JP2017008229A - Lubricant composition for sliding surface - Google Patents
Lubricant composition for sliding surface Download PDFInfo
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- JP2017008229A JP2017008229A JP2015126089A JP2015126089A JP2017008229A JP 2017008229 A JP2017008229 A JP 2017008229A JP 2015126089 A JP2015126089 A JP 2015126089A JP 2015126089 A JP2015126089 A JP 2015126089A JP 2017008229 A JP2017008229 A JP 2017008229A
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- phosphoric acid
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- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 239000000314 lubricant Substances 0.000 title abstract 3
- -1 phosphate compound Chemical class 0.000 claims abstract description 77
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 24
- 239000010452 phosphate Substances 0.000 claims abstract description 24
- 229940126062 Compound A Drugs 0.000 claims abstract description 17
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002199 base oil Substances 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 71
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 55
- 239000000126 substance Substances 0.000 claims description 49
- 239000010687 lubricating oil Substances 0.000 claims description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 19
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 17
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 13
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 239000002480 mineral oil Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 4
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 230000010354 integration Effects 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 6
- 239000010730 cutting oil Substances 0.000 description 6
- 229940055577 oleyl alcohol Drugs 0.000 description 6
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 6
- 150000003016 phosphoric acids Chemical class 0.000 description 6
- 238000012644 addition polymerization Methods 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229960000735 docosanol Drugs 0.000 description 4
- LBIYNOAMNIKVKF-FPLPWBNLSA-N palmitoleyl alcohol Chemical compound CCCCCC\C=C/CCCCCCCCO LBIYNOAMNIKVKF-FPLPWBNLSA-N 0.000 description 4
- LBIYNOAMNIKVKF-UHFFFAOYSA-N palmitoleyl alcohol Natural products CCCCCCC=CCCCCCCCCO LBIYNOAMNIKVKF-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- MEESPVWIOBCLJW-KTKRTIGZSA-N [(z)-octadec-9-enyl] dihydrogen phosphate Chemical compound CCCCCCCC\C=C/CCCCCCCCOP(O)(O)=O MEESPVWIOBCLJW-KTKRTIGZSA-N 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CFOQKXQWGLAKSK-KTKRTIGZSA-N (13Z)-docosen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCCO CFOQKXQWGLAKSK-KTKRTIGZSA-N 0.000 description 2
- DCNHQNGFLVPROM-QXMHVHEDSA-N (z)-n,n-dimethyloctadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN(C)C DCNHQNGFLVPROM-QXMHVHEDSA-N 0.000 description 2
- JTQQDDNCCLCMER-CLFAGFIQSA-N (z)-n-[(z)-octadec-9-enyl]octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCNCCCCCCCC\C=C/CCCCCCCC JTQQDDNCCLCMER-CLFAGFIQSA-N 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 2
- CFOQKXQWGLAKSK-UHFFFAOYSA-N 13-docosen-1-ol Natural products CCCCCCCCC=CCCCCCCCCCCCCO CFOQKXQWGLAKSK-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000199 molecular distillation Methods 0.000 description 2
- MJCJUDJQDGGKOX-UHFFFAOYSA-N n-dodecyldodecan-1-amine Chemical compound CCCCCCCCCCCCNCCCCCCCCCCCC MJCJUDJQDGGKOX-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- SWZDQOUHBYYPJD-UHFFFAOYSA-N tridodecylamine Chemical compound CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC SWZDQOUHBYYPJD-UHFFFAOYSA-N 0.000 description 2
- QEDAEETYODHMOJ-FPLPWBNLSA-N CCCCCC/C=C\CCCCCCCCOP(=O)(O)OP(=O)(O)O Chemical compound CCCCCC/C=C\CCCCCCCCOP(=O)(O)OP(=O)(O)O QEDAEETYODHMOJ-FPLPWBNLSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- JLDUYUMFDHGEEJ-FPLPWBNLSA-N [(Z)-hexadec-9-enyl] dihydrogen phosphate Chemical compound CCCCCC\C=C/CCCCCCCCOP(O)(O)=O JLDUYUMFDHGEEJ-FPLPWBNLSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- WFFZELZOEWLYNK-CLFAGFIQSA-N bis[(z)-octadec-9-enyl] hydrogen phosphate Chemical compound CCCCCCCC\C=C/CCCCCCCCOP(O)(=O)OCCCCCCCC\C=C/CCCCCCCC WFFZELZOEWLYNK-CLFAGFIQSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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- Lubricants (AREA)
Abstract
Description
本発明は摺動面用潤滑油組成物に関し、更に詳しくは摺動面のスティックスリップ現象を防止するとともに、低摩擦で水分離性及び保存安定性に優れた摺動面用潤滑油組成物に関する。 The present invention relates to a lubricating oil composition for a sliding surface, and more particularly to a lubricating oil composition for a sliding surface that prevents stick-slip phenomenon on the sliding surface and that has low friction and excellent water separation and storage stability. .
工作機械には、工具や被削材を、前後、左右、上下等の任意の方向に動かすために摺動面が存在し、かかる摺動面としてすべり案内面が主に用いられている。すべり案内面が多用されている工作機械はマザーマシンと呼ばれ、工業製品製造の要であり、その精度、品質、信頼性が直接製品の品質を左右するため、すべり案内面の摺動特性は極めて重要である。そして、すべり案内面の摺動運動を円滑に行うことは、工作機械の寿命の延長やランニングコストの低減等にも大きく寄与する。 A machine tool has a sliding surface for moving a tool or a work material in an arbitrary direction such as front and rear, left and right, and up and down, and a sliding guide surface is mainly used as the sliding surface. Machine tools that use a lot of slip guide surfaces are called mother machines, and are the key to industrial product manufacturing. The accuracy, quality, and reliability directly affect the quality of products. Very important. The smooth sliding movement of the sliding guide surface greatly contributes to extending the life of the machine tool and reducing running costs.
ところで、前記の摺動運動は工具送りのように低速度で行われる場合が多いのでスティックスリップ現象を起こしやすく、それが原因で製品の精度、機械の寿命に悪影響を及ぼす場合が多い。スティックスリップ現象を防止するためには、用いる摺動面用潤滑油組成物を、低速度における動摩擦係数μの小さいものにするとともに、すべり速度ｖの増加にともなって摩擦係数が上昇する摩擦特性のものにする必要がある。このような速度依存性を正勾配化することで、発生したスティックスリップ現象を早く減衰させることができる。 By the way, the above-mentioned sliding movement is often performed at a low speed as in the case of tool feeding, so that a stick-slip phenomenon is liable to occur, which often has an adverse effect on the accuracy of the product and the life of the machine. In order to prevent the stick-slip phenomenon, the sliding surface lubricating oil composition to be used has a small dynamic friction coefficient μ at a low speed, and the friction characteristic increases as the sliding speed v increases. It needs to be a thing. By making such speed dependence a positive gradient, the generated stick-slip phenomenon can be quickly attenuated.
