1359862 (1) 九 '發明說明 【發明所屬之技術領域】 本發明係有關新穎之冷凍機油組成物，特別是使用自 然系冷媒之潤滑性優良的冷凍機油組成物。 【先前技術】 一般冷凍機，例如由壓縮機、凝縮器、膨脹閥、蒸發 器所組成之壓縮型冷凍機的壓縮式冷凍循環系統內具有， 能使冷媒及潤滑油之混合液循環於該密閉系內之構造。先 前該壓縮型冷凍機所使用之冷媒爲，二氯二氟甲烷（R-12) 、氯二氟甲烷（R-22)等氯氟碳，或倂用其製造多數潤滑油 。但將先前冷媒用之該呋喃化合物放出大氣中時，會有破 壞存在於成層圈之臭氧層等污染環境問題，因此改用1，1 ，1，2-四氟乙烷（R-134 a)所代表之氫氟碳或氟碳等新冷媒 。該氫氟碳等雖不會破壞臭氧層，但大氣中壽命非常長而 會影響地球暖化，故近年來開始討論使用無前述問題之自 然系冷媒。 又，冷凍機油組成物所使用之特壓劑爲，三甲酚磷酸 酯（TCP)所代表之磷系添加劑。但該磷系極壓劑會因熱分 解，加水分觸或摩擦面之摩擦化學反應等而變質污染化之 問題產生。另外變質污染化會消耗磷系添加劑，故無法長 時間維持潤滑性能，而導致燒結及磨損。 先前提案之使用呋喃系冷媒的冷凍機用潤滑油組成物 如，添加有機硫化合物而具有優良耐熱性、耐磨損性，..及 -4- (2) (2)1359862 對溫度變化之黏度變化較少，且具有優良呋喃溶解性之含 硫潤滑油（專利文獻1 )。專利文獻1之該呋喃系冷凍機用潤 滑油組成物中’有機硫化合物之含量係重點，又，例如以 礦物油作爲基油用時，有機硫化合物可爲存在礦物油中之 天然物。但，僅控制使用自然系冷媒之冷凍機用潤滑油組 成物中的硫含量時，將無法得到充分之耐磨損性及特壓性 〇 專利文獻1 :特開昭5 8- 1 03 5 94號公報 【發明內容】 爲了解決上述課題，因此本發明之目的爲，提供能長 時間維持潤滑性能，且冷凍循環時不阻塞毛細管之使用自 然系冷媒的冷凍機用潤滑油組成物。 本發明者針對具有上述特性之冷凍機用潤滑油組成物 專心硏究後發現，特定基油中含有特定之有機硫化合物的 冷凍機油使用自然系冷媒時，可長時間維持潤滑性能’且 冷凍循環時不阻塞毛細管，而完成本發明。 即，本發明係提供含有（A)聚烷二醇、多元醇酯、聚 烯烴、烷基苯及礦物油中所選出至少一種所形成之基 油、（Β)硫含量爲35質量％以下之有機硫化合物及（C)碳酸 氣體、烴及氨中所選出至少1種所形成之冷媒的冷凍機油 組成物中，全硫量對（Α)成分及（Β)成分之合計量爲0·01至 0.1質量％的冷凍機油組成物。 (3) (3)1359862 實施發明之最佳形態 本發明之潤滑油組成物所使用的基油爲，（A)聚烷二 醇、多元醇酯、聚α-烯烴、烷基苯及礦物油中所選出至 少1種。 聚烷二醇較佳爲下列一般式（I)所示之物。 R，-[(〇R2)m-〇R3]n (I) 式中’ R1爲氫、碳數1至10之烷基、硫基或具有2至6 個鍵結部位之脂肪族烴基，R2爲碳數2至4之伸烷基，且可 爲單獨聚合物或共聚物。R3爲氫、碳數1至10之烷基或醯 基’ η爲1至6之整數，m爲mxn之平均値爲6至80的整數 〇 烷基可爲直鏈狀、支鏈狀或環狀、該烷基之具體例如 ，甲基、乙基、η-丙基、異丙基、各種丁基、各種戊基、 各種己基、環戊基、環己基等。該烷基之碳數較佳爲10以 下’ 1 0以下時對冷媒可得充分之相溶性。 又’醯基之烷基部分可爲直鏈狀、支鏈狀或環狀。該 醯基之烷基部分的具體例如，甲基、乙基、η_丙基、異丙 基、各種丁基、各種戊基、各種己基、環戊基、環己基等 。該醯基之碳數較佳同烷基爲10以下，10以下時對冷媒可 得充分之相溶性。 上述R1及R3可相同或相異。本發明之式⑴所示聚烷 二醇較佳爲，R1或R3中任何—方爲氫，而另一方爲烷基 -6- (4) (4)1359862 ，且該烷基較佳爲碳數1至3之烷基，特佳爲甲基。又較佳 爲，R1或R3均爲碳數1至3之烷基，特佳爲R1或R3均爲甲 基。本發明所使用之基油可爲，複數種聚烷二醇之混合物 〇 多元醇酯如，至少含有2個羥基之多價羥基化合物的 羧酸酯，較佳如下列一般式（Π)所示之物。 R4[OCOR5]f (II) 式中，R4爲烴基，R5爲氫原子或碳數1至22之烴基，f 爲2至6之整數，且複數[OCOR5]可相同或相異。 一般式（Π)中，R4所示烴基可爲直鏈狀或支鏈狀，較 佳爲碳數2至10之烷基。R5爲氫原子或碳數1至20之烴基， 較佳爲碳數2至16之烷基。一般式（II)所示多元醇酯可由， 下列一般式（ΙΠ) R4(OH)f (III) (式中，R4同上述） 所示多價醇與下列一般式（IV) R5COOH (IV) (式中，R5同上述） (5) (5)1359862 所示羧酸或其酯及酸鹵化物等反應性衍生物反應而得。 —般式（III)所示多價醇可爲各種之物，例如乙二醇、 丙二醇、丁二醇、新戊二醇、三羥甲基乙烷、三羥甲基丙 烷、甘油、季戊四醇、二季戊四醇、山梨糖醇等。又， (IV)所示羧.酸並無特別限制，例如丙酸、丁酸、三甲基乙 酸、戊酸、己酸、庚酸、3-甲基己酸、2_乙基己酸、辛酸 、壬酸、癸酸、月桂酸、肉豆蔻酸、棕櫚酸等。本發明所 使用之基油可爲，複數種多元醇酯之混合物。 聚- 烯烴爲碳數3至12之烯烴的低聚物，其分子 量爲200至5000，更佳爲300至2000。本發明所使用之基油 可爲複數種聚·α -烯烴之混合物。 烷基苯爲’以乙烯、丙烯、丁烯、異丁烯等低級單烯 烴；丙烯聚合而得之碳數6至40的支鏈狀烯烴；蠟、重質 油、石油餾分、聚乙烯、聚丙烯等熱分解而得之碳數6至 40的支鏈狀烯烴等爲烷基化劑，將苯、甲苯、二甲苯、乙 基苯、甲基乙基苯、二乙基苯及其混合物等芳香族烷基化 之物。烷基苯中苯所具有之烷基數爲1至3，特佳爲含有較 多具有2個烷基之烷基苯。又，本發明所使用之基油可爲 複數種烷基苯之混合物。 本發明基油所使用之礦物油並無特別限制，例如石鱲 系礦物油、萘系礦物油等’較佳爲硫含量2〇〇質量ppm以 下之物。礦物油中之硫含量會因原料用原油中之硫含量而 異’但較佳爲精製至200質量ppm以下。本發明所使用之 基油可爲複數種礦物油之混合物。 (6) (6)1359862 以上之物適用爲本發明之（A)基油，其中就安定性、 蒸發減量觀點特佳爲聚烷二醇、多元醇酯、聚-α-烯烴、 烷基苯。又，其可單獨使用或2種以上混合使用。 本發明所使用之（Α)基油的40 °C動黏度較佳爲3至 100Omm2/s。3mm2/s以上時可得充分之潤滑性能，1000 mm2/s以下時雖會使負荷過量，但可提高能量效率。就以 上觀點，基油之40°C動黏度又以5至500mm2/s爲佳，更佳 爲 5至 150mm2/s。 其次本發明之（B)成分的特徵爲，含有硫含量3 5質量％ 以下之有機硫黃化合物。硫含量超過35質量％時，會產生 變質污泥化。具體上會有如1分子中具有3個以上之硫般聚 硫化物的危險性。又，硫含量多於5質量％時，會降低（B) 成分之添加量而不宜。 本發明所使用之（B)有機硫化合物較佳如，脂肪族硫 化合物、雜環式硫化合物、芳香族硫化合物等。 脂肪族硫化合物之碳數較佳爲1 2以上，更佳爲1 4以上 ，特佳爲1 8以上。具體例如，二辛基硫化物、二十二烷基 硫化合物、二十四烷基硫化合物等。 雜環式硫化合物之碳多較佳爲8以上，更佳爲1 0以上 ’特佳爲12以上。具體例如，苯並噻吩、二苯並噻吩、吩 噻嗪、苯並噻喃、噻喃、噻嗯、二苯並噻喃、二伸苯基二 硫化物及其烷基衍生物。 芳香族硫化合物之碳數較佳爲1 2以上，更佳爲1 6以上 。具體例如，4，4'-硫雙（3-甲基-6-t-丁基苯酚）、二苯基 (7) (7)1359862 硫化物、二辛基二苯基硫化物、二烷基二伸苯基硫化物等 〇 其他可使用碳數8以上之脂肪族硫化合物、雜環式硫 化合物及芳香族硫化合物以外之有機硫化合物，例如碳數 8以上，較佳爲碳數10以上之分子內具有1個以上S原子之 有機硫化合物，具體例如，環丁硕、二苯基亞硯、二苯基 硯、噻唑、噻唑衍生物、硫金剛烷、2-噻嗯基甲醇、噻吩 乙酸等。 以上之有機硫化合物中又以使用二伸苯基二硫化物、 吩噻嗪、二烷基二伸苯基硫化物爲佳。 本發明之冷凍機油組成物中，以（A)成分及（B)成分之 合計量爲基準時，硫含量需爲0.01至0.1質量％。硫含量爲 0.01質量％以上時可得充分之潤滑性能，又，0.1質量％以 下時可充分抑制變質等而產生污泥。就以上觀點，硫含量 又以0.02至0.05質量％爲佳，更佳爲0.025至0.035質量％。 本發明之潤滑油組成物可添加一般冷凍機油組成物所 使用之添加劑，特佳爲添加防氧化劑、酸補足劑及消泡劑 〇 防氧化劑並無特別限制，例如可使用苯酚系防氧化劑 、胺系防氧化劑等。添加酸捕捉劑之目的爲，使冷凍機油 組成物具有加水分解安定性，其例如，苯基縮水甘油醚、 烷基縮水甘油醚、烷二醇縮水甘油醚、環己烯氧化物、 α -烯烴氧化物、環氧化大豆油等環氧化合物。其中就相 溶性較佳爲，苯基縮水甘油醚、烷基縮水甘油醚、烷二醇 -10- (8) (8)1359862 縮水甘油醚、環己烯氧化物及α-烯烴氧化物。