TWI465560B - 水性金屬加工油劑 - Google Patents

水性金屬加工油劑 Download PDF

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TWI465560B
TWI465560B TW097128854A TW97128854A TWI465560B TW I465560 B TWI465560 B TW I465560B TW 097128854 A TW097128854 A TW 097128854A TW 97128854 A TW97128854 A TW 97128854A TW I465560 B TWI465560 B TW I465560B
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oil agent
component
acid
oil
mass
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TW200920839A (en
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Hiroshi Kawasaki
Fumiaki Takagi
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Idemitsu Kosan Co
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Description

水性金屬加工油劑
本發明係有關用於切削、磨削等金屬加工之水性金屬加工油劑。
用於金屬加工之金屬加工油劑有油系(油性)與水系(水性)，而多半使用冷卻性、浸潤性良好之無火災危險性的水性(水溶性)型態。該水性(水溶性)金屬加工油劑中，由於以水稀釋後使用，故被要求防鏽性、耐腐蝕性。依不同用途，更於必要時務必為消泡性、碎粉沈澱性及潤滑性。
作為水溶性金屬加工油劑之成份者，先行技術中被廣泛使用無機鹽與烷醇胺之混合系、無機鹽與烷醇胺及聚伸烷基二醇之混合系、或無機鹽與烷醇胺及直鏈脂肪酸胺鹽之混合系等(如：文獻1：特公平6-76590號公報、文獻2：特開2002-285186號公報)。實際上使用此等水溶性金屬加工油劑時，將主成份稀釋成20~100倍使用之。
惟，上述文獻1、2所載之水溶性金屬加工油劑中，並不易取得理想均衡之防鏽性與防腐蝕性，而被期待進一步之改良。
另外，環境問題與世界性化學物質規制均極嚴苛。於日本除毒劇法、勞安法、化審法，更於1999年被制定PRTR法(化學物質排出掌控管理促進法)該法律係考量對於化學物質之致癌性、或特定內臟器官之慢性毒性，登錄恐危害人體健康或、生態系之化學物質的排出與移動，防止環保護上之問題產生的法律。第1種指定化學物質被指定水性金屬加工油劑之主要基材之單乙醇胺、硼酸。又，最近水性金屬加工油劑之使用自主的受限於變更為體內發癌性之亞硝基化合物之二級胺、勞安法通知物之乙醇胺類之使用。因此，無法單純採用具有強力的防鏽作用、強力的殺菌性、制菌性之化學物質。
因此，本發明係以提供一種具有良好的防鏽性與耐腐蝕性、同時其環境負擔低、對人體有害性少之水性金屬加工油劑為其目的。
本發明為解決該課題，提供一種如以下所示之水性金屬加工油劑。
[1]其特徵為含有(A)下述式(1)所示之烷醇胺及/或(B)下述式(2)所示之烷醇胺，與(C)2-吡啶基硫代-1-氧化物鹽之水性金屬加工油劑。
(式中，R1 為氫或碳數1~3之烷基。n為2或3。各個R1 可各自為相同，亦可為相異，而R1 不會有均為氫之情況)
