WO2013147136A1 - Lubricating oil composition for metalworking - Google Patents
Lubricating oil composition for metalworking Download PDFInfo
- Publication number
- WO2013147136A1 WO2013147136A1 PCT/JP2013/059488 JP2013059488W WO2013147136A1 WO 2013147136 A1 WO2013147136 A1 WO 2013147136A1 JP 2013059488 W JP2013059488 W JP 2013059488W WO 2013147136 A1 WO2013147136 A1 WO 2013147136A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mass
- lubricating oil
- oil composition
- oil
- metal
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 43
- 238000005555 metalworking Methods 0.000 title claims abstract description 28
- 239000003921 oil Substances 0.000 claims abstract description 48
- 239000005077 polysulfide Substances 0.000 claims abstract description 32
- 229920001021 polysulfide Polymers 0.000 claims abstract description 32
- 150000008117 polysulfides Polymers 0.000 claims abstract description 32
- 150000002148 esters Chemical class 0.000 claims abstract description 31
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 27
- 239000000194 fatty acid Substances 0.000 claims abstract description 27
- 229930195729 fatty acid Natural products 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 25
- 238000012545 processing Methods 0.000 claims abstract description 24
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 22
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000002199 base oil Substances 0.000 claims abstract description 20
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 19
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 19
- 239000010959 steel Substances 0.000 claims abstract description 19
- 239000002480 mineral oil Substances 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 235000010446 mineral oil Nutrition 0.000 claims description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 22
- 239000011593 sulfur Substances 0.000 claims description 22
- 229910052717 sulfur Inorganic materials 0.000 claims description 22
- -1 alkaline earth metal sulfonate Chemical class 0.000 claims description 20
- 229920000193 polymethacrylate Polymers 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000460 chlorine Substances 0.000 abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 abstract description 5
- 230000001050 lubricating effect Effects 0.000 abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- 125000000217 alkyl group Chemical group 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000011575 calcium Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 235000011187 glycerol Nutrition 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 6
- 150000005215 alkyl ethers Chemical class 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 3
- 150000004671 saturated fatty acids Chemical class 0.000 description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 3
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- QAPVYZRWKDXNDK-UHFFFAOYSA-N P,P-Dioctyldiphenylamine Chemical compound C1=CC(CCCCCCCC)=CC=C1NC1=CC=C(CCCCCCCC)C=C1 QAPVYZRWKDXNDK-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QTIMEBJTEBWHOB-PMDAXIHYSA-N [3-[(z)-octadec-9-enoyl]oxy-2,2-bis[[(z)-octadec-9-enoyl]oxymethyl]propyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COC(=O)CCCCCCC\C=C/CCCCCCCC)(COC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC QTIMEBJTEBWHOB-PMDAXIHYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- FLAJFZXTYPQIBY-CLFAGFIQSA-N bis[(z)-octadec-9-enyl] hydrogen phosphite Chemical compound CCCCCCCC\C=C/CCCCCCCCOP(O)OCCCCCCCC\C=C/CCCCCCCC FLAJFZXTYPQIBY-CLFAGFIQSA-N 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 102200082816 rs34868397 Human genes 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/043—Sulfur; Selenenium; Tellurium
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/106—Naphthenic fractions
- C10M2203/1065—Naphthenic fractions used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
- C10M2207/2835—Esters of polyhydroxy compounds used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbased sulfonic acid salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/049—Phosphite
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/41—Chlorine free or low chlorine content compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/52—Base number [TBN]
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
Definitions
- the present invention relates to a lubricating oil composition for metal working, and more particularly to a lubricating oil composition for metal working used under severe lubricating conditions such as steel pipe expansion.
- Lubricating oils used for metal processing are usually required to have excellent load bearing performance because they are used under severe lubricating conditions. Moreover, since the lubricating oil used for metal processing needs to be removed by washing the lubricating oil adhering to the workpiece after metal processing, it is also required to have excellent cleaning properties.
- steel pipe expansion processing such as mechanical steel pipe expansion (mechanical expander)
- a steel pipe having a diameter of 30 inches or more, a thickness of 6 to 25 mm, and a length of 10 m or more is usually used as a workpiece.
- the pipe is formed and the steel pipe having tough strength is expanded by the expander.
- the lubricating oil used for steel pipe expansion processing is required to have extremely high load bearing performance.
- the oil adhering to the steel pipe is washed with warm water also serving as a water pressure inspection. Therefore, the lubricating oil used for steel pipe expansion processing is required to have excellent cleaning properties.
- chlorinated oil has been used as a lubricating oil for steel pipe expansion processing.
- Chlorine-based oils have high polarity due to the use of chlorine, have excellent load bearing performance, and also have excellent detergency that can be washed away with water in steel pipe expansion processing.
- the movement to abolish chlorinated oils is spreading from the viewpoint of reducing environmental impact, and the development of non-chlorinated lubricants that realize this is being promoted worldwide.
- Patent Document 1 proposes to use water-soluble polyethylene glycol as a lubricant for steel pipe expansion processing.
- water-soluble polyethylene glycol has detergency, load-bearing performance is reduced. Therefore, in order to improve lubricity, an excessively high viscosity oil agent must be used, which is inferior in handling. Further, the high-pressure viscosity of the water-soluble substrate is very low, and the sliding portion having a high surface pressure cannot be lubricated, and seizure occurs. Thus, it turns out that the method of using water-soluble polyethylene glycol has room for improvement in terms of load bearing performance and handling.
- the sulfur-based oil agent that is most often used as an alternative to the chlorine-based oil agent cannot achieve its purpose because it cannot provide cleaning properties even if it can provide load bearing performance. Under such circumstances, development of a metal processing lubricant, particularly a steel pipe expansion lubricant, having high load-bearing performance and excellent cleanability without using a chlorinated oil is desired.
- the present invention is a metalworking lubrication that has high load-bearing performance and excellent cleaning properties without using a chlorinated oil, and can be used under severe lubrication conditions such as steel pipe expansion.
- the object is to provide an oil composition.
- the present inventors have found that a composition obtained by combining specific additives can achieve its purpose.
- the present invention has been completed based on such findings. That is, the present invention
- a base oil (b) a metal sulfonate, (c) an active polysulfide, (d) a fatty acid partial ester of a polyhydric alcohol, and (e) a nonionic surfactant.
- a lubricating oil composition for metal working wherein the viscosity is 50 mm 2 / s or more and 1000 mm 2 / s or less, 2.
- C ′ the lubricating oil composition for metalworking according to 1 above, further comprising powdered sulfur, 3.
- Lubricating oil composition 8).
- the lubricating oil composition for metal working according to 8 above, wherein the polyoxyalkylene type nonionic surfactant has a polyoxyethylene group and a polyoxypropylene group, 10.
- a lubricating oil composition can be provided.
- the lubricating oil composition for metal processing of the present invention comprises (a) a base oil, (b) a metal sulfonate, (c) an active polysulfide, (d) a fatty acid partial ester of a polyhydric alcohol, and (e) a nonionic interface. It contains an active agent, and the kinematic viscosity at 40 ° C. of the composition is from 50 mm 2 / s to 1000 mm 2 / s.
- the base oil used as the component (a) in the present invention is not particularly limited, and can be appropriately selected from known mineral base oils and synthetic base oils that have been used conventionally.
- the mineral oil base oil for example, a distillate obtained by atmospheric distillation of paraffinic crude oil, intermediate (base) crude oil, or naphthenic crude oil, or vacuum distillation of residual oil of atmospheric distillation.
- refined oils obtained by refining them according to conventional methods for example, solvent refined oil, hydrorefined oil, hydrocracked oil, dewaxed oil, clay-treated oil, mineral oil-based wax, Fischer-Tropsch process, etc. And the like (base oil produced by isomerizing a gas-liquid liquid).
- examples of synthetic oils include poly- ⁇ -olefins, which are ⁇ -olefin oligomers having 8 to 14 carbon atoms, ester-based synthetic oils such as polybutene and polyol esters, aromatic hydrocarbons such as alkylbenzene, and polymethacrylates. Mention may be made of molecular compounds.
- the base oil one kind of the above mineral oil may be used, or two or more kinds may be used in combination.
- the said synthetic oil may be used 1 type and may be used in combination of 2 or more type.
- one or more mineral oils and one or more synthetic oils may be used in combination.
- the base oil in the present invention preferably has a kinematic viscosity at 40 ° C. of 50 mm 2 / s to 1000 mm 2 / s, and more preferably 100 mm 2 / s to 800 mm 2 / s. If the base oil has a kinematic viscosity at 40 ° C. of less than 50 mm 2 / s, the oil film under high surface pressure may break, and the performance as a lubricating oil may be insufficient. On the other hand, if it exceeds 1000 mm 2 / s, it may be difficult to handle with a normal pump, and there may be a residual after washing with warm water.
- a base oil containing a mineral oil is preferable as the base oil.
- a mineral oil mineral oil only
- one or more selected from mineral oil, an ester synthetic oil, and polymethacrylate is used.
- the inclusion is more preferable.
- Mineral oil includes a mixture of two or more mineral oils.
- the blending ratio of mineral oil to one or more selected from ester synthetic oil and polymethacrylate in the case of mixing and using ester synthetic oil or polymethacrylate in mineral oil is not particularly limited, but usually [mineral oil]:
- the mass ratio of [one or more selected from ester-based synthetic oils and polymethacrylates] is preferably in the range of 70:30 to 40:60. When the blending ratio of both is within the above range, a composition satisfying the dissolution stability of the composition at the same time as the washing performance and load bearing performance can be obtained.
- the mineral oil used in the present invention may be any of paraffinic mineral oil, intermediate (base) mineral oil, or naphthenic mineral oil as described above, but naphthenic mineral oil has better detergency and dissolution stability of the oil agent. It is preferable at the point which can be maintained.
- the kinematic viscosity at 40 ° C. of the mineral oil, 20 mm 2 / s or more 1000 mm 2 / s can be used following ones, the following are more preferable 30 mm 2 / s or more 800mm 2 / s, 80mm 2 / s or more 500 mm 2 Particularly preferred is / s or less.
- Specific examples of preferred mineral oils include, for example, bright stock oil (BS) and 500 neutral oil (500 N), and particularly preferred is bright stock oil or a mixture of bright stock oil and 500 neutral oil.
- ester synthetic oil used in the present invention an ester compound having two or more ester bonds in the molecule can be used.
- ester compounds include polyol esters formed from polyhydric alcohols and fatty acids.
- polyhydric alcohol that forms the polyol ester dihydric to hexahydric ones are usually used.
- Preferred polyhydric alcohols include, for example, ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan and the like. Of these, trimethylolpropane and pentaerythritol are more preferable.
- the fatty acid forming the polyol ester is preferably a monobasic acid, and usually a fatty acid having 2 to 24 carbon atoms is used.
- the fatty acid may be linear or branched, and may be saturated or unsaturated. Among these, a saturated fatty acid having 8 to 22 carbon atoms or an unsaturated fatty acid is preferable, and a saturated fatty acid having 12 to 18 carbon atoms or an unsaturated fatty acid is more preferable.
- ester synthetic oil formed from the polyhydric alcohol and the fatty acid include trimethylolpropane or pentaerythritol having 8 to 22 carbon atoms, more preferably 12 to 18 carbon atoms, and particularly preferably 16 to 18 carbon atoms.
- the fatty acid esters are preferred.
- the polymethacrylate used in the present invention may be either a dispersion type or a non-dispersion type.
- the mass average molecular weight is preferably 10,000 or more and 1,000,000 or less, more preferably 50,000 or more and 800,000 or less, and still more preferably 100,000 or more and 700,000 or less. When the mass average molecular weight is 10,000 or more and 1,000,000 or less, a thickening effect can be imparted and load bearing performance can be enhanced.
- metal salts can be used as the metal sulfonate used as the component (b).
- alkaline earth metal sulfonates such as Ca, Mg, and Ba are preferable from the viewpoint of enhancing the load bearing performance.
- Ca sulfonate and Mg sulfonate are more preferable, and Ca sulfonate is particularly preferable.
- the metal sulfonate may be neutral, basic, or overbased, but it is an overbased Ca sulfonate, specifically, a base number by the perchloric acid method is 150 mgKOH / g or more.
- a Ca sulfonate of 500 mgKOH / g or less is preferable, and a Ca sulfonate of 250 mgKOH / g or more and 500 mgKOH / g or less is particularly preferable.
- the content of the metal sulfonate as the component (b) is preferably 1% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less based on the total amount of the composition. If the content of the metal sulfonate is 1% by mass or more, the effect of improving the load bearing performance is exhibited, and if it is 20% by mass or less, the dissolution stability can be kept good.
- active polysulfide is used as the component (c).
- active polysulfide for example, dihydrocarbyl polysulfide represented by the following general formula (1) is preferably used.
- R 1 -S x -R 2 (1)
- each of the hydrocarbyl groups R 1 and R 2 independently represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, or an arylalkyl group, It may be the same or different.
- x represents an integer of 2 to 10.
- the hydrocarbyl group of R 1 and R 2 is more preferably an alkyl group having 6 to 18 carbon atoms.
- alkyl group a linear or branched, saturated or unsaturated alkyl group is used. it can.
- active polysulfide any of linear or branched dihexyl polysulfide, dioctyl polysulfide, dinonyl polysulfide, didecyl polysulfide, didodecyl polysulfide, diundecyl polysulfide, ditetradecyl polysulfide, dihexadecyl polysulfide, Examples thereof include polysulfide having a branched alkyl group having 6 to 15 carbon atoms derived from dioctadecyl polysulfide, propylene or isobutylene.
- dialkyl polysulfides having an alkyl group having 8 to 16 carbon atoms are preferable.
- the sulfur content of the active polysulfide is preferably 20% by mass or more and particularly preferably 30% by mass or more in order to improve load bearing performance.
- the content of the active polysulfide as the component (c) in the present invention is preferably 2% by mass or more and 25% by mass or less, more preferably 5% by mass or more and 20% by mass or less based on the total amount of the composition. If the content of the active polysulfide is 2% by mass or more, the load bearing performance is satisfactorily exhibited, and if it is 25% by mass or less, corrosion does not become a problem.
- powdered sulfur can be included as the component (c ′) together with the active polysulfide. This can further enhance the load bearing performance.
- the blending amount is not particularly limited, but is preferably 0.05% by mass or more and 3% by mass or less, more preferably 0.1% by mass or more and 1% by mass or less based on the total amount of the composition.
- 0.2 mass% or more and 0.7 mass% or less are more preferable, and 0.3 mass% or more and 0.5 mass% or less are especially preferable.
- content of powdered sulfur is 0.05% by mass or more, the effect of further enhancing the load bearing performance of the composition of the present invention is exhibited.
- content of powder sulfur is 3 mass% or less, there is no possibility that powder sulfur will precipitate.
- a fatty acid partial ester of a polyhydric alcohol is used as the component (d).
- the polyhydric alcohol those having 2 to 6 valences are usually used. Specific examples thereof include ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan and the like. Among these, glycerin and sorbitan are preferable, and glycerin is particularly preferable.
- the fatty acid that forms the fatty acid partial ester a fatty acid having 6 to 24 carbon atoms is usually used.
