CN113874479B - Metal working oil - Google Patents
Metal working oil Download PDFInfo
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- CN113874479B CN113874479B CN202080040605.7A CN202080040605A CN113874479B CN 113874479 B CN113874479 B CN 113874479B CN 202080040605 A CN202080040605 A CN 202080040605A CN 113874479 B CN113874479 B CN 113874479B
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- CN
- China
- Prior art keywords
- metal working
- working oil
- component
- mass
- oil according
- Prior art date
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- 238000005555 metalworking Methods 0.000 title claims abstract description 188
- 239000003921 oil Substances 0.000 claims abstract description 202
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 230000007704 transition Effects 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 239000002199 base oil Substances 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 15
- -1 fatty acid esters Chemical class 0.000 claims description 39
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 33
- 229930195729 fatty acid Natural products 0.000 claims description 33
- 239000000194 fatty acid Substances 0.000 claims description 33
- 239000007769 metal material Substances 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 150000004665 fatty acids Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 238000010273 cold forging Methods 0.000 claims description 13
- 229920006395 saturated elastomer Polymers 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 10
- 230000000994 depressogenic effect Effects 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 150000001735 carboxylic acids Chemical class 0.000 claims description 7
- 229920001021 polysulfide Polymers 0.000 claims description 7
- 239000005077 polysulfide Substances 0.000 claims description 7
- 150000008117 polysulfides Polymers 0.000 claims description 7
- 125000004434 sulfur atom Chemical group 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 239000004519 grease Substances 0.000 claims 1
- 235000019198 oils Nutrition 0.000 description 146
- 238000012360 testing method Methods 0.000 description 25
- 239000002253 acid Substances 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 9
- 238000005245 sintering Methods 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000005237 degreasing agent Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YWHLKYXPLRWGSE-UHFFFAOYSA-N Dimethyl trisulfide Chemical compound CSSSC YWHLKYXPLRWGSE-UHFFFAOYSA-N 0.000 description 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MBMBGCFOFBJSGT-KUBAVDMBSA-N all-cis-docosa-4,7,10,13,16,19-hexaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCC(O)=O MBMBGCFOFBJSGT-KUBAVDMBSA-N 0.000 description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 2
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- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
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- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 2
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- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
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Classifications
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
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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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
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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
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/04—Hydroxy compounds
- C10M129/06—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
- C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/70—Esters of monocarboxylic acids
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- 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
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- 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
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
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- 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
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- 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
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- 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
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- C10N2040/20—Metal working
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Abstract
Provided is a metal working oil comprising a base oil (A) and a compound (B) which is liquid at a pressure of 0.1MPa and undergoes a phase transition from liquid to solid as the pressure increases in the range of from 0.1MPa to 300 MPa.
Description
Technical Field
The present invention relates to metal working oils.
Background
In a metal working oil for plastic working, which is used for press working, drawing, ironing, bending, rolling, cold forging, etc., of a metal material, lubricity such as seizure resistance is required for use under severe lubrication conditions.
For example, patent document 1 describes a lubricating oil composition for plastic working, which contains 5 to 99 mass% of zinc dithiophosphate having a specific structure, 1 to 95 mass% of a metal salt of sulfonic acid, and 0 to 80 mass% of a base oil, with the object of providing a lubricating oil composition for plastic working, which is excellent in lubricity and can be used in press working, cold forging working, or the like even under severe lubrication conditions.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2013-173957.
Disclosure of Invention
Problems to be solved by the invention
Under such circumstances, a novel metal working oil is demanded.
Means for solving the problems
The present invention provides a metal working oil comprising a base oil and a compound which is liquid at normal pressure and undergoes a phase change from liquid to solid at an elevated pressure.
That is, the present invention provides the following [1] to [14].
[1] A metal working oil comprising: a base oil (a) and a compound (B) which is liquid at a pressure of 0.1MPa and undergoes a phase transition from liquid to solid as the pressure increases in the range of from 0.1MPa to 300 MPa.
[2] The metal working oil according to the above [1], wherein the kinematic viscosity of the metal working oil at 40℃is 100mm 2 And/s or less.
[3] The metal working oil according to the above [1] or [2], wherein the component (B) contains 1 or more compounds selected from the group consisting of carboxylic esters, carboxylic acids, and alcohols, which undergo the aforementioned phase transition.
[4] The metal working oil according to the above [3], wherein the carboxylic acid ester is a saturated carboxylic acid ester,
the aforementioned carboxylic acid is a saturated carboxylic acid,
the alcohol is a saturated alcohol.
[5] The metal working oil according to any one of the above [1] to [4], wherein the component (B) comprises a compound which undergoes the aforementioned phase transition represented by any one of the following general formulae (B-1) to (B-3),
[ chemical formula 1]
(in the above formula, R 1 、R 2 And R is 3 Each independently is an alkyl group having 10 to 40 carbon atoms, R 4 Is an alkyl group having 1 to 10 carbon atoms. ).
[6] The metalworking oil according to any one of the above [1] to [5], wherein the content of the component (B) is 0.1 to 50% by mass based on the total amount of the metalworking oil.
[7] The metal working oil according to any one of the above [1] to [6], further comprising a sulfur-based extreme pressure agent (C).
[8] The metalworking oil according to any one of the above [1] to [7], wherein the content of the component (C) in terms of sulfur atoms is 6.5 mass% or more based on the total amount of the metalworking oil.
[9] The metal working oil according to any one of the above [1] to [8], wherein the metal working oil further comprises 1 or more compounds (D) which are not the component (B) and are selected from fatty acids and fatty acid esters.
[10] The metalworking oil according to any one of the above [1] to [9], wherein a pour point depressant (E) is further contained.
[11] The metalworking oil according to any one of the above [1] to [10], wherein the content of water is less than 1.0 mass% based on the total amount of the metalworking oil.
[12] The metalworking oil according to any one of the above [1] to [11], which is used for cold forging of a metal material.
[13] The use of a metal working oil according to any one of the above [1] to [12] for cold forging of a metal material.
[14] A metal working method, wherein the metal material is cold-forged by using the metal working oil according to any one of the above [1] to [12 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The metal working oil according to one embodiment of the present invention is excellent in workability of a metal material, and the metal working oil according to one embodiment of the present invention is excellent in balance between low viscosity and seizure resistance, and is particularly suitable for cold forging of a metal material.