消泡劑如 ，聚矽氧烷油及氟化聚矽氧烷油等。 又，不妨害本發明之目的下，可添加其他添加劑，例 如苯并***及其衍生物等之銅不活性化劑等。該添加劑之 添加量一般各自爲0.005至5質量％。 本發明之潤滑油組成物所使用的冷媒爲，碳酸氣體、 烴及氨中所選出至少一種。其中烴可爲一般冷媒用之物， 例如丙烷、丁烷及其混合物等。 冷凍機油組成物中冷媒之含量一般爲10至99質量％。 10質量％以上時可充分發揮冷凍能力，又，99質量％以下 時因存在足夠量之潤滑油，故無燒結及磨損問題。就以上· 觀點又以3 0至95質量％爲佳。 本發明之冷凍機油組成物可使用於各種用途，例如空 調用、冷藏庫用、氣熱唧筒（GHP)用、自動販賣機、陣列 冷凍用、汽車空調用、供溫水用、地板加熱器用等。 【實施方式】 實施例 下面將以實施例詳細說明本發明，但本發明非限於該 例。 (評估方法） 1.密封管試驗（熱安定性） 將各實施例及比較例所記載之方法所得的冷凍機油組 -11 - (9) (9)1359862 成物放入內容積l〇ml之玻璃管中，再加入銅、鋁及鐵之 金屬觸媒。密纣玻璃管後保存於175 °C下30天，再評估冷 凍機油組成物之外觀、銅外觀及有無污染。 2 .密閉法列克司試驗（潤滑性） 利用密閉式法列克司摩擦試驗機，以ASTM D2670求 取磨損量（mg)。又，試驗條件爲，荷重1335N、回轉數 3 00rpm、溫度80°C '試驗時間1小時，使用AISIC1137之 栓及SAE3135之裝置。 3 .毛細阻塞試驗 使用圖1所示之試驗機，評估1 〇 〇 〇小時後毛細管流量 之降低率。該試驗裝置爲特開平11-183334所揭示，其中 備有壓縮機2、減少溫壓用毛細管3、按通壓縮機2之吐出 口 2A及毛細管3之入口 3A的高溫側流路4'接通毛細管3 之出口 3B及壓縮機2之吸入口 2B的低溫側流路5、設於高 溫側流路4及低溫側流路5途中的使各流路4及5間進行冷媒 熱交換用的熱交換器6，又’高溫側流路4中壓縮機2與熱 交換器6之間設有吐出側壓內計7，低溫側流路5中熱交換 器6與壓縮機2之間設有吸入側壓力計8，且下方流側設有 真空啷筒接連用閥9’而由以上構造零件構成含冷凍機油 之冷媒循環用的模擬循環系1〇。 試驗條件爲，吸入側壓力（Ps)0_4MPa、吐出側壓力 (Pd)3.3MPa、熱交換機入口溫度（Td)110°C、熱交換機出 -12- (10) (10)1359862 口溫度（Ts)30°C。所使用之冷媒爲異丁烷（R600a)，又，混 合試料油（（A)成分及（B)成分之合計量）與冷媒各4〇〇g後進 行試驗》 實施例1至8、比較例1至7 依第1表所示調製（A)基油及（B)特定有機化合物所組 成之冷凍機油後’以上述評估方法評估，結果如第1表所 不 ° 其中所使用之（A)成分及（B)成分記號如下所示。 A-1:聚丙二醇二甲基醚（40°C黏度：46mm2/s) A-2:聚乙二醇聚丙二醇共聚物二甲基醚（40 °C黏度： 1 00mm2/s) A-3·:季戊四醇與2-乙基己酸/3，5，5-三甲基己酸之1:] 混合物的酯（40°C黏度：65mm2/s) A-4:聚-α-烯（40°C 黏度：63mm2/s) A-5 :烷基苯（40°C 黏度：38mm2/s) Α·6:石蠟系礦物油（4 0°C黏度：90mm2/s，硫含量5質量 ppm以下） A-7:萘系礦物油（4 0°C黏度：10mm2/s，硫含量107質量 ppm) A-8:蔡系礦物油（40°C黏度：56mm2/s，硫含量3000質量 PPm) 8-1:苯并噻吩（硫含量23.9質量％) B-2:二苯并噻吩（硫含量17.4質量％) -13- (11) (11)1359862 B-3 :二伸苯基二硫化物（硫含量29.6質量％) B - 4 :吩噻嗪（硫含量1 6 . 1質量％) B-5 :二苯基硫化物（硫含量17.2質量％) B - 6 :二辛基二苯基硫化物（硫含量7 · 8質量％) B - 7 :二辛基聚硫化物（硫含量3 9質量％) B-8 :三甲酚磷酸酯1359862 (1) IX Technical Description [Technical Field] The present invention relates to a novel refrigerating machine oil composition, particularly a refrigerating machine oil composition excellent in lubricity using a natural refrigerant. [Prior Art] A general-purpose refrigerator, such as a compression type refrigerating cycle system of a compression type refrigerator composed of a compressor, a condenser, an expansion valve, and an evaporator, has a refrigerant liquid and a lubricating oil mixture circulating therein. The structure within the system. Previously, the refrigerant used in the compression type refrigerator was chlorofluorocarbon such as dichlorodifluoromethane (R-12) or chlorodifluoromethane (R-22), or used to produce most lubricating oils. However, when the furan compound used in the previous refrigerant is released into the atmosphere, there is a problem of polluting the environment such as the ozone layer existing in the layering ring, so the 1,1,1,2-tetrafluoroethane (R-134 a) is used instead. Represents new refrigerants such as hydrofluorocarbon or fluorocarbon. Although the hydrofluorocarbon or the like does not destroy the ozone layer, the life in the atmosphere is extremely long and the global warming is affected. Therefore, in recent years, natural refrigerants having no such problems have been discussed. Further, the extreme pressure agent used in the composition of the refrigerator oil is a phosphorus-based additive represented by tricresol phosphate (TCP). However, this phosphorus-based extreme pressure agent is caused by heat decomposition, addition of a moisture contact or a tribochemical reaction of a friction surface, and the like. In addition, the deterioration of the pollution will consume the phosphorus-based additive, so that the lubrication performance cannot be maintained for a long period of time, resulting in sintering and abrasion. The previously proposed lubricating oil composition for a refrigerator using a furan-based refrigerant has excellent heat resistance and wear resistance by adding an organic sulfur compound, and -4- (2) (2) 