TW252994B - - Google Patents

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TW252994B
TW252994B TW083110170A TW83110170A TW252994B TW 252994 B TW252994 B TW 252994B TW 083110170 A TW083110170 A TW 083110170A TW 83110170 A TW83110170 A TW 83110170A TW 252994 B TW252994 B TW 252994B
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Taiwan
Prior art keywords
acid
lubricating oil
oil composition
refrigerators
carboxylic acid
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TW083110170A
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Chinese (zh)
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Mitsui Petroleum Chemicals Ind
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/50—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/008—Lubricant compositions compatible with refrigerants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/38—Esters of polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/42—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/48—Esters of carbonic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M131/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing halogen
    • C10M131/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing halogen containing carbon, hydrogen, halogen and oxygen
    • C10M131/10—Alcohols; Ethers; Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/2805—Esters used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/286—Esters of polymerised unsaturated acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C10M2207/301—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/32—Esters of carbonic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/32—Esters of carbonic acid
    • C10M2207/325—Esters of carbonic acid used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
    • C10M2207/345—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/02—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only
    • C10M2211/022—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only aliphatic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/04—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen, halogen, and oxygen
    • C10M2211/042—Alcohols; Ethers; Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/06—Perfluorinated compounds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04C—ROTARY-PISTON, OR OSCILLATING-PISTON, POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; ROTARY-PISTON, OR OSCILLATING-PISTON, POSITIVE-DISPLACEMENT PUMPS
    • F04C2210/00—Fluid
    • F04C2210/26—Refrigerants with particular properties, e.g. HFC-134a

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)

Description

^52994 A7 B7 五、發明説明（3 ) 發明 > 刹用铕城 (請先閲讀背面之注意事項再填寫本頁) 本發明係有蘭冷凍機用潤》油組成物，尤指用於其中 使用氫化氟硝化物（HFC)作為冷媒之汽車空氣調節機，電 冰箱及室内空氣調節機之壓縮型冷凍機器用之潤滑油組成 物。 發明赀署 迄今係使用氣氟硪化物（C F C )如R - 1 2 ( C C 1 2 F 2〉或氫化 氯輻磺化物（HCFC〉如R-22(CHC1F2)作為汽車空氣調節機、 家用電冰箱及室內空氣調節機用壓编型冷凍機器中之冷媒 ,惟由防止臭氧層破壊之觀點觀之，目前該等冷媒由於含 有氣因而難以被使用。 現在，氫化氟硪化物（HFC)如1,1, 1,2 -四氟乙烷（R-134a)已發展成不破壊奥氧層之冷媒。已開發如HFC之冷凍 機用潤滑油之實例包含聚伸烷二醇及其衍生物，羧酸酷衍 生物及磺酸酯行生物。 經濟部中央標準局員工消費合作社印製 日本特開平3-12497說明一種包括Μ下式表示的含氟 烷基之醇類及多元酵化合物之潤滑油組成物，顯示出與 HFC之良好相容性及在抗燃燒性質方面亦優越。^ 52994 A7 B7 5. Description of the invention (3) Invention > Eu city for brakes (please read the precautions on the back before filling in this page) The present invention is a composition of oil used for moisturizer of blue refrigerator, especially used in it Lubricating oil composition for automobile air conditioners that use hydrogenated fluoronitride (HFC) as a refrigerant, compression refrigerators for refrigerators and indoor air conditioners. The invention department has so far used gas fluoride compounds (CFC) such as R-1 2 (CC 1 2 F 2) or hydrogen chloride sulfonated compounds (HCFC) such as R-22 (CHC1F2) as car air conditioners and household refrigerators. And the refrigerant in the compression-type freezing machine for indoor air conditioners, but from the viewpoint of preventing the ozone layer from breaking, currently these refrigerants are difficult to use because they contain gas. Now, hydrogen fluoride (HFC) such as 1,1 , 1,2-tetrafluoroethane (R-134a) has been developed as a refrigerant that does not break the oxygen layer. Examples of lubricants for refrigerators that have been developed include HFC. Examples include polyalkylene glycol and its derivatives, carboxylic acid Cool derivatives and sulfonate esters. The Ministry of Economic Affairs, Central Standards Bureau, Employee Consumer Cooperatives printed Japanese Patent Laid-Open No. 3-12497 to describe a lubricating oil composition that includes fluoroalkyl-containing alcohols and poly-fermented compounds represented by the following formula , Showing good compatibility with HFC and superior in anti-combustion properties.

Rf-R1 -0Η 式中R1為含2至15値硝原子之伸烷基，Rf為含5至16個确 原子之氟烷基，在Rf基中氟原子數目至少為Zn-3(n為Rf 基之硝原子數），且至少一値櫬原子係鍵結至Rf基之各硪 原子上。 _至於汽車空氣調節機、家用霄冰箱之懕縮型冷凍機等 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) 252994 A 7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（4 ) ,目前已提出一棰新穎冷媒条統作為不破壊奥氧層之糸統 ,亦即其中使用HFC如R-134a作為冷媒冷凍裝置条統，係 使用一種包括聚伸烷二酵或其衍生物，羧酸酯衍生物、硝 酸酯衍生物等之潤滑油，且此冷凍裝置係由適用此潤滑油 之材料製成。 然而，此新潁条統含有若干問題，即笛進行反覆耐久 試驗時，在壓縮型冷凍機之滑動零件之金羼磨耗量大且滑 動零件之耐磨性亦不足。 因而，需要發展一種可顯箸減少其中使用氫化氟磺化 物如R-134a作為冷媒之壓縮型冷凍機之滑動零件之金羼磨 耗量之冷凍機器用潤滑油。 發明目的 本發明意欲解決上述先行技術伴隨的問題，且本發明 之一目的為提供一種可顯著減少其中使用簠化氟硪化物如 R-134a作為冷媒之壓縮型冷凍機之滑動零件之金羼磨耗量 之冷凍機用潤滑油組成物。 發明槪沭 本發明之冷凍機用濶滑油組成物包括：1〇〇重量份之 具有數目平均分子量（Mn)200至5, 000及在100¾之動黏度 2至lOOcSt之羧酸醋，或具有數目平均分子量（Mn)200至 5,00 0及在100^0之動黏度2至100〇51之磺酸酯，及 0.001至15重量份之含氟烷基之醇。 含氱烷基之醇之分子量Μ在30至2,000之範圍為宜。 _本發明之潤播•油組成物較好使用於鼷縮型冷凍機，尤 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 裝 、可. '泉 4 252994 A7 B7 五、發明説明（5 ) 物 化 硪 氟 化 氫 用 使 等 該 指 者 媒 冷 爲 作 明 說 細 之 明 發 下 如 明 說 細 詳 將 分 成 組 油 滑 潤 用 機 凍 冷 之 明 發 本 特定 有待 具有 之具 量或 定酯 特酸 括羧 包之 分度 成黏 組動 油定 滑特 潤及 \)/ 用 η Λκ Μ 機 < 凍s 冷子 之分 明均 發平 本目 數 定 醇 之 基 烷 親 〇 含 油 及 基 , 之 酯 油 酸 滑 硪 潤 之 為 度 作 黏 用 動 使 定 係 特 醋 及 酸 η)磷 (Μ或 量 子 分 幾 百 0 數 類 酯 酸 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本發明所用的羧酸酯於其分子中至少有一醋基，且由 GPC測得之數目平均分子量（Μη)之係在200至5,000,以 300至4,000為宜，W300至3, 000為最宜。