Brief description of the drawings
FIG. 1 is a schematic view of an example of a high-voltage test apparatus for confirming phase transition behavior.
Detailed Description
The numerical ranges described in the present specification may be arbitrarily combined with the upper limit value and the lower limit value. For example, when the numerical range is described as "preferably 30 to 100, more preferably 40 to 80", the numerical range of "30 to 80" and the numerical range of "40 to 100" are also included in the numerical range described in the present specification. For example, when the numerical range is described as "preferably 30 or more, more preferably 40 or more, and still more preferably 100 or less, more preferably 80 or less", the numerical range described in the present specification includes the range of "30 to 80" and the range of "40 to 100".
In addition, as the numerical ranges described in the present specification, for example, the description of "60 to 100" means a range of "60 or more and 100 or less".
[ constitution of metalworking oil ]
For example, a conventional metal working oil for plastic working has been used in which the kinematic viscosity at 40℃as the viscosity is adjusted to a value exceeding 100mm 2 And/s, a means for suppressing sintering on the metal material. However, such a high-viscosity metalworking oil has a problem in that it is difficult to supply the metalworking oil to the metal material because of its poor operability. In addition, the high viscosity metalworking oil may have a disadvantage in that fluidity is lowered due to an increase in viscosity when it is used in a low temperature environment, and the metalworking oil is solidified when the metal material is processed according to circumstances.
On the other hand, a low viscosity metal working oil can suppress such a problem as described above, but has a problem in that sintering on a metal material is liable to occur. Particularly, when the metal material is used for cold forging, the occurrence frequency of sintering on the metal material becomes high.
In order to solve such problems, the metal working oil of the present invention is prepared so as to contain a base oil (a) and a compound (B) (hereinafter also referred to as "phase-change compound") which is liquid at a pressure of 0.1MPa and undergoes a phase change from liquid to solid as the pressure increases in the range of 0.1MPa to 300MPa, thereby solving the problems.
The phase change compound used as the component (B) is liquid at normal pressure (at a pressure of 0.1 MPa), and therefore, the workability of the metal working oil can be maintained well. In addition, even when a high-viscosity base oil is used as the base oil (a), the phase change compound of the component (B) is liquid at normal pressure, and thus, by containing the phase change compound, a metal working oil having good handleability can be formed.
Further, when the phase change compound used as the component (B) is formed at a high pressure during plastic working, it is thought that a firm oil film is formed by solidifying the surface of the metal material as the work material, and the metal working oil of the present invention can effectively suppress the occurrence of sintering on the metal material.
Therefore, the metal working oil according to one embodiment of the present invention is excellent in balance between low viscosity and seizure resistance, and is particularly suitable for use in cold forging of metal materials.
The kinematic viscosity at 40℃of the metal working oil according to one embodiment of the present invention is preferably 100mm from the viewpoint of forming a metal working oil having good handleability 2 Less than/s, more preferably 90mm 2 Preferably less than or equal to/s, more preferably 80mm 2 And/s or less, more preferably 70mm 2 In addition, it is preferably 10mm or less from the viewpoint of maintaining a firm oil film and reducing evaporation loss 2 At least/s, more preferably 20mm 2 At least/s, more preferably 30mm 2 Higher than/s, more preferably 40mm 2 And/s.
From the same point of view as described above, the kinematic viscosity at 100℃of the metal working oil according to one embodiment of the present invention is preferably 12.0mm 2 And/s or less, more preferably 11.0mm 2 And/s is less than or equal to, more preferably 10.0mm 2 And/s or less, more preferably 9.0mm 2 Preferably not more than/s, and more preferably 2.0mm 2 At least/s, more preferably 3.0mm 2 At least/s, more preferably 4.0mm 2 Higher than/s, more preferably 4.5mm 2 And/s.
The viscosity index of the metal working oil according to one embodiment of the present invention is preferably 60 or more, more preferably 70 or more, still more preferably 80 or more, and still more preferably 85 or more.
In the present specification, the kinematic viscosity and the viscosity index refer to those according to JIS K2283:2000 measured and calculated values.
The metal working oil according to one embodiment of the present invention preferably further contains at least 1 selected from the group consisting of a sulfur-based extreme pressure agent (C), 1 or more selected from the group consisting of fatty acids and fatty acid esters other than the component (B), and a pour point depressant (E), more preferably 2 or more selected from the group consisting of the components (C), (D), and (E), and still more preferably contains the components (C), (D), and (E) together.
The metal working oil according to one embodiment of the present invention may contain other components than the above components (a) to (E) within a range that does not impair the effects of the present invention.
In the metal working oil according to one embodiment of the present invention, the total content of the components (a) and (B) is preferably 25 to 100 mass%, more preferably 35 to 100 mass%, even more preferably 45 to 100 mass%, even more preferably 55 to 100 mass%, and particularly preferably 60 to 100 mass%, based on the total amount (100 mass%) of the metal working oil.
In the metal working oil according to one embodiment of the present invention, the total content of the components (a), (B), (C), (D) and (E) is preferably 50 to 100 mass%, more preferably 60 to 100 mass%, even more preferably 70 to 100 mass%, even more preferably 80 to 100 mass%, and particularly preferably 90 to 100 mass%, based on the total amount (100 mass%) of the metal working oil.
The following describes details of each component contained in the metal working oil according to one embodiment of the present invention.
< component (A): base oil >
The base oil (a) used in one embodiment of the present invention includes 1 or more kinds selected from mineral oils and synthetic oils.
Examples of the mineral oil include an atmospheric residue obtained by atmospheric distillation of crude oils such as paraffinic crude oil, intermediate crude oil, and naphthenic crude oil; distillate oil obtained by vacuum distillation of these atmospheric residues; refined oil obtained by subjecting the distillate oil to one or more refining treatments such as solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, and hydrofining.