1359862 viscosity to temperature change. A sulfur-containing lubricating oil which has little change and has excellent furan solubility (Patent Document 1). In the lubricating oil composition for a furan-type refrigerator of Patent Document 1, the content of the organic sulfur compound is important, and when, for example, mineral oil is used as the base oil, the organic sulfur compound may be a natural product in the presence of mineral oil. However, when only the sulfur content in the lubricating oil composition for a refrigerating machine using a natural refrigerant is controlled, sufficient wear resistance and extreme pressure are not obtained. Patent Document 1: JP-A-Open No. 5 8- 1 03 5 94 SUMMARY OF THE INVENTION In order to solve the above problems, it is an object of the present invention to provide a lubricating oil composition for a refrigerator which can maintain a lubricating property for a long period of time and which does not block a capillary during a refrigeration cycle and which uses a natural refrigerant. The present inventors have focused on the lubricating oil composition for a refrigerating machine having the above characteristics, and found that when a refrigerating machine oil containing a specific organic sulfur compound in a specific base oil uses a natural refrigerant, the lubricating property can be maintained for a long time' and the refrigeration cycle The present invention was completed without blocking the capillary. That is, the present invention provides a base oil containing at least one selected from the group consisting of (A) a polyalkylene glycol, a polyol ester, a polyolefin, an alkylbenzene, and a mineral oil, and the (Β) sulfur content is 35% by mass or less. In the refrigerating machine oil composition in which at least one of the organic sulfur compound and (C) carbonic acid gas, hydrocarbon, and ammonia is selected, the total amount of total sulfur (Α) component and (Β) component is 0·01. To 0.1% by mass of the refrigerator oil composition. (3) (3) 1359862 Best Mode for Carrying Out the Invention The base oil used in the lubricating oil composition of the present invention is (A) a polyalkylene glycol, a polyhydric alcohol ester, a poly-α-olefin, an alkylbenzene, and a mineral oil. At least one of the selected ones. The polyalkylene glycol is preferably the one represented by the following general formula (I). R,-[(〇R2)m-〇R3]n (I) wherein R 1 is hydrogen, an alkyl group having 1 to 10 carbon atoms, a thio group or an aliphatic hydrocarbon group having 2 to 6 bonding sites, R 2 It is an alkylene group having 2 to 4 carbon atoms and may be a single polymer or copolymer. R 3 is hydrogen, alkyl having 1 to 10 carbon atoms or fluorenyl ' η is an integer from 1 to 6, m is an integer m of 6 to 80, and the average 値 alkyl group of m to n may be linear, branched or Specific examples of the cyclic group and the alkyl group include a methyl group, an ethyl group, an η-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, a cyclopentyl group, a cyclohexyl group and the like. When the number of carbon atoms of the alkyl group is preferably 10 or less, the compatibility with the refrigerant can be sufficiently obtained. Further, the alkyl moiety of the thiol group may be linear, branched or cyclic. Specific examples of the alkyl moiety of the mercapto group include a methyl group, an ethyl group, a η-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, a cyclopentyl group, a cyclohexyl group and the like. The carbon number of the mercapto group is preferably 10 or less in the same alkyl group, and when it is 10 or less, sufficient compatibility with the refrigerant can be obtained. The above R1 and R3 may be the same or different. The polyalkylene glycol of the formula (1) of the present invention preferably