201211233 六、發明說明： 【發明所屬之技術領域】 '本發明是關於一種用於冷凍機油等工業用潤滑油等的 組成物。 【先前技術】 近年來’冷凍機用的冷媒係使用臭氧破壞潛勢（ozone depletion potential)為零且地球溫暖化潛勢（global warming potential ’亦即GWP)更低的氫氟碳化物 (hydrofluorocarbon，亦即 HFC)。二氟甲烧冷媒（HFC-32) 的GWP是比現在所使用的冷媒[R-410A(二氟甲烷與五氟乙 烷的混合物）、R-407C(二氟曱烷與五氟乙烷與1，1，1，2-四 氟乙烷的混合物）等]低約1/3至1/4，並且性能係數 (coefficient of performance，亦即 C0P)也較 R-410A、 R-407C提高約5至13%，所以，從節約能源化的觀點而言 是理想的冷媒（非專利文獻1)。 在專利文獻1中雖揭示二氟甲烷冷媒用冷凍機油中所 用的季戊四醇與脂肪酸的酯，但該酯對於二氟甲烷冷媒的 相溶性等仍為不足。 [先前參考文獻] [專利文獻] [專利文獻Π日本特開2002-129177號公報 [非專利文獻] [非專利文獻1]「潤滑經濟」2〇〇4年6月號（NO. 460)， ρ· 17 ° 3 323263 201211233 【發明内容】 [發明要解決的課題] 本發明的目的是提供一種對二氟甲烷冷媒有優異相溶 性的冷凍機油等所使用的組成物。 [解決課題的手段] 本發明提供如下之[1]至[3]所述的組成物。 [1] 一種組成物，係含有：季戊四醇與由異丁酸及3, 5, 5-三曱基己酸所構成之羧酸的四酯，以及新戊二醇與含 有異丁酸及/或3, 5, 5-三曱基己酸之羧酸的二酯。 [2] 如[1]所述的組成物，其中，構成前述四酯的羧酸中， 異丁酸與3, 5, 5-三甲基己酸之莫耳比（異丁酸/3, 5, 5-三曱基己酸的比例）係在20/80至80/20之範圍。 [3] 如[1]或[2]所述的組成物，其中，前述組成物中之前 述四酯與前述二酯的質量比（四酯/二酯的比例）係在 60/40至97/3的範圍。 · [發明的效果] 由本發明可提供一種組成物，該組成物係用於對二氟 甲烷冷媒有優異相溶性等的冷凍機油等。 【實施方式】 以下，詳細說明本發明的較合適的實施形態。 本發明的組成物係含有：（A)季戊四醇與由異丁酸及 3, 5, 5_三曱基己酸所構成之羧酸的四酯（以下有時稱為「四 酯（A)」），與（B)新戊二醇與含有異丁酸及/或3, 5, 5-三甲 基己酸之羧酸的二酯（以下有時稱為「二酯（B)」）。在該組 4 323263 201211233 成物中，四酯（A)與二酯（B)的質量比係以60/40至97/3(四 酯：二酯）的範圍為理想。 四酯（A)係如上述，是季戊四醇與由異丁酸及3, 5,5-三甲基己酸所構成之羧酸的混合酯（此處，四酯是指將季戊 四醇的4個羥基以4分子的羧酸完全酯化所得的化合物）。 在構成該四酯的羧酸中的異丁酸與3, 5, 5-三曱基己酸的莫 耳比（異丁酸/3, 5, 5-三甲基己酸的比例）係以在20/80至 80/20的範圍為理想，以在30/70至60/40的範圍更理想。 混合S旨的四酯（A)包含下述（i)至（i i i)各態樣： (i)在同一分子中的構成羧酸是由異丁酸及3, 5, 5-三甲基 己酸雙方所構成的季戊四醇的四酯 (i i)季戊四醇與異丁酸的四酯及季戊四醇與3, 5, 5-三甲基 己酸的四酯之混合物 (iii) 上述（i)與（ii)的混合物。 又，在四酯（A)中亦可含有季戊四醇的三酯等作為雜 質。 另一方面，二酯（B)係如上述，是新戊二醇與含有異丁 酸及/或3, 5, 5-三甲基己酸之羧酸的混合酯（此處，二酯是 指將新戊二醇的2個羥基以2分子的羧酸完全酯化所得的 化合物）。 當構成二酯（B)的羧酸含有異丁酸及3, 5,5-三曱基己 酸時，混合酯的二酯（B)包含下述（iv)至（vii)的各態樣： (iv) 在同一分子中的構成羧酸是含有異丁酸及3, 5, 5-三曱 基己酸雙方的新戊二醇的二酯 5 323263 201211233 (V)新戊二醇與含有異丁酸之羧酸的二酯 (Vi)新戊二醇與含有3, 5, 5-三曱基己酸之羧酸的二酯 (vii)上述（iv)至（vi)t至少2種以上的混合物。 構成二酯（B)的羧酸亦可分別含有上述異丁酸及 3, 5, 5-三曱基己酸以外的其他羧酸。就其他羧酸而言，例 如可列舉：乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、 壬酸、癸酸、十二烧酸（dodecanoic acid)、十四烧酸、十 六烷酸、十八烷酸等直鏈的脂肪族羧酸，2-曱基丁酸、3-曱基丁酸、2, 2-二曱基丙酸、2-乙基丁酸、2-曱基戊酸、 4-曱基戊酸、2-甲基己酸、2-乙基戊酸、2-乙基-2-曱基丁 酸、2, 2-二曱基-戊酸、2-甲基庚酸、2-乙基己酸、3-乙基 己酸、2-乙基-2-曱基戊酸、2-甲基辛酸、2, 2-二曱基庚酸、 異十三烷酸、異硬脂酸等支鏈狀的脂肪族羧酸等。 在構成二酯（B)的羧酸中的其他羧酸的含量，只要是在 不損害本發明的組成物對二氟曱烷冷媒的相溶性等優異特 性的範圍内即可。其他羧酸與異丁酸及/或3, 5, 5-三甲基 己酸的莫耳比[其他羧酸/(異丁酸及/或3, 5, 5-三曱基己酸） 的比例]係以在0/100至5/100的範圍為理想。 構成二酯（B)的羧酸更佳為下述之任一者：只由異丁酸 所構成者、只由3, 5, 5-三甲基己酸所構成者、或只由異丁 酸及3, 5, 5-三曱基己酸所構成者。又，當羧酸是只由異丁 酸及3, 5, 5-三曱基己酸所構成者時，在二酯（B)中，除了 含有新戊二醇與異丁酸及3, 5, 5-三曱基己酸的酯以外，亦 可含有新戊二醇與異丁酸的二酯及/或新戊二醇與3, 5, 5- 6 323263 201211233 二曱基己酸的二醋。 在本發明的組成物中之四酯（A)的含量與二酯（B)的含 量的和，以組成物全質量為基準，係以在9〇質量％以上為 理想。在本發明的組成物中的四酯（A)及二酯（B)以外的成 为’例如可列舉：本發明所用的四酯（A)及二酯⑻以外的 脂肪族酯（脂肪族單酯、多元醇的脂肪酸酯、脂肪族多元酸 醋等）等。 四酯（A)係例如可藉由將季戊四醇與異丁酸及3, 5, 5_ 三曱基己酸在觸媒的存在下，在12(TC至25(TC反應5至 60小時而製造。 就觸媒而言，例如可列舉：礦酸（minera〖 acid)、有 機酸、路易氏酸、有機金屬、固體酸等。就礦酸的具體例 而言，例如可列舉：鹽酸、氫氟酸、硫酸、磷酸、硝酸等。 就有機酸的具體例而言，例如可列舉：對甲苯石黃酸、苯續 酸、丁磺酸、丙磺酸、乙磺酸、甲磺酸等。就路易氏酸的 具體例而言，例如可列舉：三氟化硼、氯化鋁、四氯化錫、 四氯化鈦等。就有機金屬的具體例而言，例如可列舉：四 丙氧化鈦（tetrapropoxytitanium)、四丁氧化鈦 (tetrabutoxytitanium)、四（2-乙基己氧基）鈦（tetrakis (2-ethylhexyloxy) titanium)等。就固體酸的具體例而 言，例如可列舉：陽離子交換樹脂等。 異丁酸的使用量與3, 5, 5-三曱基己酸的使用量之和， 相對於所使用的季戊四醇的經基，係以1. 1至1. 4倍莫耳 為理想。 7 323263 201211233 在前述反應令亦可使用溶媒，就溶媒而言，例如可列 舉：苯、曱苯、二甲苯等。 較佳係一邊將反應中所生成的水從反應混合物中除 去，一邊進行反應。將反應中所生成的水從反應混合物中 除去時，有時也會將異丁酸從反應混合物中除去。 反應後，視需要，亦可將本發明的季戊四醇的四酯以 有機合成化學上通常使用的方法（使用水及/或鹼性水溶液 洗淨、以活性碳或吸附劑等處理、各種層析法、蒸餾法等） 精製。 二酯（B)除了使用的醇及羧酸的種類不同以外，可藉由 與四酯（A)同樣的方法製造。 本發明的組成物可藉由將上述所得的四酯（A)與二酯 (B)混合而得。四酯（A)與二酯（B)的質量比是以在60/40至 9 7 / 3的範圍内為理想。 本發明的組成物係對二氟甲烷冷媒有優異的相溶性、 優異的低溫流動性、優異的潤滑性等。 將本發明的組成物用於空調機用冷凍機油時，該組成 物在40°C的動黏度較佳為在20至70mm2/秒的範圍，二層 分離溫度較佳為在-15°C以下。本發明的組成物除了用於冷 束機油之外，也可用於引擎油、齒輪油、滑脂（grease)、 可塑劑等。 使用本發明的組成物的冷凍機油，例如可列舉：含有 四酉旨（A)、二酯（B)及潤滑油用添加劑的冷柬機油等。在使 用本發明之組成物的冷凍機油中，該組成物係使用作為潤 8 323263 201211233 滑油基油。 就潤滑油用添加劑而言，可舉例如：抗氧化劑、摩耗 減低劑（耐摩耗劑、抗燒附劑、極壓劑等）、摩擦調整劑、 酸捕捉劑、金屬去活化劑、消泡劑等通常做為调滑劑添加 劑而使用的添加劑等。這些添加劑的含量在冷凍機油中分 別以0· 001至5重量％為理想。 