Examples of the synthetic oil include polyalphaolefins such as alpha-olefin homopolymers and alpha-olefin copolymers (for example, alpha-olefin copolymers having 8 to 14 carbon atoms such as ethylene-alpha-olefin copolymers); isoparaffins; polyalkylene glycols; ester-based oils such as polyol esters, dibasic acid esters, and phosphoric acid esters; ether-based oils such as polyphenylene ether; an alkylbenzene; alkyl naphthalene; and synthetic oils (GTLs) obtained by isomerizing waxes produced from natural gas (GTL waxes (natural gas-to-synthetic oil waxes)) by the fischer-tropsch process or the like.
The kinematic viscosity at 40℃of the base oil (A) used in one embodiment of the present invention is preferably 10mm from the viewpoint of forming a metal working oil having further improved seizure resistance 2 At least/s, more preferably 20mm 2 At least/s, more preferably 30mm 2 At least/s, more preferably 40mm 2 At least/s, more preferably 100mm 2 At least/s, more preferably 200mm 2 Higher than/s, more preferably 300mm 2 At least/s, more preferably 350mm 2 At least/s, particularly preferably 400mm 2 And/s.
The metal working oil of the present invention has a kinematic viscosity of 100mm even when used at 40 ℃ 2 The base oil of/s or more is a phase-change compound containing the component (B) which is liquid at normal pressure (at a pressure of 0.1 MPa), and thus the kinematic viscosity of the obtained metal working oil can be appropriately adjusted, and a metal working oil excellent in handleability can be obtained.
On the other hand, the base oil (A) used in one embodiment of the present invention preferably has a kinematic viscosity at 40℃of 1000mm 2 /sLower, more preferably 900mm 2 And is not more than/s, more preferably 800mm 2 And/s or less, more preferably 700mm 2 Preferably less than/s, particularly preferably 600mm 2 And/s or less.
From the same point of view as described above, the base oil (A) used in one embodiment of the present invention preferably has a kinematic viscosity at 100℃of 2.0mm 2 At least/s, more preferably 3.0mm 2 At least/s, more preferably 4.0mm 2 Higher than/s, more preferably 4.5mm 2 At least/s, more preferably 7.0mm 2 At least/s, more preferably 10.0mm 2 Higher than/s, more preferably 12.5mm 2 At least/s, particularly preferably 15.0mm 2 At least/s, preferably 40.0mm 2 Preferably less than/s, more preferably 35.0mm 2 And is not more than/s, more preferably 30.0mm 2 And/s or less, more preferably 27.0mm 2 Preferably less than/s, particularly preferably 25.0mm 2 And/s or less.
The viscosity index of the base oil (a) used in one embodiment of the present invention is preferably 2 or more, more preferably 5 or more, still more preferably 10 or more, still more preferably 20 or more, and particularly preferably 30 or more.
In one embodiment of the present invention, when a mixed oil obtained by combining 2 or more types of base oils is used as the base oil (a), the kinematic viscosity and viscosity index of the mixed oil are preferably in the above-described ranges.
In the metal working oil according to one embodiment of the present invention, the content of the component (a) is preferably 20 to 99.9 mass%, more preferably 30 to 95 mass%, even more preferably 35 to 90 mass%, even more preferably 40 to 80 mass%, and particularly preferably 45 to 70 mass%, based on the total amount (100 mass%) of the metal working oil.
< component (B): phase change compound >, phase change material
The metal working oil of the present invention comprises a compound (B) which undergoes a phase transition from a liquid to a solid at a pressure rise in the range from 0.1MPa to 300 MPa.
The component (B) is liquid at normal pressure (at a pressure of 0.1 MPa), but changes phase to solid at a pressure rise up to 300 MPa. Therefore, it is considered that, when the pressure is high during plastic working, the component (B) contained in the metalworking oil is solidified on the surface of the metal material as the workpiece, and a firm oil film can be formed. As a result, it is considered that the metal working oil of the present invention can effectively exhibit excellent seizure resistance during plastic working.
In the present specification, whether or not the "phase change compound" is a component (B) can be confirmed using, for example, a high-pressure test apparatus for confirming phase change behavior as shown in fig. 1. The specific confirmation method can be determined based on the method described in the examples described below.
The component (B) used in the metal working oil according to one embodiment of the present invention may be any compound that undergoes a phase transition from a liquid to a solid at a pressure increase in the range of from 0.1MPa to 300MPa, and preferably contains 1 or more compounds selected from carboxylic acid esters, carboxylic acids, and alcohols that undergo the aforementioned phase transition.
In the metal working oil according to one embodiment of the present invention, the content of the compound that undergoes the phase transition selected from the group consisting of a carboxylate, a carboxylic acid, and an alcohol is preferably 60 to 100 mass%, more preferably 70 to 100 mass%, even more preferably 80 to 100 mass%, even more preferably 90 to 100 mass%, and particularly preferably 95 to 100 mass% relative to the total amount (100 mass%) of the component (B) contained in the metal working oil.
It should be noted that saturated compounds tend to be more prone to the aforementioned phase changes than unsaturated compounds.
Therefore, the carboxylic acid ester is preferably a saturated carboxylic acid ester, the carboxylic acid is a saturated carboxylic acid, and the alcohol is a saturated alcohol.
In addition, from the viewpoint of easiness of occurrence of the phase transition, the component (B) is preferably a compound containing an alkyl group having 10 to 40 carbon atoms, and more preferably a compound containing an alkyl group having 10 to 40 carbon atoms selected from the group consisting of saturated carboxylic acid esters, saturated carboxylic acids, and saturated alcohols.
That is, the component (B) used in the metal working oil according to one embodiment of the present invention further preferably contains a compound that undergoes the aforementioned phase transition represented by any one of the following general formulae (B-1) to (B-3).
[ chemical formula 2]
In the above formula, R 1 、R 2 And R is 3 Each independently is an alkyl group having 10 to 40 carbon atoms, R 4 Is an alkyl group having 1 to 10 carbon atoms.
Can be selected as R 1 、R 2 And R is 3 The alkyl group may be a linear alkyl group or a branched alkyl group, and is preferably a linear alkyl group from the viewpoint of easiness in generation of the phase transition.
As can be selected as R 1 、R 2 And R is 3 The number of carbon atoms of the alkyl group is preferably 9 to 39, more preferably 9 to 29, still more preferably 10 to 23, still more preferably 11 to 19, from the viewpoint of easiness of occurrence of the phase transition.