has any one of R1 or R3 as hydrogen and the other is alkyl-6-(4)(4)1359862, and the alkyl group is preferably carbon. An alkyl group of 1 to 3, particularly preferably a methyl group. Further preferably, R1 or R3 is an alkyl group having 1 to 3 carbon atoms, and particularly preferably R1 or R3 is a methyl group. The base oil used in the present invention may be a mixture of a plurality of polyalkylene glycols, a polyhydric alcohol ester such as a carboxylic acid ester of a polyvalent hydroxy compound having at least two hydroxyl groups, preferably as the following general formula (Π) Show things. R4[OCOR5]f (II) wherein R4 is a hydrocarbon group, R5 is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, f is an integer of 2 to 6, and the plural [OCOR5] may be the same or different. In the general formula (Π), the hydrocarbon group represented by R4 may be linear or branched, and more preferably an alkyl group having 2 to 10 carbon atoms. R5 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group having 2 to 16 carbon atoms. The polyol ester of the general formula (II) can be represented by the following general formula (ΙΠ) R4(OH)f (III) (wherein R4 is as defined above) and the following general formula (IV) R5COOH (IV) (In the formula, R5 is the same as above) (5) (5) 1359862 The carboxylic acid or its ester and a reactive derivative such as an acid halide are reacted. The polyvalent alcohol represented by the general formula (III) may be various materials such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, Dipentaerythritol, sorbitol, and the like. Further, the carboxylic acid represented by (IV) is not particularly limited, and examples thereof include propionic acid, butyric acid, trimethylacetic acid, valeric acid, caproic acid, heptanoic acid, 3-methylhexanoic acid, and 2-ethylhexanoic acid. Caprylic acid, citric acid, citric acid, lauric acid, myristic acid, palmitic acid, and the like. The base oil used in the present invention may be a mixture of a plurality of polyol esters. The poly-olefin is an oligomer of an olefin having 3 to 12 carbon atoms and has a molecular weight of 200 to 5,000, more preferably 300 to 2,000. The base oil used in the present invention may be a mixture of a plurality of poly-?-olefins. The alkylbenzene is a lower monoolefin such as ethylene, propylene, butylene or isobutylene; a branched olefin having a carbon number of 6 to 40 obtained by polymerization of propylene; a wax, a heavy oil, a petroleum fraction, a polyethylene, a polypropylene, etc. A branched olefin having 6 to 40 carbon atoms obtained by thermal decomposition is an alkylating agent, and aromatic such as benzene, toluene, xylene, ethylbenzene, methylethylbenzene, diethylbenzene or a mixture thereof Alkylated material. The benzene of the alkylbenzene has an alkyl group of from 1 to 3, particularly preferably an alkylbenzene having more than two alkyl groups. Further, the base oil used in the present invention may be a mixture of a plurality of alkylbenzenes. The mineral oil to be used in the base oil of the present invention is not particularly limited, and for example, a samarium-based mineral oil, a naphthalene-based mineral oil or the like is preferably a substance having a sulfur content of 2 〇〇 mass ppm or less. The sulfur content in the mineral oil varies depending on the sulfur content in the raw material crude oil, but is preferably refined to 200 ppm by mass or less. The base oil used in the present invention may be a mixture of a plurality of mineral oils. (6) (6) 1359862 The above is applicable to the (A) base oil of the present invention, wherein the viewpoint of stability and evaporation reduction is particularly preferably a polyalkylene glycol, a polyhydric alcohol ester, a poly-α-olefin, an alkylbenzene. . Further, these