一方、工作機械には、クーラントとして水溶性の切削油等が広く使用されるようになってきている。しかし、工作機械の摺動面にこれらの水溶性切削油が入り、摺動面用潤滑油組成物に混入すると、摺動面用潤滑油組成物の性能は損なわれ、摺動特性を低下させ、油不溶性スラッジが生成する等の問題を生じる。また水溶性切削油は、一般的に、切削加工部に供給され、切りくずを分離して、循環使用される。したがって、水溶性切削油に摺動面用潤滑油組成物が混入して分離することなく乳化状態となると、水溶性切削油の性能は著しく低下し、また腐敗が生じることとなる。これを回避して良好な循環使用を確保するために、摺動面用潤滑油組成物には水溶性切削油と分離しやすい性能が求められる。 On the other hand, water-soluble cutting oil or the like is widely used as a coolant for machine tools. However, if these water-soluble cutting oil enters the sliding surface of the machine tool and mixes with the lubricating oil composition for the sliding surface, the performance of the lubricating oil composition for the sliding surface is impaired, and the sliding characteristics are deteriorated. This causes problems such as the formation of oil-insoluble sludge. Moreover, water-soluble cutting oil is generally supplied to a cutting part, and is used by circulating after separating chips. Therefore, when the lubricating oil composition for sliding surfaces is mixed into the water-soluble cutting oil and becomes an emulsified state without separation, the performance of the water-soluble cutting oil is remarkably lowered and spoilage occurs. In order to avoid this and to ensure good circulation use, the sliding surface lubricating oil composition is required to have a performance that is easily separated from the water-soluble cutting oil.
従来、工作機械等の摺動面用潤滑油組成物としては、基油に、リン酸エステルと硫黄系極圧剤やポリアルキレングリコール誘導体とを併用したもの（例えば特許文献１参照）、また分岐鎖のリン酸エステルと直鎖のリン酸エステルとを組み合わせて併用したもの（例えば特許文献２参照）等が提案されている。しかし、これら従来の摺動面用潤滑油組成物には、年々高精度化が進む工作機械等の摺動面用潤滑油組成物に求められるスティックスリップ現象防止性、低摩擦性、水分離性及び保存安定性において不充分という問題がある。 Conventionally, as a lubricating oil composition for a sliding surface of a machine tool or the like, a base oil used in combination with a phosphate ester and a sulfur-based extreme pressure agent or a polyalkylene glycol derivative (see, for example, Patent Document 1) or branched A combination of a chain phosphate ester and a linear phosphate ester in combination (for example, see Patent Document 2) has been proposed. However, these conventional lubricating oil compositions for sliding surfaces have the ability to prevent stick-slip phenomenon, low friction, water separation properties required for lubricating oil compositions for sliding surfaces of machine tools and the like, which are becoming increasingly accurate year by year. In addition, there is a problem of insufficient storage stability.
本発明が解決しようとする課題は、摺動面のスティックスリップ現象を防止するとともに、低摩擦で水分離性及び保存安定性に優れた摺動面用潤滑油組成物を提供するところにある。 The problem to be solved by the present invention is to provide a lubricating oil composition for a sliding surface that prevents stick-slip phenomenon on the sliding surface and that is low in friction and excellent in water separation and storage stability.
本発明者らは、前記の課題を解決すべく研究した結果、基油と特定のリン酸化合物とを特定割合で含有して成る摺動面用潤滑油組成物が正しく好適であることを見出した。 As a result of studies to solve the above-mentioned problems, the present inventors have found that a lubricating oil composition for a sliding surface comprising a base oil and a specific phosphoric acid compound in a specific ratio is correctly suitable. It was.
すなわち本発明は、基油を９４〜９９．９質量％及び下記のリン酸化合物を０．１〜６質量％（合計１００質量％）の割合で含有して成る摺動面用潤滑油組成物であって、該リン酸化合物が下記のリン酸化合物Ａと下記のリン酸化合物Ｂとから成り、且つ下記の数１から求められるリン酸化合物ＡのＰ核積分比率（Ｐ核ＮＭＲ積分値のうちで下記の化１で示されるリン酸エステルに帰属されるＰ核ＮＭＲ積分値から算出されるＰ核積分比率）が５〜３０％となるようにしたことを特徴とする摺動面用潤滑油組成物に係る。 That is, the present invention provides a lubricating oil composition for a sliding surface, comprising 94 to 99.9% by mass of a base oil and 0.1 to 6% by mass (total of 100% by mass) of the following phosphoric acid compounds. The phosphoric acid compound is composed of the following phosphoric acid compound A and the following phosphoric acid compound B, and the P nuclear integral ratio (P nuclear NMR integral value of the phosphoric acid compound A obtained from the following formula 1 is calculated. Among them, the lubrication for sliding surfaces characterized in that the P nuclear integral ratio calculated from the P nuclear NMR integral value attributed to the phosphate ester represented by the chemical formula 1 below is 5 to 30%. According to the oil composition.
リン酸化合物Ａ：下記の化１で示されるリン酸エステル及び下記の化１で示されるリン酸エステルの有機アミン塩から選ばれる一つ又は二つ以上。 Phosphoric acid compound A: One or two or more selected from the phosphoric acid ester represented by the following chemical formula 1 and the organic amine salt of the phosphoric acid ester represented by the chemical formula 1 below.