亦可將本發明的組成物與其他的潤滑油基油併用。就 其他的潤滑油基油而言，例如可列舉礦物油、合成基油等。 就礦物油而言，例如可列舉：石蠟基系原油、中間基 系原油、環烷烴（naphthene)基系原油等。又，亦可使用將 此等以蒸餾等而精製的精製油。 就合成基油而言，可舉例如：聚烯烴（聚丁烯、聚 丙烯、碳數8至14的烯烴寡聚物等）、本發明所使用 的季戊四醇的四酯及本發明所使用的新戊二醇的二酯以外 的脂肪族酯（脂肪族單酯、多元醇的脂肪酸酯、脂肪族多元 酸酯等）、芳香族酯（芳香族單酯、多元醇的芳香族酯、芳 香族多元酸醋等）、聚烧二醇（polyalkylene glycol)、聚 乙烯醚、聚笨醚、烷基苯、碳酸酯、人山 Q戍環炊煙f。 又，本發明的季戊四醇的四酯，其 、 三。坐(benzotriazole)等金屬去活性冑，丨、々*優異的將笨並 系消泡劑等潤滑油用添加劑予以溶解的^$夕氧（S111C〇ne) 添加劑係例如為了延長潤滑油、使用斗、=力。該潤滑油用 命而溶解於潤滑油中使用。該潤滑油用^ 4的機@等的哥 戊四醇S旨的溶解度低（日本㈣平=劑一般對於季 ^的394號公報）。 g_ 323263 9 201211233 又’苯並三唑對於礦油及/或合成油的溶解度低（日本特開 昭59-189195號公報）。但是，例如’屬於本發明組成物的 組成物4至6(後述的實施例4至6)中的笨並三唑的溶解度 (25°c)是在0· 005g/g以上’任一組成物皆對苯ϋ三唑顯示 高的溶解度。 又’在洗淨使用本發明組成物做為潤滑油後的機器 時’可藉由氟化物系洗淨劑、醇系洗淨劑等洗淨劑而容易 地將機器洗淨。 [實施例] 以下’以實施例、合成例及試驗例更具體說明本發明， » 但不受以下的實施例所限定。 針對以下的合成例1至3所製造的四酯1直3、以及 合成例5所製造的二酯b，分別測定核磁共振譜I^H-NMR， 曰本電子公司製GSX-400(400MHz)，標準物：四甲基矽烷， 溶媒：CDCI3]，依以下之公式算出在季戊四醇的四酯或新 戊二醇的二酯中的異丁酸與3, 5, 5-三甲基己酸的莫耳比。 異丁酸/3, 5, 5-三甲基己酸 =尖峰X的積分值/尖峰γ的積分值 此處’尖峰X是相當於異丁酸的次甲基（methine group) 上的氫原子的尖峰’尖峰γ是相當於3, 5, 5_三甲基己酸的 次甲基上的氯原子的尖峰。 [合成例1 :異丁酸與3, 5, 5-三甲基己酸的莫耳比（異丁酸 /3, 5, 5-三甲基己酸的比例）為39/61的季戊四醇的四酯 (四酯1)的製造] 323263 10 201211233 吸附劑是使用協和化學工業公司製的Kyoward 500。 活性碳是使用日本Envirochemicals公司製的白鷺P。 在附有迪安-斯塔克分離器（Dean Stark trap)的反應 器中裝入季戊四醇1634g(12. 0莫耳，廣榮Perstope公司 製）、異丁酸1979g(22.5莫耳，東京化成公司製）及3,5,5-三甲基己酸5560g(35. 1莫耳，協和發酵化學公司製），一 邊將混合物攪拌一邊於室溫下進行氮氣冒泡30分鐘，而將 混合物脫氣。 其次’一邊進行氮氣冒泡，一邊將混合物在155至230 °C下攪拌12.5小時’繼而在反應混合物中添加四丁氧化鈦 1· 3g，繼而將反應混合物在23(TC攪拌12小時。反應後， 將反應生成物在1. lkPa的減壓下於225°C攪拌1小時，顧 去反應生成物中的未反應的羧酸。將反應生成物以含有相 對於該反應生成物的酸價為2倍莫耳的氫氧化鈉之鹼性水 溶液2L在77°C洗淨1小時。繼而將反應生成物以水2L在 68°C於1小時洗淨3次。其次’一邊進行氮氣冒泡，一邊 將反應生成物在1. IkPa的減壓下於68°C攪拌1小時，而 將反應生成物乾燥。 在反應生成物中添加吸附劑141g(相當於反應生成物 的2重量«及活性碳141g(相當於反應生成物的2重量◦/〇)， 一邊進行氮氣冒泡一邊將反應生成物在1.3kPa的減壓於 11 (TC攪拌2小時後’使用過濾助劑過濾而得6402g的四酯 1 0 [合成例2:異丁酸與3, 5, 5-三曱基己酸的莫耳比（異丁酸/ 11 323263 % 201211233 3, 5, 5-二甲基己酸的比例）為25/75的李戊四醇的四醋（四 酯2)的製造] 除了將季戊四醇、異丁酸及3, 5, 5-三曱基己酸的使用 量的莫耳比（季戊四醇/異丁酸/3, 5, 5-三甲基己酸的比例） 改成1/1. 20/3. 60以外，與合成例丨同樣操作，而得四酯 2 ° [合成例3 :異丁酸與3, 5, 5-三甲基己酸的莫耳比（異丁酸 /3,5,5-三甲基己酸的比例）為3〇/7〇的季戊四醇的四酯 (四酯3)的製造] 除了將季戊四醇、異丁酸及3, 5, 5_三甲基己酸的使用 量的莫耳比（季戊四醇/異丁酸/3, 5, 5—三甲基己酸的比例） 改成1/1.44/3.36以外，與合成例丨同樣操作，而得四酯 3 ° [合成例4:新戊二醇與3, 5, 5_三甲基己酸的二酯（二酯幻 的製造] 除了使用新戊二醇代替季戊四醇，並將新戊二醇、異 丁I及3, 5’ 5-二甲基己酸的使用量的莫耳比（新戊二醇/異 丁酸/3, 5, 5-三甲基己酸的比例）設成1/〇/24以外，與合 f例1同樣操作’而得二酉旨a。町述試驗例2的方㈣ 定的二醋3在40°C的動黏度為13· 0mm2/秒。 [合成例5:異丁酸與3, 5,5_三甲基己酸的莫耳比（異丁酸 /3, 5, 5 一甲基己酸的比例）為38/62的新戊二醇與異丁酸 及3, 5’ 5_三甲基己酸的混合酯（二酯b)的製造] 除了使用新戊二醇代替季戊四醇，並將新戊二醇、異 323263 12 201211233 丁酸及3, 5, 5-三甲基己酸的使用量的莫耳比（新戊二醇/異 丁酸/3, 5, 5-三甲基己酸的比例）設成1/1.2/1.2以外，與 合成例1同樣操作，而得二酯b。以下述試驗例2的方法 測定的二S旨b在40°C的動黏度為7. 1mm2/秒。 [合成例6 :新戊二醇與3, 5, 5-三甲基己酸的二酯（二酯c) 的製造] 除了使用新戊二醇代替季戊四醇，並將新戊二醇、異 丁酸及3, 5, 5-三曱基己酸的使用量的莫耳比（新戊二醇/異 丁酸/3, 5, 5-三曱基己酸的比例）設成1/4. 9/0以外，與合 成例1同樣操作，而得二酯c。以下述試驗例2的方法測 定的二i旨a在40°C的動黏度為2. 5mm2/秒。 [實施例1] 將60質量份的四醋1與40質量份的二自旨a混合，而 調製組成物1。 [實施例2] 將73質量份的四酯1與27質量份的二酯b混合，而 調製組成物2。 [實施例3] 將8 3質量份的四醋1與17質量份的二醋c混合，而 調製組成物3。 [實施例4] 將90質量份的四酯1與10質量份的二酯a混合，而 調製組成物4。 [實施例5] 13 323263 201211233 將93. 3質量份的四酯1與6. 7質量份的二酯b混合， 而調製組成物5。 [實施例6] 將96質量份的四酯1與4質量份的二酯c混合，而調 製組成物6。 [實施例7] 將86.2質量份的四酯1與13 8質量份的二酯b混合， 而調製組成物7。 [實施例8] 將94質ϊ份的四_ i與6質量份的二醋&混合，而調 製組成物8。 [實施例9] 將68質量份的四_ 2與32質量份的二S旨b混合，而 調製組成物9。 [實施例10] 將96.7質莖份的四自旨3與3 3質量份的二b混合， 而調製組成物10。 [試驗例1 :流動點的测定] 使用自動流動點測定器Rpp一〇1CML(離合公司製），遵 照JIS K2269-1987的方法測定組成物丨至10的流動點。 結果示於第1表。 [試驗例2 :動黏度的測定] 使用佳能范氏黏度計（Canon-Fenske viscometer)，遵 照JIS K2283 : 2000的方法測定組成物1至10在40°c的 14 323263 201211233 動黏度。結果示於第1表。 [試驗例3 :二層分離溫度的測定] 二 遵照JISK22in 2009的方法測定組成物i至1〇的 層分離溫度。將組成物i幻〇的各〇 4g與二氣甲烧冷媒 3. 6g分別封入於耐壓玻璃管内，將混合物由3〇。〇起以每分 鐘0.5 C的速度冷卻，將混合物分離二層或產生白濁的溫 度做為二層分離溫度。結果示於第1表。 [第1表] 動黏度 流動點 二層分離溫度 (mm2/秒） （°c) (°c) 組成物201211233 VI. Description of the Invention: [Technical Field to Be Invented by the Invention] The present invention relates to a composition for industrial lubricating oils and the like such as refrigerating machine oil. [Prior Art] In recent years, the refrigerant used in the refrigerator uses a hydrofluorocarbon (hydrofluorocarbon) having a zero ozone depletion potential and a lower global warming potential (or GWP). That is HFC). The GWP of difluoromethane-refrigerated refrigerant (HFC-32) is more than the refrigerant currently used [R-410A (mixture of difluoromethane and pentafluoroethane), R-407C (difluorodecane and pentafluoroethane). a mixture of 1,1,1,2-tetrafluoroethane), etc.] is about 1/3 to 1/4 lower, and the coefficient of performance (COP) is also higher than that of R-410A and R-407C. Since it is 5 to 13%, it is an ideal refrigerant from the viewpoint of energy saving (Non-Patent Document 1). In Patent Document 1, an ester of pentaerythritol and a fatty acid used in a refrigerating machine oil for a difluoromethane refrigerant is disclosed, but the compatibility of the ester with a difluoromethane refrigerant is still insufficient. [Patent Document] [Patent Document] JP-A-2002-129177 [Non-Patent Document] [Non-Patent Document 1] "Lubrication Economy" No. 4, June issue (No. 460), ρ· 17 ° 3 323263 201211233 [Problem to be Solved by the Invention] An object of the present invention is to provide a composition for use in a refrigerating machine oil or the like which has excellent compatibility with a difluoromethane refrigerant. [Means for Solving the Problem] The present invention provides the composition according to [1] to [3] below. [1] A composition comprising: a tetraester of pentaerythritol and a carboxylic acid composed of isobutyric acid and 3,5,5-tridecylhexanoic acid, and neopentyl glycol and isobutyric acid and/or a diester of a carboxylic acid of 3,5,5-tridecylhexanoic acid. [2] The composition according to [1], wherein among the carboxylic acids constituting the tetraester, a molar ratio of isobutyric acid to 3,5,5-trimethylhexanoic acid (isobutyric acid/3, The ratio of 5,5-tridecylhexanoic acid) is in the range of 20/80 to 80/20. [3] The composition according to [1] or [2] wherein the mass ratio of the tetraester to the diester (the ratio of the tetraester/diester) in the composition is 60/40 to 97. The range of /3. [Effects of the Invention] According to the present invention, a composition for use in a refrigerating machine oil having excellent compatibility with a difluoromethane refrigerant or the like can be provided. [Embodiment] Hereinafter, a more appropriate embodiment of the present invention will be described in detail. The composition of the present invention contains: (A) a tetraester of pentaerythritol and a carboxylic acid composed of isobutyric acid and 3,5,5-tridecylhexanoic acid (hereinafter sometimes referred to as "tetraester (A)" And (B) neopentyl glycol and a diester of a carboxylic acid containing isobutyric acid and/or 3,5,5-trimethylhexanoic acid (hereinafter sometimes referred to as "diester (B)"). In the group 4 323263 201211233, the mass ratio of the tetraester (A) to the diester (B) is preferably in the range of 60/40 to 97/3 (tetraester: diester). The tetraester (A) is a mixed ester of pentaerythritol and a carboxylic acid composed of isobutyric acid and 3,5,5-trimethylhexanoic acid as described above (here, the tetraester means 4 hydroxyl groups of pentaerythritol) The resulting compound is completely esterified with 4 molecules of carboxylic acid). The molar ratio of isobutyric acid to 3,5,5-tridecylhexanoic acid (the ratio of isobutyric acid/3,5,5-trimethylhexanoic acid) in the carboxylic acid constituting the tetraester is It is ideal in the range of 20/80 to 80/20, and is more desirable in the range of 30/70 to 60/40. The tetraester (A) to be mixed contains the following aspects (i) to (iii): (i) The constituent carboxylic acid in the same molecule is composed of isobutyric acid and 3,5,5-trimethylhexyl a tetraester of pentaerythritol composed of both acids (ii) a