may be used alone or in combination of two or more. The (Α) base oil used in the present invention preferably has a dynamic viscosity at 40 ° C of from 3 to 100 °m 2 /s. A sufficient lubrication performance is obtained at 3 mm 2 /s or more, and an excessive load is caused at 1000 mm 2 /s or less, but energy efficiency can be improved. From the above point of view, the 40 ° C dynamic viscosity of the base oil is preferably 5 to 500 mm 2 /s, more preferably 5 to 150 mm 2 / s. Next, the component (B) of the present invention is characterized by containing an organic sulfur compound having a sulfur content of 35 % by mass or less. When the sulfur content exceeds 35% by mass, deterioration sludge formation occurs. Specifically, there is a risk of having three or more sulfur-like polysulfides in one molecule. Further, when the sulfur content is more than 5% by mass, the amount of the component (B) to be added is lowered, which is not preferable. The (B) organic sulfur compound used in the present invention is preferably an aliphatic sulfur compound, a heterocyclic sulfur compound, an aromatic sulfur compound or the like. The carbon number of the aliphatic sulfur compound is preferably 12 or more, more preferably 14 or more, and particularly preferably 18 or more. Specifically, for example, a dioctyl sulfide, a behenyl sulfide compound, a tetracosylsulfide compound, or the like. The carbon content of the heterocyclic sulfur compound is preferably 8 or more, more preferably 10 or more, and particularly preferably 12 or more. Specifically, for example, benzothiophene, dibenzothiophene, phenothiazine, benzothiopyran, thiopyran, thiophene, dibenzothiopyran, diphenylene disulfide, and alkyl derivatives thereof. The carbon number of the aromatic sulfur compound is preferably 12 or more, more preferably 16 or more. Specifically, for example, 4,4'-thiobis(3-methyl-6-t-butylphenol), diphenyl (7) (7) 1359862 sulfide, dioctyldiphenyl sulfide, dialkyl Other than the aliphatic sulfur compound having a carbon number of 8 or more, the heterocyclic sulfur compound, and the organic sulfur compound other than the aromatic sulfur compound, for example, a carbon number of 8 or more, preferably a carbon number of 10 or more. An organic sulfur compound having one or more S atoms in the molecule, and specifically, for example, cyclobutene, diphenylarylene, diphenylphosphonium, thiazole, thiazole derivative, thioadamantane, 2-thiol methanol, thiophene Acetic acid, etc. Among the above organic sulfur compounds, diphenyl phenyl disulfide, phenothiazine, and dialkyl diphenyl sulfide are preferably used. In the refrigerating machine oil composition of the present invention, the sulfur content is required to be 0.01 to 0.1% by mass based on the total amount of the components (A) and (B). When the sulfur content is 0.01% by mass or more, sufficient lubricating performance can be obtained, and when it is 0.1% by mass or less, sludge can be sufficiently suppressed from being deteriorated. From the above viewpoints, the sulfur content is preferably 0.02 to 0.05% by mass, more preferably 0.025 to 0.035 mass%. The lubricating oil composition of the present invention may be added with an additive used in a general refrigerator oil composition, and particularly preferably an antioxidant, an acid remedy agent, and an antifoaming agent. The antioxidant is not particularly limited, and for example, a phenol-based antioxidant or an amine may be used. It is an antioxidant. The purpose of adding an acid scavenger is to impart a hydrolytical stability to the refrigerating machine oil composition, for example, phenyl glycidyl ether, alkyl glycidyl ether, alkanediol glycidyl ether, cyclohexene oxide, α-olefin An epoxy compound such as an oxide or an epoxidized soybean oil. Among