化１において、
Ｒ１：炭素数８〜２４の不飽和結合を有する脂肪族アルコールから水酸基を除いた残基又は炭素数８〜２４の不飽和結合を有する脂肪族アルコールにエチレンオキサイド及び／又はプロピレンオキサイドを合計で１〜２０モル付加したものから水酸基を除いた残基
Ｒ２：水素原子、炭素数８〜２４の不飽和結合を有する脂肪族アルコールから水酸基を除いた残基又は炭素数８〜２４の不飽和結合を有する脂肪族アルコールにエチレンオキサイド及び／又はプロピレンオキサイドを合計で１〜２０モル付加したものから水酸基を除いた残基
ｎ：２又は３の整数
In chemical formula 1,
R 1 : ethylene oxide and / or propylene oxide in total in the residue obtained by removing the hydroxyl group from the aliphatic alcohol having an unsaturated bond having 8 to 24 carbon atoms or the aliphatic alcohol having an unsaturated bond having 8 to 24 carbon atoms Residue obtained by removing a hydroxyl group from a compound added with 1 to 20 moles R 2 : A residue obtained by removing a hydroxyl group from an aliphatic alcohol having an unsaturated bond having 8 to 24 carbon atoms or an unsaturated group having 8 to 24 carbon atoms Residues obtained by adding 1 to 20 mol of ethylene oxide and / or propylene oxide in total to aliphatic alcohol having a bond, and removing the hydroxyl group n: an integer of 2 or 3
リン酸化合物Ｂ：下記の化２で示されるリン酸エステル、下記の化２で示されるリン酸エステルの有機アミン塩、下記の化３で示されるリン酸エステル及び下記の化３で示されるリン酸エステルの有機アミン塩から選ばれる一つ又は二つ以上 Phosphoric acid compound B: phosphoric acid ester represented by the following chemical formula 2, organic amine salt of the phosphoric acid ester represented by the chemical formula 2 below, phosphoric acid ester represented by the chemical formula 3 below and phosphorus represented by the chemical formula 3 below One or more selected from organic amine salts of acid esters
化２及び化３において、
Ｒ３，Ｒ４，Ｒ５：炭素数８〜２４の不飽和結合を有する脂肪族アルコールから水酸基を除いた残基又は炭素数８〜２４の不飽和結合を有する脂肪族アルコールにエチレンオキサイド及び／又はプロピレンオキサイドを合計で１〜２０モル付加したものから水酸基を除いた残基
In Chemical Formula 2 and Chemical Formula 3,
R 3 , R 4 , R 5 : ethylene oxide and / or a residue obtained by removing a hydroxyl group from an aliphatic alcohol having an unsaturated bond having 8 to 24 carbon atoms or an aliphatic alcohol having an unsaturated bond having 8 to 24 carbon atoms Or the residue which remove | excluded the hydroxyl group from what added 1-20 mol of propylene oxide in total
数１において、
Ｐ化１：化１で示されるリン酸エステルに帰属されるＰ核ＮＭＲ積分値
Ｐ化２：化２で示されるリン酸エステルに帰属されるＰ核ＮＭＲ積分値
Ｐ化３：化３で示されるリン酸エステルに帰属されるＰ核ＮＭＲ積分値
In Equation 1,
P: 1: P nuclear NMR integrated value attributed to the phosphate ester represented by Chemical Formula 1: P Chemical 2: P nucleus NMR integrated value attributed to the phosphate ester represented by Chemical Formula 2: P Chemical 3: shown by Chemical Formula 3 P-nuclear NMR integral value attributed to phosphate ester
本発明に係る摺動面用潤滑油組成物（以下、本発明の組成物という）は、基油を９４〜９９．９質量％及び前記したリン酸化合物を０．１〜６質量％（合計１００質量％）の割合で含有して成るものであって、該リン酸化合物が前記したリン酸化合物Ａと前記したリン酸化合物Ｂとから成り、且つ前記した数１から求められるリン酸化合物ＡのＰ核積分比率が５〜３０％となるようにしたものである。 The lubricating oil composition for a sliding surface according to the present invention (hereinafter referred to as the composition of the present invention) comprises 94 to 99.9% by mass of the base oil and 0.1 to 6% by mass of the phosphate compound described above (total). 100% by mass), and the phosphoric acid compound is composed of the phosphoric acid compound A and the phosphoric acid compound B described above, and the phosphoric acid compound A obtained from the above-mentioned formula 1 The P nuclear integral ratio is set to 5 to 30%.
なかでも本発明の組成物としては、基油を９７〜９９．７質量％及び前記したリン酸化合物を０．３〜３質量％（合計１００質量％）の割合で含有して成るものが好ましい。 In particular, the composition of the present invention preferably contains 97 to 99.7% by mass of the base oil and 0.3 to 3% by mass (total of 100% by mass) of the above-described phosphoric acid compound. .
本発明の組成物において、基油としては、鉱物油、合成油及びこれらの混合油から選ばれるものが挙げられる。なかでも基油としては、４０℃における動粘度が２０〜３００ｍｍ2／ｓ、また流動点が−１０℃以下及び粘度指数が９０以上のものが好ましい。鉱物油としては、パラフィン基系原油、中間基系原油、ナフテン基系原油を常圧蒸留又は減圧蒸留して得られる潤滑油留分を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、接触脱ろう、水素化精製、硫酸洗浄、白土処理等の常法にしたがって精製した精製油などが使用できる。また合成油としては、α−オレフィン共重合体、ポリブテン、二塩基酸エステル、ポリグリコール、ヒンダードエステル、アルキルベンゼン、ポリエーテル、アルキルナフタレン等を使用できる。これらは、単独でも又は２種以上を組み合わせて使用してもよい。 In the composition of the present invention, examples of the base oil include those selected from mineral oils, synthetic oils, and mixed oils thereof. Among these, a base oil having a kinematic viscosity at 40 ° C. of 20 to 300 mm 2 / s, a pour point of −10 ° C. or lower, and a viscosity index of 90 or higher is preferable. As mineral oils, lubricating oil fractions obtained by atmospheric distillation or vacuum distillation of paraffinic, intermediate, and naphthenic crude oils are solvent stripped, solvent extracted, hydrocracked, and solvent dewaxed. Refined oil refined according to conventional methods such as catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment can be used. As the synthetic oil, α-olefin copolymer, polybutene, dibasic acid ester, polyglycol, hindered ester, alkylbenzene, polyether, alkylnaphthalene and the like can be used. These may be used alone or in combination of two or more.