- the fatty acid may be linear or branched, and may be saturated or unsaturated. Among these, fatty acid having 12 to 22 carbon atoms is preferable, saturated or unsaturated fatty acid having 16 to 18 carbon atoms is more preferable, and oleic acid is particularly preferable from the viewpoint of effects and availability.
- the fatty acid partial ester as the component (d) includes glycerin monoester (monoglyceride) and glycerin diester (diglyceride). In the present invention, glycerin monoester (monoglyceride) is more preferable.
- the nonionic surfactant used as the component (e) in the present invention may be any type such as a polyhydric alcohol type nonionic surfactant and a polyoxyalkylene type nonionic surfactant.
- the nonionic surfactant is blended mainly for imparting detergency to the lubricating oil composition. Therefore, it is preferable to easily adjust HLB (hydrophilic lipophilic balance), and polyoxyalkylene nonionic surfactants that can easily be obtained from various HLBs are particularly preferably used.
- nonionic surfactant polyoxyethylene alkyl ether (however, the alkyl group constituting the alkyl ether preferably has 6 to 18 carbon atoms), polyoxyethylene polyoxypropylene alkyl ether ( However, polyoxyethylene polyoxypropylene may be random copolymerization or block copolymerization, and the alkyl group constituting the alkyl ether preferably has 6 to 18 carbon atoms).
- nonionic surfactants may be used alone or in combination of two or more. In this invention, it is preferable to mix
- the present invention comprises the components (a) to (e) or (a) to (e) and (c ′) described above, but further impairs the object of the present invention as desired.
- various additives such as an antioxidant, a rust inhibitor, a corrosion inhibitor, and an antifoaming agent can be blended within the range.
- the antioxidant include phenolic antioxidants such as 2,6-di-tert-butyl-4-methylphenol and 4,4′-methylenebis (2,6-di-tert-butylphenol), phenyl
- examples thereof include amine-based antioxidants such as - ⁇ -naphthylamine and 4,4'-dioctyldiphenylamine.
- Examples of the rust inhibitor and corrosion inhibitor include fatty acid, alkenyl succinic acid half ester, fatty acid soap, alkyl sulfonate, fatty acid amine, paraffin oxide, alkyl polyoxyethylene ether, and the like.
- Examples of the antifoaming agent include dimethylpolysiloxane and polyacrylate. These additives can be used individually by 1 type or in mixture of 2 or more types. Moreover, the compounding quantity of these additives is normally mix
- the lubricating oil composition for metal working of the present invention has a kinematic viscosity at 40 ° C. of 50 mm 2 / s to 1000 mm 2 / s, preferably 100 mm 2 / s to 500 mm 2 / s, more preferably 110 mm 2 / s. s to 300 mm 2 / s. If the kinematic viscosity at 40 ° C. of the composition is 50 mm 2 / s or more, the oil film is prevented from being broken under high surface pressure and the performance as a lubricating oil is exhibited. If the composition is 1000 mm 2 / s or less, the viscosity is It is not too high to be handled with a pump, and no residual material is generated when washing with hot water.
- (I) Pull-out load The pull-out load when 60 mm was pulled was measured. It shows that a low pull-out load is good.
- (Ii) Surface damage The surface of the workpiece when it was pulled out by 60 mm was observed, and the presence and extent of damage due to seizure or galling was measured visually. The damage area was evaluated as the degree of damage based on the following evaluation criteria. (Evaluation criteria) None: No damage on both sides Fine: Scratches less than 10% of surface area on one side Small: Scratches of 10% to 30% of surface area on one side Medium: Scratches of 30% or less of surface area on both sides Large: Surface area on both sides There are more than 30% of scratches
- Detergency test (test method) An SPCC plate (60 mm ⁇ 80 mm ⁇ 0.7 mm (thickness)) was dipped in the oil, and then suspended for 30 minutes to drain the oil. Subsequently, it was washed with a warm water (40 ° C.) shower with a water pressure of 40 kgf / cm 2 for 40 seconds and further immersed in running water. Thereafter, the wetted area was visually measured and evaluated according to the following criteria. (Evaluation criteria) A: The wetted area exceeds 70% B: The wetted area exceeds 40% and is 70% or less C: The wetted area is 40% or less
- Examples 1 to 8 and Comparative Examples 1 to 5 Using the base oils and additives shown in Tables 1 and 2 and mixing at the ratios shown in Tables 1 and 2, metalworking fluids were prepared, and their properties and performance were determined. The results are shown in Tables 1 and 2.
- compositions of Examples 1 to 8 of the present invention have a drawing load in a draw bead test of 260 kgf or less, almost no surface damage, and good cleanability.
- Comparative Example 1 which does not contain the component (b) has a high pulling load (288 kgf) and a large surface damage.
- the comparative example 2 which does not contain (c) component (active polysulfide) has a high extraction load (330 kgf), and its surface damage is also large.
- blended the phosphorus extreme pressure agent with the comparative example 2 which does not contain (c) component (active polysulfide) has shown that neither a drawing load nor surface damage fully recovers.
- the comparative example 4 which does not contain the component (d) has a high pulling load (270 kgf), and the surface damage is also poor.
- the lubricating oil composition for metal working of the present invention even without using a chlorinated oil, it has a high load-bearing performance and at the same time has an excellent cleaning property, and is subjected to severe lubrication conditions such as steel pipe expansion processing.
- a metalworking lubricating oil composition that can be used below can be provided. Therefore, it can be effectively used as a high-performance lubricating oil composition for metal working that has solved environmental problems.
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Abstract
Provided is a lubricating oil composition for metalworking that can simultaneously offer high load resistance performance and exceptional cleaning properties without requiring a chlorine-based oil to be used, and can be used under severe lubricating conditions such as steel pipe expansion processing by using a lubricating oil composition containing (a) a base oil, (b) a metal sulfonate, (c) an active polysulfide, (d) a fatty acid partial ester of a polyhydric alcohol, and (e) a non-ionic surfactant; and having a kinematic viscosity at 40°C of 50 to 1000 mm2/s.
Description
本発明は、金属加工用潤滑油組成物に関し、詳しくは、鋼管拡張加工などの過酷な潤滑条件下で用いられる金属加工用潤滑油組成物に関するものである。
The present invention relates to a lubricating oil composition for metal working, and more particularly to a lubricating oil composition for metal working used under severe lubricating conditions such as steel pipe expansion.
金属加工に用いられる潤滑油は、通常過酷な潤滑条件下で用いられるため優れた耐荷重性能を有することが求められる。また、金属加工に用いられる潤滑油は、金属加工後には加工品に付着した潤滑油を洗浄して除去されることが必要であるため、洗浄性に優れることも同時に要求される。
金属加工の中でも、例えば、機械式鋼管拡張（メカニカルエキスパンダー）などの鋼管拡張加工では、通常被加工材として、およそ直径３０インチ以上、厚さ６～２５ｍｍ、長さ１０ｍ以上の鋼管が用いられる。このように管を形成して強靭な強度を有する鋼管をエキスパンダーで拡張することになる。この拡張工程では、管の内面とエキスパンダーの拡張部材とで形成される摺動部に、非常に大きい面圧がかかる。したがって鋼管拡張加工に用いる潤滑油には、極めて高い耐荷重性能が求められる。
また、鋼管拡張加工では加工後に、鋼管に付着した油剤を水圧検査を兼ねて温水によって洗浄することが行われている。したがって、鋼管拡張加工に用いる潤滑油には、優れた洗浄性を兼ね備えることが要求される。 Lubricating oils used for metal processing are usually required to have excellent load bearing performance because they are used under severe lubricating conditions. Moreover, since the lubricating oil used for metal processing needs to be removed by washing the lubricating oil adhering to the workpiece after metal processing, it is also required to have excellent cleaning properties.
Among metal processing, for example, in steel pipe expansion processing such as mechanical steel pipe expansion (mechanical expander), a steel pipe having a diameter of 30 inches or more, a thickness of 6 to 25 mm, and a length of 10 m or more is usually used as a workpiece. Thus, the pipe is formed and the steel pipe having tough strength is expanded by the expander. In this expansion process, a very large surface pressure is applied to the sliding portion formed by the inner surface of the tube and the expansion member of the expander. Therefore, the lubricating oil used for steel pipe expansion processing is required to have extremely high load bearing performance.
Moreover, in the steel pipe expansion process, after processing, the oil adhering to the steel pipe is washed with warm water also serving as a water pressure inspection. Therefore, the lubricating oil used for steel pipe expansion processing is required to have excellent cleaning properties.
金属加工の中でも、例えば、機械式鋼管拡張（メカニカルエキスパンダー）などの鋼管拡張加工では、通常被加工材として、およそ直径３０インチ以上、厚さ６～２５ｍｍ、長さ１０ｍ以上の鋼管が用いられる。このように管を形成して強靭な強度を有する鋼管をエキスパンダーで拡張することになる。この拡張工程では、管の内面とエキスパンダーの拡張部材とで形成される摺動部に、非常に大きい面圧がかかる。したがって鋼管拡張加工に用いる潤滑油には、極めて高い耐荷重性能が求められる。
また、鋼管拡張加工では加工後に、鋼管に付着した油剤を水圧検査を兼ねて温水によって洗浄することが行われている。したがって、鋼管拡張加工に用いる潤滑油には、優れた洗浄性を兼ね備えることが要求される。 Lubricating oils used for metal processing are usually required to have excellent load bearing performance because they are used under severe lubricating conditions. Moreover, since the lubricating oil used for metal processing needs to be removed by washing the lubricating oil adhering to the workpiece after metal processing, it is also required to have excellent cleaning properties.
Among metal processing, for example, in steel pipe expansion processing such as mechanical steel pipe expansion (mechanical expander), a steel pipe having a diameter of 30 inches or more, a thickness of 6 to 25 mm, and a length of 10 m or more is usually used as a workpiece. Thus, the pipe is formed and the steel pipe having tough strength is expanded by the expander. In this expansion process, a very large surface pressure is applied to the sliding portion formed by the inner surface of the tube and the expansion member of the expander. Therefore, the lubricating oil used for steel pipe expansion processing is required to have extremely high load bearing performance.
Moreover, in the steel pipe expansion process, after processing, the oil adhering to the steel pipe is washed with warm water also serving as a water pressure inspection. Therefore, the lubricating oil used for steel pipe expansion processing is required to have excellent cleaning properties.
従来、鋼管拡張加工用潤滑油としては、塩素系油剤が用いられてきた。塩素系油剤は、塩素を使用しているため極性が高く、優れた耐荷重性能を有するとともに、鋼管拡張加工において水で洗い流せる、優れた洗浄性をも有する。
しかし、環境負荷低減の観点から塩素系油剤を廃止しようとする動きが広がっており、それを実現する非塩素化潤滑油の開発が世界的に進められている。 Conventionally, chlorinated oil has been used as a lubricating oil for steel pipe expansion processing. Chlorine-based oils have high polarity due to the use of chlorine, have excellent load bearing performance, and also have excellent detergency that can be washed away with water in steel pipe expansion processing.
However, the movement to abolish chlorinated oils is spreading from the viewpoint of reducing environmental impact, and the development of non-chlorinated lubricants that realize this is being promoted worldwide.
しかし、環境負荷低減の観点から塩素系油剤を廃止しようとする動きが広がっており、それを実現する非塩素化潤滑油の開発が世界的に進められている。 Conventionally, chlorinated oil has been used as a lubricating oil for steel pipe expansion processing. Chlorine-based oils have high polarity due to the use of chlorine, have excellent load bearing performance, and also have excellent detergency that can be washed away with water in steel pipe expansion processing.
However, the movement to abolish chlorinated oils is spreading from the viewpoint of reducing environmental impact, and the development of non-chlorinated lubricants that realize this is being promoted worldwide.
例えば、特許文献１は、鋼管拡張加工用潤滑油剤として、水溶性ポリエチレングリコールを用いることを提案している。
しかしながら、水溶性ポリエチレングリコールは、洗浄性は有するものの、耐荷重性能を低下させてしまう。そのため、潤滑性を高めるために、過剰に高粘度の油剤を使用しなければならず扱いやすさの点で劣る。また、水溶性基材の高圧粘度は非常に低く、高面圧の摺動部を潤滑することができず、焼付きが発生してしまう。
このように水溶性ポリエチレングリコールを使用する方法は、耐荷重性能や、ハンドリングの点において改良の余地があることが分かる。
また、塩素系油剤の代替で最もよく使用されている硫黄系の油剤では、耐荷重性能を付与させることができても洗浄性を付与することができないため、その目的を達成することができない。
このような状況から、塩素系油剤を用いないで、高い耐荷重性能と優れた洗浄性を有する金属加工用潤滑油、特に鋼管拡張加工用潤滑油の開発が望まれている。 For example, Patent Document 1 proposes to use water-soluble polyethylene glycol as a lubricant for steel pipe expansion processing.
However, although water-soluble polyethylene glycol has detergency, load-bearing performance is reduced. Therefore, in order to improve lubricity, an excessively high viscosity oil agent must be used, which is inferior in handling. Further, the high-pressure viscosity of the water-soluble substrate is very low, and the sliding portion having a high surface pressure cannot be lubricated, and seizure occurs.
Thus, it turns out that the method of using water-soluble polyethylene glycol has room for improvement in terms of load bearing performance and handling.
In addition, the sulfur-based oil agent that is most often used as an alternative to the chlorine-based oil agent cannot achieve its purpose because it cannot provide cleaning properties even if it can provide load bearing performance.
Under such circumstances, development of a metal processing lubricant, particularly a steel pipe expansion lubricant, having high load-bearing performance and excellent cleanability without using a chlorinated oil is desired.
しかしながら、水溶性ポリエチレングリコールは、洗浄性は有するものの、耐荷重性能を低下させてしまう。そのため、潤滑性を高めるために、過剰に高粘度の油剤を使用しなければならず扱いやすさの点で劣る。また、水溶性基材の高圧粘度は非常に低く、高面圧の摺動部を潤滑することができず、焼付きが発生してしまう。
このように水溶性ポリエチレングリコールを使用する方法は、耐荷重性能や、ハンドリングの点において改良の余地があることが分かる。
また、塩素系油剤の代替で最もよく使用されている硫黄系の油剤では、耐荷重性能を付与させることができても洗浄性を付与することができないため、その目的を達成することができない。
このような状況から、塩素系油剤を用いないで、高い耐荷重性能と優れた洗浄性を有する金属加工用潤滑油、特に鋼管拡張加工用潤滑油の開発が望まれている。 For example, Patent Document 1 proposes to use water-soluble polyethylene glycol as a lubricant for steel pipe expansion processing.
However, although water-soluble polyethylene glycol has detergency, load-bearing performance is reduced. Therefore, in order to improve lubricity, an excessively high viscosity oil agent must be used, which is inferior in handling. Further, the high-pressure viscosity of the water-soluble substrate is very low, and the sliding portion having a high surface pressure cannot be lubricated, and seizure occurs.
Thus, it turns out that the method of using water-soluble polyethylene glycol has room for improvement in terms of load bearing performance and handling.