(式中，R2 為碳數1~10之烷基。Z1 、Z2 係各自獨立地代表碳數2~8之伸烷基。)
[2]前述之本發明水性金屬加工油劑中，其特徵為該(B)成份之R2 為含有環烷基構造之水性金屬加工油劑。
[3]前述之本發明水性金屬加工油劑中，其特徵係以該水性金屬加工油劑全量基準下，(A)成份為0~50質量%、(B)成份為0~50質量%及(C)成份為0.01~5質量%之水性金屬加工油劑。
[4]使前述之本發明水性金屬加工油劑其特徵以質量比計為以5~200倍之水進行稀釋之水性金屬加工油劑。
本發明係提供一種，含有特定構造之烷醇胺與2-吡啶基硫代-1-氧化物鹽，故可滿足防鏽作用、耐腐蝕性(殺菌性、靜菌性)之作為水性金屬加工油劑之基本性能，且未含PRTR法指定化學物質、二級胺、亦不產生甲醛，因此為環境及對人體有害性少之水性金屬加工油劑。
 [發明實施之最佳形態]
以下進行說明本發明之實施形態。
本發明之水性金屬加工油劑其特徵係含有(A)下述式(1)所示之烷醇胺及/或(B)下述式(2)所示之烷醇胺、及(C) 2-吡啶基硫代-1-氧化物鹽。
首先，針對(A)成份進行說明。(A)成份係特別作為發揮防鏽性所使用的成份。上述式(1)中，R1 為氫或碳數1~3之烷基。n為2或3。各R1 係各自可相同，亦可相異，惟R1 不會有全部為氫之情況。亦即，作為(A)成份之烷醇胺不為單乙醇胺。其中，n為4以上時，則(A)成份之水溶性降低而不理想。n為2為最佳，n為1則經由分解容易釋放甲醛呈不理想者。又，任意之R1 為碳數4以上時，對於水溶性及鐵之防鏽性方面不理想。
作為(A)成份之具體例者，如：1-胺基-2-丙醇、2-胺基-2-甲基-1-丙醇、1-胺基-2-丁醇、2-胺基-1-丙醇、3-胺基-2-丁醇等例。其中又特別以1-胺基-2-丙醇、2-胺基-2-甲基-1-丙醇對於鐵之防鏽性最佳。
本發明中該(A)成份可使用1種，亦可使用2個以上。
接著，針對(B)成份之烷醇胺進行說明。(B)成份不僅可期待防鏽性，亦可期待耐腐蝕性。(B)成份係如上述式(2)所示，式中，R2 為碳數1~10之烷基。當R2 為氫時，則耐腐蝕性將變差而不理想。R2 為非環狀構造時，碳數為1~4者宜，更佳者為碳數1。當R2 之碳數為11以上時，則(B)成份之水溶性、防鏽性將降低，而不理想。又，Z1 、Z2 係各自獨立為碳數2~8之伸烷基。Z1 、Z2 之至少其一之碳數為1時，則將分解甲醛，對環境不理想。又，Z1 、Z2 之至少其一為碳數9以上時，將降低(B)成份之水溶性而不理想。
作為(B)成份之具體例者如：N-甲基二乙醇胺、N-乙基二乙醇胺、環己二乙醇胺、N-n-丙基二乙醇胺、N-i-丙基二乙醇胺、N-n-丁基二乙醇胺、N-i-丁基二乙醇胺、及N-t-丁基二乙醇胺等例。另外，R2 為含有支鏈烷基構造、環烷基構造時，在提昇耐腐蝕性方面較理想，特別理想者如：環己基二乙醇胺。
本發明中，該(B)成份可使用1種，亦可使用2種以上。
構成本發明水性金屬加工油劑之(C)成份為2-吡啶基硫代-1-氧化物鹽。該成份係發揮殺菌劑之效果。
(C)成份之具體例如：2-吡啶基硫代-1-氧化鈉、雙(2-吡啶基二硫代-1-氧化物)鋅、及雙(2-硫化吡啶-1-原)銅等例。其中，對於低濃度廣範圍之一般細菌、黴菌具效果之面視之，特別以2-吡啶硫代-1-氧化鈉為最佳。
本發明之水溶性金屬加工油劑亦可由上述(A)成份與(C)成份所構成者，又，亦可由上述(B)成份與(C)成份所構成。
該水溶性金屬加工油劑由掌控性之觀點視之，以調製成高濃度原液者宜，使用自體係以適當水進行稀釋作成金屬加工油使用之。
作為構成原液之溶媒者，以水為最佳者，而亦可為鑛油、合成油。