本発明の組成物において、リン酸化合物はリン酸化合物Ａとリン酸化合物Ｂとから成るものであり、このリン酸化合物Ａは前記の化１で示されるリン酸エステル及び前記の化１で示されるリン酸エステルの有機アミン塩から選ばれる一つ又は二つ以上である。化１中のＲ１は、パルミトレイルアルコール、オレイルアルコール、エルシルアルコール等の炭素数８〜２４の不飽和結合を有する脂肪族アルコールから水酸基を除いた残基又はこれらの脂肪族アルコールにエチレンオキサイド及び／又はプロピレンオキサイドを合計で１〜２０モル付加したものから水酸基を除いた残基であるが、なかでもパルミトレイルアルコール、オレイルアルコール等の炭素数１２〜１８の不飽和結合を有する脂肪族アルコールから水酸基を除いた残基又はこれらの脂肪族アルコールにエチレンオキサイド及び／又はプロピレンオキサイドを合計で１〜２０モル付加したものから水酸基を除いた残基が好ましい。 In the composition of the present invention, the phosphoric acid compound comprises phosphoric acid compound A and phosphoric acid compound B, and this phosphoric acid compound A is represented by the phosphoric acid ester represented by the chemical formula 1 and the chemical formula 1 shown above. One or more selected from organic amine salts of phosphoric acid esters. R 1 in Chemical Formula 1 is a residue obtained by removing a hydroxyl group from an aliphatic alcohol having an unsaturated bond having 8 to 24 carbon atoms, such as palmitoleyl alcohol, oleyl alcohol, erucyl alcohol, or the like. And / or a residue obtained by removing a hydroxyl group from a total of 1 to 20 moles of propylene oxide, among which aliphatic alcohols having an unsaturated bond of 12 to 18 carbon atoms such as palmitoleyl alcohol and oleyl alcohol A residue obtained by removing a hydroxyl group from a residue obtained by adding 1 to 20 mol of ethylene oxide and / or propylene oxide in total to a residue obtained by removing a hydroxyl group from these aliphatic alcohols is preferred.
また化１中のＲ２は、水素原子、パルミトレイルアルコール、オレイルアルコール、エルシルアルコール等の炭素数８〜２４の不飽和結合を有する脂肪族アルコールから水酸基を除いた残基又はこれらの脂肪族アルコールにエチレンオキサイド及び／又はプロピレンオキサイドを合計で１〜２０モル付加したものから水酸基を除いた残基であるが、なかでも水素原子、パルミトレイルアルコール、オレイルアルコール等の炭素数１２〜１８の不飽和結合を有する脂肪族アルコールから水酸基を除いた残基又はこれらの脂肪族アルコールにエチレンオキサイド及び／又はプロピレンオキサイドを合計で１〜２０モル付加したものから水酸基を除いた残基が好ましい。 R 2 in Chemical Formula 1 is a residue obtained by removing a hydroxyl group from an aliphatic alcohol having an unsaturated bond having 8 to 24 carbon atoms such as a hydrogen atom, palmitoleyl alcohol, oleyl alcohol, erucyl alcohol, or the like. This is a residue obtained by removing 1 to 20 mol of ethylene oxide and / or propylene oxide in total from alcohol and removing a hydroxyl group. Among them, hydrogen atoms, palmitoleyl alcohol, oleyl alcohol, etc. Residues obtained by removing hydroxyl groups from aliphatic alcohols having a saturated bond or residues obtained by adding 1 to 20 mol of ethylene oxide and / or propylene oxide in total to these aliphatic alcohols are preferred.
具体的にリン酸化合物Ａとしては、モノパルミトレイルピロホスフェート、ジパルミトレイルポリホスフェート、ジオレイルポリホスフェート等のリン酸エステル、これらのリン酸エステルの有機アミン塩が挙げられる。ここで有機アミンとしては、ラウリルアミン，オレイルアミン，ジラウリルアミン，ジオレイルアミン，ジメチルモノオレイルアミン，トリラウリルアミン，トリオレイルアミン等が挙げられる。 Specific examples of the phosphoric acid compound A include phosphoric esters such as monopalmitoleyl pyrophosphate, dipalmitoleyl polyphosphate, dioleyl polyphosphate, and organic amine salts of these phosphate esters. Examples of the organic amine include laurylamine, oleylamine, dilaurylamine, dioleylamine, dimethylmonooleylamine, trilaurylamine, and trioleylamine.
本発明の組成物において、リン酸化合物Ｂは前記の化２で示されるリン酸エステル、前記の化２で示されるリン酸エステルの有機アミン塩、前記の化３で示されるリン酸エステル及び前記の化３で示されるリン酸エステルの有機アミン塩から選ばれる一つ又は二つ以上である。化２及び化３中のＲ３、Ｒ４及びＲ５は、化１中のＲ１について前記したことと同様である。 In the composition of the present invention, the phosphoric acid compound B includes the phosphoric acid ester represented by the chemical formula 2, the organic amine salt of the phosphoric acid ester represented by the chemical formula 2, the phosphoric acid ester represented by the chemical formula 3 and the above One or two or more selected from organic amine salts of phosphate esters represented by Chemical Formula 3 R 3 , R 4 and R 5 in Chemical Formula 2 and Chemical Formula 3 are the same as those described above for R 1 in Chemical Formula 1 .
具体的にリン酸化合物Ｂとしては、ジパルミトレイルホスフェート、ジオレイルホスフェート、パルミトレイルオレイルホスフェート、ジエルシルホスフェート、エルシルオレイルホスフェート、モノパルミトレイルホスフェート、モノオレイルホスフェート等のリン酸エステル、これらのリン酸エステルの有機アミン塩が挙げられる。ここで有機アミンとしては、ラウリルアミン，オレイルアミン，ジラウリルアミン，ジオレイルアミン，ジメチルモノオレイルアミン，トリラウリルアミン，トリオレイルアミンが挙げられる。 Specific examples of the phosphoric acid compound B include dipalmitoleyl phosphate, dioleyl phosphate, palmitoleyl oleyl phosphate, diercyl phosphate, erucyl oleyl phosphate, monopalmitoleyl phosphate, monooleyl phosphate and the like, and phosphorous thereof. Organic amine salts of acid esters are mentioned. Here, examples of the organic amine include laurylamine, oleylamine, dilaurylamine, dioleylamine, dimethylmonooleylamine, trilaurylamine, and trioleylamine.