In addition, the sulfur-based oil agent that is most often used as an alternative to the chlorine-based oil agent cannot achieve its purpose because it cannot provide cleaning properties even if it can provide load bearing performance.
Under such circumstances, development of a metal processing lubricant, particularly a steel pipe expansion lubricant, having high load-bearing performance and excellent cleanability without using a chlorinated oil is desired.
本発明は、塩素系油剤を使用しなくとも、高い耐荷重性能を有すると同時に、優れた洗浄性をも有し、鋼管拡張加工などの過酷な潤滑条件下で用いることができる金属加工用潤滑油組成物を提供することを目的とするものである。
The present invention is a metalworking lubrication that has high load-bearing performance and excellent cleaning properties without using a chlorinated oil, and can be used under severe lubrication conditions such as steel pipe expansion. The object is to provide an oil composition.
本発明者らは、特定の添加剤を組合わせて得られる組成物がその目的を達成し得ることを見出した。本発明は、かかる知見に基づいて完成したものである。すなわち、本発明は、
The present inventors have found that a composition obtained by combining specific additives can achieve its purpose. The present invention has been completed based on such findings. That is, the present invention
１．（ａ）基油、（ｂ）金属系スルホネート、（ｃ）活性ポリサルファイド、（ｄ）多価アルコールの脂肪酸部分エステル、及び（ｅ）非イオン系界面活性剤を含み、組成物の４０℃における動粘度が５０ｍｍ2／ｓ以上１０００ｍｍ2／ｓ以下であることを特徴とする金属加工用潤滑油組成物、
２．さらに（ｃ’）粉末硫黄を含む上記１に記載の金属加工用潤滑油組成物、
３．（ａ）成分である基油が、鉱油、又は、鉱油とエステル系合成油及びポリメタクリレートから選ばれる１種以上とを含むものである上記１又は２に記載の金属加工用潤滑油組成物、
４．エステル系合成油が炭素数２～６の多価アルコールと炭素数２～２４の脂肪族酸とのエステルである上記３に記載の金属加工用潤滑油組成物、
５．（ｂ）成分である金属系スルホネートが、過塩基性アルカリ土類金属スルホネートである上記１～４のいずれかに記載の金属加工用潤滑油組成物、
６．（ｃ）成分である活性ポリサルファイドの硫黄分含有量が、２０質量％以上である上記１～５のいずれかに記載の金属加工用潤滑油組成物、
７．（ｄ）成分である多価アルコールの脂肪酸部分エステルが、炭素数２～６の多価アルコールと炭素数６～２４の脂肪酸との部分エステルである上記１～６のいずれかに記載の金属加工用潤滑油組成物、
８．（ｅ）成分である非イオン系界面活性剤が、ポリオキシアルキレン型非イオン系界面活性剤である上記１～７のいずれかに記載の金属加工用潤滑油組成物、
９．ポリオキシアルキレン型非イオン系界面活性剤が、ポリオキシエチレン基及びポリオキシプロピレン基を有するものである上記８に記載の金属加工用潤滑油組成物、
１０．組成物全量基準で（ｂ）金属系スルホネートを１質量％以上２０質量％以下、（ｃ）活性ポリサルファイドを２質量％以上２５質量％以下、（ｃ’）粉末硫黄を３質量％以下、（ｄ）多価アルコールの脂肪酸部分エステルを１質量％以上２０質量％以下、及び（ｅ）非イオン系界面活性剤を２質量％以上２５質量％以下含む上記１～９のいずれかに記載の金属加工用潤滑油組成物、
１１．鋼管拡張加工に用いられる上記１～１０のいずれかに記載の金属加工用潤滑油組成物、
を提供するものである。 1. (A) a base oil, (b) a metal sulfonate, (c) an active polysulfide, (d) a fatty acid partial ester of a polyhydric alcohol, and (e) a nonionic surfactant. A lubricating oil composition for metal working, wherein the viscosity is 50 mm 2 / s or more and 1000 mm 2 / s or less,
2. (C ′) the lubricating oil composition for metalworking according to 1 above, further comprising powdered sulfur,
3. The lubricating oil composition for metalworking according to 1 or 2 above, wherein the base oil as component (a) comprises mineral oil or one or more selected from mineral oil and ester synthetic oil and polymethacrylate,
4). 4. The lubricating oil composition for metal processing according to 3 above, wherein the ester-based synthetic oil is an ester of a polyhydric alcohol having 2 to 6 carbon atoms and an aliphatic acid having 2 to 24 carbon atoms,
5. The lubricating oil composition for metal working according to any one of 1 to 4 above, wherein the metal sulfonate as component (b) is an overbased alkaline earth metal sulfonate,
6). The lubricating oil composition for metal working according to any one of 1 to 5 above, wherein the sulfur content of the active polysulfide as the component (c) is 20% by mass or more,
7). 7. The metal processing according to any one of 1 to 6 above, wherein the fatty acid partial ester of the polyhydric alcohol as component (d) is a partial ester of a polyhydric alcohol having 2 to 6 carbon atoms and a fatty acid having 6 to 24 carbon atoms. Lubricating oil composition,
8). The lubricating oil composition for metal processing according to any one of 1 to 7 above, wherein the nonionic surfactant as the component (e) is a polyoxyalkylene type nonionic surfactant,
9. 9. The lubricating oil composition for metal working according to 8 above, wherein the polyoxyalkylene type nonionic surfactant has a polyoxyethylene group and a polyoxypropylene group,
10. (B) 1% by mass or more and 20% by mass or less of metal sulfonate, (c) 2% by mass or more and 25% by mass or less of active polysulfide, (c ′) 3% by mass or less of powder sulfur, 10. The metal processing according to any one of 1 to 9 above, comprising 1% by mass to 20% by mass of a fatty acid partial ester of a polyhydric alcohol, and (e) 2% by mass to 25% by mass of a nonionic surfactant. Lubricating oil composition,
11. The lubricating oil composition for metal working according to any one of 1 to 10 above, which is used for steel pipe expansion processing,
Is to provide.
２．さらに（ｃ’）粉末硫黄を含む上記１に記載の金属加工用潤滑油組成物、
３．（ａ）成分である基油が、鉱油、又は、鉱油とエステル系合成油及びポリメタクリレートから選ばれる１種以上とを含むものである上記１又は２に記載の金属加工用潤滑油組成物、
４．エステル系合成油が炭素数２～６の多価アルコールと炭素数２～２４の脂肪族酸とのエステルである上記３に記載の金属加工用潤滑油組成物、
５．（ｂ）成分である金属系スルホネートが、過塩基性アルカリ土類金属スルホネートである上記１～４のいずれかに記載の金属加工用潤滑油組成物、
６．（ｃ）成分である活性ポリサルファイドの硫黄分含有量が、２０質量％以上である上記１～５のいずれかに記載の金属加工用潤滑油組成物、
７．（ｄ）成分である多価アルコールの脂肪酸部分エステルが、炭素数２～６の多価アルコールと炭素数６～２４の脂肪酸との部分エステルである上記１～６のいずれかに記載の金属加工用潤滑油組成物、
８．（ｅ）成分である非イオン系界面活性剤が、ポリオキシアルキレン型非イオン系界面活性剤である上記１～７のいずれかに記載の金属加工用潤滑油組成物、
９．ポリオキシアルキレン型非イオン系界面活性剤が、ポリオキシエチレン基及びポリオキシプロピレン基を有するものである上記８に記載の金属加工用潤滑油組成物、
１０．組成物全量基準で（ｂ）金属系スルホネートを１質量％以上２０質量％以下、（ｃ）活性ポリサルファイドを２質量％以上２５質量％以下、（ｃ’）粉末硫黄を３質量％以下、（ｄ）多価アルコールの脂肪酸部分エステルを１質量％以上２０質量％以下、及び（ｅ）非イオン系界面活性剤を２質量％以上２５質量％以下含む上記１～９のいずれかに記載の金属加工用潤滑油組成物、
１１．鋼管拡張加工に用いられる上記１～１０のいずれかに記載の金属加工用潤滑油組成物、
を提供するものである。 1. (A) a base oil, (b) a metal sulfonate, (c) an active polysulfide, (d) a fatty acid partial ester of a polyhydric alcohol, and (e) a nonionic surfactant. A lubricating oil composition for metal working, wherein the viscosity is 50 mm 2 / s or more and 1000 mm 2 / s or less,
2. (C ′) the lubricating oil composition for metalworking according to 1 above, further comprising powdered sulfur,
3. The lubricating oil composition for metalworking according to 1 or 2 above, wherein the base oil as component (a) comprises mineral oil or one or more selected from mineral oil and ester synthetic oil and polymethacrylate,
4). 4. The lubricating oil composition for metal processing according to 3 above, wherein the ester-based synthetic oil is an ester of a polyhydric alcohol having 2 to 6 carbon atoms and an aliphatic acid having 2 to 24 carbon atoms,
5. The lubricating oil composition for metal working according to any one of 1 to 4 above, wherein the metal sulfonate as component (b) is an overbased alkaline earth metal sulfonate,
6). The lubricating oil composition for metal working according to any one of 1 to 5 above, wherein the sulfur content of the active polysulfide as the component (c) is 20% by mass or more,
7). 7. The metal processing according to any one of 1 to 6 above, wherein the fatty acid partial ester of the polyhydric alcohol as component (d) is a partial ester of a polyhydric alcohol having 2 to 6 carbon atoms and a fatty acid having 6 to 24 carbon atoms. Lubricating oil composition,
8). The lubricating oil composition for metal processing according to any one of 1 to 7 above, wherein the nonionic surfactant as the component (e) is a polyoxyalkylene type nonionic surfactant,
9. 9. The lubricating oil composition for metal working according to 8 above, wherein the polyoxyalkylene type nonionic surfactant has a polyoxyethylene group and a polyoxypropylene group,
10. (B) 1% by mass or more and 20% by mass or less of metal sulfonate, (c) 2% by mass or more and 25% by mass or less of active polysulfide, (c ′) 3% by mass or less of powder sulfur, 10. The metal processing according to any one of 1 to 9 above, comprising 1% by mass to 20% by mass of a fatty acid partial ester of a polyhydric alcohol, and (e) 2% by mass to 25% by mass of a nonionic surfactant. Lubricating oil composition,
11. The lubricating oil composition for metal working according to any one of 1 to 10 above, which is used for steel pipe expansion processing,
Is to provide.
本発明によれば、塩素系油剤を使用しなくとも、高い耐荷重性能を有すると同時に、優れた洗浄性をも有し、鋼管拡張加工などの過酷な潤滑条件下で用いることができる金属加工用潤滑油組成物を提供することができる。
According to the present invention, even without using a chlorine-based oil agent, it has a high load-bearing performance and at the same time has excellent cleaning properties, and can be used under severe lubrication conditions such as steel pipe expansion processing. A lubricating oil composition can be provided.
本発明の金属加工用潤滑油組成物は、（ａ）基油、（ｂ）金属系スルホネート、（ｃ）活性ポリサルファイド、（ｄ）多価アルコールの脂肪酸部分エステル、及び（ｅ）非イオン系界面活性剤を含み、組成物の４０℃における動粘度が５０ｍｍ2／ｓ以上１０００ｍｍ2／ｓ以下であることを特徴とする。
The lubricating oil composition for metal processing of the present invention comprises (a) a base oil, (b) a metal sulfonate, (c) an active polysulfide, (d) a fatty acid partial ester of a polyhydric alcohol, and (e) a nonionic interface. It contains an active agent, and the kinematic viscosity at 40 ° C. of the composition is from 50 mm 2 / s to 1000 mm 2 / s.
〔（ａ）基油〕
本発明において（ａ）成分として用いる基油は、特に制限はなく、従来使用されている公知の鉱物系基油及び合成系基油の中から適宜選択して用いることができる。
ここで、鉱油系基油としては、例えばパラフィン系原油、中間（基）系原油、あるいはナフテン系原油を常圧蒸留するか、又は常圧蒸留の残渣油を減圧蒸留して得られる留出油、あるいはこれらを常法に従って精製することによって得られる精製油（例えば溶剤精製油、水素化精製油、水素化分解油、脱ろう処理油、白土処理油、鉱油系ワックスやフィッシャートロプシュプロセス等により製造されるワックス（ガストゥリキッドワックス）を異性化することによって製造される基油）などを挙げることができる。
一方、合成油としては、例えば炭素数８～１４のα－オレフィンオリゴマーであるポリα－オレフィン、ポリブテン、ポリオールエステルなどのエステル系合成油、アルキルベンゼンなどの芳香族炭化水素、並びにポリメタクリレートなどの高分子化合物を挙げることができる。
本発明においては、基油として、上記鉱油を一種用いてもよく、二種以上を組み合わせて用いてもよい。また、上記合成油を一種用いてもよく、二種以上を組み合わせて用いてもよい。さらには、鉱油一種以上と合成油一種以上とを組み合わせて用いてもよい。 [(A) Base oil]
The base oil used as the component (a) in the present invention is not particularly limited, and can be appropriately selected from known mineral base oils and synthetic base oils that have been used conventionally.
Here, as the mineral oil base oil, for example, a distillate obtained by atmospheric distillation of paraffinic crude oil, intermediate (base) crude oil, or naphthenic crude oil, or vacuum distillation of residual oil of atmospheric distillation. Or refined oils obtained by refining them according to conventional methods (for example, solvent refined oil, hydrorefined oil, hydrocracked oil, dewaxed oil, clay-treated oil, mineral oil-based wax, Fischer-Tropsch process, etc. And the like (base oil produced by isomerizing a gas-liquid liquid).
On the other hand, examples of synthetic oils include poly-α-olefins, which are α-olefin oligomers having 8 to 14 carbon atoms, ester-based synthetic oils such as polybutene and polyol esters, aromatic hydrocarbons such as alkylbenzene, and polymethacrylates. Mention may be made of molecular compounds.
In the present invention, as the base oil, one kind of the above mineral oil may be used, or two or more kinds may be used in combination. Moreover, the said synthetic oil may be used 1 type and may be used in combination of 2 or more type. Further, one or more mineral oils and one or more synthetic oils may be used in combination.
本発明において（ａ）成分として用いる基油は、特に制限はなく、従来使用されている公知の鉱物系基油及び合成系基油の中から適宜選択して用いることができる。
ここで、鉱油系基油としては、例えばパラフィン系原油、中間（基）系原油、あるいはナフテン系原油を常圧蒸留するか、又は常圧蒸留の残渣油を減圧蒸留して得られる留出油、あるいはこれらを常法に従って精製することによって得られる精製油（例えば溶剤精製油、水素化精製油、水素化分解油、脱ろう処理油、白土処理油、鉱油系ワックスやフィッシャートロプシュプロセス等により製造されるワックス（ガストゥリキッドワックス）を異性化することによって製造される基油）などを挙げることができる。
一方、合成油としては、例えば炭素数８～１４のα－オレフィンオリゴマーであるポリα－オレフィン、ポリブテン、ポリオールエステルなどのエステル系合成油、アルキルベンゼンなどの芳香族炭化水素、並びにポリメタクリレートなどの高分子化合物を挙げることができる。
本発明においては、基油として、上記鉱油を一種用いてもよく、二種以上を組み合わせて用いてもよい。また、上記合成油を一種用いてもよく、二種以上を組み合わせて用いてもよい。さらには、鉱油一種以上と合成油一種以上とを組み合わせて用いてもよい。 [(A) Base oil]
The base oil used as the component (a) in the present invention is not particularly limited, and can be appropriately selected from known mineral base oils and synthetic base oils that have been used conventionally.
