した物は、極めて良好な酸化安定性を有している。
【００３２】
【発明の効果】
本発明の電気絶縁油は、燃焼点が高く、流動点が低く、生分解性及び電気特性に優れた、すなわち、これらの特性においてバランスがとれ、実用性能に優れているという格別の効果を奏する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrical insulating oil excellent in flame retardancy, electrical characteristics, and biodegradability.
[0002]
[Prior art]
In recent years, transformers and the like are often installed in underground malls, and many electrical insulating oils having excellent flame retardancy have been demanded. As this flame-retardant electrical insulating oil, silicone oil has been widely used since the production of PCB (polychlorinated biphenyl) was prohibited. However, silicone oils generally have high viscosity, poor heat conductivity, and insufficient cooling characteristics, making it difficult to make transformers compact and having a low relative dielectric constant.
[0003]
As an alternative to this, for example, an ester consisting of dipentaerythritol and a fatty acid having 7 to 12 carbon atoms alone, or a mixture of this and an ester consisting of this other neopentyl polyol and a fatty acid having 7 to 12 carbon atoms An electrical insulating oil having a flash point of 250 ° C. or higher and a pour point of −30 ° C. or lower has been proposed (see Patent Document 1).
[0004]
However, electrical insulating oils composed of this kind of polyol ester have problems in any of flame retardancy (burning point), electrical properties (dielectric loss tangent), pour point and biodegradability, and all of these are satisfied. Little has been found to do.
[0005]
[Patent Document 1]
Japanese Patent Publication No. 8-8012 [0006]
[Problems to be solved by the invention]
The present invention has the above properties and performance, that is, the combustion point is high (280 ° C. or higher), the pour point is low (−35 ° C. or lower), and the electrical characteristics and biodegradability are excellent. The object is to provide an electrical insulating oil that is balanced and has excellent practical performance.
[0007]
[Means for Solving the Problems]
In the present invention, trimethylolpropane and / or pentaerythritol and a linear fatty acid having 7 to 18 carbon atoms, 3,5,5-trimethylhexanoic acid and 2-ethylhexanoic acid in a molar ratio of 60:23:17 to 85 : An ester consisting of 10: 5 is contained in an amount of 90% by mass or more based on the total amount of base oil, kinematic viscosity at 40 ° C. is 20 to 40 mm 2 / s, biodegradability is 60% or more, combustion point is 280 ° C. or more, pour point Is an electrical insulating oil having a temperature of −35 ° C. or lower, preferably any one of a phenolic and / or amine-based compound as an antioxidant and a carbodiimide and / or an epoxy compound as a hydrolysis inhibitor in the insulating oil. The seeds or more are each 0.05 to 1% by mass based on the total mass of the electrical insulating oil, or the triazole compound as an antistatic agent is 5 to 100 based on the total mass of the electrical insulating oil. In which according to the electric insulating oil consisting in the addition mass ppm.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The electrical insulating oil of the present invention comprises trimethylolpropane and / or pentaerythritol, a linear fatty acid having 7 to 18 carbon atoms and 3,5,5-trimethylhexanoic acid, or 2-ethylhexanoic acid in addition to these acids. The main component of the base oil is an ester with a mixed acid obtained by mixing the above and the straight chain saturated fatty acid having 7 to 18 carbon atoms such as heptanoic acid, caprylic acid, pelargonic acid, capric acid, undecane. Examples thereof include acid, lauric acid, tridecanoic acid, myristylic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid and stearic acid. If the number of carbon atoms is 6 or less, the flash point of the resulting ester will be low, and if it is 19 or more, the pour point will be high.
[0009]
The ester is a mixture of either trimethylolpropane or pentaerythritol or a mixture of both, one or more linear fatty acids having 7 to 18 carbon atoms and 3,5,5-trimethylhexanoic acid, or these acids. Produced by esterifying a mixture of 2-ethylhexanoic acid and non-catalyst or in the presence of a strong acid catalyst such as sulfuric acid or alkylsulfonic acid or a metal chloride catalyst such as tin chloride or titanium chloride. it can. Moreover, the obtained ester is good to refine | purify by a series of processes, such as deoxidation, water washing, dehydration, decoloring, and filtration similarly to the case where the normal ester is refine | purified.
[0010]
In the production of the ester, when the linear fatty acid having 7 to 18 carbon atoms and 3,5,5-trimethylhexanoic acid are mixed, the linear fatty acid is 77 to 90 mol% based on the total mole of the acid. 3,5,5-trimethylhexanoic acid is 10 to 23 mol%, and when 2-ethylhexanoic acid is mixed with these acids, the linear fatty acid is added in an amount of 60 to 85 mol% based on the total mol of the acid. By mixing 10 to 23 mol% of 3,5,5-trimethylhexanoic acid and 5 to 17 mol% of 2-ethylhexanoic acid, an electrical insulating oil having excellent biodegradability can be obtained.