此羧酸酯在1〇〇 t之動黏度為2至lOOcSt, Μ2.5至80cSt為宜，Μ3.0至 70c St為最宜。於本發明中，係使用述於例如下列公報之羧酸酯。 日本特開平3-227397號說明由含2至6値硪原子之脂 肪酸（例如丁酸、2 -甲基丙酸、戊酸、2 -甲基丁酸、3 -甲 基丁酸、己酸、2-乙基丁酸、2-甲基戊酸及其混合物）與 新戊基多元醇（例如季戊四醇、二季戊四醇、三季戊四酵 、四季戊四醇、二（三羥甲基）丙烷及其混合物〉所得之羧 酸酯。該等羧酸酯之實例包含二-2-甲基己酸新戊酯、二 丁酸新戊酯、二癸酸新戊酯及二庚酸新戊醋。其中以二2--甲基己酸新戊酯為佳。日本特開平3-128991號說明由至少一種不具有醚鍵結 本纸張尺度適用中國國家標準(CNS)A4规格(210X297公釐) 5 A 7 B7 252994 五、發明説明（6 ) (請先閱讀背面之注意事項再填寫本頁) 之含5至12個硝原子之二價醇與至少一棰含3至18個磺原 子之直鏈或支鏈單價脂肪酸而得的羧酸酯，及由至少一種 不具有醚鍵結之含5至12個磺原子之二價醇，與至少一種 含3至18個硪原子之直鍵或支鏈單價脂肪酸及至少一種含 4至14個磺原子之多元酸而得的羧酸酯。該羧酸酯之實例 ，包含二癸酸2, 2-二甲基-1,3-丙烷二醇酯、二癸酸2-丁 基-2-乙基-1,3 -丙烷二酵酯、2, 2 -二甲基-3-甲基戊酸酯 及二-2-甲基己酸3 -甲基-1,5 -戊烷二醇酯。其中，M2, 2-二甲基-3-甲基戊酸酯及二-2-甲基己酸3-甲基-1,5-戊烷 二醇酯爲最佳。 不具有醚鍵結之含5至12艢硪原子之二價醇之實例， 包含新戊二醇2, 2-二乙基-1，3-丙烷二醇、2-丁基-2-乙基 -1,3-丙烷二醇、3-甲基-1,5-戊烷二醇、2,2, 4-三甲基-1,3-戊烷二醇及2-乙基-1,3-己烷二醇。 經濟部中央標準局員工消費合作社印製 含3至18艏磺原子之直鍵或支鏈單價腊肪酸之實例， 包含丙酸、異丙酸、丁酸、異丁酸、戊酸、己酸、庚酸、 異庚酸、辛酸、2-乙基己酸、壬酸、3,5, 5-三甲基己酸、 癸酸、十一磺酸、月桂酸、豆蓊酸、棕櫊酸、硬脂酸、異 硬脂酸、油酸、亞麻仁油酸及次亞麻仁油醸。 含4至14掴硝原子之多元酸之實例，包含丁二酸、戊 二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、對苯 二甲酸及順丁烯二酸。 再者，日本特開平4 - 2 0 597號、3 - 2 1 7 49 3號及3-128992號說明由多元酵（例如三羥甲基乙烷、三羥甲基丙 本紙張尺度適用中國國家標準(CNS)A4規格(2]〇X 297公釐) 6 ^2994 Α7 ___ Β7 五、發明説明（7 ) 院、季戊四酵及新戊二酵）及單羧酸（例如2 -乙基己酸、庚 酸及癸酸〉或其衍生物而得的羧酸酯。該羧酸醢之實例包 (請先閲讀背面之注意事項再填寫本頁) 含： ⑴由三羥甲基丙烷（1與耳）與2 -乙基己酸（3其耳〉構成之 —醋，係Μ下式表示： C2H5C[CH2〇OCCH2(C2H5><CH2)3CH3]3; ⑵由三羥甲基丙烷U其耳〉及3, 5, 5 -三甲基己酸構成之三 酷，係以下式表示： C2H5[CH2〇OCCH2CH(CH3>CH2C(CH3)3]3; (3)由三羥甲基丙烷（1其耳），2 -乙基己酸U. 5與耳）及3， 3, 5-三甲基己酸（1. 5其耳）構成之三酯； ⑷由二（三羥甲基丙烷）（1冥耳〉，正己酸（2其耳〉及2,4-二甲基戊酸（2其耳）構成之四酯，係以下式表示： [RCOOCH2]2C(C2H5)CH2〇CH2C(C2H5>[CH2〇COR]2 (式中，R 爲-<CH2)4CH3或-CH(CH3)CH2CH-(CH3)2),及 ⑹由二（三羥甲基丙烷）（1莫耳〉及3,3, 5 -三甲基己酸（4 與耳）構成之四酷，係Μ下式表示： 經濟部中央標準局員工消費合作杜印製 [RC00CH232C(C2H5)CH20CH2C(C2Hb)[CH20C0R]2 [式中，R 為-C Η 2 C H C ( C Η 3〉C Η 2 c ( C Η 3 ) 3 ], 由多元酵及單羧基酸或其衍生物而得之後酸醋中，以 ⑴至⑹之羧酸酯爲宜，且Μ羧酸酯⑵，⑷及⑹爲最宜。 不同於羧酸酯⑴至⑸之其他羧酸酯之寶例包含四丁酸 季戊四醇酯、四戊酸季戊四醇酯、四庚酸季戊四醇酷、四 癸酸季戊四酵酯、四-2 -甲基己酸季戊四酵醋及四-2,2 -二 7 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) L52994 A7 B7 五、發明説明（8 ) (請先閲讀背面之注意事項再填寫本頁) 甲基-3-甲基戊酸季戊四醇酯。其中，Μ四丁酸季戊四醇 醋，四戊酸季戊四醇酯、四癸酸季戊四醇酯、四-2 -甲基 己酸季戊四醇酯及四-2,2 -二甲基-3-甲基戊酸季戊四醇_ 為宜，且Μ四-2-甲基己酸季戊四酵酯及四-2,2-二甲基 -3 -甲基戊酸季戊四醇酯為最宜。 另外，國際專利由諳案之日太太國/△吿室笛 505602/1991號說明由含有至少二値羥基之多元羥基化合 物與羧酸而得之羧酸酯。 多元羥基化合物之實例包含乙二醇、二乙二醇、三乙 二醇、丙二醇、二丙二酵、丙三醇、新戊二醇、12-丁二 醇、1,3-丁二酵、1,4-丁二酵、季戊四醇、二季戊四酵、 三季戊四醇、三丙三醇、四羥甲基丙烷及山梨糖醇。 羧酸之實例包含直鐽飽和單羧醚如甲酸、乙酸、丙酸 、丁酸、戊酸、己酸及庚酸；支鍵飽和單羧酸如2 -乙基-正丁酸，2 -己基癸酸，異硬脂酸，2 -甲基己酸，3,5, 5_三 甲基己酸，2 -乙基己酸，新庚酸及新癸酸；飽和二羧酸如 琥珀酸；及不飽和二羧酸如順丁烯二酸。 經濟部中央標準局員工消費合作社印製 上逑該羧酸酯之實例包含六丁酸山梨耱醇酷及六戊山 梨糖酵醋。 若前述的羧酸酯依其適宜順序排列時，其依序為國際 專利申請案之日本本國公告案第505602/1991號所述的羧 酸醋，日本特開平4-2 0597號、3-217493號及3-128992號 所述的羧酸醋，日本特開平3- 1 2 8 99 1號所述之羧酸酷及曰 本特開平3-227397號所述之羧酸酯。 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) 8 A 7 B7 C52994 五、發明説明（9 ) 硪酸曲 (請先閱讀背面之注意事項再塡寫本頁) 本發明所用的磺酸酯之分子中具有至少一個碳酸酯基 ，且由GPC測得之數目平均分子量（Mr〇為200至5, 000, Μ 300至4, 000為宜，Μ300至3 ,000為最宜。此硝酸酯在100 t之動黏度為2至lOOcSt, Μ2.5至80cSt為宜，Μ3.0至 70cSt為最宜。 該磺酸醋之實例包含由含1至6個一级羥基之脂肪醇 (例如三羥甲基乙烷、三羥甲基丙烷及新戊二醇）與碩酸之 低级酷（例如，磺酸二甲酯、硪酸二乙酷、磺酸二苯酯、 硝酸伸乙酯及磺酸伸丙酷）或羰基鹵化物（例如光氣）而得 者。特別值得一提者為二（甲基己基磺酸）3_甲基-1,5 -伸 戊基酯、二（甲基己基磺酸）3 -乙基-3-丁基-1,5 -伸戊基酯 等。此等硪酸酯述於日本特開平3-217498號中。 碩酸酯之其他實例為述於日本特開平4-18490號之下 列之化合物。 經濟部中央標準局員工消費合作社印製 ⑴式U0C00CH2)4C之化合物，式中R為異己基或異庚基， ⑵式（R0C00CH2〉3CCH3之化合物，式中R為異己基或異庚 基，及 ⑶式（R0C00CH2>3CCH20CH2C(CH20C00R)3之化合物，式中 R為異丙基或異丁基。 不同於上述碳酸酯，亦可使用於日本特開平3-247695 號所述之二醇醚碳酸醋，其係以下式表示： Ri-0-[(R3)0]n-C00-R2 式中1^及112各為含1至20偏碳原子之脂族、脂瓌、芳 9 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) 252994 A7 B7 經濟部中央標準局員工消費合作社即製 五、發明説明（1〇) 番族基或芳番-脂族烴，R3為伸乙基或伸丙基，且η為2 至100之整數。 由上式表示的二醇隧破酸酯之實例，包含下式之化合 物： (1) CH3-[C3H6〇]-COO-C3H6CH3 (2) n-C4H9〇-[C3H6〇]n-CO〇-CH3 式中η爲2至100之整數，以5至90之整數為佳，M10至 60之整數為更佳。 再者，可使用由糖如山梨耱酵衍生而得的聚硝酸酷， 及不具瓌狀結構且及Μ下式表示之聚碩酸酯： CH3-〇-[C3H6〇]n-CO〇-[C3H6〇]nCH3 式中η為2至100之整數，M3至90之整數為佳，M5至 60之整數為更佳。 上示的硝酸酯中，較好使用日本特開平3-247695號所 述的上式二醇醚磺酸酯，而耱如山梨糖酵衍生而得聚磺酸 酯及不具環狀結構之聚碳酸酯。 若前述磺酸酯依其適宜順序排列時，依序為日本特開 平3-247695號所述的上式二醇_硝酸酯，由糖如山梨糖酵 衍生而得的聚磺酸酯，及不具環狀結構之上式聚硪酸酯， 及日本特開平3-217498號所述的磺酸酯。 僉鐘烷某 > 酵 本發明所使用的含氟烷基之醇具有之分子量通常為 30 至 2,00 0, Μ50 至 1,000 為宜，Μ100 至 9 0 0 為更宜。 含氟烷基之醇之實例，包含含單價氟烷基之醇類如三 本紙張尺度適用中國國家標準(CNS)A4規格(2WX297公釐） ι 〇 (請先閱讀背面之注意事項再填寫本頁) 裝 、可 ，果. 52994 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（；Π) 氟乙醇、全«己基乙酵、全«辛基乙醇、全氟癸基乙醇、 1Η,2Η,5Η -八氟戊醇及六氟基異丙醇；及含氟烷基之二價 醇類如3-(2 -全氟己基）乙氧基-1,2 -二羥基丙烷及Ν-2, 3-二羥基正丙基全氟辛基磺醯胺。其中，較好使用全氟己基 乙醇、全氟辛基乙醇及全氰癸基乙酵為宜。 此等含氟烷基之醇類可單獨使用或合併使用。 本發明中，含氰烷基之醇之使用量，M100重量份之 羧酸酯或碳酸酯為準，係0.001至15重量份，W0.1至10重 量份為佳，Ml至8重量份更佳。 當含氪烷基之酵Μ上述量使用時，則使用HFC如R-134a作為冷媒之壓縮型冷凍機之滑動零件之金靥磨耗量可 顯著減少。再者，羧酸酯或碉酸酯可避免降低溶解度，且 可避免冷凍機用潤滑油組成物大為減少酏力黏度。 本發明之冷凍機用潤滑油組成物由於使用相當少量之 上述之昂貴含氟烷基醇，因此非常經濟。 本發明之冷凍機用潤滑油，除了作為潤滑油基油之羧 酸酯或磺酸酯及含氟烷基之醇之外，又可含有已知之磨耗 降低劑。 該磨耗降低劑之實例包含磷酸酯；酸性磷酸酯；酸性 磷酸酯之胺塩；脂肪酸；單酵如癸酵、月桂醇、2 -乙基己 酵及2 -乙基-1,3 -己二醇；多元醇如1,2 -癸二醇，1,2 -辛 二醇，三乙二醇及二乙二酵；環氧乙烷/瓖氧丙烷嵌段共 聚物之二甲基醚；胺甲酸醋；二硫代磷酸鋅；羧酸酯；亞 硫酸塩；硫酵；及烷基聚矽氧烷氟化物。該等磨耗降低劑 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐） 11 (請先閲讀背面之注意事項再塡寫本頁) 裝· 、?τ. '#· A7 B7 52994 五、發明説明（12 ) 可單獼使用或合併使用。 (請先閲讀背面之注意事項再填寫本頁) 本發明中，冷凍機用潤滑油組成物又可含有通常被使 用於潤滑油諸如冷凍機油中之油性改良劑，消泡劑，抗腐 蝕劑及著色薄I,但Μ本發明之目的不受損為限。 本發明之冷凍機用潤滑油組成物可由例如加入特定量 之含氟烷基醇至特定量之羧酸醋或碘酸酯中，接著攪拌而 得。 於攪拌時之液溫以在室溫至150¾之範園為宜。攪拌 較好在惰性氣體下進行。 發明^效果 如上所述，本發明之冷凍機用潤滑油組成物，包括 100重量份之具有數目平均分子童（Mn)200至5, 000及在 10010之動黏度為2至lOOcSt之羧酸醋或具有數目平均分 子量（Μη〉200至5 ,000及在100t：之動黏度爲2至lOOcSt之 磺酸酯，及0.001至15重量份之含氟烷基醇。因此，此組 成物可顯著地減少其中使用氫化氟碳化物如R_134a作為冷 媒之壓縮型冷凍機之滑動部分之金鼷磨耗Λ。 經濟部中央標準局員工消費合作社印製 再者，本發明之潤滑油組成物亦可使用於不同於壓縮 型冷凍機，此乃歸因於其優越的潤滑性質。 奮掄例 本發明可參考下列實施例而進一步予Μ說明，惟其並 非受此等實施例所限制。 於此等實施例中，各種性質之測試係依下列方法進行 12 本紙張尺度適用中國國家標準(CNS)A4规格(210X297公釐) C52994 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（13) [試驗方法] a.在10〇υ及40T之動黏度及黏度指數 此試驗係依JIS Κ2283進行。 b .密度 此試驗係依JIS K2249進行。 c .傾滾黏 此試驗係依JIS K2265進行。 d.負荷能力（潤滑油耐壓耐熱值） 依據ASTM D-2670,使用潤滑油耐壓耐熱測試器在 250磅負載下，經5分鐘溫車蓮轉操作後，持續增加負 載，且在燒痕出現時，所得之增加負載值作為負荷能力 〇 e .電阻 此試驗係依J I s C 2 1 0 1進行。 f .缌酸價 此試驗係依JIS K2501進行。 g.與R-134a之相容性 潤滑油組成物及R-134aM不同比例加入玻璃管内， 接著密封，且組成物與R-134a依JIS K2211作成相互間 可相容Μ觀察其兩者相互間之可相容的最高及最低溫度 (臨界溫度）。 h .