JPS6333520B2 - - Google Patents
Info
- Publication number
- JPS6333520B2 JPS6333520B2 JP55137791A JP13779180A JPS6333520B2 JP S6333520 B2 JPS6333520 B2 JP S6333520B2 JP 55137791 A JP55137791 A JP 55137791A JP 13779180 A JP13779180 A JP 13779180A JP S6333520 B2 JPS6333520 B2 JP S6333520B2
- Authority
- JP
- Japan
- Prior art keywords
- oil
- compound
- test
- ether
- aromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003921 oil Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 13
- 229920000570 polyether Polymers 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000010721 machine oil Substances 0.000 claims description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 claims description 4
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical group C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 claims description 4
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 claims description 3
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- NHJIDZUQMHKGRE-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-(7-oxabicyclo[4.1.0]heptan-4-yl)acetate Chemical compound C1CC2OC2CC1OC(=O)CC1CC2OC2CC1 NHJIDZUQMHKGRE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 150000004982 aromatic amines Chemical group 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- -1 polyoxyethylene Polymers 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000000654 additive Substances 0.000 description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000002199 base oil Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000003507 refrigerant Substances 0.000 description 3
- 238000005057 refrigeration Methods 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- YHCCCMIWRBJYHG-UHFFFAOYSA-N 3-(2-ethylhexoxymethyl)heptane Chemical compound CCCCC(CC)COCC(CC)CCCC YHCCCMIWRBJYHG-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- YHYKLKNNBYLTQY-UHFFFAOYSA-N 1,1-diphenylhydrazine Chemical compound C=1C=CC=CC=1N(N)C1=CC=CC=C1 YHYKLKNNBYLTQY-UHFFFAOYSA-N 0.000 description 1
- PHQXTYBYTIDEQT-UHFFFAOYSA-N 1-butoxybutane dodecanoic acid Chemical compound C(CCCCCCCCCCC)(=O)O.C(CCC)OCCCC PHQXTYBYTIDEQT-UHFFFAOYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 description 1
- HBXWUCXDUUJDRB-UHFFFAOYSA-N 1-octadecoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCCCC HBXWUCXDUUJDRB-UHFFFAOYSA-N 0.000 description 1
- HANWHVWXFQSQGJ-UHFFFAOYSA-N 1-tetradecoxytetradecane Chemical compound CCCCCCCCCCCCCCOCCCCCCCCCCCCCC HANWHVWXFQSQGJ-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- TZLVUWBGUNVFES-UHFFFAOYSA-N 2-ethyl-5-methylpyrazol-3-amine Chemical compound CCN1N=C(C)C=C1N TZLVUWBGUNVFES-UHFFFAOYSA-N 0.000 description 1