Here, as the mineral oil base oil, for example, a distillate obtained by atmospheric distillation of paraffinic crude oil, intermediate (base) crude oil, or naphthenic crude oil, or vacuum distillation of residual oil of atmospheric distillation. Or refined oils obtained by refining them according to conventional methods (for example, solvent refined oil, hydrorefined oil, hydrocracked oil, dewaxed oil, clay-treated oil, mineral oil-based wax, Fischer-Tropsch process, etc. And the like (base oil produced by isomerizing a gas-liquid liquid).
On the other hand, examples of synthetic oils include poly-α-olefins, which are α-olefin oligomers having 8 to 14 carbon atoms, ester-based synthetic oils such as polybutene and polyol esters, aromatic hydrocarbons such as alkylbenzene, and polymethacrylates. Mention may be made of molecular compounds.
In the present invention, as the base oil, one kind of the above mineral oil may be used, or two or more kinds may be used in combination. Moreover, the said synthetic oil may be used 1 type and may be used in combination of 2 or more type. Further, one or more mineral oils and one or more synthetic oils may be used in combination.
本発明における基油は、４０℃における動粘度が、５０ｍｍ2／ｓ以上１０００ｍｍ2／ｓ以下であることが好ましく、より好ましくは１００ｍｍ2／ｓ以上８００ｍｍ2／ｓ以下である。
基油の４０℃における動粘度が５０ｍｍ2／ｓ未満では高面圧下における油膜が破断してしまい、潤滑油としての性能が不足する恐れがある。また、１０００ｍｍ2／ｓ超であれば、通常のポンプでの取り扱いが困難になる恐れがあり、また、温水での洗浄時に後残りが発生する恐れもある。 The base oil in the present invention preferably has a kinematic viscosity at 40 ° C. of 50 mm 2 / s to 1000 mm 2 / s, and more preferably 100 mm 2 / s to 800 mm 2 / s.
If the base oil has a kinematic viscosity at 40 ° C. of less than 50 mm 2 / s, the oil film under high surface pressure may break, and the performance as a lubricating oil may be insufficient. On the other hand, if it exceeds 1000 mm 2 / s, it may be difficult to handle with a normal pump, and there may be a residual after washing with warm water.
基油の４０℃における動粘度が５０ｍｍ2／ｓ未満では高面圧下における油膜が破断してしまい、潤滑油としての性能が不足する恐れがある。また、１０００ｍｍ2／ｓ超であれば、通常のポンプでの取り扱いが困難になる恐れがあり、また、温水での洗浄時に後残りが発生する恐れもある。 The base oil in the present invention preferably has a kinematic viscosity at 40 ° C. of 50 mm 2 / s to 1000 mm 2 / s, and more preferably 100 mm 2 / s to 800 mm 2 / s.
If the base oil has a kinematic viscosity at 40 ° C. of less than 50 mm 2 / s, the oil film under high surface pressure may break, and the performance as a lubricating oil may be insufficient. On the other hand, if it exceeds 1000 mm 2 / s, it may be difficult to handle with a normal pump, and there may be a residual after washing with warm water.
本発明においては、基油として、鉱油（鉱油系基油）を含む基油が好ましく、例えば、鉱油（鉱油のみ）、又は、鉱油とエステル系合成油及びポリメタクリレートから選ばれる１種以上とを含むものがより好ましい。鉱油には、二種以上の鉱油の混合物が含まれる。
鉱油を含む基油を用いることにより、洗浄性を高め、かつ組成物の溶解安定性（混合安定性）を良好に保つことができる。
また、その鉱油にエステル系合成油及びポリメタクリレートから選ばれる１種以上を配合することによって、耐荷重性能を更に高めることができる。 In the present invention, a base oil containing a mineral oil (mineral oil base oil) is preferable as the base oil. For example, a mineral oil (mineral oil only), or one or more selected from mineral oil, an ester synthetic oil, and polymethacrylate is used. The inclusion is more preferable. Mineral oil includes a mixture of two or more mineral oils.
By using a base oil containing a mineral oil, it is possible to enhance the detergency and to keep the dissolution stability (mixing stability) of the composition good.
Moreover, load-bearing performance can be further improved by mix | blending 1 or more types chosen from ester synthetic oil and polymethacrylate with the mineral oil.
鉱油を含む基油を用いることにより、洗浄性を高め、かつ組成物の溶解安定性（混合安定性）を良好に保つことができる。
また、その鉱油にエステル系合成油及びポリメタクリレートから選ばれる１種以上を配合することによって、耐荷重性能を更に高めることができる。 In the present invention, a base oil containing a mineral oil (mineral oil base oil) is preferable as the base oil. For example, a mineral oil (mineral oil only), or one or more selected from mineral oil, an ester synthetic oil, and polymethacrylate is used. The inclusion is more preferable. Mineral oil includes a mixture of two or more mineral oils.
By using a base oil containing a mineral oil, it is possible to enhance the detergency and to keep the dissolution stability (mixing stability) of the composition good.
Moreover, load-bearing performance can be further improved by mix | blending 1 or more types chosen from ester synthetic oil and polymethacrylate with the mineral oil.
鉱油にエステル系合成油やポリメタクリレートを混合して使用する場合の、鉱油とエステル系合成油及びポリメタクリレートから選ばれる１種以上との配合割合は、特に制限はないが、通常〔鉱油〕：〔エステル系合成油及びポリメタクリレートから選ばれる１種以上〕の質量比で７０：３０～４０：６０の範囲が好ましい。両者の配合割合が、上記の範囲であれば、洗浄性と耐荷重性能とを同時に組成物の溶解安定性を満たす組成物を得ることができる。
The blending ratio of mineral oil to one or more selected from ester synthetic oil and polymethacrylate in the case of mixing and using ester synthetic oil or polymethacrylate in mineral oil is not particularly limited, but usually [mineral oil]: The mass ratio of [one or more selected from ester-based synthetic oils and polymethacrylates] is preferably in the range of 70:30 to 40:60. When the blending ratio of both is within the above range, a composition satisfying the dissolution stability of the composition at the same time as the washing performance and load bearing performance can be obtained.
本発明で用いる前記鉱油は、前記のとおりパラフィン系鉱油、中間（基）系鉱油あるいはナフテン系鉱油のいずれであってもよいが、ナフテン系鉱油が、洗浄性と油剤の溶解安定性をより良好に保つことができる点で好ましい。
前記鉱油の４０℃における動粘度については、２０ｍｍ2／ｓ以上１０００ｍｍ2／ｓ以下のものが使用でき、３０ｍｍ2／ｓ以上８００ｍｍ2／ｓ以下のものがより好ましく、８０ｍｍ2／ｓ以上５００ｍｍ2／ｓ以下のものが特に好ましい。好ましい鉱油の具体例としては、例えば、ブライトストック油（ＢＳ）や５００ニュートラル油（５００Ｎ）が好ましく、特にブライトストック油又はブライトストック油と５００ニュートラル油との混合物がより好ましい。 The mineral oil used in the present invention may be any of paraffinic mineral oil, intermediate (base) mineral oil, or naphthenic mineral oil as described above, but naphthenic mineral oil has better detergency and dissolution stability of the oil agent. It is preferable at the point which can be maintained.
The kinematic viscosity at 40 ° C. of the mineral oil, 20 mm 2 / s or more 1000 mm 2 / s can be used following ones, the following are more preferable 30 mm 2 / s or more 800mm 2 / s, 80mm 2 / s or more 500 mm 2 Particularly preferred is / s or less. Specific examples of preferred mineral oils include, for example, bright stock oil (BS) and 500 neutral oil (500 N), and particularly preferred is bright stock oil or a mixture of bright stock oil and 500 neutral oil.
前記鉱油の４０℃における動粘度については、２０ｍｍ2／ｓ以上１０００ｍｍ2／ｓ以下のものが使用でき、３０ｍｍ2／ｓ以上８００ｍｍ2／ｓ以下のものがより好ましく、８０ｍｍ2／ｓ以上５００ｍｍ2／ｓ以下のものが特に好ましい。好ましい鉱油の具体例としては、例えば、ブライトストック油（ＢＳ）や５００ニュートラル油（５００Ｎ）が好ましく、特にブライトストック油又はブライトストック油と５００ニュートラル油との混合物がより好ましい。 The mineral oil used in the present invention may be any of paraffinic mineral oil, intermediate (base) mineral oil, or naphthenic mineral oil as described above, but naphthenic mineral oil has better detergency and dissolution stability of the oil agent. It is preferable at the point which can be maintained.
The kinematic viscosity at 40 ° C. of the mineral oil, 20 mm 2 / s or more 1000 mm 2 / s can be used following ones, the following are more preferable 30 mm 2 / s or more 800mm 2 / s, 80mm 2 / s or more 500 mm 2 Particularly preferred is / s or less. Specific examples of preferred mineral oils include, for example, bright stock oil (BS) and 500 neutral oil (500 N), and particularly preferred is bright stock oil or a mixture of bright stock oil and 500 neutral oil.
本発明で用いる前記エステル系合成油としては、分子中にエステル結合を２個以上有するエステル化合物を用いることができる。
このようなエステル化合物としては、例えば、多価アルコールと脂肪酸から形成されるポリオールエステルが挙げられる。
上記ポリオールエステルを形成する多価アルコールとしては、通常２～６価のものが用いられる。好ましい多価アルコールとしては、例えばエチレングリコール、プロピレングリコール、ネオペンチルグリコール、グリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール、ソルビタンなどが挙げられる。中でも、トリメチロールプロパンやペンタエリスリトールがより好ましい。
一方、ポリオールエステルを形成する脂肪酸としては、一塩基酸が好ましく、通常炭素数２～２４の脂肪酸が用いられる。その脂肪酸は直鎖のものでも分枝のものでもよく、また飽和のものでも不飽和のものでもよい。これらの中でも、炭素数８～２２の飽和脂肪酸、又は不飽和脂肪酸が好ましく、炭素数１２～１８の飽和脂肪酸、又は不飽和脂肪酸がより好ましい。
前記多価アルコールと脂肪酸から形成されるエステル系合成油の代表例としては、トリメチロールプロパンもしくはペンタエリスリトールの炭素数８～２２、より好ましくは炭素数１２～１８、特に好ましくは炭素数１６～１８の脂肪酸エステルが好ましい。 As the ester synthetic oil used in the present invention, an ester compound having two or more ester bonds in the molecule can be used.
Examples of such ester compounds include polyol esters formed from polyhydric alcohols and fatty acids.
As the polyhydric alcohol that forms the polyol ester, dihydric to hexahydric ones are usually used. Preferred polyhydric alcohols include, for example, ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan and the like. Of these, trimethylolpropane and pentaerythritol are more preferable.
On the other hand, the fatty acid forming the polyol ester is preferably a monobasic acid, and usually a fatty acid having 2 to 24 carbon atoms is used. The fatty acid may be linear or branched, and may be saturated or unsaturated. Among these, a saturated fatty acid having 8 to 22 carbon atoms or an unsaturated fatty acid is preferable, and a saturated fatty acid having 12 to 18 carbon atoms or an unsaturated fatty acid is more preferable.
Typical examples of the ester synthetic oil formed from the polyhydric alcohol and the fatty acid include trimethylolpropane or pentaerythritol having 8 to 22 carbon atoms, more preferably 12 to 18 carbon atoms, and particularly preferably 16 to 18 carbon atoms. The fatty acid esters are preferred.
このようなエステル化合物としては、例えば、多価アルコールと脂肪酸から形成されるポリオールエステルが挙げられる。
上記ポリオールエステルを形成する多価アルコールとしては、通常２～６価のものが用いられる。好ましい多価アルコールとしては、例えばエチレングリコール、プロピレングリコール、ネオペンチルグリコール、グリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール、ソルビタンなどが挙げられる。中でも、トリメチロールプロパンやペンタエリスリトールがより好ましい。
一方、ポリオールエステルを形成する脂肪酸としては、一塩基酸が好ましく、通常炭素数２～２４の脂肪酸が用いられる。その脂肪酸は直鎖のものでも分枝のものでもよく、また飽和のものでも不飽和のものでもよい。これらの中でも、炭素数８～２２の飽和脂肪酸、又は不飽和脂肪酸が好ましく、炭素数１２～１８の飽和脂肪酸、又は不飽和脂肪酸がより好ましい。
前記多価アルコールと脂肪酸から形成されるエステル系合成油の代表例としては、トリメチロールプロパンもしくはペンタエリスリトールの炭素数８～２２、より好ましくは炭素数１２～１８、特に好ましくは炭素数１６～１８の脂肪酸エステルが好ましい。 As the ester synthetic oil used in the present invention, an ester compound having two or more ester bonds in the molecule can be used.
Examples of such ester compounds include polyol esters formed from polyhydric alcohols and fatty acids.
As the polyhydric alcohol that forms the polyol ester, dihydric to hexahydric ones are usually used. Preferred polyhydric alcohols include, for example, ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan and the like. Of these, trimethylolpropane and pentaerythritol are more preferable.
On the other hand, the fatty acid forming the polyol ester is preferably a monobasic acid, and usually a fatty acid having 2 to 24 carbon atoms is used. The fatty acid may be linear or branched, and may be saturated or unsaturated. Among these, a saturated fatty acid having 8 to 22 carbon atoms or an unsaturated fatty acid is preferable, and a saturated fatty acid having 12 to 18 carbon atoms or an unsaturated fatty acid is more preferable.
Typical examples of the ester synthetic oil formed from the polyhydric alcohol and the fatty acid include trimethylolpropane or pentaerythritol having 8 to 22 carbon atoms, more preferably 12 to 18 carbon atoms, and particularly preferably 16 to 18 carbon atoms. The fatty acid esters are preferred.
本発明における前記ポリメタクリレートとしては、従来粘度指数向上剤として知られているものを用いることができる。したがって、本発明に用いるポリメタクリレートは分散型、非分散型のどちらでもよい。またその質量平均分子量は、好ましくは１万以上１００万以下、より好ましくは５万以上８０万以下、さらに好ましくは１０万以上７０万以下である。質量平均分子量が１万以上１００万以下であれば、増粘効果を付与し、耐荷重性能を高めることができる。
As the polymethacrylate in the present invention, those conventionally known as viscosity index improvers can be used. Therefore, the polymethacrylate used in the present invention may be either a dispersion type or a non-dispersion type. The mass average molecular weight is preferably 10,000 or more and 1,000,000 or less, more preferably 50,000 or more and 800,000 or less, and still more preferably 100,000 or more and 700,000 or less. When the mass average molecular weight is 10,000 or more and 1,000,000 or less, a thickening effect can be imparted and load bearing performance can be enhanced.