本発明の組成物において、リン酸化合物は、以上説明したリン酸化合物Ａとリン酸化合物Ｂとから成るものであって、且つ前記の数１から求められるリン酸化合物ＡのＰ核積分比率が５〜３０％となるようにしたものである。リン酸化合物ＡのＰ核積分比率は、リン酸エステル及び／又はリン酸エステルの有機アミン塩をこれらに過剰の水酸化カリウムを加えて中和し、これを３１Ｐ−ＮＭＲに供して、その測定値から算出することができる。一般的におおよそ、化１で示されるリン酸エステルに帰属されるピークは０ｐｐｍ未満、化２で示されるリン酸エステルに帰属されるピークは０〜４ｐｐｍ、化３で示されるリン酸エステルに帰属されるピークは４ｐｐｍ超に現れるので、それぞれのピークの積分値を求め、前記した数１により算出する。 In the composition of the present invention, the phosphoric acid compound is composed of the phosphoric acid compound A and the phosphoric acid compound B described above, and the P nuclear integral ratio of the phosphoric acid compound A obtained from the above formula 1 is It is intended to be 5-30%. The P nuclear integral ratio of the phosphoric acid compound A is determined by neutralizing the phosphoric acid ester and / or the organic amine salt of the phosphoric acid ester by adding excess potassium hydroxide thereto, and subjecting this to 31 P-NMR. It can be calculated from the measured value. Generally, the peak attributed to the phosphate ester represented by Chemical Formula 1 is less than 0 ppm, the peak attributed to the phosphate ester represented by Chemical Formula 2 is 0 to 4 ppm, and the peak attributed to the phosphate ester represented by Chemical Formula 3 Since the peak to be generated appears at more than 4 ppm, the integrated value of each peak is obtained and calculated by the above-described formula 1.
数１から求められるリン酸化合物ＡのＰ核積分比率は５〜３０％となるようにするが、なかでも１０〜３０％となるようにするのが好ましい。 The P nucleus integral ratio of the phosphoric acid compound A obtained from Equation 1 is set to 5 to 30%, and preferably 10 to 30%.
以上説明した本発明の組成物は、工作機械のように、工作物や切削工具を任意の方向に移動できる摺動面（すべり案内面）を有する機構の中で、摺動面のスティックスリップ現象を防止するとともに、低摩擦で水分離性及び保存安定性に優れる。切削のために水溶性クーラントを使用しても、優れた摺動性能を発揮でき、クーラントを再使用できるのである。 The composition of the present invention described above is a stick-slip phenomenon of a sliding surface in a mechanism having a sliding surface (sliding guide surface) capable of moving a workpiece or a cutting tool in an arbitrary direction like a machine tool. In addition to low friction and excellent water separation and storage stability. Even if water-soluble coolant is used for cutting, excellent sliding performance can be exhibited and the coolant can be reused.
以下、本発明の構成及び効果をより具体的にするため、実施例等を挙げるが、本発明がこれらの実施例に限定されるというものではない。尚、以下の実施例及び比較例において、部は質量部を、また％は質量％を意味する。 Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples. In the following Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass”.
試験区分１（リン酸化合物の合成等）
・リン酸化合物（Ｐ−１）の合成等
反応容器にオレイルアルコール３８１部を仕込み、１２０℃で０．０５ＭＰａ以下の条件下に２時間脱水処理した。その後、常圧に戻し、撹拌しながら６０±５℃で五酸化二燐９０部を１時間かけて投入した。その後、８０℃にて３時間熟成させ、リン酸化合物（Ｐ−１）を合成した。
Test category 1 (Synthesis of phosphate compounds, etc.)
-Synthesis | combination of phosphoric acid compound (P-1) The reaction container was charged with 381 parts of oleyl alcohol, and dehydrated for 2 hours at 120 ° C under 0.05 MPa or less. Thereafter, the pressure was returned to normal pressure, and 90 parts of diphosphorus pentoxide was added over 1 hour at 60 ± 5 ° C. with stirring. Thereafter, the mixture was aged at 80 ° C. for 3 hours to synthesize a phosphoric acid compound (P-1).
・リン酸化合物（Ｐ−１）のＰ核積分比率の算出
リン酸化合物（Ｐ−１）に過剰のＫＯＨを加えてｐＨ１２以上にした条件で、３１Ｐ−ＮＭＲに供してＰ核ＮＭＲ積分値を測定し、Ｐ核積分比率を算出したところ、化１で示されるリン酸エステルに帰属されるものが１５％、化２で示されるリン酸エステルに帰属されるものが３６％、化３で示されるリン酸エステルに帰属されるものが４９％であった。
-Calculation of the P nuclear integral ratio of the phosphoric acid compound (P-1) Under the condition that an excess of KOH was added to the phosphoric acid compound (P-1) to pH 12 or higher, it was subjected to 31 P-NMR and P nuclear NMR integral value When the P nuclear integral ratio was calculated, 15% was attributed to the phosphate ester represented by Chemical Formula 1, 36% was attributed to the phosphate ester represented by Chemical Formula 2, and 49% was attributed to the phosphate ester shown.
Ｐ核積分比率を算出するためのＰ核ＮＭＲ積分値は、３１Ｐ‐ＮＭＲ（ＶＡＬＩＡＮ社製の、ＭＥＲＣＵＲＹ ｐｌｕｓ ＮＭＲ Ｓｐｅｃｔｒｏｍｅｔｏｒ Ｓｙｓｔｅｍ、３００ＭＨｚ）を用いて測定した。またこのときの溶媒としては、Ｄ２Ｏ（重水）／ＴＨＦ（テトラヒドロフラン）＝８／２（容量比）の混合溶媒を用いた。 The P nuclear NMR integrated value for calculating the P nuclear integral ratio was measured using 31 P-NMR (Mercury plus NMR Spectrometer System, 300 MHz, manufactured by VALIAN). In addition, a mixed solvent of D 2 O (heavy water) / THF (tetrahydrofuran) = 8/2 (volume ratio) was used as the solvent at this time.
・リン酸化合物（Ｐ−２〜Ｐ−５）、（Ｐ−９〜Ｐ−１１）及び（Ｐ−１４）の合成等
リン酸化合物（Ｐ−１）と同様にして、リン酸化合物（Ｐ−２〜Ｐ−５）、（Ｐ−９〜Ｐ−１１）及び（Ｐ−１４）を合成し、これらについてＰ核積分比率を算出した。
-Synthesis of phosphoric acid compounds (P-2 to P-5), (P-9 to P-11) and (P-14) etc. In the same manner as the phosphoric acid compound (P-1), the phosphoric acid compound (P -2 to P-5), (P-9 to P-11) and (P-14) were synthesized, and the P nuclear integral ratio was calculated for these.