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- ASZFCDOTGITCJI-UHFFFAOYSA-N 6-oxabicyclo[3.1.0]hex-2-ene Chemical compound C1C=CC2OC12 ASZFCDOTGITCJI-UHFFFAOYSA-N 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- MELPJGOMEMRMPL-UHFFFAOYSA-N 9-oxabicyclo[6.1.0]nonane Chemical compound C1CCCCCC2OC21 MELPJGOMEMRMPL-UHFFFAOYSA-N 0.000 description 1
- ADAHGVUHKDNLEB-UHFFFAOYSA-N Bis(2,3-epoxycyclopentyl)ether Chemical compound C1CC2OC2C1OC1CCC2OC21 ADAHGVUHKDNLEB-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- MAYUYFCAPVDYBQ-UHFFFAOYSA-N butoxymethylbenzene Chemical compound CCCCOCC1=CC=CC=C1 MAYUYFCAPVDYBQ-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- FSWDLYNGJBGFJH-UHFFFAOYSA-N n,n'-di-2-butyl-1,4-phenylenediamine Chemical compound CCC(C)NC1=CC=C(NC(C)CC)C=C1 FSWDLYNGJBGFJH-UHFFFAOYSA-N 0.000 description 1
- PTRSTXBRQVXIEW-UHFFFAOYSA-N n,n-dioctylaniline Chemical compound CCCCCCCCN(CCCCCCCC)C1=CC=CC=C1 PTRSTXBRQVXIEW-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- OIJHFHYPXWSVPF-UHFFFAOYSA-N para-Nitrosodiphenylamine Chemical compound C1=CC(N=O)=CC=C1NC1=CC=CC=C1 OIJHFHYPXWSVPF-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
Landscapes
- Lubricants (AREA)
Description
本発明は冷凍機用潤滑油に関し、より詳しくは
冷凍機内でフロンと共存した場合の安定性に優れ
た高粘度ポリエーテル系合成油の冷凍機油組成物
に関する。
従来、家庭用冷蔵庫、空調機、業務用小型冷蔵
庫等の冷凍機には、高度に精製を加えたナフテン
系ないしパラフイン系の鉱物油が用いられて来
た。
しかし近年、冷凍機に対して小型化及び冷却効
率向上の要請が強まり、冷凍機油の使用条件が厳
しくなつて、従来の鉱物油では性能的に不満足な
点が多くなつてきた。すなわち冷凍機の圧縮機は
冷媒であるフロンに対する気密性が必要とされる
が、気密性を高めるために高粘度の鉱物油を用い
るとワツクス分が析出してフロンとの相容性が低
下し、潤滑特性が著しく悪くなり種々のトラブル
が生じる。
これらの点を改善するためにフロンと相溶性の
良い高粘度のポリエーテル系合成油が開発されて
いるが、冷凍機油のように苛酷な使用条件の下で
は、このポリエーテル系合成油でも添加剤を加え
ない単独品では性能的に不十分である。すなわ
ち、冷凍機の圧縮機内部は金属表面が露出してお
り、そこに冷凍機油とフロンとが共存しているの
で、高温で長時間の運転中に金属が触媒作用を起
こして化学反応を引きおこし、塩酸の生成、金属
の腐食およびスラツジの発生が起つて冷凍機の故
障の原因となる。
本発明者らは、このポリエーテル系合成油につ
いて冷凍機油としての上記の問題点を解決するた
めに鋭意検討を行なつた結果、ポリエーテル系合
成油にエポキシシクロアルキル基を有する化合物
を配合したものが、化学的安定性に優れているこ
とを見出し、本発明を完成した。
本発明は、ポリエーテル系合成油に、エポキシ
シクロアルキル基を有する化合物0.1〜4重量%
および必要により分子内に窒素原子を1〜2個有
するかあるいは窒素原子1個とイオウ原子1個と
を有する芳香族系酸化防止剤0.1〜4重量%を配
合してなる冷凍機油組成物に関するものである。
本発明において冷凍機油の基油となるポリエー
テル系合成油としては、1〜6価のアルコールに
アルキレンオキシドを所定量付加させた化合物ま
たは上記付加物の末端基を置換した化合物であ
り、動粘度10〜200cst(100℃)のものが使用でき
る。
上記のポリエーテル系合成油としては例えばポ
リオキシプロピレングリコール、ポリオキシエチ
レングリコール、ポリオキシ−1,2−ブチレン
グリコール、ポリオキシ−2,3−ブチレングリ
コール、ポリオキシエチレンポリオキシプロピレ
ングリコール、ポリオキシエチレンポリオキシテ
トラメチレングリコール;および上記ポリオキシ
アルキレングリコールのモノメチルエーテル、モ
ノエチルエーテル、モノブチルエーテル、モノオ
クチルエーテル、モノ−2−エチルヘキシルエー
テル、モノドデシルエーテル、モノテトラデシル
エーテル、モノオクタデシルエーテル、モノアリ
ルエーテル、モノベンジルエーテル、メチレング
リコールジエーテル、1,4−ブタンジオールジ