As a specific R 1 、R 2 And R is 3 Examples thereof include decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl (stearyl), eicosyl, and tetracosyl.
Wherein R is from the viewpoint of easiness of occurrence of the phase transition 1 、R 2 And R is 3 Each independently is preferably undecyl, dodecyl (lauryl), tridecyl, tetradecyl, hexadecyl, heptadecyl, or octadecyl (stearyl), more preferably heptadecyl.
In addition, can be selected as R 4 The alkyl group may be a linear alkyl group or a branched alkyl group, and is preferably a linear alkyl group from the viewpoint of easiness in generation of the phase transition.
From the viewpoint of easiness in generation of the aforementioned phase transitionConsider that can be chosen as R 4 The number of carbon atoms of the alkyl group is 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, still more preferably 1 to 2, and particularly preferably 1.
As a specific R 4 Examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl and the like.
Wherein R is from the viewpoint of easiness of occurrence of the phase transition 4 The methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, or n-octyl group is preferable, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, or n-hexyl group is more preferable, methyl group, ethyl group, n-propyl group, or n-butyl group is more preferable, methyl group or ethyl group is still more preferable, and methyl group is particularly preferable.
In the metal working oil according to one embodiment of the present invention, the content of the compound that undergoes the phase transition represented by any one of the above general formulae (B-1) to (B-3) is preferably 60 to 100 mass%, more preferably 70 to 100 mass%, even more preferably 80 to 100 mass%, even more preferably 90 to 100 mass%, and particularly preferably 95 to 100 mass%, relative to the total amount (100 mass%) of the component (B) contained in the metal working oil.
The melting point of the component (B) used in the metal working oil according to one embodiment of the present invention is preferably 10 to 70 ℃, more preferably 14 to 60 ℃, still more preferably 17 to 55 ℃, still more preferably 25 to 50 ℃ from the viewpoint of being easy to cause the phase transition.
In the present specification, the melting point is a value measured using a Differential Scanning Calorimeter (DSC), and specifically, a value measured by the following method.
[ method for measuring melting Point Using differential scanning calorimeter ]
After holding the sample at-10℃for 5 minutes under nitrogen atmosphere, the temperature was raised to 190℃at 10℃per minute and held at 190℃for 5 minutes. Then, the temperature was lowered to-10℃at 5℃per minute, and the mixture was kept at-10℃for 5 minutes. Then, a peak observed from a melting endothermic curve obtained by heating to 190℃at 10℃per minute was set as a melting point (Tm).
In the metal working oil according to one embodiment of the present invention, the content of the component (B) is preferably 0.1 to 50% by mass, more preferably 1.0 to 40% by mass, still more preferably 3.0 to 35% by mass, still more preferably 5.0 to 30% by mass, and particularly preferably 7.5 to 25% by mass, based on the total amount (100% by mass) of the metal working oil.
< component (C): sulfur extreme pressure agent
In the metal working oil according to one embodiment of the present invention, the sulfur-based extreme pressure agent (C) is preferably further contained from the viewpoint of forming the metal working oil to further improve the seizure resistance.
Examples of the sulfur-based extreme pressure agent (C) used in one embodiment of the present invention include sulfurized olefins, polysulfides, sulfurized esters, thiazoles, thiadiazoles, zinc dithiophosphates, molybdenum dithiocarbamates, and powdered sulfur.
These sulfur-based extreme pressure agents (C) may be used alone or in combination of 2 or more.
Among them, polysulfide is preferably contained as the sulfur-based extreme pressure agent (C).
The polysulfide used in one embodiment of the present invention has a sulfur chain length of preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, and further preferably 10 or less.
Specific polysulfides include, for example, dimethyl trisulfide, diethoxy disulfide, ethyl hydrosulfide, diacetyl disulfide, and di-tert-dodecyl trisulfide.
In the metal working oil according to one embodiment of the present invention, the content of the component (C) is preferably 7 to 50% by mass, more preferably 10 to 45% by mass, still more preferably 12 to 40% by mass, still more preferably 15 to 35% by mass, and particularly preferably 17 to 35% by mass, based on the total amount (100% by mass) of the metal working oil, from the viewpoint of forming the metal working oil to further improve the seizure resistance, and from the viewpoint of avoiding deterioration of the working environment due to generation of odor or the like.
In the metal working oil according to one embodiment of the present invention, the content of the component (C) in terms of sulfur atoms is preferably 6.5 to 30 mass%, more preferably 7.0 to 20 mass%, even more preferably 7.5 to 17 mass%, even more preferably 8.0 to 15 mass%, and particularly preferably 8.5 to 12 mass%, based on the total amount (100 mass%) of the metal working oil, from the above point of view.
In the present specification, the content of sulfur atoms means that according to JIS K2541-6: 2013.
< component (D): fatty acids and fatty acid esters >
In the metal working oil according to one embodiment of the present invention, from the viewpoint of forming the metal working oil having improved lubricity, it is preferable that the metal working oil contains 1 or more compounds (D) which are not the component (B) and are selected from fatty acids and fatty acid esters.
In the present specification, fatty acids and fatty acid esters which undergo a phase transition from liquid to solid at a pressure rise in the range of from 0.1MPa to 300MPa are contained in the above-described component (B). That is, the component (D) refers to fatty acids and fatty acid esters not belonging to the phase change compound.
In one embodiment of the present invention, examples of the fatty acid used as the component (D) include saturated aliphatic monocarboxylic acid, unsaturated aliphatic monocarboxylic acid, saturated aliphatic dicarboxylic acid, and unsaturated aliphatic dicarboxylic acid.
These fatty acids may be used alone or in combination of 2 or more.
The number of carbon atoms of these fatty acids is preferably 10 to 30, more preferably 12 to 24, and still more preferably 14 to 20.
In one embodiment of the present invention, the fatty acid as component (D) is used in combination with component (B), and preferably contains an unsaturated aliphatic monocarboxylic acid from the viewpoint of forming a metal working oil having more improved lubricity.
Examples of the unsaturated aliphatic monocarboxylic acid include undecylenic acid, dodecanoic acid, oleic acid, elaidic acid, erucic acid, nervonic acid, linoleic acid, γ -linolenic acid, arachidonic acid, α -linolenic acid, stearidonic acid, eicosapentaenoic acid, and docosahexaenoic acid, and oleic acid is preferable.