磨耗量 磨耗試驗係使用潤滑油耐壓耐熱測試器在下列條件 下進行，且磨耗量係在磨耗試驗後Μ測試片（V塊，軸 (請先閲讀背面之注意事項再塡寫本頁) 裝.Rf-R1 -0Η Where R1 is an extended alkyl group containing 2 to 15 nitrile atoms, Rf is a fluoroalkyl group containing 5 to 16 exact atoms, and the number of fluorine atoms in the Rf group is at least Zn-3 (n is The number of nitrate atoms in the Rf group), and at least one atom is bonded to each atom in the Rf group. _As for car air conditioners, condensed refrigerators for household refrigerators, etc., this paper standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 252994 A 7 B7 Printed by the Employees Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Description of the invention (4), a novel refrigerant system has been proposed as a system that does not break the oxygen layer of the oxygen layer, that is, where HFC such as R-134a is used as the refrigerant refrigeration system system, a system including polycondensate is used Or its derivatives, carboxylic acid ester derivatives, nitrate derivatives and other lubricating oils, and this refrigeration device is made of materials suitable for this lubricating oil. However, this new system has several problems, that is, when the flute is subjected to repeated durability tests, the sliding parts of the compression type refrigerator have a large amount of wear and the wear resistance of the sliding parts is also insufficient. Therefore, there is a need to develop a lubricating oil for refrigeration machines that can significantly reduce the consumption of the gold rollers of sliding parts of compression-type refrigerators in which hydrofluorosulfonates such as R-134a are used as refrigerants. OBJECT OF THE INVENTION The present invention is intended to solve the problems associated with the aforementioned prior art, and an object of the present invention is to provide a significant reduction in the wear and tear of sliding parts of a compression-type refrigerator in which a fluorochemical compound such as R-134a is used as a refrigerant The amount of lubricating oil composition for refrigerators. Invention 槪 Shu The lubricating oil composition for a refrigerator of the present invention includes: 100 parts by weight of a carboxylic acid vinegar having a number average molecular weight (Mn) of 200 to 5,000 and a dynamic viscosity of 100 to 2 to 100 cSt, or having The number average molecular weight (Mn) is 200 to 5,000 and the sulfonic acid ester with a dynamic viscosity of 2 to 100〇51 at 100 ^ 0, and 0.001 to 15 parts by weight of fluoroalkyl group-containing alcohol. The molecular weight M of the alcohol containing the alkyl group is preferably in the range of 30 to 2,000. _The oil sowing and oil composition of the present invention is preferably used in a refrigerating refrigerator, especially the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before filling this page ) Installed, OK. 'Quan 4 252994 A7 B7 V. Description of the invention (5) The use of chemical hydrogen fluoride, etc. The referent's medium cooling is for the sake of clarity, and it will be divided into groups of oily lubricating machines. The specific amount of the specific or specific esters to be prepared, including the specific acid, including the carboxyl package, is divided into viscous groups, kinetic oil, smooth and smooth, and \) / with the η Λκ Μ machine < The number of alcohols and bases of the alkyl alcohols of alcohols is defined in this heading. The esters of oleic acid are smooth and lubricating. They are used as a viscous agent to make special vinegars and acids η) phosphorus (M or quantum fractions of hundreds of ester acids ( Please read the precautions on the back before filling this page.) The carboxylic acid ester used in the invention printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs has at least one vinegar group in its molecule, and the number average molecular weight (Μη) measured by GPC Of It ranges from 200 to 5,000, preferably 300 to 4,000, and W300 to 3,000 is the most suitable. The dynamic viscosity of this carboxylic acid ester at 100t is 2 to 100 cSt, M2.5 to 80 cSt, M3.0 It is most suitable to 70c St. In the present invention, the carboxylic acid esters described in the following gazettes are used, for example. Japanese Patent Laid-Open No. 3-227397 describes fatty acids (eg butyric acid, 2-methanoic acid containing 2 to 6 atoms) Propionic acid, valeric acid, 2-methylbutyric acid, 3-methylbutyric acid, hexanoic acid, 2-ethylbutyric acid, 2-methylpentanoic acid and mixtures thereof) and neopentyl polyols (eg pentaerythritol , Dipentaerythritol, tripentaerythritol, four season pentaerythritol, bis (trimethylol) propane and mixtures of the resulting carboxylic acid esters. Examples of such carboxylic acid esters include neopentyl di-2-methylhexanoate, Neopentyl dibutyrate, neopentyl dicaprate and neopentyl diheptanoate. Among them, neopentyl di-2-methylhexanoate is preferred. Japanese Patent Laid-Open No. 3-128891 indicates that at least one does not have The paper size of the ether-bonded paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 5 A 7 B7 252994 V. Invention description (6) (Please read the precautions on the back before filling in this ), A carboxylic acid ester obtained from a divalent alcohol containing 5 to 12 nitrate atoms and at least one linear or branched monovalent fatty acid containing 3 to 18 sulfonic atoms, and is composed of at least one type that does not have ether linkage A carboxylic acid ester of a divalent alcohol containing 5 to 12 sulfonic atoms, at least one straight bond or branched chain monovalent fatty acid containing 3 to 18 sulfonic atoms, and at least one polybasic acid containing 4 to 14 sulfonic atoms. Examples of the carboxylic acid esters include 2,2-dimethyl-1,3-propanediol didecanoate, 2-butyl-2-ethyl-1,3-propanediase dicapric acid, 2, 2-Dimethyl-3-methylpentanoate and di-2-methylhexanoic acid 3-methyl-1,5-pentanediol ester. Among