有關原液調製所使用之溶媒之鑛油、合成油者，一般只要作為金屬加工油之基油所使用者即可，並未特別限定，通常於40℃下動黏度為1~50mm2 /s之範圍者宜，更佳者為2~30mm2 /s之範圍者。當基油之動黏度太高時，則油劑將附著於被加工物上，帶走量變多，經濟面不理想。反之，太低將產生重霧，導致作業性不良。另外，有關該基油之低溫流動性指標之流動面，並未特別限定，一般為-10℃以下者宜。
該鑛油、合成油有各式各樣，通常因應各種用途，進行適當選擇即可。作為鑛油者如：使石蠟基系原油，中間基系原油、或環烷基系原油進行常壓蒸餾、或將常壓蒸餾之殘渣油進行減壓蒸餾取得餾出油，或將此依常法經由精製取得精製油、如：溶劑精製油、氫化精製油、脫蠟處理油、白土處理油等例。
另外，作成合成油例者如：聚α-烯烴、α-烯烴共聚物、聚丁烯、烷基苯、聚醇酯、二鹼酸酯、聚氧化烯二醇、聚氧化烯二醇酯、聚氧化烯二醇醚、聚矽氧油等例。合成油中為聚α-烯烴、α-烯烴共聚物者宜。該基油可分別單獨，或組合2種以上使用之，亦可組合鑛油與合成油。
原液中(A)成份之理想比例於原液總量基準下為0~50質量%者宜，較佳者為10~45質量%、更佳者為20~40質量%。當(A)成份之比例超出50質量%並無法進一步提昇對鐵的防鏽性，對於高成本之經濟不良面不理想。
原液中(B)成份之理想比例於原液總量基準下為0~50質量%者宜，較佳者為10~45質量%，更佳者為20~40質量%。當(B)成份之比例超出50質量%並無法進一步提昇對鐵的防鏽性，對於高成本之經濟不良面亦不理想。
原液中(C)成份之理想比例於原液總量基準下為0.01~5質量%之範圍者宜，較佳者為0.05~2質量%、更佳者為0.05~1質量%。當(C)成份之比例未達0.01質量%時，則油劑之殺菌效果降低、耐腐蝕性變差而不理想、反之，超出5質量%則形成金屬離子與錯化物，容易變色為不理想者。甚至高成本，經濟性之面亦不理想。
本發明水性金屬加工油劑中，併用(A)成份與(B)成份，與(C)成份作成3成份系使用後，可進一步提昇防鏽性與耐腐蝕性為特別理想者。
另外，有關(A)~(C)成份，其原液中之該合計量為70質量%以下者宜。當此等各成份之合計量超出70質量%時，則原液調製時各成份不易溶於溶媒(特別是水)。
使用本發明水性金屬加工油劑時，對於該原液而言，以質量比計為以5~200倍之水進行稀釋者宜。較理想之稀釋倍率者為10~100倍，更佳者為30~50倍。當稀釋倍率未達5倍則成本變高，而不理想。反之，稀釋倍率超出200倍時，則防鏽性與耐腐蝕性不足，為不理想。
又，本發明之水性金屬加工油劑中，在不阻礙本發明目的之範圍下，可適當配合各種公知的添加劑。如：脂肪族羧酸、乳化劑、極壓劑、油性劑、消泡劑等。
脂肪族羧酸係進一步提昇油劑的切削性、磨削性，為進一步提昇防鏽性而添加之。如：碳原子數6~60之羧酸及/或二羧酸之例。具體例如：己酸、辛酸、壬酸、月桂酸、硬脂酸、油酸、蓖麻醇酸、羥基脂肪酸(如：蓖麻醇酸、12-羥基硬脂酸等)、花生酸、山萮酸、蜂花酸、異壬酸、新癸酸、異硬脂酸，油脂所萃取的大豆油脂肪酸、椰子油脂肪酸、菜籽油脂肪酸、石油所萃取之環烷酸、己二酸、癸二酸、十二烷2酸、單或雙羥基花生酸等。更有油酸、蓖麻醇酸、蓖麻醇酸、12-羥基硬脂酸等二量體、三量體等之合成脂肪酸例。作為特別理想之單羧酸者由其油劑之消泡性觀點及硬水之穩定性觀點視之，如：碳數8~10之己酸、壬酸、癸酸、而作為二羧酸者如：壬二酸、十一烷二酸、癸二酸、十二烷二酸等例。此等羧酸之配合量，由其配合效果面，於最後的稀釋油基準下，於原液中配合0.1~1.5質量%。