them, the solubility is preferably phenyl glycidyl ether, alkyl glycidyl ether, alkyl glycol-10-(8) (8) 1359862 glycidyl ether, cyclohexene oxide and α-olefin oxide. Defoaming agents such as polyoxyalkylene oil and fluorinated polyoxyalkylene oil. Further, other additives such as a copper inactivating agent such as benzotriazole or a derivative thereof may be added without departing from the object of the present invention. The additive is usually added in an amount of usually 0.005 to 5% by mass. The refrigerant used in the lubricating oil composition of the present invention is at least one selected from the group consisting of carbonic acid gas, hydrocarbon and ammonia. The hydrocarbon may be a general refrigerant, such as propane, butane, a mixture thereof and the like. The content of the refrigerant in the composition of the refrigerating machine oil is generally from 10 to 99% by mass. When the amount is 10% by mass or more, the refrigeration ability can be sufficiently exhibited. When the amount is 99% by mass or less, since there is a sufficient amount of lubricating oil, there is no problem of sintering and abrasion. The above viewpoint is preferably 30 to 95% by mass. The refrigerating machine oil composition of the present invention can be used for various purposes, such as air conditioning, refrigerator, gas heating cylinder (GHP), vending machine, array freezing, automobile air conditioning, for warm water, floor heater, etc. . [Embodiment] Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited thereto. (Evaluation method) 1. Sealing tube test (thermal stability) The refrigerating machine oil group -11 - (9) (9) 1359862 obtained by the methods described in the respective examples and comparative examples was placed in an internal volume of l〇ml. In the glass tube, a metal catalyst of copper, aluminum and iron is added. The glass tube was sealed and stored at 175 ° C for 30 days, and the appearance of the frozen oil composition, the appearance of the copper, and the presence or absence of contamination were evaluated. 2. Sealed Falex Test (Lubricity) The amount of wear (mg) was determined by ASTM D2670 using a closed Falex friction tester. Further, the test conditions were a load of 1335 N, a number of revolutions of 300 rpm, and a temperature of 80 ° C. The test time was 1 hour, and a plug of AISIC 1137 and a device of SAE 3135 were used. 3. Capillary blockage test Using the tester shown in Fig. 1, the rate of decrease in capillary flow rate after 1 〇 〇 〇 hours was evaluated. The test apparatus is disclosed in Japanese Laid-Open Patent Publication No. Hei 11-183334, which is characterized in that a compressor 2, a capillary tube 3 for reducing temperature and pressure, a discharge port 2A for passing the compressor 2, and a high temperature side flow path 4' for the inlet 3A of the capillary tube 3 are connected. The outlet 3B of the capillary 3 and the low-temperature side flow path 5 of the suction port 2B of the compressor 2, and the heat for heat exchange between the respective flow paths 4 and 5 in the middle of the high-temperature side flow path 4 and the low-temperature side flow path 5 In the exchanger 6, the discharge side pressure gauge 7 is provided between the compressor 2 and the heat exchanger 6 in the high temperature side flow path 4, and the suction is provided between the heat exchanger 6 and the compressor 2 in the low temperature side flow path 5. The side pressure gauge 8 is provided with a vacuum cylinder connecting valve 9' on the lower flow side, and the above-described structural component constitutes a simulated circulation system 1 for circulating refrigerant containing refrigeration oil. The test conditions are: suction side pressure (Ps) 0_4 MPa, discharge side pressure (Pd) 3.3 MPa, heat exchanger