them, M2, 2-dimethyl-3-methylvalerate and di-2-methylhexanoic acid 3-methyl-1,5-pentanediol ester are the best. Examples of divalent alcohols containing 5 to 12 艪 塪 atoms without ether linkage, including neopentyl glycol 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl -1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol and 2-ethyl-1,3 -Hexanediol. Examples of the printing of straight-chain or branched monovalent fatty acids containing 3 to 18 bowel sulfonic acids by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, including propionic acid, isopropyl acid, butyric acid, isobutyric acid, valeric acid, caproic acid , Heptanoic acid, isoheptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, 3,5, 5-trimethylhexanoic acid, capric acid, undecanesulfonic acid, lauric acid, lignin acid, palmitic acid , Stearic acid, isostearic acid, oleic acid, linseed oleic acid and linseed olein. Examples of polybasic acids containing 4 to 14 slap nitrate atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid and maleic acid Diacid. In addition, Japanese Patent Laid-Open Nos. 4-2 0 597, 3-2 1 7 49 No. 3, and No. 3-128992 indicate that multi-enzymes (such as trimethylolethane, trimethylolpropylene, etc.) are applicable to Chinese countries. Standard (CNS) A4 specification (2) 〇X 297 mm) 6 ^ 2994 Α7 ___ Β7 5. Description of the invention (7) Institute, pentaerythritol and neopentylase) and monocarboxylic acid (such as 2-ethyl Carboxylic acid ester derived from hexanoic acid, heptanoic acid and decanoic acid> or its derivatives. Example package of the carboxylic acid (please read the precautions on the back before filling this page) contains: ⑴From trimethylolpropane ( 1 and ears) and 2-ethylhexanoic acid (3 its ears) constitute the vinegar, which is represented by the following formula: C2H5C [CH2〇OCCH2 (C2H5> < CH2) 3CH3] 3; ⑵by trimethylolpropane Uchil> and 3, 5, 5-trimethylhexanoic acid constitute the three cool, is represented by the following formula: C2H5 [CH2〇OCCH2CH (CH3> CH2C (CH3) 3] 3; (3) by trimethylol Propane (1 its ears), 2-ethylhexanoic acid U. 5 and ears) and 3, 3, 5-trimethylhexanoic acid (1.5 its ears) composed of triesters; ⑷ is composed of bis (trimethylol Propane) (1 cumur>, n-hexanoic acid (2 qi)> and 2,4-dimethylvaleric acid (2 qi) The tetraester is represented by the following formula: [RCOOCH2] 2C (C2H5) CH2〇CH2C (C2H5> [CH2〇COR] 2 (where R is-< CH2) 4CH3 or -CH (CH3) CH2CH- (CH3 ) 2), and ⑹ is composed of bis (trimethylolpropane) (1 mole) and 3,3, 5-trimethylhexanoic acid (4 and ear), which is expressed by the following formula: Ministry of Economic Affairs Du Printed by the Central Bureau of Standards for Consumer Cooperation [RC00CH232C (C2H5) CH20CH2C (C2Hb) [CH20C0R] 2 [where R is -C Η 2 CHC (C Η 3> C Η 2 c (C Η 3) 3], Among the acid vinegars obtained from multi-enzymes and monocarboxylic acids or their derivatives, carboxylic acid esters of ⑴ to ⑹ are suitable, and M carboxylic acid esters ⑵, ⑷ and ⑹ are most suitable. Different from carboxylic acid esters ⑴ to ⑸ Examples of other carboxylic acid esters include pentaerythritol tetrabutyrate, pentaerythritol tetrapivalate, pentaerythritol tetraheptanoate, pentaerythritol tetracaprylate, tetra-2-methylhexanoic acid pentaerythritol And 4-2, 2-2 7 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) L52994 A7 B7 5. Invention description (8) (Please read the precautions on the back before filling this page) A Pentaerythritol Ester-3-methylpentanoate. Among them, Μ 四Pentaerythritol vinegar, pentaerythritol tetrapentate, pentaerythritol tetracaprate, pentaerythritol tetra-2-methylhexanoate, and pentaerythritol tetra-2,2-dimethyl-3-methylpentanoate Pentaerythritol tetra-2-methylhexanoate and pentaerythritol tetra-2,2-dimethyl-3-methylpentanoate are the most suitable. In addition, the international patent describes the carboxylic acid ester derived from a polyhydric hydroxyl compound containing at least two hydroxyl groups and a carboxylic acid in the case of the wife of the country of the case No. 505602/1991. Examples of polyhydroxy compounds include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene fermentation, glycerol, neopentyl glycol, 12-butanediol, 1,3-butanediol, 1,4-butanediol, pentaerythritol, dipentaerythritol, tripentaerythritol, triglycerol, tetramethylolpropane and sorbitol. Examples of carboxylic acids include straight-chain saturated monocarboxylic ethers such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, and heptanoic acid; branched saturated monocarboxylic acids such as 2-ethyl-n-butyric acid, 2-hexyl Capric acid, isostearic acid, 2-methylhexanoic acid, 3,5, 5-trimethylhexanoic acid, 2-ethylhexanoic acid, neoheptanoic acid and neodecanoic acid; saturated dicarboxylic acids such as succinic acid; And unsaturated dicarboxylic acids such as maleic acid. Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Examples of such carboxylic acid esters include sorbitan hexabutyrate and pentose sorbate. If the aforementioned carboxylic acid esters are arranged in the proper order, the order is the carboxylic acid vinegar described in Japanese National Publication No. 505602/1991 of the International Patent Application, Japanese Patent Laid-Open No. 4-2 0597, 3-217493 No. 3-128992 and the carboxylic acid vinegar described in Japanese Patent Laid-Open No. 3- 1 2 8 99 No. 1 and the carboxylic acid ester described in Japanese Patent No. 3-227397. This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 8 A 7 B7 C52994 V. Description of the invention (9) Sour koji (Please read the precautions on the back before writing this page) The sulfonate ester has at least one carbonate group in the molecule, and the number average molecular weight measured by GPC (Mr〇 is 200 to 5,000, M 300 to 4,000 is suitable, M 300 to 3,000 is most suitable. The kinetic viscosity of this nitrate ester at 100 t is 2 to 100 cSt, preferably M 