・リン酸化合物（Ｐ−６）の合成等
オクチルアルコール１３０．２ｇ（１モル）をオートクレーブに仕込み、触媒として水酸化カリウム粉末１ｇを加えた後、オートクレーブ内を充分に窒素で置換した。撹拌下に反応温度を１３０〜１５０℃に維持しつつＥＯ（エチレンオキシド、以下同じ）１７６ｇ（４モル）を圧入して付加重合反応をおこない、同温度で１時間熟成して付加重合反応を終了した。触媒をリン酸で中和した後、副生物を分子蒸留により分離して、オクチルアルコールＥＯ４モル付加体（Ａ１）を得た。反応容器にオクチルアルコールＥＯ４モル付加体（Ａ１）４３４部を仕込み、１２０℃で０．０５ＭＰａ以下の条件下に２時間脱水処理した。その後、常圧に戻し、撹拌しながら６０±５℃で五酸化二燐８１部を１時間かけて投入した。その後、８０℃にて３時間熟成させ、リン酸化合物（Ｐ−６）を合成した。リン酸化合物（Ｐ−６）について、リン酸化合物（Ｐ−１）と同様にＰ核積分比率を算出した。
Synthesis of phosphoric acid compound (P-6), etc. 130.2 g (1 mol) of octyl alcohol was charged into an autoclave, 1 g of potassium hydroxide powder was added as a catalyst, and the inside of the autoclave was sufficiently substituted with nitrogen. While maintaining the reaction temperature at 130 to 150 ° C. with stirring, 176 g (4 mol) of EO (ethylene oxide, the same shall apply hereinafter) was injected to carry out an addition polymerization reaction, followed by aging at the same temperature for 1 hour to complete the addition polymerization reaction. . After neutralizing the catalyst with phosphoric acid, the by-product was separated by molecular distillation to obtain an octyl alcohol EO4 molar adduct (A1). A reaction vessel was charged with 434 parts of an octyl alcohol EO4 molar adduct (A1) and dehydrated at 120 ° C. under a pressure of 0.05 MPa or less for 2 hours. Thereafter, the pressure was returned to normal pressure, and 81 parts of diphosphorus pentoxide was added over 1 hour at 60 ± 5 ° C. with stirring. Thereafter, the mixture was aged at 80 ° C. for 3 hours to synthesize a phosphoric acid compound (P-6). About the phosphoric acid compound (P-6), P nuclear integral ratio was computed similarly to the phosphoric acid compound (P-1).
・リン酸化合物（Ｐ−７）の合成等
ベヘニルアルコール３２６．６ｇ（１モル）をオートクレーブに仕込み、触媒として水酸化カリウム粉末１ｇを加えた後、オートクレーブ内を充分に窒素で置換した。撹拌下に反応温度を１３０〜１５０℃に維持しつつＥＯを１３２ｇ（３モル）圧入して付加重合反応を行ない、同温度で１時間熟成した後、ＰＯ（プロピレンオキシド、以下同じ）２９０ｇ（５モル）を圧入して付加重合反応をおこない、同温度で１時間熟成して、付加重合反応を終了した。触媒をリン酸で中和した後、副生物を分子蒸留により分離して、ベヘニルアルコールＥＯ３モル・ＰＯ５モル付加体（Ａ２）を得た。反応容器にベヘニルアルコールＥＯ３モル・ＰＯ５モル付加体（Ａ２）８９１部を仕込み、１２０℃で０．０５ＭＰａ以下の条件下に２時間脱水処理をした。その後、常圧に戻し、撹拌しながら６０±５℃で五酸化二燐８１部を１時間かけて投入した。その後、８０℃にて３時間熟成させ、リン酸化合物（Ｐ−７）を合成した。リン酸化合物（Ｐ−７）についてリン酸化合物（Ｐ−１）と同様にＰ核積分比率を算出した。
Synthesis of phosphoric acid compound (P-7), etc. 326.6 g (1 mol) of behenyl alcohol was charged into an autoclave, 1 g of potassium hydroxide powder was added as a catalyst, and the inside of the autoclave was sufficiently substituted with nitrogen. While maintaining the reaction temperature at 130 to 150 ° C. with stirring, 132 g (3 mol) of EO was injected to carry out an addition polymerization reaction. After aging at the same temperature for 1 hour, 290 g of PO (propylene oxide, hereinafter the same) 290 g (5 The addition polymerization reaction was carried out by injecting, and the mixture was aged at the same temperature for 1 hour to complete the addition polymerization reaction. After neutralizing the catalyst with phosphoric acid, the by-product was separated by molecular distillation to obtain an adduct (A2) of behenyl alcohol EO 3 mol / PO 5 mol. A reaction vessel was charged with 891 parts of behenyl alcohol EO 3 mol / PO 5 mol adduct (A2), and dehydrated at 120 ° C. under 0.05 MPa or less for 2 hours. Thereafter, the pressure was returned to normal pressure, and 81 parts of diphosphorus pentoxide was added over 1 hour at 60 ± 5 ° C. with stirring. Thereafter, the mixture was aged at 80 ° C. for 3 hours to synthesize a phosphoric acid compound (P-7). For the phosphoric acid compound (P-7), the P nuclear integral ratio was calculated in the same manner as the phosphoric acid compound (P-1).
・リン酸化合物（Ｐ−８）の合成等
反応容器にオレイルアルコール３８１部を仕込み、１２０℃で０．０５ＭＰａ以下の条件下に２時間脱水処理した。その後、常圧に戻し、撹拌しながら６０±５℃で五酸化二燐８１部を１時間かけて投入した。その後、８０℃にて３時間熟成させ、更に水５部を７５℃で滴下して９５℃にて２時間熟成させ、リン酸化合物（Ｐ−８）を合成した。リン酸化合物（Ｐ−８）について、リン酸化合物（Ｐ−１）と同様にＰ核積分比率を算出した。
-Synthesis | combination of phosphoric acid compound (P-8) etc. 381 parts of oleyl alcohol was prepared to reaction container, and it dehydrated for 2 hours on the conditions of 0.05 Mpa or less at 120 degreeC. Thereafter, the pressure was returned to normal pressure, and 81 parts of diphosphorus pentoxide was added over 1 hour at 60 ± 5 ° C. with stirring. Thereafter, the mixture was aged at 80 ° C. for 3 hours, and further 5 parts of water was added dropwise at 75 ° C. and aged at 95 ° C. for 2 hours to synthesize a phosphoric acid compound (P-8). About the phosphoric acid compound (P-8), P nuclear integral ratio was computed similarly to the phosphoric acid compound (P-1).