[0011]
The ester according to the present invention may be a partial ester in which some of the hydroxyl groups of trimethylolpropane or pentaerythritol remain without being esterified, but all the hydroxyl groups of the polyol are esterified. Preferably there is.
[0012]
The ester may be contained as a main component of the base oil, but in particular, from the viewpoint of satisfying all required performances such as kinematic viscosity, combustion point, pour point, biodegradability and electrical properties more reliably and in a balanced manner. The above ester is preferably contained in an amount of 50% by mass or more based on the total amount of the base oil, more preferably 80% by mass or more, further preferably 90% by mass or more, and most preferably 100% by mass of the ester.
[0013]
As the base oil of the electrical insulating oil of the present invention, in addition to the above ester, hydrocarbon oils such as mineral oil, olefin polymer, alkylbenzene, polyglycol, polyvinyl ether, ketone, polyphenyl ether, silicone, polysiloxane, Oxygen-containing synthetic oils such as perfluoroether, esters other than the above esters, and ethers may be used.
[0014]
Electrical insulating oil of the present invention, it is necessary that the kinematic viscosity at 40 ° C. is in the range of 20 to 40 mm 2 / s, is less than 20 mm 2 / s, the combustion point and flash point drops, also 40 mm 2 / s Exceeding this causes insufficient circulation of the insulating oil in the transformer, resulting in incomplete cooling and heating.
[0015]
Further, the electrical insulating oil of the present invention needs to have a biodegradability of 60% or more in order to reduce the influence on the natural environment. This biodegradability is measured by the method specified in ASTM D5864.
[0016]
Furthermore, the electrical insulating oil of the present invention cannot exhibit sufficient flame retardancy unless the combustion point is 280 ° C. or higher, and in particular, the combustion point is preferably 300 ° C. or higher. If the pour point is not lower than −35 ° C., it cannot withstand use in cold regions.
[0017]
In addition, the electrical insulating oil of the present invention preferably has a total acid value of 0.1 mgKOH / g or less in order to ensure good stability. In order to ensure excellent electrical properties, the dielectric according to JIS C2101 It is preferable that the tangent (80 ° C.) is 5% or less and the dielectric breakdown voltage according to JIS C2101 is 30 KV or more.
[0018]
In the electrical insulating oil of the present invention, one or more of each of an antioxidant, a metal deactivator, a hydrolysis inhibitor and an antistatic agent is added to the base oil mainly composed of the above ester in an amount of 1 mass percent or less. Preferably, the antioxidant or phenolic compound as the antioxidant is di-tert-butyl-p-cresol, 4,4′-methylene-bis- (2,6-di-tert- Butylphenol), bisphenol A, phenyl-α-naphthylamine, N, N-di (2-naphthyl) -p-phenylenediamine, dioctyldiphenylamine and the like.
[0019]
Examples of the triazole compound that is an antistatic agent include benzotriazole, a benzotriazole derivative, and thiadiazole. Further, examples of the carbodiimide that is a hydrolysis inhibitor include diphenylcarbodiimide, ditolylcarbodiimide, and bis ( Bis (alkylphenyl) carbodiimides such as isopropylphenyl) carbodiimide, bis (diisopropylphenyl) carbodiimide, bis (triisopropylphenyl) carbodiimide, bis (butylphenyl) carbodiimide, etc., and epoxy compounds include phenylglycidyl ether, phenylglycidyl ester And alkyl glycidyl ether having 5 to 18 carbon atoms, alkyl glycidyl ester, and the like.
[0020]
One or more of these antioxidants, hydrolysis inhibitors and antistatic agents may be added depending on the individual required performance. The addition amount should be 1% by mass or less for each additive based on the total mass of the electrical insulating oil. If it exceeds 1% by mass, sludge generation and coloring at the time of deterioration occur. In particular, for the antioxidant and a hydrolysis inhibitor, from 0.05 to 1 wt%, the antistatic agent, it is preferable to add 5 to 1000 ppm.
[0021]
In addition to the above additives, additives such as anti-wear agents such as zinc dithiophosphate, extreme pressure agents such as sulfur compounds, viscosity index improvers, pour point depressants, and cleaning dispersants may be used alone or in combination. Can also be added. The addition amount of these additives is not particularly limited, but is preferably 1% by mass or less based on the total amount of the electrical insulating oil.
[0022]
【Example】
Hereinafter, the present invention will be described in more detail based on examples. In addition, this invention is not restrict | limited at all by the following examples.