エーテル、グリセリントリエーテル、トリメチロ
ールプロパントリエーテル、ペンタエリスリトー
ルテトラエーテル、ソルビタンヘキサエーテル、
モノブチルモノベンジルエーテル、モノブチルモ
ノアリルエーテル、ジアリルエーテル、ビスフエ
ノール−A−ジエーテル、ジ−2−エチルヘキシ
ルエーテル等のエーテル類;上記ポリオキシアル
キレングリコールのモノブチルエーテルモノカプ
リル酸エステル、モノブチルエーテルモノラウリ
ン酸エステル等のエーテルエステル類などを挙げ
ることができる。
エポキシシクロアルキル基を有する化合物とし
ては例えば3,4−エポキシシクロヘキシルメチ
ル−3,4−エポキシシクロヘキサンカルボキシ
レート、ビニルシクロヘキセンジオキサイド、2
−(3,4−エポキシシクロヘキシル−5,5−
スピロ−3,4−エポキシ)シクロヘキサン−メ
タ−ジオキサン、ビス(3,4−エポキシシクロ
ヘキシルメチル)アジペート、シクロヘキセンオ
キサイド、シクロオクテンオキサイド、シクロペ
ンタジエンモノオキサイド、4−ビニルシクロヘ
キセン−1,2−オキサイド、ビス(メチルシク
ロヘキセニル)ジオキサイド、ジシクロペンタジ
エンジエポキサイド、ビス(2,3−エポキシシ
クロペンチル)エーテル、シユウ酸ビス(3,4
−エポキシシクロヘキシルメチル)エステル、
4,10−ジオキサテトラシクロ〔5,4,O,
O3,5,O9,11〕ウンデカンなどを挙げることができ
る。
分子内に窒素原子を1〜2個有する芳香族系酸
化防止剤としては、例えばフエニル−α−ナフチ
ルアミン、N−ニトロソジフエニルアミン、4−
アミノジフエニルアミン、N−イソプロピル−
N′−フエニル−p−フエニレンジアミン、N,
N′−ジフエニル−p−フエニレンジアミン、N,
N′−ジ−sec−ブチル−p−フエニレンジアミ
ン、N,N′−ジ−β−ナフチル−p−フエニレ
ンジアミン、ジフエニルアミン、ジオクチルフエ
ニルアミンなどが挙げられ、また分子内に窒素原
子及びイオウ原子を各1個含有する芳香族系酸化
防止剤としては、例えばフエノチアジンが挙げら
れる。これらのうちでも好ましいのは分子内に窒
素原子を1〜2個有する芳香族アミンであり、そ
の中でも特にフエニル−α−ナフチルアミンが良
好な効果を与える。
前記2種類の添加剤のポリエーテル系合成油へ
の配合量は、エポキシシクロアルキル基を有する
化合物0.1〜4重量%および必要により芳香族系
酸化防止剤0.1〜4重量%であるが、配合量がこ
れらより少ないと所定の効果が得られず、また多
量に配合してもそれほど効果は増大しない。
芳香族系酸化防止剤を配合すると冷凍機油組成
物が着色するので常に使用するとは限らないが、
これを併用すると金属腐食性(特に銅)を著しく
改善することができる。
本発明の冷凍機油組成物は化学的安定性が非常
に優れており、高温下でフロンおよび金属と長時
間接触しても化学反応を起こさず、優れた潤滑油
特性を保持している。
本発明の冷凍機油組成物は、回転型冷凍機、よ
り具体的にはスクリユー式、回転翼式または回転
ピストン式の冷凍機に使用すると優れた効果を発
揮する。
以下実施例および比較例によつて、本発明組成
物の有効性を説明する。
実施例 1
第1表に示す基油に添加剤を配合した冷凍機油
組成物(試料油)について、高温における化学的
安定性を評価するためにシールドチユーブテスト
を行なつた。ここで使用した基油、添加剤、金属
片、フロン(冷媒)、試験容器および試験方法は
以下のとおりである。
基油 (ポリエーテル系合成油)
・ 合成油
ポリオキシプロピレン(53)モノブチルエーテ
ル〔( )内の数字は付加モル数〕
動粘度 94.9cst(100℃)
・ 合成油
ポリオキシエチレン(20)ポリオキシテトラメ
チレン(12)グリコール
動粘度 68.4cst(100℃)
・ 合成油
ポリオキシプロピレン(61)グリセロールエー
テル
動粘度 42.6cst(100℃)
添加剤
・ エポキシシクロアルキル基を有する化合物
ビニルシクロヘキセンジオキサイド(A−1)、
3,4−エポキシシクロヘキシルメチル−3,
4−エポキシシクロヘキサンカルボキシレート
(A−2)、ビス(3,4−エポキシシクロヘキ
シルメチル)アジペート(A−3)
・ 芳香族系酸化防止剤
フエニル−α−ナフチルアミン(B−1)、N
−ニトロソジフエニルアミン(B−2)
金属片
材質:鋼、銅およびアルミニウム
形状:80×13×0.8mmの長方形板状テストピー
ス。
フロン(冷媒)
フロン R−12(化学式CCl2F2)
試験容器
SUS−316 ステンレス製オートクレーブ
(内容量100ml)
試験方法 (シールドチユーブテスト)
ステンレス製オートクレーブ中に試料油25.0
g、フロン25.0g、および金属片として鋼、銅、
アルミニウムのテストピース各一枚ずつ計3枚を
とり、密封したのち175℃の温度下で14日間(336
時間)加熱を行なつた。テスト終了後、試料油に
ついては減圧下で加熱して十分にフロンガスの除
去を行つたのち性状の測定を行つた。またテスト
ピースについては溶剤(トルエン及びエタノー
ル)で洗浄を行つたのち、重量増減の測定および
外観の観察を行つた。
試験結果
試験結果を第1表に示した。本発明の冷凍機油
組成物1〜8は、いずれも粘度変化率は−15〜+
10%の範囲内であり、テスト後にスラツジの発生
は認められず、またいずれのテストピースについ
ても錆、銅メツキ、孔蝕、腐蝕等が認められず、
フロン共存時において化学的安定性が優れている
ことがわかる。また芳香族系酸化防止剤を併用し
た組成物7と組成物8では、金属(特に銅)の重
量変化が著しく小さい。
比較例
比較のために第2表に示す組成物(試料油)に
ついて、実施例1と同様にしてシールドチユーブ
テストを行なつた。基油および添加剤の表示記号
は実施例1と同様である。
試験結果を第2表に示した。組成物比−1およ
び比−2の結果が示すように、添加剤を加えない