tetraester of pentaerythritol and isobutyric acid and a mixture of pentaerythritol and a tetraester of 3,5,5-trimethylhexanoic acid (iii) (i) and (ii) above mixture. Further, a tetraester of pentaerythritol or the like may be contained as a impurity in the tetraester (A). On the other hand, the diester (B) is a mixed ester of neopentyl glycol and a carboxylic acid containing isobutyric acid and/or 3,5,5-trimethylhexanoic acid as described above (here, the diester is A compound obtained by completely esterifying two hydroxyl groups of neopentyl glycol with two molecules of a carboxylic acid). When the carboxylic acid constituting the diester (B) contains isobutyric acid and 3,5,5-tridecylhexanoic acid, the diester (B) of the mixed ester contains the following aspects (iv) to (vii) : (iv) The constituent carboxylic acid in the same molecule is a diester of neopentyl glycol containing both isobutyric acid and 3,5,5-tridecylhexanoic acid 5 323263 201211233 (V) Neopentyl glycol and containing a diester of a carboxylic acid of isobutyric acid (Vi) neopentyl glycol and a diester of a carboxylic acid containing 3,5,5-tridecylhexanoic acid (vii) at least two of the above (iv) to (vi)t The above mixture. The carboxylic acid constituting the diester (B) may further contain other carboxylic acids other than the above isobutyric acid and 3,5,5-tridecylhexanoic acid. Examples of the other carboxylic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, dodecanoic acid, and tetradecanoic acid. a linear aliphatic carboxylic acid such as palmitic acid or octadecanoic acid, 2-mercaptobutyric acid, 3-mercaptobutyric acid, 2,2-dimercaptopropionic acid, 2-ethylbutyric acid, 2 -mercaptoic acid, 4-mercaptoleic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethyl-2-mercaptobutyric acid, 2,2-dimercapto-pentanoic acid, 2-methylheptanoic acid, 2-ethylhexanoic acid, 3-ethylhexanoic acid, 2-ethyl-2-mercaptovaleric acid, 2-methyloctanoic acid, 2,2-dimercaptoheptanoic acid, different A branched aliphatic carboxylic acid such as tridecanoic acid or isostearic acid. The content of the other carboxylic acid in the carboxylic acid constituting the diester (B) may be within a range that does not impair the excellent properties such as the compatibility of the composition of the present invention with the difluorodecane refrigerant. Mohr ratio of other carboxylic acids with isobutyric acid and/or 3,5,5-trimethylhexanoic acid [other carboxylic acids / (isobutyric acid and / or 3, 5, 5-tridecylhexanoic acid) The ratio is ideal in the range of 0/100 to 5/100. The carboxylic acid constituting the diester (B) is more preferably any one of the following: consisting of only isobutyric acid, only composed of 3,5,5-trimethylhexanoic acid, or only It is composed of acid and 3, 5, 5-tridecylhexanoic acid. Further, when the carboxylic acid is composed only of isobutyric acid and 3,5,5-tridecylhexanoic acid, in the diester (B), in addition to neopentyl glycol and isobutyric acid and 3, 5 , in addition to the ester of 5-trimercaptohexanoic acid, may also contain a diester of neopentyl glycol and isobutyric acid and/or neopentyl glycol and 3, 5, 5- 6 323263 201211233 dimercaptohexanoic acid vinegar. The sum of the content of the tetraester (A) and the content of the diester (B) in the composition of the present invention is preferably 9% by mass or more based on the total mass of the composition. In addition to the tetraester (A) and the diester (B) in the composition of the present invention, for example, an aliphatic ester (aliphatic ester other than the tetraester (A) and the diester (8) used in the present invention may be mentioned. , fatty acid esters of polyhydric alcohols, aliphatic polybasic acid vinegar, etc.). The tetraester (A) can be produced, for example, by reacting pentaerythritol