2.5 to 80 cSt, and M 3.0 to 70 cSt is most suitable. Examples of the sulfonic acid vinegar include fatty alcohols containing 1 to 6 primary hydroxyl groups (E.g. trimethylolethane, trimethylolpropane and neopentyl glycol) and low-grade carboxylic acids (e.g. dimethyl sulfonate, diethyl sulfonate, diphenyl sulfonate, ethidium nitrate) Ester and sulfonic acid propionyl chloride) or carbonyl halide (such as phosgene). Especially worth mentioning is bis (methylhexylsulfonic acid) 3_methyl-1,5-pentanyl ester, di (Methylhexyl sulfonic acid) 3-ethyl-3-butyl-1,5-pentanyl ester, etc. These esters are described in Japanese Patent Laid-Open No. 3-217498. Other examples of master esters are Narrated in Japan No. 4-18490 of the following compounds. The Ministry of Economic Affairs Central Standards Bureau Staff Consumer Cooperatives printed ⑴ formula U0C00CH2) 4C compound, where R is isohexyl or isoheptyl, ⑵ formula (R0C00CH2> 3CCH3 compound, formula Where R is isohexyl or isoheptyl, and a compound of the formula (R0C00CH2> 3CCH20CH2C (CH20C00R) 3, where R is isopropyl or isobutyl. Unlike the above carbonates, it can also be used in Japanese Patent Laid-Open No. 3 The glycol ether carbonate described in No. -247695 is represented by the following formula: Ri-0-[(R3) 0] n-C00-R2 where 1 ^ and 112 are each a fat containing 1 to 20 partial carbon atoms Clan, Zhiuan, Fang 9 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 252994 A7 B7 The Ministry of Economic Affairs Central Standards Bureau employee consumer cooperatives are prepared. V. Invention description (1〇) Fanzu or Fang Fan-aliphatic hydrocarbons, R3 is ethylidene or propylidene, and η is an integer from 2 to 100. Examples of diol tunneling esters represented by the above formula include compounds of the following formula: (1) CH3- [C3H6〇] -COO-C3H6CH3 (2) n-C4H9〇- [C3H6〇] n-CO〇-CH3 where n is an integer from 2 to 100, preferably an integer from 5 to 90, M1 Integers from 0 to 60 are more preferred. Furthermore, polynitrate derived from the fermentation of sugars such as sorbus can be used, and polyesters that do not have a scalp-like structure and are represented by the following formula: CH3-〇- [ C3H6〇] n-CO〇- [C3H6〇] nCH3 where n is an integer of 2 to 100, M3 to 90 is better, M5 to 60 is even better. Among the nitrates shown above, the above-mentioned glycol ether sulfonates described in Japanese Patent Laid-Open No. 3-247695 are preferably used, and polysulfonates derived from sorbitan and polycarbonates having no cyclic structure are obtained. ester. If the aforementioned sulfonate esters are arranged in the proper order, they are the above-mentioned diol nitrate described in Japanese Patent Laid-Open No. 3-247695, polysulfonate derived from sugar such as sorbose, and no A polyphosphate ester on the ring structure, and a sulfonate described in Japanese Patent Laid-Open No. 3-217498. Alcohol> Fermentation The fluoroalkyl group-containing alcohol used in the present invention has a molecular weight of usually 30 to 2,00 0, preferably 50 to 1,000, and more preferably 100 to 900. Examples of fluoroalkyl group-containing alcohols, including monovalent fluoroalkyl group-containing alcohols such as three paper standards are applicable to China National Standard (CNS) A4 specifications (2WX297mm) ι 〇 (please read the precautions on the back before filling in this Page) Install, OK, Fruit. 52994 A7 B7 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (; Π) Fluoroethanol, full «hexyl ethyl yeast, full« octyl ethanol, perfluorodecyl ethanol, 1Η, 2Η, 5Η-octafluoropentanol and hexafluoroisopropanol; and fluoroalkyl-containing divalent alcohols such as 3- (2-perfluorohexyl) ethoxy-1,2-dihydroxypropane and Ν-2, 3-dihydroxy n-propyl perfluorooctyl sulfonamide. Among them, perfluorohexyl ethanol, perfluorooctyl ethanol and percyanodecyl ethyl fermentation are preferably used. These fluoroalkyl group-containing alcohols can be used alone or in combination. In the present invention, the usage amount of the cyanoalkyl group-containing alcohol is M100 parts by weight of carboxylic acid ester or carbonate, which is 0.001 to 15 parts by weight, preferably W0.1 to 10 parts by weight, more preferably M1 to 8 parts by weight good. When the above-mentioned amount of krypton alkyl-containing yeast M is used, the wear amount of gold and titanium in the sliding parts of the compression refrigerator using HFC such as R-134a as the refrigerant can be significantly reduced. In addition, carboxylic acid esters or benzoic acid esters can avoid lowering the solubility, and can prevent the lubricating oil composition for refrigerators from greatly reducing the viscosities. Since the lubricating oil composition for refrigerators of the present invention uses a relatively small amount of the above-mentioned expensive fluorine-containing alkyl alcohol, it is very economical. The lubricating oil for refrigerators of the present invention may contain known abrasion-reducing agents in addition to carboxylic acid esters or sulfonic acid esters as base oils of lubricating oils and alcohols containing fluoroalkyl groups. Examples of the abrasion-reducing agent include phosphate esters; acidic phosphate esters; amine salts of acidic phosphate esters; fatty acids; single enzymes such as decanoate, lauryl alcohol, 2-ethylhexylase and 2-ethyl-1,3-hexanedi Alcohol; Polyols such as 1,2-decanediol, 1,2-octanediol, triethylene glycol, and diethylene glycol; dimethyl ether of ethylene oxide / oxopropane block copolymer; amine Formic acid vinegar; zinc dithiophosphate; carboxylic acid ester; sulfite salt; thiolease; and alkyl polysiloxane fluoride. The paper standard of these abrasion reducers is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 11 (please read the precautions on the back before writing this page), install ?,? Τ. '# · A7 B7 52994 5 2. Description of the invention (12) It can be used alone