The unsaturated aliphatic monocarboxylic acid may be a hydroxy unsaturated fatty acid such as ricinoleic acid (12-hydroxyoctadeca-9-enoic acid).
In one embodiment of the present invention, as the fatty acid ester used as the component (D), esters of a polyhydric alcohol and a fatty acid are exemplified.
The number of ester bonds in the fatty acid ester is preferably 2 to 6.
The fatty acid ester may be a full ester, or may be a partial ester, and is preferably a full ester.
Examples of the polyhydric alcohol constituting the fatty acid ester include glycols such as ethylene glycol, 1, 3-propanediol, propylene glycol, 1, 4-butanediol, 1, 2-butanediol, 2-methyl-1, 3-propanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 2-ethyl-2-methyl-1, 3-propanediol, 1, 7-heptanediol, 2-methyl-2-propyl-1, 3-propanediol, 2-diethyl-1, 3-propanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 11-undecanediol, and 1, 12-dodecanediol; trimethylolethane, trimethylolpropane, trimethylolbutane, di (trimethylolpropane), pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, polyglycerol (2 to 3 polymers of glycerol), 1,3, 5-pentanetriol, sorbitol, sorbitan, sorbitol glycerol condensate, arabitol, xylitol, mannitol and the like; xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, and the like.
These polyols may be used alone or in combination of 2 or more.
On the other hand, the fatty acid constituting the fatty acid ester may be a saturated aliphatic monocarboxylic acid, an unsaturated aliphatic monocarboxylic acid, a saturated aliphatic dicarboxylic acid, an unsaturated aliphatic dicarboxylic acid, or the like, and is preferably 1 or more kinds selected from the group consisting of a saturated aliphatic monocarboxylic acid and an unsaturated aliphatic monocarboxylic acid.
Examples of the saturated aliphatic monocarboxylic acid include caproic acid, heptanoic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, isononanoic acid, capric acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, and lignoceric acid.
The unsaturated aliphatic monocarboxylic acid may be the same as the "fatty acid" as described above, which can be selected as the component (D).
In the metal working oil according to one embodiment of the present invention, the content of the component (D) is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, still more preferably 1.0 to 20% by mass, still more preferably 1.5 to 15% by mass, and particularly preferably 2.0 to 10% by mass, based on the total amount (100% by mass) of the metal working oil, from the viewpoint of forming the metal working oil having improved lubricity.
In the metal working oil according to one embodiment of the present invention, the content of the component (D) is preferably 1 to 200 parts by mass, more preferably 5 to 150 parts by mass, still more preferably 10 to 100 parts by mass, still more preferably 15 to 70 parts by mass, and particularly preferably 20 to 50 parts by mass, based on 100 parts by mass of the total amount of the component (B), from the same point of view as described above.
< ingredient (E): pour point depressant >, and method for preparing same
The metal working oil according to one embodiment of the present invention preferably contains the pour point depressant (E) from the viewpoint of being formed into a metal working oil having good low temperature fluidity.
In the metal working oil according to one embodiment of the present invention, even when the pour point depressant (E) is contained, the seizure resistance can be maintained satisfactorily.
Examples of the component (E) used in one embodiment of the present invention include an ethylene-vinyl acetate copolymer, a condensate of chlorinated paraffin and naphthalene, a condensate of chlorinated paraffin and phenol, polymethacrylate, and polyalkylstyrene.
These components (E) may be used alone or in combination of 2 or more.
Among them, the component (E) preferably contains 1 or more selected from the group consisting of ethylene-vinyl acetate copolymer and polymethacrylate.
The mass average molecular weight (Mw) of the component (E) is usually 50000 to 150000.
In the metal working oil according to one embodiment of the present invention, the content of the component (E) is preferably 0.001 to 7.0% by mass, more preferably 0.01 to 5.0% by mass, even more preferably 0.1 to 3.0% by mass, and even more preferably 0.3 to 2.0% by mass, based on the total amount (100% by mass) of the metal working oil, from the viewpoint of forming a metal working oil having good low-temperature fluidity and capable of maintaining satisfactory seizure resistance.
< other Components >)
The metal working oil according to one embodiment of the present invention may further contain components other than the above components (a) to (E) as needed within a range that does not impair the effects of the present invention.
Examples of such other components include antioxidants, extreme pressure agents other than component (C), oil improvers other than component (D), degreasing agents, and defoaming agents.
Examples of the antioxidant include amine antioxidants such as alkylated diphenylamine, phenylnaphthylamine and alkylated phenylnaphthylamine; phenol antioxidants such as 2, 6-di-t-butylphenol, 4' -methylenebis (2, 6-di-t-butylphenol), isooctyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, and n-octadecyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate.
In the metal working oil according to one embodiment of the present invention, the content of the antioxidant is preferably 0.01 to 10 mass%, more preferably 0.05 to 5 mass%, and even more preferably 0.1 to 2 mass%, based on the total amount (100 mass%) of the metal working oil.
Examples of the extreme pressure agents other than the component (C) include phosphate esters (tricresyl phosphate, trione phosphate, etc.), acid phosphate esters (monooleyl acid phosphate, dioleyl acid phosphate, etc.), acid phosphate amine salts (oleyl acid monooleyl phosphate, etc.), phosphite esters (dioleyl acid phosphite, tridecyl phosphite, trinonyl phenyl phosphite, etc.), fats and oils (tallow, lard, soybean oil, rapeseed oil rice bran oil, coconut oil, palm oil, etc.), and the like.
In the metal working oil according to one embodiment of the present invention, the content of the extreme pressure agent other than the component (C) is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and even more preferably 0.1 to 3% by mass, based on the total amount (100% by mass) of the metal working oil.
Examples of the oil-based modifier other than the component (D) include polymers of polymerized fatty acids such as dimer acid and hydrogenated dimer acid; aliphatic saturated or unsaturated monoalcohols such as lauryl alcohol and oleyl alcohol; aliphatic saturated or unsaturated monoamines such as stearylamine and oleylamine; aliphatic saturated or unsaturated monocarboxylic acid amides such as lauramide and oleamide.