ポリエーテル系合成油は、,共にテスト後に
おいてゲル化を起こし、また金属テストピースに
対する腐食も極めて大であり、冷凍機油として使
用するには不適当である。
またポリエーテル系合成油に芳香族系酸化防止
剤だけ配合したものは、組成物比−3〜比−4の
結果が示すように、無添加の場合よりは改良が認
められるものの依然としてテスト後の試料油の粘
度変化、外観の変化、金属テストピースの腐食が
大きく安定性が不十分である。
The present invention relates to a lubricating oil for refrigerators, and more particularly to a refrigerator oil composition of high viscosity polyether-based synthetic oil that exhibits excellent stability when coexisting with fluorocarbons in a refrigerator. Conventionally, highly refined naphthenic or paraffinic mineral oils have been used in refrigerators such as household refrigerators, air conditioners, and small commercial refrigerators. However, in recent years, there has been a strong demand for miniaturization and improved cooling efficiency for refrigerators, and the conditions for using refrigerator oils have become stricter, and conventional mineral oils have become increasingly unsatisfactory in terms of performance. In other words, refrigerator compressors need to be airtight against the refrigerant fluorocarbons, but if high viscosity mineral oil is used to improve airtightness, wax will precipitate and the compatibility with fluorocarbons will decrease. , the lubricating properties deteriorate significantly and various troubles occur. In order to improve these points, high viscosity polyether-based synthetic oils with good compatibility with fluorocarbons have been developed, but even this polyether-based synthetic oil can be used under harsh operating conditions such as refrigeration oil. A stand-alone product without any additives is insufficient in terms of performance. In other words, inside the compressor of a refrigerating machine, the metal surface is exposed, and refrigerating machine oil and fluorocarbons coexist there. Therefore, during long-term operation at high temperatures, the metal can catalyze and cause a chemical reaction. oxidation, generation of hydrochloric acid, corrosion of metals, and generation of sludge, which can cause refrigerator failure. The inventors of the present invention have conducted intensive studies on this polyether-based synthetic oil in order to solve the above-mentioned problems as a refrigerating machine oil, and as a result, they have found that a compound having an epoxycycloalkyl group is blended into the polyether-based synthetic oil. They discovered that this product has excellent chemical stability, and completed the present invention. In the present invention, 0.1 to 4% by weight of a compound having an epoxycycloalkyl group is added to polyether synthetic oil.