[0023]
Pentaerythritol (PE) and trimethylolpropane (TMP) were used as alcohols, and esters were prepared by combining carboxylic acids as shown in Table 1 (molar ratio) to obtain test oils.
[0024]
[Table 1]
About the said test oil, each physical property was measured and the practical performance was evaluated. The physical property measurement and the performance evaluation test were performed by the following methods. These results are shown in Table 2.
(1) Kinematic viscosity: measured at 40 ° C. by the method specified in JIS K 2283.
(2) Biodegradability: Measured by the method specified in ASTM D 5864.
(3) Pour point: Measured by the method defined in JIS K 2269.
(4) Burning point: Measured by the method specified in JIS K 2265.
(5) Total acid value: measured by the method specified in JIS K 2514.
(6) Dielectric breakdown voltage: Measured by the method specified in JIS C2101.
(7) Dielectric loss tangent: Measured at 80 ° C. by the method defined in JIS C2101.
[0026]
[Table 2]
In the sample oil of Example 2, 2,6-di-t-butyl-p-cresol (DBPC) or phenyl-α-naphthylamine (PNA) as an antioxidant, and benzotriazole (BTA) as an antistatic agent ), Bis (butylphenyl) carbodiimide (BBPC) or phenylglycidyl ether (PGE) was added as hydrolysis inhibitors in the amounts shown in Table 3 on the basis of the total sample oil mass.
[0028]
About this, the oxidation stability test (120 degreeC and 75 hours by the method prescribed | regulated to JIS C2101) was done. The results are shown in Table 3.
[0029]
[Table 3]
From Table 2, the sample oils of Examples 1 to 5 have good kinematic viscosity, biodegradability, low-temperature fluidity, combustibility, and thermal stability, and are balanced as the performance of the electrical insulating oil.
In contrast, Comparative Example 1 has a low kinematic viscosity and combustion point, Comparative Example 2 has a too high pour point, Comparative Example 3 has a high kinematic viscosity and pour point, and low biodegradability. Comparative Example 4 Has a high pour point and low biodegradability and combustion point, Comparative Example 5 has a high pour point, Comparative Example 6 has a low biodegradability and combustion point, and has a high kinematic viscosity. Comparative Example 7 is biodegradable. Both are inferior as electrical insulating oils, such as having low properties and low combustion points and high pour points.
[0031]
Moreover, the thing which added the antioxidant of Examples 6-11, the antistatic agent, the hydrolysis inhibitor, etc. has very favorable oxidation stability.
[0032]
【The invention's effect】
The electrical insulating oil of the present invention has a high combustion point, a low pour point, and excellent biodegradability and electrical characteristics. In other words, the electrical insulating oil has a special effect that it is balanced in these characteristics and has excellent practical performance. .
Claims (2)
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| JP4502680B2 (en) * | 2004-03-26 | 2010-07-14 | 株式会社ジャパンエナジー | Electrical insulation oil |
| DE102004025939A1 (en) * | 2004-05-27 | 2005-12-22 | Cognis Deutschland Gmbh & Co. Kg | Polyol esters for transformers |
| WO2007029724A1 (en) | 2005-09-09 | 2007-03-15 | Lion Corporation | Base agent for electrical insulating oil |
| AU2006301929B2 (en) * | 2005-10-11 | 2012-02-23 | Biolectric Pty Ltd | Low viscosity vegetable oil-based dielectric fluids |
| CN101300644B (en) * | 2005-10-11 | 2013-03-06 | 百奥立克特赖斯股份有限公司 | Low viscosity vegetable oil-based dielectric fluids |
| JP5416879B2 (en) * | 2005-10-14 | 2014-02-12 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition |
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| JP5394104B2 (en) * | 2008-04-23 | 2014-01-22 | 花王株式会社 | Insulating oil composition |
| DE102009001130A1 (en) * | 2009-02-25 | 2010-08-26 | Rhein Chemie Rheinau Gmbh | A transformer oil composition comprising at least one acid scavenger |
| JP5493461B2 (en) | 2009-05-12 | 2014-05-14 | ソニー株式会社 | Solid-state imaging device, electronic apparatus, and manufacturing method of solid-state imaging device |
| DE102012103701A1 (en) * | 2012-04-26 | 2013-10-31 | Fuchs Petrolub Ag | Esters as cooling and insulating fluids for transformers |
| GB201402570D0 (en) | 2014-02-13 | 2014-04-02 | M & I Materials Ltd | Improvements in and relating to dielectric fluids |
| DK3307857T3 (en) * | 2015-06-12 | 2019-11-18 | Novamont Spa | LOW POINT TRIMETHYLOL PROPANESTERS |
| CN116478754B (en) * | 2022-01-13 | 2024-07-12 | 中国石油天然气股份有限公司 | Ester type transformer oil composition with high hydrolytic stability |
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