In the metal working oil according to one embodiment of the present invention, the content of the oiliness improver other than the component (D) is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and even more preferably 0.1 to 3% by mass, based on the total amount (100% by mass) of the metal working oil.
Examples of the degreasing agent include alkenyl sulfosuccinic acid.
In the metal working oil according to one embodiment of the present invention, the degreasing agent is preferably contained in an amount of 0.001 to 5% by mass based on the total amount (100% by mass) of the metal working oil.
Examples of the defoaming agent include methyl silicone oil, fluorosilicone oil, and polyacrylate.
In the metal working oil according to one embodiment of the present invention, the content of the antifoaming agent is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total amount (100% by mass) of the metal working oil.
Method for producing metal working oil
The method for producing a metal working oil according to one embodiment of the present invention is not particularly limited, and a method having steps of mixing the components (a) to (B) and, if necessary, the components (C) to (E) with other components is preferable. The order of compounding the components may be appropriately set.
< various Properties of Metal working oil >)
In the metal working oil according to one embodiment of the present invention, the content of sulfur atoms is preferably 6.5 mass% or more, more preferably 7.0 mass% or more, still more preferably 7.5 mass% or more, still more preferably 8.0 mass% or more, particularly preferably 8.5 mass% or more, based on the total amount (100 mass%) of the metal working oil, and is preferably 30 mass% or less, more preferably 20 mass% or less, still more preferably 17 mass% or less, still more preferably 15 mass% or less, particularly preferably 12 mass% or less, from the viewpoint of avoiding deterioration of the working environment due to odor generation or the like.
The metal working oil according to one embodiment of the present invention is preferably used in the form of an oil solution, and is distinguished from a water-soluble metal working oil solution diluted with water.
Therefore, in the metal working oil according to one embodiment of the present invention, the smaller the water content, the more preferable from the viewpoints of stability and suppression of corrosion of the metal material to be processed, and specifically, the less 1.0 mass%, more preferably the less than 0.1 mass%, still more preferably the less than 0.01 mass%, and still more preferably the less than 0.001 mass%, based on the total amount (100 mass%) of the metal working oil.
The metal working oil according to one embodiment of the present invention is preferably 5% or more, more preferably 6% or more, and even more preferably 8% or more, as the maximum reduction of area in the ball passing test performed by the method of the example described later.
[ use of metalworking oil, metalworking method ]
The metal working oil according to one embodiment of the present invention is excellent in balance between low viscosity and seizure resistance. Therefore, the metal working oil is suitable for plastic working of a metal material.
The metal material to be processed using the metal working oil according to one embodiment of the present invention is not particularly limited, and examples thereof include iron alloys such as steel, stainless steel, alloy steel, and surface-treated steel, and nonferrous alloys such as aluminum alloys, copper, titanium alloys, nickel-based alloys, niobium alloys, tantalum alloys, molybdenum alloys, and tungsten alloys.
The metal working oil according to one embodiment of the present invention can be suitably used for the press working, drawing working, ironing, bending working, rolling working, cold forging working, and the like of the above-described metal material, and is particularly preferably used for the cold forging working of the metal material.
Accordingly, the present invention also provides the following.
The metal working oil according to one embodiment of the present invention is applied to the cold forging of a metal material.
[ 2 ] A metal working method of cold forging a metal material using the metal working oil according to one embodiment of the present invention.
The details of the metal material and the metal working oil described in the above [ 1 ] and [ 2 ] are as described above.
In the use of [ 1 ] and the metal working method of [ 2 ], the metal working oil is used in contact with a metal material as a work material.
Examples
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The method for measuring various physical properties and the method for confirming the presence or absence of a phase change from liquid to solid under a pressure increase are as follows.
(1) Kinematic viscosity, viscosity index
According to JIS K2283:2000, measurement and calculation were performed.
(2) Content of sulfur atoms
According to JIS K2541-6: 2013.
(3) Melting point
The measurement was performed by the following method using a Differential Scanning Calorimeter (DSC).
After holding the sample at-10℃for 5 minutes under nitrogen atmosphere, the temperature was raised to 190℃at 10℃per minute and held at 190℃for 5 minutes. Then, the temperature was lowered to-10℃at 5℃per minute, and the mixture was kept at-10℃for 5 minutes. Then, a peak observed from a melting endothermic curve obtained by heating to 190℃at 10℃per minute was set as a melting point (Tm).
(4) Flow point
The measurement was carried out in accordance with JIS K2269.
(5) Confirming the presence or absence of phase transition from liquid to solid under pressure increase
Using a high-pressure test apparatus for confirming the phase transition behavior as shown in fig. 1, the presence or absence of phase transition from liquid to solid of a target component under a pressure increase was confirmed.
The high-voltage test device 1 for confirming the phase transition behavior shown in fig. 1 has 2 observation windows 11 and 12 at positions facing each other in a straight line in the horizontal direction on the side surface of a cylindrical space 10 in which a compound to be measured is placed, an LED light source 20 is provided outside the space 10 of one observation window 11, and an optical microscope 30 is provided outside the cylindrical space 10 of the other observation window 12. The LED light source 20, the observation window 11, the observation window 12, and the optical microscope 30 are arranged in a straight line so as to be parallel in the horizontal direction. Further, a plunger 40 movable in the vertical direction is provided above the cylindrical space 10, and is designed so that the compound to be measured placed in the cylindrical space 10 can be pressurized by applying a load in the vertical direction.
With the high-voltage test device 1 for confirming phase change behavior, first, a compound to be measured is placed in a cylindrical space 10. Then, the plunger 40 was lowered at 30℃and the state of the compound was photographed in an animated image by observation with the optical microscope 30 when pressure was applied to the compound. Then, according to the animation, the pressure at which the compound starts to change from a liquid to a solid was set to "phase transition pressure (MPa)", and the presence or absence of phase transition was confirmed.
Examples 1 to 4 and comparative examples 1 to 6
Metal working oils were prepared with the kinds and compounding amounts shown in table 1, compounding ingredients (a) to (D) and pour point depressant, respectively.
Details of each component used in the preparation of these metal working oils are shown below.
[ component (A): base oil ]
Is (a-1): kinematic viscosity at 40 ℃ = 484.7mm 2 Naphthenic base oils with viscosity index=36.