and, if necessary, a refrigerating machine oil composition containing 0.1 to 4% by weight of an aromatic antioxidant having 1 to 2 nitrogen atoms or 1 nitrogen atom and 1 sulfur atom in the molecule. It is. In the present invention, the polyether-based synthetic oil that serves as the base oil for the refrigeration oil is a compound obtained by adding a predetermined amount of alkylene oxide to a mono- to hexavalent alcohol, or a compound in which the terminal group of the above adduct is substituted, and the kinematic viscosity is 10~200cst (100℃) can be used. Examples of the above-mentioned polyether-based synthetic oils include polyoxypropylene glycol, polyoxyethylene glycol, polyoxy-1,2-butylene glycol, polyoxy-2,3-butylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene poly Oxytetramethylene glycol; and monomethyl ether, monoethyl ether, monobutyl ether, monooctyl ether, mono-2-ethylhexyl ether, monododecyl ether, monotetradecyl ether, monooctadecyl ether, monoallyl ether of the above polyoxyalkylene glycol, Monobenzyl ether, methylene glycol diether, 1,4-butanediol diether, glycerin triether, trimethylolpropane triether, pentaerythritol tetraether, sorbitan hexaether,
Ethers such as monobutyl monobenzyl ether, monobutyl monoallyl ether, diallyl ether, bisphenol-A-diether, di-2-ethylhexyl ether; monobutyl ether monocaprylic acid ester of the above polyoxyalkylene glycol, monobutyl ether monolauric acid Examples include ether esters such as esters. Examples of compounds having an epoxycycloalkyl group include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, vinylcyclohexene dioxide, 2
-(3,4-epoxycyclohexyl-5,5-
Spiro-3,4-epoxy)cyclohexane-meta-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, cyclohexene oxide, cyclooctene oxide, cyclopentadiene monooxide, 4-vinylcyclohexene-1,2-oxide, bis (methylcyclohexenyl) dioxide, dicyclopentadiene diepoxide, bis(2,3-epoxycyclopentyl)ether, bis(3,4 oxalate)
-epoxycyclohexylmethyl) ester,
4,10-dioxatetracyclo[5,4,O,
Examples include O 3,5 , O 9,11 ] undecane. Examples of aromatic antioxidants having 1 to 2 nitrogen atoms in the molecule include phenyl-α-naphthylamine, N-nitrosodiphenylamine, and 4-nitrosodiphenylamine.