〔（ｂ）金属系スルホネート〕
本発明において（ｂ）成分として用いる金属系スルホネートとしては、種々の金属塩を用いることができる。それらの中でも、耐荷重性能を高める効果の点で、Ｃａ、Ｍｇ、Ｂａ等のアルカリ土類金属スルホネートが好ましい。中でもＣａスルホネートやＭｇスルホネートがより好ましく、特にＣａスルホネートが好ましい。
また、前記金属系スルホネートとしては、中性、塩基性、過塩基性のいずれであってもよいが、過塩基性Ｃａスルホネート、具体的には、過塩素酸法による塩基価が１５０ｍｇＫＯＨ／ｇ以上５００ｍｇＫＯＨ／ｇ以下のＣａスルホネートが好ましく、特に２５０ｍｇＫＯＨ／ｇ以上５００ｍｇＫＯＨ／ｇ以下のＣａスルホネートが好ましい。
本発明においては、（ｂ）成分である金属系スルホネートの含有量は、組成物全量基準で１質量％以上２０質量％以下が好ましく、３質量％以上１５質量％以下がより好ましい。金属系スルホネートの含有量が、１質量％以上であれば、耐荷重性能を高める効果が発揮され２０質量％以下であれば、溶解安定性を良好に保つことができる。 [(B) Metal sulfonate]
In the present invention, various metal salts can be used as the metal sulfonate used as the component (b). Among these, alkaline earth metal sulfonates such as Ca, Mg, and Ba are preferable from the viewpoint of enhancing the load bearing performance. Of these, Ca sulfonate and Mg sulfonate are more preferable, and Ca sulfonate is particularly preferable.
Further, the metal sulfonate may be neutral, basic, or overbased, but it is an overbased Ca sulfonate, specifically, a base number by the perchloric acid method is 150 mgKOH / g or more. A Ca sulfonate of 500 mgKOH / g or less is preferable, and a Ca sulfonate of 250 mgKOH / g or more and 500 mgKOH / g or less is particularly preferable.
In the present invention, the content of the metal sulfonate as the component (b) is preferably 1% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less based on the total amount of the composition. If the content of the metal sulfonate is 1% by mass or more, the effect of improving the load bearing performance is exhibited, and if it is 20% by mass or less, the dissolution stability can be kept good.
本発明において（ｂ）成分として用いる金属系スルホネートとしては、種々の金属塩を用いることができる。それらの中でも、耐荷重性能を高める効果の点で、Ｃａ、Ｍｇ、Ｂａ等のアルカリ土類金属スルホネートが好ましい。中でもＣａスルホネートやＭｇスルホネートがより好ましく、特にＣａスルホネートが好ましい。
また、前記金属系スルホネートとしては、中性、塩基性、過塩基性のいずれであってもよいが、過塩基性Ｃａスルホネート、具体的には、過塩素酸法による塩基価が１５０ｍｇＫＯＨ／ｇ以上５００ｍｇＫＯＨ／ｇ以下のＣａスルホネートが好ましく、特に２５０ｍｇＫＯＨ／ｇ以上５００ｍｇＫＯＨ／ｇ以下のＣａスルホネートが好ましい。
本発明においては、（ｂ）成分である金属系スルホネートの含有量は、組成物全量基準で１質量％以上２０質量％以下が好ましく、３質量％以上１５質量％以下がより好ましい。金属系スルホネートの含有量が、１質量％以上であれば、耐荷重性能を高める効果が発揮され２０質量％以下であれば、溶解安定性を良好に保つことができる。 [(B) Metal sulfonate]
In the present invention, various metal salts can be used as the metal sulfonate used as the component (b). Among these, alkaline earth metal sulfonates such as Ca, Mg, and Ba are preferable from the viewpoint of enhancing the load bearing performance. Of these, Ca sulfonate and Mg sulfonate are more preferable, and Ca sulfonate is particularly preferable.
Further, the metal sulfonate may be neutral, basic, or overbased, but it is an overbased Ca sulfonate, specifically, a base number by the perchloric acid method is 150 mgKOH / g or more. A Ca sulfonate of 500 mgKOH / g or less is preferable, and a Ca sulfonate of 250 mgKOH / g or more and 500 mgKOH / g or less is particularly preferable.
In the present invention, the content of the metal sulfonate as the component (b) is preferably 1% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less based on the total amount of the composition. If the content of the metal sulfonate is 1% by mass or more, the effect of improving the load bearing performance is exhibited, and if it is 20% by mass or less, the dissolution stability can be kept good.
〔（ｃ）活性ポリサルファイド等〕
本発明においては（ｃ）成分として活性ポリサルファイドを用いる。この活性ポリサルファイドとしては、例えば、下記の一般式（１）で表わされるジハイドロカルビルポリサルファイドを用いることが好ましい。
Ｒ1－Ｓx－Ｒ2 ・・・（１）
上記式中、Ｒ1、Ｒ2のハイドロカルビル基は、それぞれ独立に炭素数３～２０のアルキル基、炭素数６～２０のアリール基、アルキルアリール基又はアリールアルキル基を表し、それらは互いに同一でも異なってもよい。ｘは２～１０の整数を表す。
前記Ｒ1、Ｒ2のハイドロカルビル基は、炭素数６～１８のアルキル基がより好ましく、該アルキル基としては、直鎖状又は分枝状で、飽和又は不飽和のアルキル基を用いることできる。
活性ポリサルファイドの代表例としては、いずれも直鎖状又は分枝状のジヘキシルポリサルファイド、ジオクチルポリサルファイド、ジノニルポリサルファイド、ジデシルポリサルファイド、ジドデシルポリサルファイド、ジウンデシルポリサルファイド、ジテトラデシルポリサルファイド、ジヘキサデシルポリサルファイド、ジオクタデシルポリサルファイド、プロピレン又はイソブチレンから誘導される炭素数６～１５の分枝状のアルキル基を有するポリサルファイドが例示できる。これらの中でも炭素数８～１６のアルキル基を有するジアルキルポリサルファイドが好ましい。
前記活性ポリサルファイドの硫黄分含有量については、耐荷重性能の向上を図るために、２０質量％以上が好ましく、３０質量％以上が特に好ましい。
本発明における（ｃ）成分の活性ポリサルファイドの含有量は、組成物全量基準で２質量％以上２５質量％以下が好ましく、５質量％以上２０質量％以下がより好ましい。活性ポリサルファイドの含有量が、２質量％以上であれば、耐荷重性能が良好に発揮され２５質量％以下であれば腐食が問題になることがない。 [(C) active polysulfide, etc.]
In the present invention, active polysulfide is used as the component (c). As the active polysulfide, for example, dihydrocarbyl polysulfide represented by the following general formula (1) is preferably used.
R 1 -S x -R 2 (1)
In the above formula, each of the hydrocarbyl groups R 1 and R 2 independently represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, or an arylalkyl group, It may be the same or different. x represents an integer of 2 to 10.
The hydrocarbyl group of R 1 and R 2 is more preferably an alkyl group having 6 to 18 carbon atoms. As the alkyl group, a linear or branched, saturated or unsaturated alkyl group is used. it can.
As representative examples of active polysulfide, any of linear or branched dihexyl polysulfide, dioctyl polysulfide, dinonyl polysulfide, didecyl polysulfide, didodecyl polysulfide, diundecyl polysulfide, ditetradecyl polysulfide, dihexadecyl polysulfide, Examples thereof include polysulfide having a branched alkyl group having 6 to 15 carbon atoms derived from dioctadecyl polysulfide, propylene or isobutylene. Among these, dialkyl polysulfides having an alkyl group having 8 to 16 carbon atoms are preferable.
The sulfur content of the active polysulfide is preferably 20% by mass or more and particularly preferably 30% by mass or more in order to improve load bearing performance.
The content of the active polysulfide as the component (c) in the present invention is preferably 2% by mass or more and 25% by mass or less, more preferably 5% by mass or more and 20% by mass or less based on the total amount of the composition. If the content of the active polysulfide is 2% by mass or more, the load bearing performance is satisfactorily exhibited, and if it is 25% by mass or less, corrosion does not become a problem.
本発明においては（ｃ）成分として活性ポリサルファイドを用いる。この活性ポリサルファイドとしては、例えば、下記の一般式（１）で表わされるジハイドロカルビルポリサルファイドを用いることが好ましい。
Ｒ1－Ｓx－Ｒ2 ・・・（１）
上記式中、Ｒ1、Ｒ2のハイドロカルビル基は、それぞれ独立に炭素数３～２０のアルキル基、炭素数６～２０のアリール基、アルキルアリール基又はアリールアルキル基を表し、それらは互いに同一でも異なってもよい。ｘは２～１０の整数を表す。
前記Ｒ1、Ｒ2のハイドロカルビル基は、炭素数６～１８のアルキル基がより好ましく、該アルキル基としては、直鎖状又は分枝状で、飽和又は不飽和のアルキル基を用いることできる。
活性ポリサルファイドの代表例としては、いずれも直鎖状又は分枝状のジヘキシルポリサルファイド、ジオクチルポリサルファイド、ジノニルポリサルファイド、ジデシルポリサルファイド、ジドデシルポリサルファイド、ジウンデシルポリサルファイド、ジテトラデシルポリサルファイド、ジヘキサデシルポリサルファイド、ジオクタデシルポリサルファイド、プロピレン又はイソブチレンから誘導される炭素数６～１５の分枝状のアルキル基を有するポリサルファイドが例示できる。これらの中でも炭素数８～１６のアルキル基を有するジアルキルポリサルファイドが好ましい。
前記活性ポリサルファイドの硫黄分含有量については、耐荷重性能の向上を図るために、２０質量％以上が好ましく、３０質量％以上が特に好ましい。
本発明における（ｃ）成分の活性ポリサルファイドの含有量は、組成物全量基準で２質量％以上２５質量％以下が好ましく、５質量％以上２０質量％以下がより好ましい。活性ポリサルファイドの含有量が、２質量％以上であれば、耐荷重性能が良好に発揮され２５質量％以下であれば腐食が問題になることがない。 [(C) active polysulfide, etc.]
In the present invention, active polysulfide is used as the component (c). As the active polysulfide, for example, dihydrocarbyl polysulfide represented by the following general formula (1) is preferably used.
R 1 -S x -R 2 (1)
In the above formula, each of the hydrocarbyl groups R 1 and R 2 independently represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, or an arylalkyl group, It may be the same or different. x represents an integer of 2 to 10.
The hydrocarbyl group of R 1 and R 2 is more preferably an alkyl group having 6 to 18 carbon atoms. As the alkyl group, a linear or branched, saturated or unsaturated alkyl group is used. it can.
As representative examples of active polysulfide, any of linear or branched dihexyl polysulfide, dioctyl polysulfide, dinonyl polysulfide, didecyl polysulfide, didodecyl polysulfide, diundecyl polysulfide, ditetradecyl polysulfide, dihexadecyl polysulfide, Examples thereof include polysulfide having a branched alkyl group having 6 to 15 carbon atoms derived from dioctadecyl polysulfide, propylene or isobutylene. Among these, dialkyl polysulfides having an alkyl group having 8 to 16 carbon atoms are preferable.
The sulfur content of the active polysulfide is preferably 20% by mass or more and particularly preferably 30% by mass or more in order to improve load bearing performance.
The content of the active polysulfide as the component (c) in the present invention is preferably 2% by mass or more and 25% by mass or less, more preferably 5% by mass or more and 20% by mass or less based on the total amount of the composition. If the content of the active polysulfide is 2% by mass or more, the load bearing performance is satisfactorily exhibited, and if it is 25% by mass or less, corrosion does not become a problem.
本発明においては、前記活性ポリサルファイドとともに、（ｃ’）成分として粉末硫黄を含むことができる。これによって耐荷重性能をさらに高めることができる。
この粉末硫黄を配合する場合は、その配合量は、特に制限はないが、組成物全量基準で０．０５質量％以上３質量％以下が好ましく、０．１質量％以上１質量％以下がより好ましく、０．２質量％以上０．７質量％以下がさらに好ましく、０．３質量％以上０．５質量％以下が特に好ましい。粉末硫黄の含有量が０．０５質量％以上であれば、本発明の組成物の耐荷重性能をさらに高める効果が発現される。また粉末硫黄の含有量が３質量％以下であれば、粉末硫黄が沈殿するおそれはない。 In the present invention, powdered sulfur can be included as the component (c ′) together with the active polysulfide. This can further enhance the load bearing performance.
When blending this powder sulfur, the blending amount is not particularly limited, but is preferably 0.05% by mass or more and 3% by mass or less, more preferably 0.1% by mass or more and 1% by mass or less based on the total amount of the composition. Preferably, 0.2 mass% or more and 0.7 mass% or less are more preferable, and 0.3 mass% or more and 0.5 mass% or less are especially preferable. If the content of powdered sulfur is 0.05% by mass or more, the effect of further enhancing the load bearing performance of the composition of the present invention is exhibited. Moreover, if content of powder sulfur is 3 mass% or less, there is no possibility that powder sulfur will precipitate.
この粉末硫黄を配合する場合は、その配合量は、特に制限はないが、組成物全量基準で０．０５質量％以上３質量％以下が好ましく、０．１質量％以上１質量％以下がより好ましく、０．２質量％以上０．７質量％以下がさらに好ましく、０．３質量％以上０．５質量％以下が特に好ましい。粉末硫黄の含有量が０．０５質量％以上であれば、本発明の組成物の耐荷重性能をさらに高める効果が発現される。また粉末硫黄の含有量が３質量％以下であれば、粉末硫黄が沈殿するおそれはない。 In the present invention, powdered sulfur can be included as the component (c ′) together with the active polysulfide. This can further enhance the load bearing performance.
When blending this powder sulfur, the blending amount is not particularly limited, but is preferably 0.05% by mass or more and 3% by mass or less, more preferably 0.1% by mass or more and 1% by mass or less based on the total amount of the composition. Preferably, 0.2 mass% or more and 0.7 mass% or less are more preferable, and 0.3 mass% or more and 0.5 mass% or less are especially preferable. If the content of powdered sulfur is 0.05% by mass or more, the effect of further enhancing the load bearing performance of the composition of the present invention is exhibited. Moreover, if content of powder sulfur is 3 mass% or less, there is no possibility that powder sulfur will precipitate.
〔（ｄ）多価アルコールの脂肪酸部分エステル〕
本発明においては、（ｄ）成分として多価アルコールの脂肪酸部分エステルが用いられる。
前記多価アルコールとしては、通常２～６価のものが用いられる。その具体例としては、エチレングリコール、プロピレングリコール、ネオペンチルグリコール、グリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール、ソルビタンなどが挙げられる。これらの中でもグリセリンやソルビタンが好ましく、特にグリセリンが好ましい。
前記脂肪酸部分エステルを形成する脂肪酸としては、通常炭素数６～２４の脂肪酸が用いられ、該脂肪酸は、直鎖状であっても分枝状であってもよく、飽和でも不飽和でも良い。これらの中でも炭素数１２～２２の脂肪酸炭素数が好ましく、炭素数１６～１８の飽和もしくは不飽和の脂肪酸がより好ましく、特に、効果と入手の容易性の点でオレイン酸が好ましい。
前記（ｄ）成分である脂肪酸部分エステルは、多価アルコールがグリセリンの場合、グリセリンモノエステル（モノグリセライド）、グリセリンジエステル（ジグリセライド）が含まれる。本発明においては、グリセリンモノエステル（モノグリセライド）がより好ましい。
本発明においては、上記（ｄ）成分を組成物全量基準で、１質量％以上２０質量％以下の範囲で配合するのが好ましく、２質量％以上１５質量％以下の範囲で配合することがより好ましい。（ｄ）成分の含有量が上記範囲であれば、耐荷重性能を高め、組成物の溶解安定性を損なうことはない。 [(D) Polyhydric alcohol fatty acid partial ester]
In the present invention, a fatty acid partial ester of a polyhydric alcohol is used as the component (d).