A cycloalkane base oil (a-2): kinematic viscosity at 40 ℃ =27.77 mm 2 Naphthenic base oils with viscosity index=2.
Is (a-3): kinematic viscosity at 40 ℃ =45.40 mm 2 Naphthenic base oils with viscosity index=27.
[ component (B): phase change Compound
Methyl stearate: r in the above general formula (b-1) 1 =c17 alkyl, R 4 A compound of =methyl. A phase change compound which is liquid at 0.1MPa and which has a phase change from liquid to solid was confirmed at a phase change pressure=75mpa. Melting point = 37-41 ℃.
Butyl stearate: r in the above general formula (b-1) 1 =c17 alkyl, R 4 Compound of n-butyl. A phase change compound which is liquid at 0.1MPa and which has a phase change from liquid to solid was confirmed at a phase change pressure=160 MPa. Melting point=17 to 22 ℃.
[ component (C): sulfur extreme pressure agent
Sulfur powder
Polysulfide (b): polysulfides having an average sulfur chain length of 5.
[ component (D): fatty acids and fatty acid esters not belonging to the phase-change Compounds ]
Oleic acid: a component which is liquid at a pressure of 0.1 to 300MPa and does not cause phase change. Melting point = 13.4 ℃.
Dipentaerythritol esters: a component which is liquid at a pressure of 0.1 to 300MPa and has no confirmed phase transition. Flow point = 2.5 ℃.
And (c) triglycerides: : a component which is liquid at a pressure of 0.1 to 300MPa and has no confirmed phase transition. Flow point = 7.5 ℃.
[ component (E): pour point depressant
Poly (meth) acrylic acid ester
For the produced metal working oil, the kinematic viscosity, viscosity index, sulfur atom content at 40℃and 100℃were measured or calculated, and the ball passing test was performed by using the procedure shown below to evaluate the seizure resistance. These results are shown in Table 1.
[ ball passing test ]
Ball passing test was conducted according to the method described in Japanese society of Plastic engineering, volume 34 (393) 1178-1183 (1993)
First, the metal working oil prepared in examples and comparative examples was applied to the inside of a cylindrical test piece, and the state of sintering of the inner wall of the test piece was observed when a steel ball was inserted from one end into the inside of the cylindrical test piece. The inner diameter of the tube of the test piece was adjusted so that the reduction of area (the area of the test piece which was changed after the insertion, based on the initial area in the direction in which the steel ball was inserted) became 4%, 6% and 8%.
The ball passing test was performed using test pieces having a reduction of area of 4%, 6% and 8%, and the sintering condition in the cylinder after the test was observed and compared with a standard sintered sample to confirm the presence or absence of sintering. In the case of using each metal working oil, the test piece having the smallest area reduction rate among the test pieces having the occurrence of sintering was regarded as "the largest area reduction rate in the ball passing test" of the metal working oil. The larger the maximum reduction of area is, the more excellent the seizure resistance is.
The conditions under which the ball passed the test are as follows.
Test piece (c): outer diameter=30.00 mm, inner diameter=15.00 mm (reduction of area 4%), 14.50mm (reduction of area 6%), 15.00mm (reduction of area 8%), material=s10c
And (3) steel ball: outer diameter=15.88 mm (reduction of area 4% or 6%), 16.67mm (reduction of area 8% or 10%), material=suj2
The speed of insertion of the steel ball into the mouth of the test piece=200 mm/s.
[ Table 1 ]
From table 1, the following results were obtained, that is, the metal working oils prepared in examples 1 to 4 were low in viscosity, and the maximum reduction of area in the ball passing test was high, and 6% or more, and the sintering resistance was excellent. In addition, it is seen that the metal working oils of examples 3 and 4 are compounded with pour point depressants, but maintain good seizure resistance even when compared with examples 1 and 2.
On the other hand, the metal working oils prepared in comparative examples 1 to 6 gave poor results in at least one of low viscosity and seizure resistance.
Description of symbols
1. High-voltage test device for confirming phase change behavior
10. Cylindrical space
11. 12 observation window
20 LED light source
30. Optical microscope
40. Plunger piston
Claims (37)
1. A metal working oil comprising: a base oil (A) having a kinematic viscosity at 40 ℃ of greater than 200mm, and a compound (B) 2 /s and 1000mm 2 At most/s, the compound (B) is liquid at a pressure of 0.1MPa, and undergoes a phase transition from liquid to solid as the pressure increases in the range of 0.1MPa to 300MPa, and the kinematic viscosity of the metal working oil at 40 ℃ is 40mm 2 Above/s and 100mm 2 In the range of not more than/s,
the total content of the components (A) and (B) is 55 to 100% by mass based on the total amount of the metal working oil,
the content of the component (A) is 40 mass% or more and less than 70 mass% based on the total amount of the metal working oil,
the content of the component (B) is 15 to 35% by mass based on the total amount of the metal working oil.
2. The metal working oil of claim 1, wherein the kinematic viscosity of the metal working oil at 40 ℃ is 40mm 2 Above/s and 90mm 2 And/s or less.
3. The metal working oil of claim 1, wherein the kinematic viscosity of the metal working oil at 40 ℃ is 40mm 2 Above/s and 80mm 2 And/s or less.
4. The metal working oil according to claim 1, wherein the total content of the components (a) and (B) is 60 to 100 mass% based on the total amount of the metal working oil.
5. The metal working oil according to claim 1, wherein the kinematic viscosity of component (a) at 40 ℃ is greater than 300mm 2 /s and 1000mm 2 And/s or less.
6. The metal working oil according to claim 1, wherein the kinematic viscosity of component (a) at 40 ℃ is 350mm 2 Above/s and 1000mm 2 And/s or less.
7. The metal working oil according to claim 1, wherein the kinematic viscosity of component (a) at 40 ℃ is 400mm 2 Above/s and 1000mm 2 And/s or less.
8. The metal working oil according to claim 1, wherein the content of the component (a) is 40 mass% or more and 54.6 mass% or less based on the total amount of the metal working oil.
9. The metal working oil according to claim 1, wherein component (B) contains 1 or more compounds selected from the group consisting of carboxylic esters, carboxylic acids, and alcohols, which undergo the phase transition.