or in combination. (Please read the precautions on the back before filling in this page) In the present invention, the lubricating oil composition for refrigerators may also contain oiliness improvers, defoamers, anti-corrosive agents and coloring which are commonly used in lubricating oils such as refrigerator oils Thin I, but M is not limited to the purpose of the present invention. The lubricating oil composition for refrigerators of the present invention can be obtained, for example, by adding a specific amount of a fluorine-containing alkyl alcohol to a specific amount of carboxylic acid vinegar or iodate, followed by stirring. The temperature of the liquid during stirring should be within the range of room temperature to 150¾. The stirring is preferably carried out under inert gas. Effect of the Invention As described above, the lubricating oil composition for a refrigerator of the present invention includes 100 parts by weight of carboxylic acid vinegar having a number average molecular weight (Mn) of 200 to 5,000 and a dynamic viscosity at 10010 of 2 to 100 cSt Or a sulfonate with a number-average molecular weight (Μη> 200 to 5,000 and at 100 t: a dynamic viscosity of 2 to 100 cSt, and 0.001 to 15 parts by weight of fluorine-containing alkyl alcohol. Therefore, this composition can be significantly Reduce the wear and tear on the sliding part of the sliding part of the compression chiller in which hydrofluorocarbons such as R_134a are used as refrigerant. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Furthermore, the lubricating oil composition of the present invention can also be used in different For compression freezers, this is due to its superior lubricating properties. For example, the present invention can be further explained by referring to the following examples, but it is not limited by these examples. In these examples, The testing of various properties is carried out according to the following method. 12 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) C52994 A7 B7 Printed by the Employees Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Explanation (13) [Test method] a. The dynamic viscosity and viscosity index at 10〇υ and 40T are tested in accordance with JIS K2283. B. The density is tested in accordance with JIS K2249. C. The roll tack is tested in accordance with JIS K2265. D. Load capacity (lubricating oil pressure and heat resistance value) According to ASTM D-2670, using a lubricating oil pressure and heat resistance tester under 250 pounds of load, after 5 minutes of warm car lotus turning operation, continue to increase the load, And when the burn marks appear, the resulting increased load value is taken as the load capacity. The resistance is tested in accordance with JI s C 2 101. f. The acid value is tested in accordance with JIS K2501. G. And R- The compatible lubricating oil composition of 134a and R-134aM are added to the glass tube in different proportions, and then sealed, and the composition and R-134a are made compatible with each other according to JIS K2211. Observe that the two are compatible with each other. Highest and lowest temperature (critical temperature). H. Abrasion wear test is carried out under the following conditions using a lubricating oil pressure and heat resistance tester, and the wear test is based on the M test piece (V block, shaft (please read first (Notes on the back will be written on this page).

、1T 采 本纸張尺度適用中國國家標準(CNS)A4規格(210X297公釐） 1 3 <52994 A7 B7 五、發明説明（14) 頸）之損失重量予以決定。 試胳修件： 樣品油漏：：90b 1 測試片：A4032之V塊（相當於JIS H4140合金號碼 403 2〉及依ASTM D- 32 3 3檷定的軸頸） 溢 度：125¾ 旋轉數：2 6 0 rpn 負 載：2 50磅30分鐮 氣體（冷媒）種類及流速：R-134a, 51/hr 耷者例Ί 於附有10篩板之蒸播柱之51燒瓶內，加入588g(4.98 莫耳）3-甲基-1,5-戊二醇，2,500g(21.42其耳〉甲基己醇（ 87%3_甲基己醇及13%5_甲基己醇之混合液），1 9 3 2g( 21. 45其耳）磺酸二甲酯及3.8g(0. 020莫耳〉之28重量％之 NaOCHs甲醇溶掖。 此混合液在110至160C之溫度及大氣壓力下加熱8小 時Κ皤除所得的甲醇。甲醇之產率為98¾ 。 接著，混合液在1 3 0至1 7 0 Ό之溫度及減颳（1 3 0至 lOmuHg)下加熱8小時以皤除甲醇，硪酸二甲酯，甲基己 醇及硪酸甲酯甲基己酯。 Μ含有所用NaOCHs之5倍莫耳量之硪酸銨之水溶液淸 洗所得的混合液後，利用蒸躕法去除過置的磺酸二（甲基 己）酯而得l,480g聚硕酸酯。 至於分析之結果，發現由此而得之聚硪酸酯係具有下 (請先閲讀背面之注意事項再填寫本頁) 裝· 、可. 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(2I0X 297公釐） ι 4 A7 B7 ^52994 五、發明説明（15 ) 列結構之二磺酸酯與其縮合物之混合物。 (請先閲讀背面之注意事項再填寫本頁) C7Hi50C00CH2CH2CH(CH3)CH2CH20C00C7Hi5 所得的二硝酸酯MGPC測得的數目平均分子量（Μη)為 450,密度為l,001g/nl,在lOOC之動黏度為5.67cSt,在 40t：之動黏度為29.6cSt,及總酸價為O.Olug-KOH/g。 兹者例2「羧酸醋之製備] 於附有攪拌棒、玻璃製氮氣吹氣管、溫度計及具有冷 却管之水分離器之1β四頸可分離燒瓶内，加入134g(1.0 莫耳）三羥甲基丙烷、664g(4.2莫耳）3,5, 5 -三甲基癸酸及 2g對-甲苯磺酸，而在氮氣流及1901C下進行酯化反應8小 時，同時自集統去除去成的水。 反應完成後，W250cc之10%磺酸納水溶液清洗反應 產物3次，接著在減壓之lTorr及12〇υ下乾燥1小時而得 540g三羥甲基丙烷之3, 5, 5 -三甲基癸酸三酯。 所得的羧酸醋MGPC測得的數目平均分子量（Μη)為550 ,密度為0.941g/ml,在100t之動黏度為7.1cSt,在401C 之動黏度為51.7cSt,及緦酸價為O.Olmg KOH/g。 經濟部中央標準局員工消費合作社印製 審旃例Ί 使100重置份之由參考例1而得的二硪酸酯及4重量 份之2-(全氟辛基）乙醇在8〇υ混合而得一溶液。 由此而得的濶滑油組成物進行磨耗試驗以決定金鼷磨 耗置。 結果示於表1。 此潤滑油組成物在loot：之動黏度為6_0cSt、在40Ό 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐） 15 A 7 B7 52994 五、發明説明（16) 之動黏度為32.OcSt,黏度指數為136、傾流點- 60.Ot, 負荷能力（潤滑油耐壓耐熱值）爲880磅，電阻係數3.3x 經濟部中央標準局員工消費合作社印製 10 1 5 Ω ♦ c m 及 總 酸 價 0 . 0 1 mg Κ0Η /g 0 再 評 估 潤 滑 油 組 成 物 與R- 134a 之 相 容 性 〇 由 結 果 可發 現 當 潤 滑 油 組 成 物 與 R ~ 1 34a 之 重 量 fcb 在 15 :8 5之間時， 在 較 高 側 之 臨 界 溫 度 為 9 1 V ,而 在 較 低 側 之 臨 界 溫 度 則 為 -60¾ , 且此潤滑油組成物與R -1 34 a之相容性優越( > 蓄 旃 例 2 除 了 2 - (全氟辛基） 乙 醇之 加 入 量 變 成 4 . 0重量份外， 餘 與 實 施 例 1 同 法 操 作 ， 可得 潤 滑 油 組 成 物 〇 由 此 而 得 的 潤 滑 油 組 成物 進 行 磨 耗 試 驗 Μ 決 定 金 羼磨 耗 量 〇 結 果 示 於 表 1 c > 奮 旅 例 3 除 了 使 用 1Η ,2H， 5H -八氰戊酵取代2 -( 全 氟 辛 基 )乙醇 外 » 餘 與 實 施 例 1 同 法 操 作， 可 得 潤 滑 油 組 成 物 0 由 此 而 得 的 潤 滑 油 組 成物 進 行 磨 耗 試 驗 Μ 決 定 金 羼磨 耗 量 0 結 果 示 於 表 1 ( > 旃 例 4 除 了 1 Η ,2Η , 5H -八氨戊醇之加入量改變成0 .0 4重置份 外 t 餘 與 實 施 例 3 同 法 操 作， 可 得 潤 滑 油 組 成 物 〇 由 此 而 得 的 潤 滑 油 組 成物 進 行 磨 耗 試 驗 以 決 定 金 羼磨 耗量。 (請先閲讀背面之注意事項再填寫本頁) 裝. •π. 求· 本紙張尺度適用中國國家標準(CNS)A4規格(21〇Χ Ν7公釐) 16 52994 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（17) 結果示於表1。 