inlet temperature (Td) 110 ° C, heat exchanger outlet -12- (10) (10) 1359862 temperature (Ts) 30 ° C. The refrigerant to be used was isobutane (R600a), and the mixed sample oil (the total amount of the components (A) and (B)) and the refrigerant were each tested at 4 〇〇g. Examples 1 to 8 and Comparative Examples 1 to 7 After the preparation of the (A) base oil and (B) the refrigerating machine oil composed of the specific organic compound as shown in Table 1, it is evaluated by the above evaluation method, and the results are as shown in Table 1 (A) The components and (B) component symbols are as follows. A-1: polypropylene glycol dimethyl ether (40 ° C viscosity: 46 mm 2 / s) A-2: polyethylene glycol polypropylene glycol copolymer dimethyl ether (40 ° C viscosity: 1 00 mm 2 / s) A-3 ·: ester of pentaerythritol and 2-ethylhexanoic acid/3,5,5-trimethylhexanoic acid 1:] mixture (40 ° C viscosity: 65 mm 2 / s) A-4: poly-α-ene (40 °C Viscosity: 63mm2/s) A-5: Alkylbenzene (40°C Viscosity: 38mm2/s) Α·6: Paraffinic mineral oil (40°C viscosity: 90mm2/s, sulfur content 5ppmppm or less) A-7: naphthalene mineral oil (40 ° C viscosity: 10mm2 / s, sulfur content 107 mass ppm) A-8: Cai culture oil (40 ° C viscosity: 56mm2 / s, sulfur content 3000 mass PPm) 8-1: benzothiophene (sulfur content: 23.9% by mass) B-2: dibenzothiophene (sulfur content: 17.4% by mass) -13- (11) (11) 1359862 B-3: diphenyl phenyl disulfide (Sulfur content: 29.6% by mass) B - 4 : phenothiazine (sulfur content: 16.1% by mass) B-5: diphenyl sulfide (sulfur content: 17.2% by mass) B - 6 : dioctyldiphenyl Sulfide (sulfur content 7 · 8 mass %) B - 7 : dioctyl polysulfide (sulfur content 39 % by mass) B-8 : tricresol phosphate
-14 - (12) !359862 第 γ^4_ιΙ 實施例 1 2 3 4 成分 Α-1 99.88 - - - Α-2 - 99.83 - - Α-3 - - 99.9 - A * 4 - - - 99.82 A-5 - - - - A-6 - - . A-? - - - • A-δ - - - - α)成分 B-l 0.12 - - _ B-2 - 0.17 - B-3 - - 0.1 - B-4 - - • 0.18 B-5 - - • • B-6 - • > • B-7 - • . B-8 - - . B-9 - - • 硫含量（暂量％) 0.03 0.03 0.03 0.03 密封管試驗 油外觀 良好 良好 良好 良好 銅外觀 良好 良好 良好 良好 有無污泥 组 /»\> 4Bf 姐 y 〆*、、 法列克司試驗 冷媒：C〇2 7 6 14 9 (磨損量： mg) 冷媒：丙烷 9 7 16 9 冷媒：NH3 14 - - 毛細阻塞試驗 1 1 1 1 (流量降低率；％) (13)1359862 第1表-2 實施例 5 6 7 8 (A)成分 A-1 - - - 99.7 Α·2 - - • • Α-3 - - - _ Δ * 4 - - • • Α-3 99.83 - - _ Α-6 - 99.6 - • Α-7 - > 99.6 _ Α-8 - - - _ (B)成分 Β-1 - - - _ Β-2 - - • • Β-3 - - - 0.3 Β - 4 - - - _ 6-5 0.17 - - • Β-6 - 0.4 0.4 • Β-7 - - - • Β·8 - - - • Β-9 - - - • 硫含量（質量 0.03 0.03 0.03 0.03 密封管試驗 油外觀 良好 良好 良好 良好 銅外觀 良好 良好 良好 良好 有無污泥 Μ 〆η、 Μ Μ /> ΝΝ 姐 法列克司試驗 (磨損量：mg) 冷媒：CCh 7 8 5 13 冷媒：丙烷 8 10 7 14 冷媒：NH3 - • 毛細阻塞試驗 流量降低率；％) 1 1 1 1-14 - (12) !359862 γ^4_ιΙ Example 1 2 3 4 Composition Α-1 99.88 - - - Α-2 - 99.83 - - Α-3 - - 99.9 - A * 4 - - - 99.82 A-5 - - - - A-6 - - . A-? - - - • A-δ - - - - α) Component Bl 0.12 - - _ B-2 - 0.17 - B-3 - - 0.1 - B-4 - - • 0.18 B-5 - - • • B-6 - • > • B-7 - • . B-8 - - . B-9 - - • Sulfur content (temporary %) 0.03 0.03 0.03 0.03 Sealed tube test oil Good appearance, good, good, good copper appearance, good, good, good, good with or without sludge group/»\> 4Bf sister y 〆*,, Faleks test refrigerant: C〇2 7 6 14 9 (wear: mg) Refrigerant: propane 9 7 16 9 Refrigerant: NH3 14 - - Capillary blockage test 1 1 1 1 (flow rate reduction rate; %) (13) 1359862 Table 1-2 Example 5 6 7 8 (A) Component A-1 - - - 99.7 Α · 2 - - • • Α-3 - - - _ Δ * 4 - - • • Α-3 99.83 - - _ Α-6 - 99.6 - • Α-7 - > 99.6 _ Α-8 - - - _ ( B) Component Β-1 - - - _ Β-2 - - • • Β-3 - - - 0.3 Β - 4 - - - _ 6-5 0.17 - - • Β-6 - 0.4 0.4 • Β-7 - - - • Β·8 - - - • Β-9 - - - • Sulfur content (mass 0.03 0.03 0.03 0.03 sealed tube test oil good appearance good good good copper appearance good good good good with or without contamination Loach 〆η, Μ Μ /> ΝΝ Sister Fareks test (wear: mg) Refrigerant: CCh 7 8 5 13 Refrigerant: Propane 8 10 7 14 Refrigerant: NH3 - • Capillary block test flow rate reduction rate; %) 1 1 1 1