with isobutyric acid and 3,5,5-tridecylhexanoic acid in the presence of a catalyst at 12 (TC to 25 (TC reaction for 5 to 60 hours). Examples of the catalyst include mineral acid (minera), organic acid, Lewis acid, organic metal, solid acid, etc. Specific examples of the mineral acid include hydrochloric acid and hydrofluoric acid. And sulfuric acid, phosphoric acid, nitric acid, etc. Specific examples of the organic acid include p-toluene citrate, benzoic acid, butanesulfonic acid, propanesulfonic acid, ethanesulfonic acid, methanesulfonic acid, and the like. Specific examples of the acid include, for example, boron trifluoride, aluminum chloride, tin tetrachloride, and titanium tetrachloride. Specific examples of the organic metal include titanium tetrachloride (for example). Tetrapropoxytitanium), tetrabutoxytitanium, tetrakis (2-ethylhexyloxy) titanium, etc. Specific examples of the solid acid include cation exchange resins and the like. The sum of the amount of isobutyric acid used and the amount of 3,5,5-tridecylhexanoic acid used, as opposed to The base of the pentaerythritol used is preferably 1.1 to 1.4 times Mo. 7 323263 201211233 A solvent may also be used in the above reaction, and examples of the solvent include benzene, toluene, and xylene. Preferably, the reaction is carried out while removing water formed in the reaction from the reaction mixture. When the water formed in the reaction is removed from the reaction mixture, isobutyric acid may be removed from the reaction mixture. After the reaction, if necessary, the tetraester of the pentaerythritol of the present invention may be used in a manner commonly used in organic synthetic chemistry (washing with water and/or an aqueous alkaline solution, treatment with activated carbon or an adsorbent, etc., various kinds of chromatography). The diester (B) can be produced by the same method as the tetraester (A) except that the type of the alcohol and the carboxylic acid used are different. The composition of the present invention can be obtained by the above-mentioned The tetraester (A) is mixed with the diester (B). The mass ratio of the tetraester (A) to the diester (B) is preferably in the range of 60/40 to 9 7 / 3. The composition has excellent compatibility with the difluoromethane refrigerant, Excellent low-temperature fluidity, excellent lubricity, etc. When the composition of the present invention is used for a refrigerating machine oil for an air conditioner, the dynamic viscosity of the composition at 40 ° C is preferably in the range of 20 to 70 mm 2 /sec, The layer separation temperature is preferably -15 ° C or less. The composition of the present invention can be used for engine oil, gear oil, grease, plasticizer, etc. in addition to cold beam oil. The refrigerating machine oil of the composition may, for example, be a cold rubber oil containing four additives (A), a diester (B), and an additive for lubricating oil. In the refrigerating machine oil using the composition of the present invention, the composition is Use as a lubricant base oil for Run 8 323263 201211233. Examples of the lubricant additive include an antioxidant, a friction reducing agent (anti-wear agent, anti-cavitation agent, extreme pressure agent, etc.), a friction modifier, an acid scavenger, a metal deactivator, and an antifoaming agent. Such as additives commonly used as slip agent additives. The content of these additives is preferably from 0.001 to 5% by weight in the refrigerating machine oil. The composition of the present invention can also be used in combination with other lubricating base oils. Other lubricating base oils include, for example, mineral oils, synthetic base oils and the like. The mineral oil may, for example, be a paraffinic base oil, an intermediate base crude oil or a naphthene base