aminodiphenylamine, N-isopropyl-
N'-phenyl-p-phenylenediamine, N,
N'-diphenyl-p-phenylenediamine, N,
N'-di-sec-butyl-p-phenylenediamine, N,N'-di-β-naphthyl-p-phenylenediamine, diphenylamine, dioctylphenylamine, etc., and nitrogen atoms and Examples of aromatic antioxidants each containing one sulfur atom include phenothiazine. Among these, aromatic amines having 1 to 2 nitrogen atoms in the molecule are preferred, and among these, phenyl-α-naphthylamine provides particularly good effects. The amounts of the two types of additives added to the polyether synthetic oil are 0.1 to 4% by weight of the compound having an epoxycycloalkyl group and 0.1 to 4% by weight of the aromatic antioxidant if necessary. If the amount is less than these, the desired effect cannot be obtained, and even if a large amount is blended, the effect will not increase significantly. Adding aromatic antioxidants will color the refrigerating machine oil composition, so it is not always necessary to use them.
When used in combination, metal corrosivity (especially copper) can be significantly improved. The refrigerating machine oil composition of the present invention has excellent chemical stability, does not cause a chemical reaction even when in contact with fluorocarbons and metals at high temperatures for a long time, and maintains excellent lubricating oil properties. The refrigerating machine oil composition of the present invention exhibits excellent effects when used in rotary refrigerators, more specifically screw type, rotary blade type, or rotary piston type refrigerators. The effectiveness of the composition of the present invention will be explained below using Examples and Comparative Examples. Example 1 A refrigerating machine oil composition (sample oil) prepared by blending additives with the base oil shown in Table 1 was subjected to a sealed tube test to evaluate its chemical stability at high temperatures. The base oil, additives, metal pieces, Freon (refrigerant), test container, and test method used here are as follows. Base oil (polyether-based synthetic oil) Synthetic oil polyoxypropylene (53) Monobutyl ether [The number in parentheses is the number of moles added] Kinematic viscosity 94.9cst (100℃) Synthetic oil polyoxyethylene (20) Polyoxy Tetramethylene (12) glycol Kinematic viscosity 68.4cst (100℃) Synthetic oil Polyoxypropylene (61) glycerol ether Kinematic viscosity 42.6cst (100℃) Additives Vinyl cyclohexene dioxide (A-), a compound with an epoxycycloalkyl group 1),
3,4-epoxycyclohexylmethyl-3,
4-epoxycyclohexanecarboxylate (A-2), bis(3,4-epoxycyclohexylmethyl)adipate (A-3), aromatic antioxidant phenyl-α-naphthylamine (B-1), N
- Nitrosodiphenylamine (B-2) Metal piece Material: steel, copper and aluminum Shape: 80 x 13 x 0.8 mm rectangular plate test piece. Freon (refrigerant) Freon R-12 (chemical formula CCl 2 F 2 ) Test container SUS-316 stainless steel autoclave (content 100ml) Test method (shielded tube test) Sample oil 25.0% in stainless steel autoclave
g, 25.0 g of fluorocarbons, and metal pieces such as steel, copper,
Take a total of three aluminum test pieces, seal them, and store them at a temperature of 175°C for 14 days (336°C).
time) heating was performed. After the test was completed, the sample oil was heated under reduced pressure to sufficiently remove the fluorocarbon gas, and then its properties were measured. Further, the test pieces were washed with a solvent (toluene and ethanol), and then the weight change and appearance were observed. Test Results The test results are shown in Table 1. Refrigerating machine oil compositions 1 to 8 of the present invention all have a viscosity change rate of -15 to +
Within the range of 10%, no sludge was observed after the test, and no rust, copper plating, pitting, corrosion, etc. were observed on any of the test pieces.
It can be seen that chemical stability is excellent when CFCs coexist. Furthermore, in Compositions 7 and 8, in which aromatic antioxidants were used in combination, the weight change of metals (especially copper) was extremely small. Comparative Example For comparison, a shield tube test was conducted in the same manner as in Example 1 for the compositions (sample oils) shown in Table 2. The display symbols for the base oil and additives are the same as in Example 1. The test results are shown in Table 2. As shown by the results of Composition Ratio-1 and Ratio-2, both polyether-based synthetic oils without additives caused gelation after the test and were extremely corrosive to metal test pieces. Not suitable for use as refrigeration oil. In addition, when only aromatic antioxidants were blended with polyether synthetic oil, as shown by the results for composition ratios -3 to -4, improvements were observed compared to cases without additives, but still after the test. Stability is insufficient due to significant changes in sample oil viscosity, changes in appearance, and corrosion of metal test pieces.