As the polyhydric alcohol, those having 2 to 6 valences are usually used. Specific examples thereof include ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan and the like. Among these, glycerin and sorbitan are preferable, and glycerin is particularly preferable.
As the fatty acid that forms the fatty acid partial ester, a fatty acid having 6 to 24 carbon atoms is usually used. The fatty acid may be linear or branched, and may be saturated or unsaturated. Among these, fatty acid having 12 to 22 carbon atoms is preferable, saturated or unsaturated fatty acid having 16 to 18 carbon atoms is more preferable, and oleic acid is particularly preferable from the viewpoint of effects and availability.
When the polyhydric alcohol is glycerin, the fatty acid partial ester as the component (d) includes glycerin monoester (monoglyceride) and glycerin diester (diglyceride). In the present invention, glycerin monoester (monoglyceride) is more preferable.
In this invention, it is preferable to mix | blend the said (d) component in the range of 1 mass% or more and 20 mass% or less based on the composition whole quantity, and it is more preferable to mix | blend in the range of 2 mass% or more and 15 mass% or less. preferable. When the content of the component (d) is in the above range, the load bearing performance is improved and the dissolution stability of the composition is not impaired.
本発明においては、（ｄ）成分として多価アルコールの脂肪酸部分エステルが用いられる。
前記多価アルコールとしては、通常２～６価のものが用いられる。その具体例としては、エチレングリコール、プロピレングリコール、ネオペンチルグリコール、グリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール、ソルビタンなどが挙げられる。これらの中でもグリセリンやソルビタンが好ましく、特にグリセリンが好ましい。
前記脂肪酸部分エステルを形成する脂肪酸としては、通常炭素数６～２４の脂肪酸が用いられ、該脂肪酸は、直鎖状であっても分枝状であってもよく、飽和でも不飽和でも良い。これらの中でも炭素数１２～２２の脂肪酸炭素数が好ましく、炭素数１６～１８の飽和もしくは不飽和の脂肪酸がより好ましく、特に、効果と入手の容易性の点でオレイン酸が好ましい。
前記（ｄ）成分である脂肪酸部分エステルは、多価アルコールがグリセリンの場合、グリセリンモノエステル（モノグリセライド）、グリセリンジエステル（ジグリセライド）が含まれる。本発明においては、グリセリンモノエステル（モノグリセライド）がより好ましい。
本発明においては、上記（ｄ）成分を組成物全量基準で、１質量％以上２０質量％以下の範囲で配合するのが好ましく、２質量％以上１５質量％以下の範囲で配合することがより好ましい。（ｄ）成分の含有量が上記範囲であれば、耐荷重性能を高め、組成物の溶解安定性を損なうことはない。 [(D) Polyhydric alcohol fatty acid partial ester]
In the present invention, a fatty acid partial ester of a polyhydric alcohol is used as the component (d).
As the polyhydric alcohol, those having 2 to 6 valences are usually used. Specific examples thereof include ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan and the like. Among these, glycerin and sorbitan are preferable, and glycerin is particularly preferable.
As the fatty acid that forms the fatty acid partial ester, a fatty acid having 6 to 24 carbon atoms is usually used. The fatty acid may be linear or branched, and may be saturated or unsaturated. Among these, fatty acid having 12 to 22 carbon atoms is preferable, saturated or unsaturated fatty acid having 16 to 18 carbon atoms is more preferable, and oleic acid is particularly preferable from the viewpoint of effects and availability.
When the polyhydric alcohol is glycerin, the fatty acid partial ester as the component (d) includes glycerin monoester (monoglyceride) and glycerin diester (diglyceride). In the present invention, glycerin monoester (monoglyceride) is more preferable.
In this invention, it is preferable to mix | blend the said (d) component in the range of 1 mass% or more and 20 mass% or less based on the composition whole quantity, and it is more preferable to mix | blend in the range of 2 mass% or more and 15 mass% or less. preferable. When the content of the component (d) is in the above range, the load bearing performance is improved and the dissolution stability of the composition is not impaired.
〔（ｅ）非イオン系界面活性剤〕
本発明において（ｅ）成分として用いる非イオン系界面活性剤は、多価アルコール型非イオン系界面活性剤、ポリオキシアルキレン系非イオン系界面活性剤など、いずれのタイプのものでも使用できる。
本発明においては、非イオン系界面活性剤は、主として潤滑油組成物に洗浄性を付与するために配合する。そのためＨＬＢ（親水親油バランス）を調整しやすいものが好ましく、種々のＨＬＢのものが得やすいポリオキシアルキレン系非イオン系界面活性剤が特に好適に用いられる。
そのような非イオン系界面活性剤としては、ポリオキシエチレンアルキルエーテル（但し、アルキルエーテルを構成するアルキル基の炭素数は６～１８のものが好ましい。）、ポリオキシエチレンポリオキシプロピレンアルキルエーテル（但し、ポリオキシエチレンポリオキシプロピレンはランダム共重合であっても、ブロック共重合であってもよく、アルキルエーテルを構成するアルキル基の炭素数は６～１８のものが好ましい）などが例示できる。
このような、非イオン系界面活性剤は、１種を単独で用いても、２種以上を混合して用いてもよい。
本発明においては、上記（ｅ）成分を組成物全量基準で、２質量％以上２５質量％以下の範囲で配合するのが好ましく、３質量％以上２０質量％以下が、より好ましい。（ｅ）成分の含有量が２質量％以上あれば、洗浄性が向上し、２５質量％以下であれば、油剤の混合安定性が悪化することはない。 [(E) Nonionic surfactant]
The nonionic surfactant used as the component (e) in the present invention may be any type such as a polyhydric alcohol type nonionic surfactant and a polyoxyalkylene type nonionic surfactant.
In the present invention, the nonionic surfactant is blended mainly for imparting detergency to the lubricating oil composition. Therefore, it is preferable to easily adjust HLB (hydrophilic lipophilic balance), and polyoxyalkylene nonionic surfactants that can easily be obtained from various HLBs are particularly preferably used.
As such a nonionic surfactant, polyoxyethylene alkyl ether (however, the alkyl group constituting the alkyl ether preferably has 6 to 18 carbon atoms), polyoxyethylene polyoxypropylene alkyl ether ( However, polyoxyethylene polyoxypropylene may be random copolymerization or block copolymerization, and the alkyl group constituting the alkyl ether preferably has 6 to 18 carbon atoms).
Such nonionic surfactants may be used alone or in combination of two or more.
In this invention, it is preferable to mix | blend the said (e) component in the range of 2 mass% or more and 25 mass% or less based on the composition whole quantity, and 3 mass% or more and 20 mass% or less are more preferable. (E) If content of a component is 2 mass% or more, detergency will improve and if it is 25 mass% or less, the mixing stability of an oil agent will not deteriorate.
本発明において（ｅ）成分として用いる非イオン系界面活性剤は、多価アルコール型非イオン系界面活性剤、ポリオキシアルキレン系非イオン系界面活性剤など、いずれのタイプのものでも使用できる。
本発明においては、非イオン系界面活性剤は、主として潤滑油組成物に洗浄性を付与するために配合する。そのためＨＬＢ（親水親油バランス）を調整しやすいものが好ましく、種々のＨＬＢのものが得やすいポリオキシアルキレン系非イオン系界面活性剤が特に好適に用いられる。
そのような非イオン系界面活性剤としては、ポリオキシエチレンアルキルエーテル（但し、アルキルエーテルを構成するアルキル基の炭素数は６～１８のものが好ましい。）、ポリオキシエチレンポリオキシプロピレンアルキルエーテル（但し、ポリオキシエチレンポリオキシプロピレンはランダム共重合であっても、ブロック共重合であってもよく、アルキルエーテルを構成するアルキル基の炭素数は６～１８のものが好ましい）などが例示できる。
このような、非イオン系界面活性剤は、１種を単独で用いても、２種以上を混合して用いてもよい。
本発明においては、上記（ｅ）成分を組成物全量基準で、２質量％以上２５質量％以下の範囲で配合するのが好ましく、３質量％以上２０質量％以下が、より好ましい。（ｅ）成分の含有量が２質量％以上あれば、洗浄性が向上し、２５質量％以下であれば、油剤の混合安定性が悪化することはない。 [(E) Nonionic surfactant]
The nonionic surfactant used as the component (e) in the present invention may be any type such as a polyhydric alcohol type nonionic surfactant and a polyoxyalkylene type nonionic surfactant.
In the present invention, the nonionic surfactant is blended mainly for imparting detergency to the lubricating oil composition. Therefore, it is preferable to easily adjust HLB (hydrophilic lipophilic balance), and polyoxyalkylene nonionic surfactants that can easily be obtained from various HLBs are particularly preferably used.
As such a nonionic surfactant, polyoxyethylene alkyl ether (however, the alkyl group constituting the alkyl ether preferably has 6 to 18 carbon atoms), polyoxyethylene polyoxypropylene alkyl ether ( However, polyoxyethylene polyoxypropylene may be random copolymerization or block copolymerization, and the alkyl group constituting the alkyl ether preferably has 6 to 18 carbon atoms).
Such nonionic surfactants may be used alone or in combination of two or more.
In this invention, it is preferable to mix | blend the said (e) component in the range of 2 mass% or more and 25 mass% or less based on the composition whole quantity, and 3 mass% or more and 20 mass% or less are more preferable. (E) If content of a component is 2 mass% or more, detergency will improve and if it is 25 mass% or less, the mixing stability of an oil agent will not deteriorate.
〔その他の添加剤〕
本発明は、上記（ａ）～（ｅ）又は（ａ）～（ｅ）及び（ｃ’）の各成分を配合してなるものであるが、さらに、所望に応じ、本発明の目的を損なわない範囲で、例えば、酸化防止剤、防錆剤、腐食防止剤、消泡剤等の各種添加剤を配合することができる。
前記酸化防止剤としては、例えば、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、４，４’－メチレンビス（２，６－ジ－ｔｅｒｔ－ブチルフェノール）などのフェノール系酸化防止剤、フェニル－α－ナフチルアミン、４，４’－ジオクチルジフェニルアミンなどのアミン系酸化防止剤が挙げられる。
前記防錆剤及び腐食防止剤としては、例えば、脂肪酸、アルケニルコハク酸ハーフエステル、脂肪酸セッケン、アルキルスルホン酸塩、脂肪酸アミン、酸化パラフィン、アルキルポリオキシエチレンエーテル等が挙げられる。
前記消泡剤としては、例えばジメチルポリシロキサン，ポリアクリレート等が挙げられる。
これらの添加剤は、それぞれ一種を単独で、又は二種以上を混合して使用することができる。また、これらの添加剤の配合量は、通常、それぞれ組成物全量基準で０．０００１質量％以上３質量％以下で配合される。 [Other additives]
The present invention comprises the components (a) to (e) or (a) to (e) and (c ′) described above, but further impairs the object of the present invention as desired. For example, various additives such as an antioxidant, a rust inhibitor, a corrosion inhibitor, and an antifoaming agent can be blended within the range.
Examples of the antioxidant include phenolic antioxidants such as 2,6-di-tert-butyl-4-methylphenol and 4,4′-methylenebis (2,6-di-tert-butylphenol), phenyl Examples thereof include amine-based antioxidants such as -α-naphthylamine and 4,4'-dioctyldiphenylamine.
Examples of the rust inhibitor and corrosion inhibitor include fatty acid, alkenyl succinic acid half ester, fatty acid soap, alkyl sulfonate, fatty acid amine, paraffin oxide, alkyl polyoxyethylene ether, and the like.
Examples of the antifoaming agent include dimethylpolysiloxane and polyacrylate.
These additives can be used individually by 1 type or in mixture of 2 or more types. Moreover, the compounding quantity of these additives is normally mix | blended at 0.0001 mass% or more and 3 mass% or less on the basis of the composition whole quantity, respectively.
本発明は、上記（ａ）～（ｅ）又は（ａ）～（ｅ）及び（ｃ’）の各成分を配合してなるものであるが、さらに、所望に応じ、本発明の目的を損なわない範囲で、例えば、酸化防止剤、防錆剤、腐食防止剤、消泡剤等の各種添加剤を配合することができる。
前記酸化防止剤としては、例えば、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、４，４’－メチレンビス（２，６－ジ－ｔｅｒｔ－ブチルフェノール）などのフェノール系酸化防止剤、フェニル－α－ナフチルアミン、４，４’－ジオクチルジフェニルアミンなどのアミン系酸化防止剤が挙げられる。
前記防錆剤及び腐食防止剤としては、例えば、脂肪酸、アルケニルコハク酸ハーフエステル、脂肪酸セッケン、アルキルスルホン酸塩、脂肪酸アミン、酸化パラフィン、アルキルポリオキシエチレンエーテル等が挙げられる。
前記消泡剤としては、例えばジメチルポリシロキサン，ポリアクリレート等が挙げられる。
これらの添加剤は、それぞれ一種を単独で、又は二種以上を混合して使用することができる。また、これらの添加剤の配合量は、通常、それぞれ組成物全量基準で０．０００１質量％以上３質量％以下で配合される。 [Other additives]
The present invention comprises the components (a) to (e) or (a) to (e) and (c ′) described above, but further impairs the object of the present invention as desired. For example, various additives such as an antioxidant, a rust inhibitor, a corrosion inhibitor, and an antifoaming agent can be blended within the range.
Examples of the antioxidant include phenolic antioxidants such as 2,6-di-tert-butyl-4-methylphenol and 4,4′-methylenebis (2,6-di-tert-butylphenol), phenyl Examples thereof include amine-based antioxidants such as -α-naphthylamine and 4,4'-dioctyldiphenylamine.
Examples of the rust inhibitor and corrosion inhibitor include fatty acid, alkenyl succinic acid half ester, fatty acid soap, alkyl sulfonate, fatty acid amine, paraffin oxide, alkyl polyoxyethylene ether, and the like.
Examples of the antifoaming agent include dimethylpolysiloxane and polyacrylate.
These additives can be used individually by 1 type or in mixture of 2 or more types. Moreover, the compounding quantity of these additives is normally mix | blended at 0.0001 mass% or more and 3 mass% or less on the basis of the composition whole quantity, respectively.