crude oil. Further, a refined oil purified by distillation or the like can also be used. The synthetic base oil may, for example, be a polyolefin (polybutylene, polypropylene, an olefin oligomer having 8 to 14 carbon atoms, etc.), a tetraester of pentaerythritol used in the present invention, and a novel used in the present invention. Aliphatic esters other than diesters of pentanediol (aliphatic monoesters, fatty acid esters of polyhydric alcohols, aliphatic polybasic acid esters, etc.), aromatic esters (aromatic monoesters, aromatic esters of polyhydric alcohols, aromatics) Polybasic acid vinegar, etc., polyalkylene glycol, polyvinyl ether, polyether ether, alkylbenzene, carbonate, human mountain Q ring ring 炊 f. Further, the tetraester of pentaerythritol of the present invention is three. For example, in order to extend the lubricating oil and use the hopper, it is preferable to use a metal such as benzotriazole to deactivate the hydrazine, and to dissolve the lubricating oil additive such as a defoaming agent. , = force. This lubricant is used in the lubricating oil for life. This lubricating oil has a low solubility with respect to the co-pentaerythritol S of the machine of the above-mentioned machine (Japanese (four) flat = agent generally for the quarter 394 publication). G_ 323263 9 201211233 Further, the solubility of benzotriazole in mineral oil and/or synthetic oil is low (JP-A-59-189195). However, for example, the solubility (25 ° C) of the stupid triazole in the compositions 4 to 6 (Examples 4 to 6 to be described later) belonging to the composition of the present invention is 0. 005 g/g or more 'any of the compositions Both of them show high solubility for benzotriazole. Further, when the apparatus using the composition of the present invention is used as a lubricating oil, the apparatus can be easily washed by a detergent such as a fluoride-based detergent or an alcohol-based detergent. [Examples] Hereinafter, the present invention will be more specifically described by way of Examples, Synthesis Examples and Test Examples, but is not limited by the following examples. The nuclear magnetic resonance spectrum I ^ H-NMR was measured for the tetraester 1 straight 3 manufactured in the following Synthesis Examples 1 to 3 and the diester b produced in Synthesis Example 5, and GSX-400 (400 MHz) manufactured by Sakamoto Electronics Co., Ltd. , standard: tetramethyl decane, solvent: CDCI3], according to the following formula to calculate isobutyric acid and 3, 5, 5-trimethylhexanoic acid in the tetraester of pentaerythritol or diester of neopentyl glycol Moerby. Isobutyric acid / 3, 5, 5-trimethylhexanoic acid = integral value of spike X / integral value of spike γ where 'spike X is a hydrogen atom corresponding to the methine group of isobutyric acid The spike 'peak γ is a peak corresponding to the chlorine atom on the methine of 3, 5, 5_trimethylhexanoic acid. [Synthesis Example 1: The molar ratio of isobutyric acid to 3,5,5-trimethylhexanoic acid (the ratio of isobutyric acid/3,5,5-trimethylhexanoic acid) was 39/61 of pentaerythritol. Production of tetraester (tetraester 1)] 323263 10 201211233 The adsorbent was Kyoward 500 manufactured by Kyowa Chemical Industry Co., Ltd. Activated carbon is an egret P manufactured by Envirochemicals, Japan. In a reactor equipped with a Dean Stark trap, 1634 g of pentaerythritol (12.0 m, manufactured by Kwong Perstope Co., Ltd.) and 1979 g of isobutyric acid (22.5 m., Tokyo Chemical Industry Co., Ltd.) were charged. 