-16- (14)1359862 第1表-3 比 咬例 1 2 3 4 (A)成分 A-1 99.98 99.4 99.98 99.5 A-2 - - - * A-3 - - - - A-4 - - - - A-5 - - - - A - 6 - - - - A-7 - - - - A-8 - - - - (B)成分 B-1 0.02 0.6 - - B-2 - - - - B-3 - - 0.02 1 B-4 - - - - B-5 - - - - B-6 - - - - B-7 - - - - B-8 - - - - B-9 - - - - 硫含量（質量％) 0.005 0.14 0.006 0.3 密封管試驗 油外觀 良好 薄黃 色 良好 薄黃色 銅外觀 良好 變色 良好 變色 有無污泥 姐 姐 /»\\ Μ Μ y » S\ 法列克司試驗 (磨損量：mg) 冷媒：CCh 咬住 24 咬住 29 冷媒：丙烷 咬住 38 咬住 42 冷媒：nh3 咬住 45 - - 毛細阻塞試驗 (流量降低率；％) - 6 - 8-16- (14)1359862 Table 1-3 Specific bite 1 2 3 4 (A) Component A-1 99.98 99.4 99.98 99.5 A-2 - - - * A-3 - - - - A-4 - - - - A-5 - - - - A - 6 - - - - A-7 - - - - A-8 - - - - (B) Component B-1 0.02 0.6 - - B-2 - - - - B-3 - - 0.02 1 B-4 - - - - B-5 - - - - B-6 - - - - B-7 - - - - B-8 - - - - B-9 - - - - Sulfur content (quality %) 0.005 0.14 0.006 0.3 Sealed tube test oil Appearance good Thin yellow Good thin yellow copper Appearance good discoloration Good discoloration with or without sludge sister /»\\ Μ Μ y » S\ Falex test (wear: mg) Refrigerant: CCh Biting 24 Biting 29 Refrigerant: Propane biting 38 Biting 42 Refrigerant: nh3 Biting 45 - Capillary blocking test (flow reduction rate; %) - 6 - 8
-17- (15)1359862 第1表-4 比 绞例 5 6 7 8 (A)成分 A-1 - 99.86 99.9 99 A-2 - - - - A-3 - - - - A-4 - - - - A-5 - - - - A-6 - - - - A-7 - - - - A-8 99.88 - - - (B)成分 B-1 0.12 - - - B-2 - - - - B-3 - - - - B-4 - - - - B-5 - - - - B-6 - - - - B-7 - 0.14 - - B-8 - - 0.1 - B-9 - - - 1 硫含量（質量％) 0.33 0.03 0.03 - 密封管試驗 油外觀 黃色 薄黃 色 黃色 良好 銅外觀 變色 黑色 黑色 良好 有無污泥 有 瓶 y»、、 有 Μ /\ \\ 法列克司試驗 (磨損量：m g) 冷媒：C〇2 17 18 31 - 冷媒：丙烷 21 23 35 17 冷媒：N Η 3 - - - - 毛細阻塞試驗 (流量降低率；％) 5 - - 7 -18- (16) (16)1359862 產業上利用可能性 本發明新穎之冷凍機油組成物無破壞臭氧層及地球暖 化等環境問題，及可表時間維持潤滑性能，且不會阻塞冷 凍循環系統內之毛細管。因此適合於空調用、冷藏庫用、 氣熱啷筒（GHP)用、自動販賣機用、陳列箱等冷凍用、汽 車空調用、供熱水用、地板加熱器用等。 【圖式簡單說明】 圖1爲，毛細阻塞試驗機之展示圖。 【主要元件符號說明】 1 :毛細阻塞試驗機 2 : ·壓縮機 2A :壓縮機入口 2B :壓縮機出口 3 :毛細管 3 A :毛細管入口 3B :毛細管出口 4 :高溫側流路 5 :低溫側流路 6 :熱交換器 7 :吐出側壓力計 8 :吸入側壓力計 9:真空唧筒接連用閥 -19- 1359862 (17) 1 〇 :模擬循環系-17- (15)1359862 Table 1-4 Ratios 5 5 7 8 (A) Composition A-1 - 99.86 99.9 99 A-2 - - - - A-3 - - - - A-4 - - - - A-5 - - - - A-6 - - - - A-7 - - - - A-8 99.88 - - - (B) Component B-1 0.12 - - - B-2 - - - - B-3 - - - - B-4 - - - - B-5 - - - - B-6 - - - - B-7 - 0.14 - - B-8 - - 0.1 - B-9 - - - 1 Sulfur content (quality %) 0.33 0.03 0.03 - Sealed tube test oil Appearance yellow Thin yellow yellow Good copper Appearance Discoloration Black Black Good with or without sludge y»,, Μ /\ \\ Faleks test (wear: mg) Refrigerant: C 〇 2 17 18 31 - Refrigerant: Propane 21 23 35 17 Refrigerant: N Η 3 - - - - Capillary blocking test (flow reduction rate; %) 5 - - 7 -18- (16) (16) 1359862 Industrial use possible The novel refrigerating machine oil composition of the present invention has no environmental problems such as destruction of the ozone layer and global warming, and can maintain lubrication performance for a long time without blocking the capillary tube in the refrigeration cycle system. Therefore, it is suitable for use in air conditioners, refrigerators, gas-heated cylinders (GHP), vending machines, display cases, etc. for freezing, automobile air conditioning, hot water supply, floor heaters, etc. [Simple description of the drawing] Fig. 1 is a display diagram of the capillary blocking tester. [Main component symbol description] 1 : Capillary blockage test machine 2 : · Compressor 2A : Compressor inlet 2B : Compressor outlet 3 : Capillary 3 A : Capillary inlet 3B : Capillary outlet 4 : High temperature side flow path 5 : Low temperature side flow Road 6: Heat exchanger 7: Discharge side pressure gauge 8: Suction side pressure gauge 9: Vacuum cylinder connecting valve -19- 1359862 (17) 1 〇: Simulated circulation system