・リン酸化合物（Ｐ−１２及びＰ−１３）の合成等
リン酸化合物（Ｐ−８）と同様にして、リン酸化合物（Ｐ−１２及びＰ−１３）を合成し、これらについて、リン酸化合物（Ｐ−１）と同様にＰ核積分比率を算出した。
-Synthesis of phosphoric acid compounds (P-12 and P-13), etc. Phosphoric acid compounds (P-12 and P-13) were synthesized in the same manner as phosphoric acid compound (P-8). The P nuclear integral ratio was calculated in the same manner as for the compound (P-1).
以上で合成した各リン酸化合物の内容及び算出した各リン酸化合物のＰ核積分比率を表１にまとめて示した。 Table 1 summarizes the contents of the phosphoric acid compounds synthesized above and the calculated P nuclear integral ratio of each phosphoric acid compound.
表１において、
＊１：オクチルアルコールＥＯ４モル付加体から水酸基を除いた残基
＊２：ベヘニルアルコールＥＯ３モル・ＰＯ５モル付加体から水酸基を除いた残基
In Table 1,
* 1: Residue obtained by removing a hydroxyl group from an octyl alcohol EO4 mol adduct * 2: Residue obtained by removing a hydroxyl group from a behenyl alcohol EO3 mol / PO5 mol adduct
試験区分２（摺動面用潤滑油組成物の調製）
・実施例１〜３及び比較例１〜１１
基油として、動粘度（４０℃）が６８ｍｍ２／ｓ、粘度指数が１０２及び流動点が−１２．５℃のパラフィン系鉱物油を用い、これに試験区分１で合成したリン酸化合物を表２に示す割合となるよう混合し、摺動面用潤滑油組成物を調製した。
Test category 2 (Preparation of lubricating oil composition for sliding surfaces)
-Examples 1-3 and Comparative Examples 1-11
As a base oil, a paraffinic mineral oil having a kinematic viscosity (40 ° C.) of 68 mm 2 / s, a viscosity index of 102, and a pour point of −12.5 ° C. is used. 2 were mixed to prepare a lubricating oil composition for sliding surfaces.
試験区分３（潤滑油組成物の評価）
試験区分２で調製した摺動面用潤滑油組成物を以下のように評価し、結果を表２にまとめて示した。
Test category 3 (evaluation of lubricating oil composition)
The sliding surface lubricating oil composition prepared in Test Category 2 was evaluated as follows, and the results are summarized in Table 2.
摩擦特性（スティックスリップ現象の有無、摩擦係数及び速度依存性）
摩擦特性の評価は、工作機械の摺動面におけるスティックスリップ現象をシミュレートできるＰｉｎ−ｏｎ−ｒｉｎｇ型の摩擦試験装置を用いて行なった。その詳細は、トライボロジスト、５３巻、１０号、２００８年、Ｐ６８２〜６８８頁に記載されている。本試験では合成した摺動面用潤滑油組成物の真の摩擦特性を評価することを目的に、上部及び下部試験片としてはともに鋳鉄製のものを用い、また摩擦面粗さＲｚｊｉｓは３．０〜３．５μｍ、試験は室温（約２５℃）にて実施した。面圧は０．３ＭＰａ、すべり速度は４．６×１０−５〜８．７×１０１ｍｍ／秒とし、摺動面用潤滑油組成物は、チューブ式ポンプによりリング中央から供給し、リング外側から排出して循環した。一回の試験に使用する摺動面用潤滑油組成物の総量は約２００ｍＬ、供給量は約０．６ｍＬ／分とした。摺動面用潤滑油組成物により摩擦係数が安定するまで、ならし速度を５．２ｍｍ／秒にしてならし運転を４時間行ない、その後すべり速度を変化させ、各すべり速度における摩擦係数、速度依存性、スティックスリップ現象の有無について、以下の評価基準で評価し、結果を表２にまとめて示した。
Friction characteristics (existence of stick-slip phenomenon, friction coefficient and speed dependence)
Evaluation of the friction characteristics was performed using a pin-on-ring type friction test apparatus capable of simulating the stick-slip phenomenon on the sliding surface of the machine tool. The details are described in Tribologists, Vol. 53, No. 10, 2008, p. 682-688. In this test, for the purpose of evaluating the true friction characteristics of the synthesized lubricating oil composition for sliding surfaces, both upper and lower test pieces are made of cast iron, and the friction surface roughness Rzjis is 3. The test was performed at room temperature (about 25 ° C.) from 0 to 3.5 μm. The surface pressure is 0.3 MPa, the sliding speed is 4.6 × 10 −5 to 8.7 × 10 1 mm / second, and the lubricating oil composition for the sliding surface is supplied from the center of the ring by a tube pump. It was discharged from the outside and circulated. The total amount of the lubricating oil composition for sliding surfaces used in one test was about 200 mL, and the supply amount was about 0.6 mL / min. Until the friction coefficient is stabilized by the lubricating oil composition for the sliding surface, the leveling speed is set to 5.2 mm / sec., The leveling operation is performed for 4 hours, and then the sliding speed is changed. The friction coefficient and speed at each sliding speed are changed. The dependence and the presence or absence of the stick-slip phenomenon were evaluated according to the following evaluation criteria, and the results are summarized in Table 2.
スティックスリップ現象の有無
スティックスリップ現象の有無を目視にて観察した。
Presence or absence of stick-slip phenomenon The presence or absence of stick-slip phenomenon was visually observed.
・摩擦係数
すべり速度４．６×１０−５ｍｍ／秒における摩擦係数を読み取った。
◎：０．０３０μ未満
○：０．０３０μ以上０．０６０μ未満
×：０．０６０μ以上
-Coefficient of friction The coefficient of friction was read at a sliding speed of 4.6 x 10-5 mm / sec.
◎: Less than 0.030μ ○: 0.030μ or more and less than 0.060μ ×: 0.060μ or more
・速度依存性
速度依存性αは、（すべり速度ｖ１が４．６×１０−５ｍｍ／秒の時の摩擦係数μ１）／（すべり速度ｖ２が４．６×１０−１ｍｍ／秒の時の摩擦係数μ２）により求めた。
○：αが３以上
×：αが３未満
Speed dependency The speed dependency α is (the friction coefficient μ 1 when the sliding speed v 1 is 4.6 × 10 −5 mm / second) / (the sliding speed v 2 is 4.6 × 10 −1 mm / second ). The coefficient of friction was μ 2 ).