5,5,5,5,5-trimethylhexanoic acid, 5,560 g (35.1 g, manufactured by Kyowa Fermentation Chemical Co., Ltd.), while stirring the mixture, nitrogen gas was bubbled at room temperature for 30 minutes to degas the mixture. . Next, while stirring the nitrogen gas, the mixture was stirred at 155 to 230 ° C for 12.5 hours. Then, tetrabutylammonium oxide (1.3 g) was added to the reaction mixture, and then the reaction mixture was stirred at 23 (TC for 12 hours. The reaction product was stirred at 225 ° C for 1 hour under reduced pressure of 1. lkPa to take care of the unreacted carboxylic acid in the reaction product. The reaction product was contained in an acid value relative to the reaction product. 2 L of an alkaline aqueous solution of 2 mol of sodium hydroxide was washed at 77 ° C for 1 hour, and then the reaction product was washed 3 times with water 2 L at 68 ° C for 1 hour. The reaction product was stirred at 68 ° C for 1 hour under a reduced pressure of 1. IkPa to dry the reaction product. 141 g of an adsorbent (corresponding to 2 weights of the reaction product) and activated carbon were added to the reaction product. 141 g (corresponding to 2 weights 〇/〇 of the reaction product), and the reaction product was depressurized at 1.3 kPa while stirring with nitrogen at 11 (TC was stirred for 2 hours), and then filtered using a filter aid to obtain 6402 g of four. Ester 10 [Synthesis Example 2: isobutyric acid and 3, 5, 5-tridecylhexanoic acid Manufacture of tetraacetin (tetraester 2) of molar ratio (isobutyric acid / 11 323263 % 201211233 3, 5, 5-dimethylhexanoic acid) of 25/75 of pentaerythritol] except pentaerythritol, The molar ratio of the amount of isobutyric acid and 3,5,5-tridecylhexanoic acid (the ratio of pentaerythritol / isobutyric acid / 3, 5, 5-trimethylhexanoic acid) was changed to 1 / 1. 20 In the same manner as in the synthesis example, a tetraester 2 ° was obtained in the same manner as in the synthesis example [Synthesis Example 3: Mohr ratio of isobutyric acid to 3,5,5-trimethylhexanoic acid (isobutyric acid/3, Manufacture of tetraester (tetraester 3) of pentaerythritol of 3〇/7〇] in addition to pentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid The molar ratio of the molar ratio (pentaerythritol/isobutyric acid/3,5,5-trimethylhexanoic acid) was changed to 1/1.44/3.36, and the same procedure as in the synthesis example was carried out to obtain a tetraester 3 °. [Synthesis Example 4: Diester of neopentyl glycol and 3,5,5-trimethylhexanoic acid (manufactured by diester phantom) In addition to using neopentyl glycol instead of pentaerythritol, neopentyl glycol, isobutyl I And the molar ratio of 3, 5' 5-dimethylhexanoic acid (neopentyl glycol / isobutyric acid / 3, 5, 5-trimethylhexyl) The ratio of the acid was set to 1/〇/24, and the same operation as in the case of Example 1 was carried out, and the second principle was obtained. The square viscosity of the diacetate 3 of the test example 2 (4) was 40 at 40 °C. · 0 mm 2 / sec. [Synthesis Example 5: Mohr ratio of isobutyric acid to 3,5,5-trimethylhexanoic acid (ratio of isobutyric acid / 3, 5, 5 -methylhexanoic acid) was 38 / Preparation of a mixed ester of neopentyl glycol with isobutyric acid and 3,5' 5 -trimethylhexanoic acid (diester b) in addition to neopentyl glycol instead of pentaerythritol, and neopentyl glycol 323263 12 201211233 The molar ratio of neobutyric acid and 3, 5, 5-trimethylhexanoic acid (the ratio of neopentyl glycol / isobutyric acid / 3, 5, 5-trimethylhexanoic acid) is set to The same procedure as in Synthesis Example 1 was carried out except for 1/1.2/1.2 to obtain a diester b. The kinetic viscosity at 40 ° C was 7.1 mm 2 / sec measured by the method of the following Test Example 2. [Synthesis Example 6: Production of diester of neopentyl glycol and 3,5,5-trimethylhexanoic acid (diester c)] In addition to using neopentyl glycol instead of pentaerythritol, neopentyl glycol and isobutylene were used. The molar ratio of the acid and 3,5,5-tridecylhexanoic acid used (the ratio of neopentyl glycol / isobutyric acid / 3, 5, 5-tridecylhexanoic acid) is set to 1/4. Other than 9/0, the same procedure as in Synthesis Example 1 was carried out to obtain a diester c. 5毫米2/秒。 