【表】【table】
【表】【table】
【表】
実施例 2
実施例1の第1表に示した組成物1を用いて、
小型回転式冷凍機により1000時間の実機試験運転
を行なつた。また比較品として添加剤を加えない
合成油について同様の試験を行つた。結果は第
3表に示したとおりである。[Table] Example 2 Using composition 1 shown in Table 1 of Example 1,
A 1000-hour actual test run was conducted using a small rotary refrigerator. Similar tests were also conducted on synthetic oil without additives as a comparative product. The results are shown in Table 3.
【表】
組成物1においては、実機試験運転の終了時ま
で高い気密性を保持することができ、またテスト
後の試料油粘度も大きな変化を示していなかつ
た。
一方比較品においては、初期には良好な気密性
を示したが、運転時間の経過と共に気密性の低下
が起こり、またテスト後の試料油粘度も大幅に低
下していた。[Table] Composition 1 was able to maintain high airtightness until the end of the actual machine test run, and the sample oil viscosity did not show any significant change after the test. On the other hand, the comparative product showed good airtightness initially, but the airtightness deteriorated as the operating time progressed, and the viscosity of the sample oil after the test also decreased significantly.
Claims (1)
シクロアルキル基を有する化合物0.1〜4重量%
および必要により分子内に窒素原子1〜2個を有
するかあるいは窒素原子1個とイオウ原子1個と
を有する芳香族系酸化防止剤0.1〜4重量%を配
合してなる冷凍機油組成物。 2 エポキシシクロアルキル基を有する化合物が
エポキシシクロヘキシル基を有する化合物であ
り、芳香族系酸化防止剤が窒素原子を1〜2個有
する芳香族アミンである特許請求の範囲第1項記
載の冷凍機油組成物。 3 エポキシシクロアルキル基を有する化合物が
3,4−エポキシシクロヘキシルメチル−3,4
−エポキシシクロヘキサンカルボキシレート、ビ
ニルシクロヘキセンジオキサイド、ビス(3,4
−エポキシシクロヘキシルメチル)アジペート、
または2−(3,4−エポキシシクロヘキシル−
5,5−スピロー3,4−エポキシ)シクロヘキ
サン−メタ−ジオキサンであり、芳香族系酸化防
止剤がフエニル−α−ナフチルアミンまたはN−
ニトロソジフエニルアミンである特許請求の範囲
第1項または第2項に記載の冷凍機油組成物。[Claims] 1. 0.1 to 4% by weight of a compound having an epoxycycloalkyl group in the molecule in polyether synthetic oil
and, if necessary, 0.1 to 4% by weight of an aromatic antioxidant having 1 to 2 nitrogen atoms or 1 nitrogen atom and 1 sulfur atom in the molecule. 2. Refrigerating machine oil composition according to claim 1, wherein the compound having an epoxycycloalkyl group is a compound having an epoxycyclohexyl group, and the aromatic antioxidant is an aromatic amine having 1 to 2 nitrogen atoms. thing. 3 A compound having an epoxycycloalkyl group is 3,4-epoxycyclohexylmethyl-3,4
-Epoxycyclohexane carboxylate, vinylcyclohexene dioxide, bis(3,4
-epoxycyclohexylmethyl)adipate,
or 2-(3,4-epoxycyclohexyl-
5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, and the aromatic antioxidant is phenyl-α-naphthylamine or N-
The refrigerating machine oil composition according to claim 1 or 2, which is nitrosodiphenylamine.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13779180A JPS5763395A (en) | 1980-10-03 | 1980-10-03 | Polyether refrigerator oil composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13779180A JPS5763395A (en) | 1980-10-03 | 1980-10-03 | Polyether refrigerator oil composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5763395A JPS5763395A (en) | 1982-04-16 |
JPS6333520B2 true JPS6333520B2 (en) | 1988-07-05 |
Family
ID=15206927