〔金属加工用潤滑油組成物〕
本発明の金属加工用潤滑油組成物は、４０℃の動粘度が５０ｍｍ2／ｓ以上１０００ｍｍ2／ｓ以下であり、１００ｍｍ2／ｓ以上５００ｍｍ2／ｓ以下が好ましく、より好ましくは１１０ｍｍ2／ｓ以上３００ｍｍ2／ｓ以下である。
組成物の４０℃の動粘度が５０ｍｍ2／ｓ以上であれば、高面圧下での油膜の破断を防止して潤滑油としての性能を発揮し、１０００ｍｍ2／ｓ以下であれば、粘度が高過ぎてポンプでの取扱いが難しくなることはなく、また、温水での洗浄時に後残りが発生することもない。 [Lubricating oil composition for metal working]
The lubricating oil composition for metal working of the present invention has a kinematic viscosity at 40 ° C. of 50 mm 2 / s to 1000 mm 2 / s, preferably 100 mm 2 / s to 500 mm 2 / s, more preferably 110 mm 2 / s. s to 300 mm 2 / s.
If the kinematic viscosity at 40 ° C. of the composition is 50 mm 2 / s or more, the oil film is prevented from being broken under high surface pressure and the performance as a lubricating oil is exhibited. If the composition is 1000 mm 2 / s or less, the viscosity is It is not too high to be handled with a pump, and no residual material is generated when washing with hot water.
本発明の金属加工用潤滑油組成物は、４０℃の動粘度が５０ｍｍ2／ｓ以上１０００ｍｍ2／ｓ以下であり、１００ｍｍ2／ｓ以上５００ｍｍ2／ｓ以下が好ましく、より好ましくは１１０ｍｍ2／ｓ以上３００ｍｍ2／ｓ以下である。
組成物の４０℃の動粘度が５０ｍｍ2／ｓ以上であれば、高面圧下での油膜の破断を防止して潤滑油としての性能を発揮し、１０００ｍｍ2／ｓ以下であれば、粘度が高過ぎてポンプでの取扱いが難しくなることはなく、また、温水での洗浄時に後残りが発生することもない。 [Lubricating oil composition for metal working]
The lubricating oil composition for metal working of the present invention has a kinematic viscosity at 40 ° C. of 50 mm 2 / s to 1000 mm 2 / s, preferably 100 mm 2 / s to 500 mm 2 / s, more preferably 110 mm 2 / s. s to 300 mm 2 / s.
If the kinematic viscosity at 40 ° C. of the composition is 50 mm 2 / s or more, the oil film is prevented from being broken under high surface pressure and the performance as a lubricating oil is exhibited. If the composition is 1000 mm 2 / s or less, the viscosity is It is not too high to be handled with a pump, and no residual material is generated when washing with hot water.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
なお、各例で得られた金属加工油組成物の性状及び性能は、以下に示す方法に従って求めた。
（１）動粘度
ＪＩＳ Ｋ２２８３に準拠し、４０℃における動粘度を測定した。
（２）塩基価
ＪＩＳ Ｋ２５０１の過塩素酸に準拠して測定した。
（３）硫黄分
ＪＩＳ Ｋ２５４１に準拠して測定した。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the property and performance of the metalworking oil composition obtained in each example were determined according to the following method.
(1) Kinematic viscosity According to JIS K2283, the kinematic viscosity at 40 ° C was measured.
(2) Base number It measured based on the perchloric acid of JISK2501.
(3) Sulfur content Measured according to JIS K2541.
なお、各例で得られた金属加工油組成物の性状及び性能は、以下に示す方法に従って求めた。
（１）動粘度
ＪＩＳ Ｋ２２８３に準拠し、４０℃における動粘度を測定した。
（２）塩基価
ＪＩＳ Ｋ２５０１の過塩素酸に準拠して測定した。
（３）硫黄分
ＪＩＳ Ｋ２５４１に準拠して測定した。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the property and performance of the metalworking oil composition obtained in each example were determined according to the following method.
(1) Kinematic viscosity According to JIS K2283, the kinematic viscosity at 40 ° C was measured.
(2) Base number It measured based on the perchloric acid of JISK2501.
(3) Sulfur content Measured according to JIS K2541.
（４）ドロービード試験
（試験方法）
板状の被加工材を２つのビード（ポンチ）で両面から挟んで押さえながら、被加工材を引抜き、その引抜き荷重を測定する構造のドロービード試験装置を用い、下記の条件で引抜き実験を行った。
（ｉ）被加工材：材質Ｓ４５Ｃ、形状４．５ｍｍ（厚さ）×１５ｍｍ×３００ｍｍ、硬度ＨＶ２７５
（ｉｉ）ポンチ：材質 超硬合金、形状０．５Ｒ
（ｉｉｉ）押え荷重：４００ｋｇｆ（面圧：３０００ＭＰａ）
（ｉｖ）引抜き速度：５ｍｍ／ｍｉｎ．
（ｖ）潤滑油剤の塗布方法：刷毛塗り
（評価方法）
（ｉ）引抜き荷重
６０ｍｍ引抜いた時の引抜き荷重を測定した。引抜き荷重は低いものが良いことを示している。
（ｉｉ）表面損傷
６０ｍｍ引抜いたときの被加工材の表面を観察し、焼付きやかじりによる損傷の有無と程度を目視で測定した。損傷面積を損傷の程度として、下記の評価基準に基づいて評価した。
（評価基準）
無：両面とも損傷無し
微：片面に表面積の１０％未満の傷有り
小：片面に表面積の１０％以上３０％以下の傷有り
中：両面に表面積の３０％以下の傷有り
大：両面に表面積の３０％を超える傷有り (4) Draw bead test (test method)
Using a draw bead test device with a structure that pulls out the workpiece and measures its pulling load while holding the plate-like workpiece between two beads (punch) from both sides, a drawing experiment was conducted under the following conditions. .
(I) Work material: material S45C, shape 4.5 mm (thickness) × 15 mm × 300 mm, hardness HV275
(Ii) Punch: Material Cemented carbide, shape 0.5R
(Iii) Presser load: 400 kgf (surface pressure: 3000 MPa)
(Iv) Drawing speed: 5 mm / min.
(V) Lubricant application method: Brush application (evaluation method)
(I) Pull-out load The pull-out load when 60 mm was pulled was measured. It shows that a low pull-out load is good.
(Ii) Surface damage The surface of the workpiece when it was pulled out by 60 mm was observed, and the presence and extent of damage due to seizure or galling was measured visually. The damage area was evaluated as the degree of damage based on the following evaluation criteria.
(Evaluation criteria)
None: No damage on both sides Fine: Scratches less than 10% of surface area on one side Small: Scratches of 10% to 30% of surface area on one side Medium: Scratches of 30% or less of surface area on both sides Large: Surface area on both sides There are more than 30% of scratches
（試験方法）
板状の被加工材を２つのビード（ポンチ）で両面から挟んで押さえながら、被加工材を引抜き、その引抜き荷重を測定する構造のドロービード試験装置を用い、下記の条件で引抜き実験を行った。
（ｉ）被加工材：材質Ｓ４５Ｃ、形状４．５ｍｍ（厚さ）×１５ｍｍ×３００ｍｍ、硬度ＨＶ２７５
（ｉｉ）ポンチ：材質 超硬合金、形状０．５Ｒ
（ｉｉｉ）押え荷重：４００ｋｇｆ（面圧：３０００ＭＰａ）
（ｉｖ）引抜き速度：５ｍｍ／ｍｉｎ．
（ｖ）潤滑油剤の塗布方法：刷毛塗り
（評価方法）
（ｉ）引抜き荷重
６０ｍｍ引抜いた時の引抜き荷重を測定した。引抜き荷重は低いものが良いことを示している。
（ｉｉ）表面損傷
６０ｍｍ引抜いたときの被加工材の表面を観察し、焼付きやかじりによる損傷の有無と程度を目視で測定した。損傷面積を損傷の程度として、下記の評価基準に基づいて評価した。
（評価基準）
無：両面とも損傷無し
微：片面に表面積の１０％未満の傷有り
小：片面に表面積の１０％以上３０％以下の傷有り
中：両面に表面積の３０％以下の傷有り
大：両面に表面積の３０％を超える傷有り (4) Draw bead test (test method)
Using a draw bead test device with a structure that pulls out the workpiece and measures its pulling load while holding the plate-like workpiece between two beads (punch) from both sides, a drawing experiment was conducted under the following conditions. .
(I) Work material: material S45C, shape 4.5 mm (thickness) × 15 mm × 300 mm, hardness HV275
(Ii) Punch: Material Cemented carbide, shape 0.5R
(Iii) Presser load: 400 kgf (surface pressure: 3000 MPa)
(Iv) Drawing speed: 5 mm / min.
(V) Lubricant application method: Brush application (evaluation method)
(I) Pull-out load The pull-out load when 60 mm was pulled was measured. It shows that a low pull-out load is good.
(Ii) Surface damage The surface of the workpiece when it was pulled out by 60 mm was observed, and the presence and extent of damage due to seizure or galling was measured visually. The damage area was evaluated as the degree of damage based on the following evaluation criteria.
(Evaluation criteria)
None: No damage on both sides Fine: Scratches less than 10% of surface area on one side Small: Scratches of 10% to 30% of surface area on one side Medium: Scratches of 30% or less of surface area on both sides Large: Surface area on both sides There are more than 30% of scratches
（５）洗浄性試験
（試験方法）
ＳＰＣＣの板（６０ｍｍ×８０ｍｍ×０．７ｍｍ（厚さ））を油剤に浸漬した後、３０分間吊るして油切りを行った。次いで水圧４０ｋｇｆ／ｃｍ2の温水（４０℃）シャワーで４０秒間洗浄し、さらに流水に浸漬した。その後水濡れ面積を目視で測定し、下記の基準で評価した。
（評価基準）
Ａ：水濡れ面積が７０％超
Ｂ：水濡れ面積が４０％超え７０％以下
Ｃ：水濡れ面積が４０％以下 (5) Detergency test (test method)
An SPCC plate (60 mm × 80 mm × 0.7 mm (thickness)) was dipped in the oil, and then suspended for 30 minutes to drain the oil. Subsequently, it was washed with a warm water (40 ° C.) shower with a water pressure of 40 kgf / cm 2 for 40 seconds and further immersed in running water. Thereafter, the wetted area was visually measured and evaluated according to the following criteria.
(Evaluation criteria)
A: The wetted area exceeds 70% B: The wetted area exceeds 40% and is 70% or less C: The wetted area is 40% or less
（試験方法）
ＳＰＣＣの板（６０ｍｍ×８０ｍｍ×０．７ｍｍ（厚さ））を油剤に浸漬した後、３０分間吊るして油切りを行った。次いで水圧４０ｋｇｆ／ｃｍ2の温水（４０℃）シャワーで４０秒間洗浄し、さらに流水に浸漬した。その後水濡れ面積を目視で測定し、下記の基準で評価した。
（評価基準）
Ａ：水濡れ面積が７０％超
Ｂ：水濡れ面積が４０％超え７０％以下
Ｃ：水濡れ面積が４０％以下 (5) Detergency test (test method)
An SPCC plate (60 mm × 80 mm × 0.7 mm (thickness)) was dipped in the oil, and then suspended for 30 minutes to drain the oil. Subsequently, it was washed with a warm water (40 ° C.) shower with a water pressure of 40 kgf / cm 2 for 40 seconds and further immersed in running water. Thereafter, the wetted area was visually measured and evaluated according to the following criteria.
(Evaluation criteria)
A: The wetted area exceeds 70% B: The wetted area exceeds 40% and is 70% or less C: The wetted area is 40% or less
＜実施例１～８及び比較例１～５＞
第１表、第２表に示す基油及び添加剤を用い、第１表、第２表に示す割合で混合して、金属加工油剤を調製し、その性状及び性能を求めた。結果を第１表及び第２表に示す。
<Examples 1 to 8 and Comparative Examples 1 to 5>
Using the base oils and additives shown in Tables 1 and 2 and mixing at the ratios shown in Tables 1 and 2, metalworking fluids were prepared, and their properties and performance were determined. The results are shown in Tables 1 and 2.
第１表、第２表に示す基油及び添加剤を用い、第１表、第２表に示す割合で混合して、金属加工油剤を調製し、その性状及び性能を求めた。結果を第１表及び第２表に示す。
<Examples 1 to 8 and Comparative Examples 1 to 5>
Using the base oils and additives shown in Tables 1 and 2 and mixing at the ratios shown in Tables 1 and 2, metalworking fluids were prepared, and their properties and performance were determined. The results are shown in Tables 1 and 2.