奮旃例5 除 了 2- (全氟辛基） 乙 醇 之 加 入 量 改 變 成 6 重 量 份 外 ， 餘 與 賨 施 例 1 同 法 操 作 » 可 得 潤 滑 油 組 成 物 〇 由 此 而 得 的 潤 滑 油 組 成 物 進 行 磨 耗 試 驗 Μ 決 定 金 屬 磨 耗 置 0 結 果 示 於 表 1 < SL m 例 6 除 了 使 用 參 考 例 2 之 羧 酸 醋 Μ 取 代 參 考 例 1 之 二 磺 酸 酯 外 } 餘 與 實 施 例 1 同 法 操 作 可 得 潤 滑 油 組 成 物 〇 由 此 而 得 的 潤 滑 油 組 成 物 進 行 磨 耗 試 驗 Μ 決 定 金 鼷 磨 耗 量 〇 結 果 示 於 表 1 ( hh 較 例 1 僅 參 考 例 1 之 二 硪 酸 酯 進 行 磨 耗 試 驗 Μ 決 定 金 屬 磨 耗 量 〇 結 果 示 於 表 1 _ y fcL 較 例 2 除 了 2- (全氟辛基） 乙 酵 之 加 入 量 改 變 成 0 . 000 4 重 量 份 外 J 餘 與 實 施 例 1 同 法 操 作 可 得 潤 滑 油 組 成 物 〇 由 此 而 得 的 潤 滑 油 組 成 物 進 行 磨 耗 試 驗 Μ 決 定 金 羼 磨 耗 量 0 結 果 示 於 表 1 0 hh 較 例 3 僅 參 考 例 2 之 羧 酸 酯 進 行 磨 耗 試 驗 以 決 定 金 羼 磨 耗 量 (請先閲讀背面之注意事項再填寫本頁) 裝 、\=° 綰果示於表1。 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐） 17 252994 五、發明説明j；8 ) 表 A 7 B7 潤滑 油基 油 含氟烷基之 酵類 磨 耗 [證g] 量 種 類 用量 棰類 用量 V塊 軸頸 全部 實施例1 參考例1 之羰酸醋 100 A 4 0 1 1 實施例2 參考例1 之羰酸酯 100 A 0.4 1 9 10 實施例3 參考例1 之羰酸酯 100 B 4 1 1 2 實施例4 參考例1 之羰酸酯 100 B 0.04 1 11 12 實施例5 參考例1 之羰酸酯 100 A 6 1 2 3 實施例6 參考例2 之羧酸酯 100 A 4 2 10 12 比較例1 參考例1 之羰酸酯 100 - - 4 15 19 比較例2 參考例1 之類酸酯 100 A 0.004 4 14 18 比較例3 參考例2 之羧酸酯 100 - - 7 20 27 .....I.....I.........A 裝 .....I.....訂 ..........一、'*". (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 備註： ⑴碩酸酯、羧酸酯及含氟烷基之醇類之各用置單位爲重量 份。 ⑵含氟烷基之酵類棰類 A: 2-(全氟辛基〉乙醇 B: 1H,2H,5H -八氟戊醇 本紙張尺度適用中國國家標準(CNS)A4規格(210><297公釐） 18、 1T Mining The size of this paper is in accordance with Chinese National Standard (CNS) A4 specification (210X297mm) 1 3 < 52994 A7 B7 V. Invention description (14) Neck) The weight loss is determined. Trial repair parts: Sample oil leakage :: 90b 1 Test piece: V block of A4032 (equivalent to JIS H4140 alloy number 403 2> and journal according to ASTM D-32 3 3) Overflow: 125¾ Number of rotations: 2 6 0 rpn Load: 2 50 pounds 30 minutes Sickle gas (refrigerant) Type and flow rate: R-134a, 51 / hr Example Ί In a 51 flask equipped with a 10 sieve plate steaming column, add 588g (4.98 Mohr) 3-methyl-1,5-pentanediol, 2,500g (21.42 mol> methylhexanol (a mixture of 87% 3-methylhexanol and 13% 5-methylhexanol), 1 9 3 2 g (21.45 mol) of dimethyl sulfonate and 3.8 g (0.020 mol) of 28% by weight of NaOCHs methanol are dissolved. This mixed liquid is heated at a temperature of 110 to 160C and atmospheric pressure After 8 hours, the obtained methanol was removed by K. The yield of methanol was 98¾. Next, the mixed liquid was heated at a temperature of 130 to 170 ° and reduced scraping (130 to 10 muHg) for 8 hours to remove methanol, Dimethyl sulfate, methylhexanol and methyl hexanoate. Μ An aqueous solution containing 5 times the molar amount of NaOCHs used to wash the resulting mixture and remove it by steaming Di (methylhexyl) sulfonate I obtained 1,480g of polyester. As a result of the analysis, it was found that the resulting polyester had the following (please read the precautions on the back before filling out this page). The size of the paper printed by the Bureau ’s Consumer Cooperatives is applicable to the Chinese National Standard (CNS) A4 specification (2I0X 297 mm) ι 4 A7 B7 ^ 52994 5. Description of the invention (15) A mixture of disulfonic acid esters and their condensates. (Please read the precautions on the back before filling this page) C7Hi50C00CH2CH2CH (CH3) CH2CH20C00C7Hi5 The number average molecular weight (Μη) measured by the obtained dinitrate MGPC is 450, the density is 1,001g / nl, and the dynamic viscosity at 100C is 5.67cSt at 40t: The dynamic viscosity is 29.6cSt, and the total acid value is O. Olug-KOH / g. Example 2 "Preparation of carboxylic acid vinegar] with a stir bar, glass nitrogen gas blower, thermometer Into a 1β four-necked separable flask with a water separator with a cooling tube, add 134g (1.0 mol) of trimethylolpropane, 664g (4.2 mol) of 3,5,5-trimethyldecanoic acid and 2g of -Toluene sulfonic acid, and the esterification reaction was carried out under nitrogen flow and 1901C for 8 hours, and at the same time from the system After the reaction is completed, the reaction product is washed with 10% aqueous solution of sodium sulfonate W250cc 3 times, and then dried under reduced pressure of lTorr and 12〇υ for 1 hour to obtain 540g of trimethylolpropane 3, 5, 5-Trimethyldecanoic acid triester. The number average molecular weight (Μη) of the resulting carboxylic acid MGPC measured was 550, the density was 0.941g / ml, the dynamic viscosity at 100t was 7.1cSt, the dynamic viscosity at 401C was 51.7cSt, and the acid value was O. Olmg KOH / g. The Ministry of Economic Affairs, Central Bureau of Standards, Staff Cooperative Printed an Examination Example Ί 100 parts of the dibasic acid ester obtained in Reference Example 1 and 4 parts by weight of 2- (perfluorooctyl) ethanol were mixed in 8〇υ And get a solution. The thus-obtained lubricating oil composition was subjected to an abrasion test to determine the consumption of the gold halide mill. The results are shown in Table 1. This lubricating oil composition has a dynamic viscosity of 6_0cSt at 40 °. This paper standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 15 A 7 B7 52994 5. The invention description (16) has a dynamic viscosity of 32 .OcSt, viscosity index is 136, pour point-60.Ot, load capacity (pressure and heat resistance value of lubricating oil) is 880 pounds, resistivity is 3.3x printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 10 1 5 Ω ♦ cm And the total acid value of 0.01 mg Κ0Η / g 0 and then evaluate the compatibility of the lubricating oil composition with R-134a. From the results, it can be found that the weight fcb of the lubricating oil composition and R ~ 1 34a is 15: 8 5 In between, the critical temperature on the higher side is 9 1 V, and the critical temperature on the lower side is -60¾, and the compatibility of this lubricating oil composition with R -1 34 a is excellent (> Example 2 Except that the addition amount of 2- (perfluorooctyl) ethanol became 4.0 parts by weight, the same method as in Example 1 was performed, and a lubricating oil composition was obtained. The composition was subjected to an abrasion test Μ to determine the amount of abrasion. The results are shown in Table 1 c. Example 3 of Fenlv Except for the use of 1Η, 2H, 5H-octapentanopentanyl instead of 2- (perfluorooctyl) ethanol. Example 1 In the same way, the lubricating oil composition can be obtained. 