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13779180A Granted JPS5763395A (en) | 1980-10-03 | 1980-10-03 | Polyether refrigerator oil composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5763395A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02309518A (en) * | 1989-05-24 | 1990-12-25 | Matsushita Electric Ind Co Ltd | Push button device |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60123577A (en) * | 1983-12-08 | 1985-07-02 | Nishi Nippon Tsusho Kk | Refrigerating machine oil composition |
JPH06102792B2 (en) * | 1987-10-30 | 1994-12-14 | 出光興産株式会社 | Lubricating oil for fluorine-containing alkane refrigerant |
KR940001530B1 (en) | 1987-10-30 | 1994-02-23 | 이데미쓰 고산 가부시끼가이샤 | Lubricating oil for alkane refrigerant containing fluorine |
JPH0819430B2 (en) * | 1988-04-06 | 1996-02-28 | 日本石油株式会社 | Refrigerating machine oil composition for refrigerating equipment |
US5543068A (en) * | 1988-04-08 | 1996-08-06 | Japan Energy Corporation | Lubricating oils for flon compressors, compositions adapted for flon compressors and composed of mixtures of said lubricating oils and flon, and process for lubricating flon compressor by using said lubricating oils |
JP2556548B2 (en) * | 1988-04-08 | 1996-11-20 | 株式会社ジャパンエナジー | Lubricating oil used for CFC compressors |
JP2556547B2 (en) * | 1988-04-08 | 1996-11-20 | 株式会社ジャパンエナジー | Lubricating oil for CFC compressors for car air conditioners |
JPH0823030B2 (en) * | 1988-04-22 | 1996-03-06 | 日本石油株式会社 | Refrigerator oil composition for car air conditioners |
GB8905379D0 (en) * | 1989-03-09 | 1989-04-19 | Shell Int Research | Refrigeration lubricants |
US5238590A (en) * | 1989-09-29 | 1993-08-24 | Mitsui Petrochemical Industries, Ltd. | Lubricant oil, polyalkylene glycol polycarbonates and process for preparing them |
JP2831400B2 (en) * | 1989-11-02 | 1998-12-02 | 三井化学株式会社 | Lubricating oil composition for refrigerator |
JP2573111B2 (en) * | 1990-09-12 | 1997-01-22 | 花王 株式会社 | Composition for working fluid of refrigerator |
JP3038062B2 (en) * | 1991-10-15 | 2000-05-08 | 旭電化工業株式会社 | Lubricants for refrigerators |
JPH05302094A (en) * | 1992-04-28 | 1993-11-16 | Tonen Corp | Refrigerator oil composition |
JP2613526B2 (en) | 1992-07-04 | 1997-05-28 | 花王株式会社 | Composition for working fluid of refrigerator |
JP2901529B2 (en) * | 1996-01-09 | 1999-06-07 | 株式会社日立製作所 | Refrigeration oil composition |
JPH08231972A (en) * | 1996-01-09 | 1996-09-10 | Hitachi Ltd | Refrigerating unit |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53140469A (en) * | 1977-05-13 | 1978-12-07 | Nippon Oil Co Ltd | Component of high viscosity refrigerator oil |
-
1980
- 1980-10-03 JP JP13779180A patent/JPS5763395A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53140469A (en) * | 1977-05-13 | 1978-12-07 | Nippon Oil Co Ltd | Component of high viscosity refrigerator oil |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02309518A (en) * | 1989-05-24 | 1990-12-25 | Matsushita Electric Ind Co Ltd | Push button device |
Also Published As
Publication number | Publication date |
---|---|
JPS5763395A (en) | 1982-04-16 |
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