[規則26に基づく補充 15.04.2013]
[Supplement under Rule 26 15.04.2013]
[規則26に基づく補充 15.04.2013]
[Supplement under Rule 26 15.04.2013]
［注］
１）ナフテン系ブライトストック（４０℃動粘度：４３３．８ｍｍ2／ｓ、硫黄分：０．０４質量％）
２）ナフテン系５００ニュートラル（４０℃動粘度：１０４．７ｍｍ2／ｓ、硫黄分：０．０４質量％）
３）パラフィン系ブライトストック（４０℃動粘度：４３５．１ｍｍ2／ｓ、硫黄分：０．０２質量％）
４）パラフィン系５００ニュートラル（４０℃動粘度：９０．４８ｍｍ2／ｓ、硫黄分０．０１質量％）
５）エステル系合成油（ペンタエリスリトールテトラオレエート、４０℃動粘度：４．７１ｍｍ2／ｓ）
６）ポリメタクリレート（非分散型、質量平均分子量（Ｍｗ）：５５万、１５０ニュートラル鉱油に３５質量％濃度で希釈）
７）金属系スルホネート（カルシウムスルフォネート、Ｃａ分：１２．５質量％、硫黄分：２．４質量％、塩基価（過塩素酸法）：３２０ｍｇＫＯＨ／ｇ）
８）活性ポリサルファイド（下記の化学式（２）で表されるジラウリルポリサルファド、硫黄分含有量：３２質量％）
Ｃ12Ｈ25－Ｓ5－Ｃ12Ｈ25 ・・・ （２）
９）りん系極圧剤（ジオレイルハイドロジェンフォスファイト）
１０）粉末硫黄（硫黄分：９９．８質量％以上）
１１）多価アルコールの部分エステル（オレイン酸モノグリセライド）
１２）非イオン系界面活性剤－１（ポリオキシエチレンポリオキシプロピレンアルキルエーテル（ブロック型、アルキル基の炭素数は１０～１３）、ＨＬＢ：１２．７）
１３）非イオン系界面活性剤－２（ポリオキシエチレンオレイルエーテル、ＨＬＢ：８．８） [note]
1) Naphthenic bright stock (40 ° C. kinematic viscosity: 433.8 mm 2 / s, sulfur content: 0.04 mass%)
2) Naphthenic 500 neutral (40 ° C. kinematic viscosity: 104.7 mm 2 / s, sulfur content: 0.04 mass%)
3) Paraffin-type bright stock (40 ° C. kinematic viscosity: 435.1 mm 2 / s, sulfur content: 0.02% by mass)
4) Paraffin-based 500 neutral (40 ° C. kinematic viscosity: 90.48 mm 2 / s, sulfur content 0.01 mass%)
5) Ester-based synthetic oil (pentaerythritol tetraoleate, 40 ° C. kinematic viscosity: 4.71 mm 2 / s)
6) Polymethacrylate (non-dispersed, mass-average molecular weight (Mw): 550,000, diluted to 150 neutral mineral oil at a concentration of 35% by mass)
7) Metal sulfonate (calcium sulfonate, Ca content: 12.5% by mass, sulfur content: 2.4% by mass, base number (perchloric acid method): 320 mgKOH / g)
8) Active polysulfide (dilauryl polysulfide represented by the following chemical formula (2), sulfur content: 32% by mass)
C 12 H 25 -S 5 -C 12 H 25 (2)
9) Phosphorus extreme pressure agent (Dioleyl hydrogen phosphite)
10) Powdered sulfur (Sulfur content: 99.8% by mass or more)
11) Partial ester of polyhydric alcohol (oleic acid monoglyceride)
12) Nonionic surfactant-1 (polyoxyethylene polyoxypropylene alkyl ether (block type, the alkyl group has 10 to 13 carbon atoms), HLB: 12.7)
13) Nonionic surfactant-2 (polyoxyethylene oleyl ether, HLB: 8.8)
１）ナフテン系ブライトストック（４０℃動粘度：４３３．８ｍｍ2／ｓ、硫黄分：０．０４質量％）
２）ナフテン系５００ニュートラル（４０℃動粘度：１０４．７ｍｍ2／ｓ、硫黄分：０．０４質量％）
３）パラフィン系ブライトストック（４０℃動粘度：４３５．１ｍｍ2／ｓ、硫黄分：０．０２質量％）
４）パラフィン系５００ニュートラル（４０℃動粘度：９０．４８ｍｍ2／ｓ、硫黄分０．０１質量％）
５）エステル系合成油（ペンタエリスリトールテトラオレエート、４０℃動粘度：４．７１ｍｍ2／ｓ）
６）ポリメタクリレート（非分散型、質量平均分子量（Ｍｗ）：５５万、１５０ニュートラル鉱油に３５質量％濃度で希釈）
７）金属系スルホネート（カルシウムスルフォネート、Ｃａ分：１２．５質量％、硫黄分：２．４質量％、塩基価（過塩素酸法）：３２０ｍｇＫＯＨ／ｇ）
８）活性ポリサルファイド（下記の化学式（２）で表されるジラウリルポリサルファド、硫黄分含有量：３２質量％）
Ｃ12Ｈ25－Ｓ5－Ｃ12Ｈ25 ・・・ （２）
９）りん系極圧剤（ジオレイルハイドロジェンフォスファイト）
１０）粉末硫黄（硫黄分：９９．８質量％以上）
１１）多価アルコールの部分エステル（オレイン酸モノグリセライド）
１２）非イオン系界面活性剤－１（ポリオキシエチレンポリオキシプロピレンアルキルエーテル（ブロック型、アルキル基の炭素数は１０～１３）、ＨＬＢ：１２．７）
１３）非イオン系界面活性剤－２（ポリオキシエチレンオレイルエーテル、ＨＬＢ：８．８） [note]
1) Naphthenic bright stock (40 ° C. kinematic viscosity: 433.8 mm 2 / s, sulfur content: 0.04 mass%)
2) Naphthenic 500 neutral (40 ° C. kinematic viscosity: 104.7 mm 2 / s, sulfur content: 0.04 mass%)
3) Paraffin-type bright stock (40 ° C. kinematic viscosity: 435.1 mm 2 / s, sulfur content: 0.02% by mass)
4) Paraffin-based 500 neutral (40 ° C. kinematic viscosity: 90.48 mm 2 / s, sulfur content 0.01 mass%)
5) Ester-based synthetic oil (pentaerythritol tetraoleate, 40 ° C. kinematic viscosity: 4.71 mm 2 / s)
6) Polymethacrylate (non-dispersed, mass-average molecular weight (Mw): 550,000, diluted to 150 neutral mineral oil at a concentration of 35% by mass)
7) Metal sulfonate (calcium sulfonate, Ca content: 12.5% by mass, sulfur content: 2.4% by mass, base number (perchloric acid method): 320 mgKOH / g)
8) Active polysulfide (dilauryl polysulfide represented by the following chemical formula (2), sulfur content: 32% by mass)
C 12 H 25 -S 5 -C 12 H 25 (2)
9) Phosphorus extreme pressure agent (Dioleyl hydrogen phosphite)
10) Powdered sulfur (Sulfur content: 99.8% by mass or more)
11) Partial ester of polyhydric alcohol (oleic acid monoglyceride)
12) Nonionic surfactant-1 (polyoxyethylene polyoxypropylene alkyl ether (block type, the alkyl group has 10 to 13 carbon atoms), HLB: 12.7)
13) Nonionic surfactant-2 (polyoxyethylene oleyl ether, HLB: 8.8)
第１表及び第２表より、本発明の実施例１～８の組成物は、ドロービード試験における引抜き荷重が２６０ｋｇｆ以下であり、表面損傷がほとんどなく、洗浄性も良好であることが分かる。
これに対し、（ｂ）成分を含まない比較例１は、引抜き荷重が高く（２８８ｋｇｆ）、表面損傷も大きい。
また（ｃ）成分（活性ポリサルファイド）を含まない比較例２は、引抜き荷重が高く（３３０ｋｇｆ）、表面損傷も大きい。また、（ｃ）成分（活性ポリサルファイド）を含まない比較例２にリン系極圧剤を配合した比較例３は、引抜き荷重、表面損傷とも充分に回復しないことを示している。
さらに（ｄ）成分を含まない比較例４は、引抜き荷重が高く（２７０ｋｇｆ）、表面損傷も不良である。また、（ｅ）成分を含まない比較例５は、洗浄性が劣っている。 From Tables 1 and 2, it can be seen that the compositions of Examples 1 to 8 of the present invention have a drawing load in a draw bead test of 260 kgf or less, almost no surface damage, and good cleanability.
On the other hand, Comparative Example 1 which does not contain the component (b) has a high pulling load (288 kgf) and a large surface damage.
Moreover, the comparative example 2 which does not contain (c) component (active polysulfide) has a high extraction load (330 kgf), and its surface damage is also large. Moreover, the comparative example 3 which mix | blended the phosphorus extreme pressure agent with the comparative example 2 which does not contain (c) component (active polysulfide) has shown that neither a drawing load nor surface damage fully recovers.
Furthermore, the comparative example 4 which does not contain the component (d) has a high pulling load (270 kgf), and the surface damage is also poor. Moreover, the comparative example 5 which does not contain (e) component is inferior in washability.
これに対し、（ｂ）成分を含まない比較例１は、引抜き荷重が高く（２８８ｋｇｆ）、表面損傷も大きい。
また（ｃ）成分（活性ポリサルファイド）を含まない比較例２は、引抜き荷重が高く（３３０ｋｇｆ）、表面損傷も大きい。また、（ｃ）成分（活性ポリサルファイド）を含まない比較例２にリン系極圧剤を配合した比較例３は、引抜き荷重、表面損傷とも充分に回復しないことを示している。
さらに（ｄ）成分を含まない比較例４は、引抜き荷重が高く（２７０ｋｇｆ）、表面損傷も不良である。また、（ｅ）成分を含まない比較例５は、洗浄性が劣っている。 From Tables 1 and 2, it can be seen that the compositions of Examples 1 to 8 of the present invention have a drawing load in a draw bead test of 260 kgf or less, almost no surface damage, and good cleanability.
On the other hand, Comparative Example 1 which does not contain the component (b) has a high pulling load (288 kgf) and a large surface damage.
Moreover, the comparative example 2 which does not contain (c) component (active polysulfide) has a high extraction load (330 kgf), and its surface damage is also large. Moreover, the comparative example 3 which mix | blended the phosphorus extreme pressure agent with the comparative example 2 which does not contain (c) component (active polysulfide) has shown that neither a drawing load nor surface damage fully recovers.
Furthermore, the comparative example 4 which does not contain the component (d) has a high pulling load (270 kgf), and the surface damage is also poor. Moreover, the comparative example 5 which does not contain (e) component is inferior in washability.
本発明の金属加工用潤滑油組成物によれば、塩素系油剤を使用することなくとも、高い耐荷重性能を有すると同時に、優れた洗浄性をも有する、鋼管拡張加工などの過酷な潤滑条件下で用いることができる金属加工用潤滑油組成物を提供することができる。したがって、環境問題を解消した高性能の金属加工用潤滑油組成物として有効に利用することができる。
According to the lubricating oil composition for metal working of the present invention, even without using a chlorinated oil, it has a high load-bearing performance and at the same time has an excellent cleaning property, and is subjected to severe lubrication conditions such as steel pipe expansion processing. A metalworking lubricating oil composition that can be used below can be provided. Therefore, it can be effectively used as a high-performance lubricating oil composition for metal working that has solved environmental problems.
Claims (11)
- （ａ）基油、（ｂ）金属系スルホネート、（ｃ）活性ポリサルファイド、（ｄ）多価アルコールの脂肪酸部分エステル、及び（ｅ）非イオン系界面活性剤を含み、組成物の４０℃における動粘度が５０ｍｍ2／ｓ以上１０００ｍｍ2／ｓ以下であることを特徴とする金属加工用潤滑油組成物。 (A) a base oil, (b) a metal sulfonate, (c) an active polysulfide, (d) a fatty acid partial ester of a polyhydric alcohol, and (e) a nonionic surfactant. A lubricating oil composition for metal working, wherein the viscosity is 50 mm 2 / s or more and 1000 mm 2 / s or less.
- さらに（ｃ’）粉末硫黄を含む請求項１に記載の金属加工用潤滑油組成物。 The metal working lubricating oil composition according to claim 1, further comprising (c ′) powdered sulfur.
- （ａ）成分である基油が、鉱油、又は、鉱油とエステル系合成油及びポリメタクリレートから選ばれる１種以上とを含むものである請求項１又は２に記載の金属加工用潤滑油組成物。 The lubricating oil composition for metal working according to claim 1 or 2, wherein the base oil as component (a) contains mineral oil, or one or more selected from mineral oil and ester synthetic oil and polymethacrylate.
- エステル系合成油が、炭素数２～６の多価アルコールと炭素数２～２４の脂肪族酸とのエステルである請求項３に記載の金属加工用潤滑油組成物。 The lubricating oil composition for metal working according to claim 3, wherein the ester synthetic oil is an ester of a polyhydric alcohol having 2 to 6 carbon atoms and an aliphatic acid having 2 to 24 carbon atoms.
- （ｂ）成分である金属系スルホネートが、過塩基性アルカリ土類金属スルホネートである請求項１～４のいずれかに記載の金属加工用潤滑油組成物。 5. The lubricating oil composition for metal processing according to claim 1, wherein the metal sulfonate as component (b) is an overbased alkaline earth metal sulfonate.
- （ｃ）成分である活性ポリサルファイドの硫黄分含有量が、２０質量％以上である請求項１～５のいずれかに記載の金属加工用潤滑油組成物。 6. The lubricating oil composition for metal working according to claim 1, wherein the content of sulfur in the active polysulfide as the component (c) is 20% by mass or more.
- （ｄ）成分である多価アルコールの脂肪酸部分エステルが、炭素数２～６の多価アルコールと炭素数６～２４の脂肪酸との部分エステルである請求項１～６のいずれかに記載の金属加工用潤滑油組成物。 The metal according to any one of claims 1 to 6, wherein the fatty acid partial ester of the polyhydric alcohol as component (d) is a partial ester of a polyhydric alcohol having 2 to 6 carbon atoms and a fatty acid having 6 to 24 carbon atoms. Lubricating oil composition for processing.
- （ｅ）成分である非イオン系界面活性剤が、ポリオキシアルキレン型非イオン系界面活性剤である請求項１～７のいずれかに記載の金属加工用潤滑油組成物。 The lubricating oil composition for metal working according to any one of claims 1 to 7, wherein the nonionic surfactant as the component (e) is a polyoxyalkylene type nonionic surfactant.
- ポリオキシアルキレン型非イオン系界面活性剤が、ポリオキシエチレン基及びポリオキシプロピレン基を有するものである請求項８に記載の金属加工用潤滑油組成物。 The lubricating oil composition for metal working according to claim 8, wherein the polyoxyalkylene type nonionic surfactant has a polyoxyethylene group and a polyoxypropylene group.
- 組成物全量基準で、（ｂ）金属系スルホネートを１質量％以上２０質量％以下、（ｃ）活性ポリサルファイドを２質量％以上２５質量％以下、（ｃ’）粉末硫黄を３質量%以下、（ｄ）多価アルコールの脂肪酸部分エステルを１質量％以上２０質量％以下、及び（ｅ）非イオン系界面活性剤を２質量％以上２５質量％以下含む請求項１～９のいずれかに記載の金属加工用潤滑油組成物。 (B) 1% by mass to 20% by mass of metal sulfonate, (c) 2% by mass to 25% by mass of active polysulfide, (c ′) 3% by mass of powder sulfur, d) a fatty acid partial ester of a polyhydric alcohol of 1 to 20% by mass and (e) a nonionic surfactant of 2 to 25% by mass. Lubricating oil composition for metal working.
- 鋼管拡張加工に用いられる請求項１～１０のいずれかに記載の金属加工用潤滑油組成物。 The lubricating oil composition for metal working according to any one of claims 1 to 10, which is used for steel pipe expansion processing.
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| JP2009209325A (en) * | 2008-03-06 | 2009-09-17 | Idemitsu Kosan Co Ltd | Lubricating oil composition for fine blanking |
| JP2009215482A (en) * | 2008-03-12 | 2009-09-24 | Idemitsu Kosan Co Ltd | Metal processing oil composition |
| JP2010235791A (en) * | 2009-03-31 | 2010-10-21 | Idemitsu Kosan Co Ltd | Rolling oil |
| JP2011001516A (en) * | 2009-06-22 | 2011-01-06 | Jatco Ltd | Oil composition for metal machining |
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| DE3163392D1 (en) * | 1981-07-29 | 1984-06-07 | Viscosud Of Dott Ing Mario Fio | Application of polyglycols soluble in water as lubricant in mechanical expanders effecting the cold straightening and gauging of lengthwise welded steel tubes |
| JP5259215B2 (en) * | 2008-02-29 | 2013-08-07 | 出光興産株式会社 | Processing oil for brittle materials |
| JP5576615B2 (en) * | 2009-03-11 | 2014-08-20 | 出光興産株式会社 | Metalworking fluid |
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| JP2009209325A (en) * | 2008-03-06 | 2009-09-17 | Idemitsu Kosan Co Ltd | Lubricating oil composition for fine blanking |
| JP2009215482A (en) * | 2008-03-12 | 2009-09-24 | Idemitsu Kosan Co Ltd | Metal processing oil composition |
| JP2010235791A (en) * | 2009-03-31 | 2010-10-21 | Idemitsu Kosan Co Ltd | Rolling oil |
| JP2011001516A (en) * | 2009-06-22 | 2011-01-06 | Jatco Ltd | Oil composition for metal machining |
| JP2012062488A (en) * | 2011-12-27 | 2012-03-29 | Idemitsu Kosan Co Ltd | Working/rust preventive oil composition |
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| EP3098289A4 (en) * | 2014-01-20 | 2017-09-13 | Idemitsu Kosan Co., Ltd | Metalworking oil composition |
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