○: α is 3 or more ×: α is less than 3
・水分離性
水分離性は、ＪＩＳ−Ｋ２５２０に準じて評価した。すなわち、摺動面用潤滑油組成物４０ｍＬと水４０ｍＬを撹拌して混合し、撹拌終了から３０分後の乳化相の残存量を以下の基準で評価した。
○：乳化相の残存量が３０ｍＬ未満
×：乳化相の残存量が３０ｍＬ以上８０ｍＬ以下
-Water separability Water separability was evaluated according to JIS-K2520. That is, 40 mL of the lubricating oil composition for sliding surfaces and 40 mL of water were stirred and mixed, and the remaining amount of the emulsified phase 30 minutes after the end of stirring was evaluated according to the following criteria.
○: Remaining amount of emulsified phase is less than 30 mL ×: Remaining amount of emulsified phase is 30 mL or more and 80 mL or less
・保存安定性
摺動面用潤滑油組成物を３０℃の条件にて７日間保管し、外観を目視で観察した。
○：析出物無し
×：析出物有り
-Storage stability The lubricating oil composition for sliding surfaces was stored for 7 days at 30 ° C, and the appearance was visually observed.
○: No precipitate ×: Precipitate
Claims (4)
リン酸化合物Ａ：下記の化１で示されるリン酸エステル及び下記の化１で示されるリン酸エステルの有機アミン塩から選ばれる一つ又は二つ以上。
Ｒ１：炭素数８〜２４の不飽和結合を有する脂肪族アルコールから水酸基を除いた残基又は炭素数８〜２４の不飽和結合を有する脂肪族アルコールにエチレンオキサイド及び／又はプロピレンオキサイドを合計で１〜２０モル付加したものから水酸基を除いた残基
Ｒ２：水素原子、炭素数８〜２４の不飽和結合を有する脂肪族アルコールから水酸基を除いた残基又は炭素数８〜２４の不飽和結合を有する脂肪族アルコールにエチレンオキサイド及び／又はプロピレンオキサイドを合計で１〜２０モル付加したものから水酸基を除いた残基
ｎ：２又は３の整数）
リン酸化合物Ｂ：下記の化２で示されるリン酸エステル、下記の化２で示されるリン酸エステルの有機アミン塩、下記の化３で示されるリン酸エステル及び下記の化３で示されるリン酸エステルの有機アミン塩から選ばれる一つ又は二つ以上。
Ｒ３，Ｒ４，Ｒ５：炭素数８〜２４の不飽和結合を有する脂肪族アルコールから水酸基を除いた残基又は炭素数８〜２４の不飽和結合を有する脂肪族アルコールにエチレンオキサイド及び／又はプロピレンオキサイドを合計で１〜２０モル付加したものから水酸基を除いた残基）
Ｐ化１：化１で示されるリン酸エステルに帰属されるＰ核ＮＭＲ積分値
Ｐ化２：化２で示されるリン酸エステルに帰属されるＰ核ＮＭＲ積分値
Ｐ化３：化３で示されるリン酸エステルに帰属されるＰ核ＮＭＲ積分値） A lubricating oil composition for a sliding surface comprising 94 to 99.9% by weight of a base oil and 0.1 to 6% by weight (100% by weight in total) of the following phosphoric acid compound, The phosphoric acid compound is composed of the following phosphoric acid compound A and the following phosphoric acid compound B, and the P nuclear integral ratio of the phosphoric acid compound A obtained from the following formula 1 is set to 5 to 30%. A lubricating oil composition for sliding surfaces.
Phosphoric acid compound A: One or two or more selected from the phosphoric acid ester represented by the following chemical formula 1 and the organic amine salt of the phosphoric acid ester represented by the chemical formula 1 below.
R 1 : ethylene oxide and / or propylene oxide in total in the residue obtained by removing the hydroxyl group from the aliphatic alcohol having an unsaturated bond having 8 to 24 carbon atoms or the aliphatic alcohol having an unsaturated bond having 8 to 24 carbon atoms Residue obtained by removing a hydroxyl group from a compound added with 1 to 20 moles R 2 : A residue obtained by removing a hydroxyl group from an aliphatic alcohol having an unsaturated bond having 8 to 24 carbon atoms or an unsaturated group having 8 to 24 carbon atoms A residue obtained by adding 1 to 20 mol of ethylene oxide and / or propylene oxide in total to a fatty alcohol having a bond, and removing a hydroxyl group n: an integer of 2 or 3)
Phosphoric acid compound B: phosphoric acid ester represented by the following chemical formula 2, organic amine salt of the phosphoric acid ester represented by the chemical formula 2 below, phosphoric acid ester represented by the chemical formula 3 below and phosphorus represented by the chemical formula 3 below One or more selected from organic amine salts of acid esters.
R 3 , R 4 , R 5 : ethylene oxide and / or a residue obtained by removing a hydroxyl group from an aliphatic alcohol having an unsaturated bond having 8 to 24 carbon atoms or an aliphatic alcohol having an unsaturated bond having 8 to 24 carbon atoms Or a residue obtained by removing a hydroxyl group from a total of 1 to 20 moles of propylene oxide added)
P: 1: P nuclear NMR integrated value attributed to the phosphate ester represented by Chemical Formula 1: P Chemical 2: P nucleus NMR integrated value attributed to the phosphate ester represented by Chemical Formula 2: P Chemical 3: shown by Chemical Formula 3 P-nuclear NMR integrated value attributed to phosphate ester)
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|---|---|---|---|---|
| JPH05271259A (en) * | 1992-01-10 | 1993-10-19 | Oceanfloor Ltd | Polyether phosphate esters |
| JP2002275489A (en) * | 2001-03-19 | 2002-09-25 | Japan Energy Corp | Lubricating oil composition for sliding face |
| JP2004067770A (en) * | 2002-08-02 | 2004-03-04 | Chubu Kiresuto Kk | Lubricant/rust inhibitor and metal working oil agent containing the same |
| WO2010079744A1 (en) * | 2009-01-09 | 2010-07-15 | 株式会社ジャパンエナジー | Lubricant composition |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05271259A (en) * | 1992-01-10 | 1993-10-19 | Oceanfloor Ltd | Polyether phosphate esters |
| JP2002275489A (en) * | 2001-03-19 | 2002-09-25 | Japan Energy Corp | Lubricating oil composition for sliding face |
| JP2004067770A (en) * | 2002-08-02 | 2004-03-04 | Chubu Kiresuto Kk | Lubricant/rust inhibitor and metal working oil agent containing the same |
| WO2010079744A1 (en) * | 2009-01-09 | 2010-07-15 | 株式会社ジャパンエナジー | Lubricant composition |
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