0 The lubricating oil composition thus obtained is subjected to an abrasion test. M The amount of gold wear is determined. The results are shown in Table 1 (> Example 4 except 1 Η, 2Η, The amount of 5H-octapentyl alcohol added was changed to 0.0 4 except for the rest. The operation was the same as in Example 3. The lubricating oil composition was obtained. The resulting lubricating oil composition was subjected to an abrasion test to determine The consumption of Jin Yun. (Please read the precautions on the back before filling in this page) Pack. • π. This paper size is applicable to China National Standards (CNS) A4 specifications (21〇Χ Ν7 mm) 16 52994 A7 B7 Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the consumer cooperative V. Description of the invention (17) The results are shown in Table 1. Example 5 Except that the addition amount of 2- (perfluorooctyl) ethanol was changed to 6 parts by weight, I proceeded in the same way as in Example 1 »A lubricating oil composition was obtained. The resulting lubricating oil composition Perform the abrasion test Μ to determine the metal abrasion and set it to 0. The results are shown in Table 1 < SL m Example 6 Except that the carboxylic acid vinegar M of Reference Example 2 was used instead of the disulfonate of Reference Example 1, the same method as Example 1 was used. The lubricating oil composition was obtained. The resulting lubricating oil composition was subjected to an abrasion test Μ to determine the amount of gold wear. The results are shown in Table 1 (hh Comparative Example 1 only the reference example 1 bis acrylate was subjected to the abrasion test M to determine the metal Abrasion loss 〇 The results are shown in Table 1 _ y fcL Comparative Example 2 except 2- (full (Fluorooctyl)) The amount of ethyl yeast added was changed to 0.004 parts by weight except for J. The same composition as in Example 1 was used to obtain a lubricating oil composition. The resulting lubricating oil composition was subjected to an abrasion test. Abrasion amount 0 The results are shown in Table 1 0 hh Comparative Example 3 Only the carboxylic acid ester of Example 2 was subjected to the abrasion test to determine the amount of gold and abrasion (please read the precautions on the back before filling this page). Shown in Table 1. The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 17 252994 V. Description of the invention j; 8) Table A 7 B7 Lubricating oil base oil containing fluoroalkyl fermented attrition [certification g] Amount of type, amount of use, type of V, all of the journal of the block Example 1 Reference Example 1 Carbonate 100 A 4 0 1 1 Example 2 Reference Example 1 Carbonate 100 A 0.4 1 9 10 Example 3 Reference Example 1 Carbonate 100 B 4 1 1 2 Example 4 Reference Example 1 Carbonate 100 B 0.04 1 11 12 Example 5 Reference Example 1 Carbonate Ester 100 A 6 1 2 3 Example 6 Carboxylate of Reference Example 2 100 A 4 2 10 12 Comparative Example 1 Carbonate 100 of Reference Example 1--4 15 19 Comparative Example 2 Reference Example 1 100 A 0.004 4 14 18 Comparative Example 3 Reference Example 2 Carboxylate 100--7 20 27 ..... I ..... I ......... A Pack ..... I ..... order .......... 1. '* ". (please read the notes on the back before filling in this page) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs: ⑴ The unit of each of the master ester, carboxylic acid ester and fluoroalkyl group-containing alcohol is parts by weight. ⑵Fluorinated alkyl-containing yeast A: 2- (perfluorooctyl) ethanol B: 1H, 2H, 5H-octafluoropentanol This paper standard is applicable to China National Standards (CNS) A4 specifications (210 > < 297 mm) 18

Claims (1)

5299 i /λ..厶、口 ..1- /卜 A8 B8 C8 D8 申請專利範圍 1 · 一種冷凍機用潤滑油組成物，包括： 100重量份之具有數目平均分子量（Mn)200至5,000 及在lOOt之動黏度2至lOOcSt之羧酸醋、或具有數目 平均分子量^1〇200至5,000及在100^之動黏度2至 lOOcSt之碩酸酯，及 0.001至15重量份之含氰烷基之醇。 2. 如申請專利範圍第1項之冷陳機用濶滑油組成物，其 中含氟烷基之醇之分子量為30至2,000。 3. 如申請專利範圍第1或2項之冷凍機用潤滑油組成物 ，其中該組成物係使用於壓縮型冷凍機。 4. 如申請專利範圍第3項之冷凍機用潤滑油組成物，其 中該組成物係使用於其中使用氫化轘碳化物（HFC)作為 冷媒之壓縮型冷凍機。 --------Γ裝！ (請先閲讀背面之注$項再填寫本頁) 、1T 經濟部中央標準局負工消費合作社印製 本紙張尺度適用中國國家揉準（CNS ) Α4规格（210Χ297公釐） 195299 i / λ .. 厶 、 口 ..1- / Bu A8 B8 C8 D8 Patent application scope 1 · A lubricating oil composition for refrigerators, including: 100 parts by weight having a number average molecular weight (Mn) 200 to 5,000 and Carboxylic acid ester with a dynamic viscosity of 2 to 100 cSt at 100 t, or a master ester with a number average molecular weight of ^ 1200 to 5,000 and a dynamic viscosity of 2 to 100 cSt at 100 ^, and 0.001 to 15 parts by weight of cyano-containing alkyl groups Of alcohol. 2. For example, the cold lubricating oil composition for cold aging machine according to item 1 of the patent application, wherein the molecular weight of the fluoroalkyl group-containing alcohol is 30 to 2,000. 3. As for the lubricating oil composition for refrigerators in the scope of patent application item 1 or 2, the composition is used in compression-type refrigerators. 4. As for the lubricating oil composition for refrigerators according to item 3 of the patent application, the composition is used in a compression type refrigerator in which hydrogenated carbide (HFC) is used as a refrigerant. -------- Γ installed! (Please read the note $ item on the back and then fill out this page), Printed by 1T Ministry of Economic Affairs, Central Standards Bureau, Negative Consumers Cooperative. This paper size is applicable to China National Standardization (CNS) Α4 specification (210Χ297mm) 19
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EP0655494A1 (en) 1995-05-31
CA2135839A1 (en) 1995-05-17
JPH07138588A (en) 1995-05-30

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