The kinetic viscosity at a temperature of 40 ° C was 2. 5mm2 / sec. [Example 1] 60 parts by mass of tetravine vinegar 1 was mixed with 40 parts by mass of the two components a to prepare the composition 1. [Example 2] Composition 2 was prepared by mixing 73 parts by mass of tetraester 1 with 27 parts by mass of diester b. [Example 3] The composition 3 was prepared by mixing 83 parts by mass of tetraacetone 1 with 17 parts by mass of diacetate c. [Example 4] Composition 4 was prepared by mixing 90 parts by mass of tetraester 1 with 10 parts by mass of diester a. [Example 5] 13 323263 201211233 The composition 5 was prepared by mixing 93.3 parts by mass of the tetraester 1 with 6.7 parts by mass of the diester b. [Example 6] Composition 6 was prepared by mixing 96 parts by mass of tetraester 1 with 4 parts by mass of diester c. [Example 7] Composition 7 was prepared by mixing 86.2 parts by mass of tetraester 1 with 13 8 parts by mass of diester b. [Example 8] Composition 8 was prepared by mixing 94 mass parts of tetrakis with 6 parts by mass of diacetate & [Example 9] The composition 9 was prepared by mixing 68 parts by mass of tetra-2 with 32 parts by mass of two S-b. [Example 10] A composition of 10 was prepared by mixing 96.7 g of the stem portion and 3 parts by mass of the b b. [Test Example 1: Measurement of the flow point] The flow point of the composition 丨 to 10 was measured in accordance with the method of JIS K2269-1987 using an automatic flow point measuring device Rpp-1CML (manufactured by Seiko Co., Ltd.). The results are shown in Table 1. [Test Example 2: Measurement of dynamic viscosity] The dynamic viscosity of the composition 1 to 10 at 40 ° C of 14 323263 201211233 was measured in accordance with the method of JIS K2283: 2000 using a Canon-Fenske viscometer. The results are shown in Table 1. [Test Example 3: Measurement of two-layer separation temperature] The layer separation temperature of the composition i to 1 Torr was measured in accordance with the method of JIS K22in 2009. 4 g of each of the composition i 〇 与 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 〇 〇 〇 〇 〇 〇 〇 〇 〇 The pick-up was cooled at a rate of 0.5 C per minute, and the mixture was separated into two layers or a white turbid temperature was used as the two-layer separation temperature. The results are shown in Table 1. [Table 1] Dynamic viscosity Flow point Two-layer separation temperature (mm2/sec) (°c) (°c) Composition
3(實施例 3) 29.2 -52. 4 (實施例4 ) -29 54. 5 -45. -23 5 (實施例5 ) 6(實施例6) 7 (實施例7 ) 8(實施例8) 9(實施例9) 54.5 54.4 44. 1 59. 3 30. -45. 0 -45. -47.2 -42. -23 -24 -25 22 -52. 1〇(實施例10) 67.2 -203 (Example 3) 29.2 - 52.4 (Example 4) -29 54. 5 - 45. -23 5 (Example 5) 6 (Example 6) 7 (Example 7) 8 (Example 8) 9 (Example 9) 54.5 54.4 44. 1 59. 3 30. -45. 0 -45. -47.2 -42. -23 -24 -25 22 -52. 1〇 (Example 10) 67.2 -20
由第1表可知，組成物1至1〇在40〇C的動黏度為29. 2 至67· 2mm2/秒，流動點為-42. 5至-52. 5°C，有優異的低溫 流動性，且二層分離溫度為_15至_3〇t，對二氟甲烷冷煤 323263 15 201211233 有優異的相溶性。 [產業上的可利用性] 藉由本發明可提供一種組成物，其係使用於對二氟甲 烷冷媒具有優異相溶性的冷凍機油等。 【圖式簡單說明】 無。 【主要元件符號說明】 無。 16 323263As shown in the first table, the composition 1 to 1 〇 has a dynamic viscosity of 40. 2 to 67·2 mm 2 /sec, and a pour point of -42. 5 to -52. 5 ° C, excellent low-temperature flow. The separation temperature of the two layers is _15 to _3 〇t, and the compatibility with the difluoromethane cold coal 323263 15 201211233 is excellent. [Industrial Applicability] According to the present invention, a composition for use in a refrigerating machine oil having excellent compatibility with a difluoromethane refrigerant can be provided. [Simple description of the diagram] None. [Main component symbol description] None. 16 323263