作為極壓劑者如：硫系極壓劑、磷系極壓劑、含有硫及金屬之極壓劑，含有磷及金屬之極壓劑之例。此等極壓劑可單獨使用1種，或組合2種以上使用之。作為極壓劑者，只要分子中含有硫原子及/或磷原子之可發揮耐荷重性、耐磨損性者即可。作為分子中含硫之極壓劑者如：硫化油脂、硫化脂肪酸、硫化酯、硫化烯烴、二氫碳醯聚硫化物、噻二唑化合物、烷基硫代氨基甲醯化合物、三嗪化合物、硫代萜化合物、二烷基硫代二丙酸酯化合物等例。此等極壓劑之配合量由其配合效果面視之，以最後的稀釋油基準下，於原液中配合0.05~0.5質量%。
油性劑例如：脂肪族醇、脂肪酸、脂肪酸金屬鹽等之脂肪酸化合物、聚醇酯、山梨糖醇酐酯、甘油等之酯化合物、脂肪族胺等之胺化合物等例。此等油性劑之配合量由其配合效果面視之，以最後的稀釋油基準下，於原液中配合0.2~2質量%。
作為消泡劑者如：聚甲基矽氧烷油、聚氟矽氧烷油、聚丙烯酸酯等例。此等消泡劑之配合量，由配合效果面視之，以最後的稀釋油基準下，於原液中配合0.004~0.04質量%。
本發明之水性金屬加工油劑係如上述，依其使用目的以適度的水進行稀釋作成適當之濃度，可適用始於切削加工、磨削加工之研磨、絞碎、拉伸、壓延等之各種金屬加工領域。而本發明水性金屬加工油劑，不僅對於金屬製品具有防鏽作用、耐磨蝕作用之良好特性，且對於環境、人體之有害性極少。
[實施例]
接著，藉由實施例，進行本發明更詳細的說明，惟本發明並未受限於此等例中。
[實施例1~9、比較例1~5]
藉由表1、2所示之配合處方調製水性金屬加工油劑(原液)，以水稀釋成適當的濃度後，針對以下各特性進行評定。評定結果示於表3、4。
(1)防鏽性(DIN51360-02-A基準)
使用以自來水稀釋成1.00、1.25、2.00、3.33、5.00及10.0質量%之原液濃度之稀釋液，進行防鏽試驗(室溫、2小時)，使鏽程度為0之最低濃度作為防鏽極限濃度(質量%)。
(2)耐腐蝕性(靜菌性)
藉由振盪培養法(30℃、4週)，評定靜菌法。具體而言，以自來水進行稀釋作成原液為3.3質量%之水溶液，於其100ml中每週連續進行接種A 5ml與菌B 5ml。其中菌A、B係指於實際使用水溶性切削液之工廠現場A、B中之腐蝕液。
再以EG Kalut法進行測定4週後之各種細菌數。具體而言，各細菌使用如下之簡易培養基(finland之Orion公司製)，藉由特定對照表決定細菌數或細菌之繁殖程度。
一般細菌：EG kalut TTC
黴菌‧酵母：EG kalut M
硫酸還原菌：EG kalut S
所測定之各評定項目及其評定基準(評定分數)示於表5。實用上其評定分數為10分以上者宜。
[評定結果]
由表3、4之結果證明，實施例1~9之該本發明水性金屬加工油劑均具有良好的防鏽性及耐腐蝕性，且對於人體亦未含有害成份。相較於此之比較例1~5所使用之水性金屬加工油劑卻欠缺本發明之必須成份，因此其防鏽性與耐腐蝕性之均衡性不良。

Claims (4)

  1. 一種水性金屬加工油劑，其特徵係含有(A)下述式(1)所示之烷醇胺與(B)下述式(2)所示之烷醇胺、以及(C)2-吡啶基硫代-1-氧化物鹽、 (式中，R1 為氫或碳數1~3之烷基、n為2或3、各個R1 可各自為相同，亦可為相異，惟R1 不會有均為氫之情況) (式中，R2 為碳數1~10之烷基、Z1 、Z2 各自獨立地代表碳數2~8之伸烷基)。
  2. 一種水性金屬加工油劑，其係於申請專利範圍第1項之水性金屬加工油劑中，其特徵係該(B)成份之R2 為含有環烷構造。
  3. 一種水性金屬加工油劑，其係於申請專利範圍第1項之水性金屬加工油劑中，其特徵係以該水性金屬加工油劑全量基準下，(A)成份為0~50質量%、(B)成份為0~50質量%，及(C)成份為0.01~5質量%。
  4. 一種水性金屬加工油劑，其特徵係以質量比計，以5~200倍之水進行稀釋申請專利範圍第1項至第3項中任一項之水性金屬加工油劑。
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