10. The metal working oil according to claim 1, wherein component (B) is a carboxylate.
11. The metal working oil according to claim 1, wherein component (B) is a carboxylic acid.
12. The metal working oil according to claim 1, wherein component (B) is an alcohol.
13. The metal working oil according to claim 9, wherein the carboxylic acid ester is a saturated carboxylic acid ester,
the carboxylic acid is a saturated carboxylic acid,
the alcohol is a saturated alcohol.
14. The metal working oil according to claim 1, wherein the component (B) contains a compound that undergoes the phase transition represented by any one of the following general formulae (B-1) to (B-3),
In the above formula, R 1 、R 2 And R is 3 Each independently is an alkyl group having 10 to 40 carbon atoms, R 4 Is an alkyl group having 1 to 10 carbon atoms.
15. The metal working oil of claim 14, wherein,
R 1 、R 2 and R is 3 Each independently is undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, heptadecyl, or octadecyl,
R 4 is methyl, ethyl, n-propyl or n-butyl.
16. The metal working oil according to claim 14 or 15, wherein component (B) contains a compound that undergoes the phase transition represented by the above general formula (B-1).
17. The metal working oil according to claim 14 or 15, wherein component (B) contains a compound that undergoes the phase transition represented by the above general formula (B-2).
18. The metal working oil according to claim 14 or 15, wherein component (B) contains a compound that undergoes the phase transition represented by the above general formula (B-3).
19. The metal working oil according to claim 1, wherein the melting point of the component (B) is 10 to 70 ℃.
20. The metal working oil according to claim 1, wherein the content of the component (B) is 15 to 30 mass% based on the total amount of the metal working oil.
21. The metal working oil according to claim 1, further comprising a sulfur-based extreme pressure agent (C).
22. The metal working oil of claim 21, wherein component (C) comprises polysulfide.
23. The metal working oil according to claim 21, wherein a content of the component (C) in terms of sulfur atoms is 6.5 mass% or more based on the total amount of the metal working oil.
24. The metal working oil according to claim 21, wherein the content of the component (C) is 7 to 50 mass% based on the total amount of the metal working oil.
25. The metal working oil according to claim 1, further comprising 1 or more compounds (D) which are not component (B) and are selected from fatty acids and fatty acid esters.
26. The metal working oil according to claim 25, wherein the content of the component (D) is 0.1 to 30 mass% based on the total amount of the metal working oil.
27. The metal working oil according to claim 25 or 26, wherein the content ratio of the component (D) is 1 to 200 parts by mass based on 100 parts by mass of the total amount of the component (B).
28. The metalworking oil of claim 1, further comprising a pour point depressant (E).
29. The metal working oil according to claim 28, wherein the content of the component (E) is 0.001 to 7.0 mass% based on the total amount of the metal working oil.
30. The metal working oil according to claim 21, wherein the content of grease as an extreme pressure agent other than the component (C) is 3 mass% or less based on the total amount of the metal working oil.
31. The metal working oil according to claim 21, wherein the oil or fat is not contained as an extreme pressure agent other than the component (C).
32. The metal working oil according to claim 1, wherein the content of water is less than 1.0 mass% based on the total amount of the metal working oil.
33. The metal working oil according to claim 1, further comprising at least 1 of a compound (D) selected from the group consisting of a sulfur-based extreme pressure agent (C), 1 or more of fatty acids and fatty acid esters not belonging to the component (B), and a pour point depressant (E),
the total content of the components (A), (B), (C), (D) and (E) is 60 to 100% by mass based on the total amount of the metal working oil.
34. The metal working oil according to claim 1, further comprising at least 1 of a compound (D) selected from the group consisting of a sulfur-based extreme pressure agent (C), 1 or more of fatty acids and fatty acid esters not belonging to the component (B), and a pour point depressant (E),
the total content of the components (A), (B), (C), (D) and (E) is 90 to 100% by mass based on the total amount of the metal working oil.
35. The metal working oil according to claim 1, which is used for cold forging processing of a metal material.
36. Use of a metalworking oil according to any of claims 1 to 35 in cold forging of metallic materials.
37. A metal working method, wherein the metal material is cold-forged by using the metal working oil according to any one of claims 1 to 35.
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| JP2001354984A (en) * | 2000-06-14 | 2001-12-25 | Asahi Denka Kogyo Kk | Metal processing lubricant |
| JP4392154B2 (en) * | 2001-12-10 | 2009-12-24 | 三洋化成工業株式会社 | Metal processing oil |
| US7045055B2 (en) * | 2004-04-29 | 2006-05-16 | Chevron U.S.A. Inc. | Method of operating a wormgear drive at high energy efficiency |
| JP2015189929A (en) * | 2014-03-28 | 2015-11-02 | 出光興産株式会社 | Lubricating oil composition for metal processing |
| JP6957145B2 (en) * | 2016-11-18 | 2021-11-02 | Ｅｎｅｏｓ株式会社 | Metalworking oil composition |
| JP6807288B2 (en) * | 2017-08-28 | 2021-01-06 | Ｅｎｅｏｓ株式会社 | Lubricating oil composition for manual transmission |
-
2020
- 2020-06-03 CN CN202080040605.7A patent/CN113874479B/en active Active
- 2020-06-03 WO PCT/JP2020/021990 patent/WO2020246514A1/en active Application Filing
- 2020-06-03 JP JP2021524882A patent/JP7519351B2/en active Active
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| JP2002038181A (en) * | 2000-07-28 | 2002-02-06 | Idemitsu Kosan Co Ltd | Lubricating oil composition |
| JP2008013682A (en) * | 2006-07-06 | 2008-01-24 | Nippon Oil Corp | Metal working fluid composition |
| JP2010195912A (en) * | 2009-02-25 | 2010-09-09 | Sumitomo Light Metal Ind Ltd | Lubricant for press-working stainless alloy plate or steel plate, and method for press-working stainless alloy plate or steel plate therewith |
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| Publication number | Publication date |
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| CN113874479A (en) | 2021-12-31 |
| JPWO2020246514A1 (en) | 2020-12-10 |
| WO2020246514A1 (en) | 2020-12-10 |
| JP7519351B2 (en) | 2024-07-19 |
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