WO2020175595A1 - 金属加工油組成物 - Google Patents

金属加工油組成物 Download PDF

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Publication number
WO2020175595A1
WO2020175595A1 PCT/JP2020/007892 JP2020007892W WO2020175595A1 WO 2020175595 A1 WO2020175595 A1 WO 2020175595A1 JP 2020007892 W JP2020007892 W JP 2020007892W WO 2020175595 A1 WO2020175595 A1 WO 2020175595A1
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Prior art keywords
carbon atoms
group
flux
composition
metal
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PCT/JP2020/007892
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English (en)
French (fr)
Japanese (ja)
Inventor
知晃 岡野
順英 谷野
杉井　秀夫
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出光興産株式会社
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Application filed by 出光興産株式会社 filed Critical 出光興産株式会社
Priority to CN202080016999.2A priority Critical patent/CN113438999B/zh
Priority to JP2021502351A priority patent/JP7431213B2/ja
Publication of WO2020175595A1 publication Critical patent/WO2020175595A1/ja

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Classifications

    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups 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
    • 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
    • C10M141/06—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 nitrogen-containing compound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • 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
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • 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
    • 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
    • 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
    • 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
    • C10M129/08—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least 2 hydroxy groups

Definitions

  • the present invention relates to a metalworking oil composition, a metalworking method using the same, a brazing method, a method for producing a metal article, and a flux adhesion improving agent used for the same.
  • Heat exchangers and mechanical parts have a large number of parts.
  • a heat exchanger typically has a heat transfer tube through which a refrigerant flows, and fins for exchanging heat with the air outside the heat transfer tube.
  • the heat transfer tubes and fins are usually made of a metal material having a high thermal conductivity and a low specific gravity, such as an aluminum material (including aluminum and an aluminum alloy).
  • heat exchangers are manufactured by manufacturing metal parts of metal materials using metal-added oil (cutting, rolling, drawing, pressing, forging, etc.) to form components such as heat transfer tubes and fins, and then manufacturing. This is done by assembling the components and then brazing and joining the assembled parts.
  • Examples of the metal-working oil used when processing a metal material such as an aluminum material include a metal-working oil composition as described in Patent Document 1.
  • Patent Document 1 JP-A 7-2 5 8 6 7 2
  • the present invention includes the following embodiments.
  • 8 1 represents a hydrocarbon group of 6-3 0 carbon atoms
  • 8 1 and 8 2 each independently represent a single bond or a polyoxyalkylene group, ⁇ 0 2020/175595 3 (: 170? 2020 /007892
  • Eighty three represents a polyoxyalkylene group
  • Is an alkyl group or an alkenyl group having 6 to 30 carbon atoms is a hydrogen atom
  • And 8 1 and 8 2 are each independently a single bond or a polyoxyalkylene group
  • Eight 3 is a polyoxyalkylene group
  • 1- is an alkylene group having 1 to 8 carbon atoms
  • [8] is 0, The composition according to any one of [1] to [7].
  • the amine compound at least one kind of base oil selected from mineral oil and synthetic oil, and, if necessary, at least one friction selected from alcohol having 6 to 30 carbon atoms and alkyl glycerol.
  • Brazing is performed by bringing a flux into contact with the surface of a metal article to which the composition according to any one of [1] to [8] or the composition obtained by the method according to [9] is attached. Brazing method, including that.
  • a method for producing a metal article which comprises the following step (1).
  • Step (1) A metal material is processed using the composition according to any one of [1] to [8] or the composition obtained by the method according to [9]. Processing process.
  • Step (2) After the step (1), with the composition remaining on a part of the surface of the metal material, a flux is brought into contact with the surface of the metal material to perform brazing treatment. Attaching process.
  • 2 to 4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms
  • 8 1 and 8 2 each independently represent a single bond or a polyoxyalkylene group. ⁇ 0 2020/175595 5 (: 170? 2020 /007892
  • Eighty three represents a polyoxyalkylene group
  • the present invention has one or more of the following effects.
  • a metalworking oil composition having good flux adhesion is provided.
  • the metalworking oil composition of the present invention is suitably used, for example, as a metalworking oil composition in metalworking of metal articles such as heat exchanger parts.
  • the metalworking oil composition of the present invention can impart good flux adhesion to metalworked metal parts, it is possible to omit or simplify the cleaning treatment of metal parts before applying flux. You can In a preferred embodiment, the metal component obtained by metalworking using the metalworking oil composition of the present invention can be directly fluxed and brazed.
  • a metalworking oil composition capable of satisfying both flux adhesion and metalworkability (low friction).
  • the “hydrocarbon group” is a straight chain, cyclic group or cyclic group having a specified number of carbon atoms. ⁇ 0 2020/175 595 6 ⁇ (: 170? 2020 /007892
  • a group obtained by removing one or more hydrogen atoms from a branched or saturated hydrocarbon include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkylene group and an alkenylene group.
  • alkyl group means a linear or branched monovalent saturated aliphatic hydrocarbon group having the specified number of carbon atoms.
  • cycloalkyl group means a cyclic monovalent saturated aliphatic hydrocarbon group having the specified number of carbon atoms.
  • Alkylene group means a linear, cyclic, or branched divalent saturated aliphatic hydrocarbon group having the specified number of carbon atoms.
  • Alkenyl group means a linear or branched monovalent hydrocarbon group having the specified number of carbon atoms and at least one carbon-carbon double bond.
  • Alkenylene group means a linear or branched divalent hydrocarbon group having the specified number of carbon atoms and at least one carbon-carbon double bond. Examples of “alkenyl” and “alkenylene” include, but are not limited to, monene, gen, triene, tetraene and the like.
  • aryl group means an aromatic hydrocarbon cyclic group.
  • alkylaryl group means an aryl having one or more alkyls bonded.
  • Arylalkyl group means an alkyl bound to an aryl ring.
  • Polyoxyalkylene group means a divalent group composed of a polymerized chain of alkylene oxide, and specifically, “((3 ⁇ 4 ⁇ ) 111 _” ([3 ⁇ 4 appears. Each independently represents an alkylene group, Is an integer of 1 or more).
  • Form _ of the present invention relates to metalworking oil compositions.
  • the metalworking oil composition comprises ⁇ 0 2020/175 595 7 ⁇ (: 170? 2020 /007892
  • the metalworking oil composition may optionally contain another compound produced by modifying or reacting at least a part of the blended components, and such a form also has the metalworking oil composition of the present invention. It is intended to be included in the composition.
  • the metalworking oil composition contains an amine compound represented by the following general formula ( ⁇ ) (hereinafter, also simply referred to as "amine compound”).
  • Oil stain refers to stains or stains (stains) that remain on the part where the metalworking oil composition adheres to the part after it is exposed to high temperature and volatilizes the metalworking oil.
  • excellent is meant less such oil stains remain on the metal surface.
  • the amine compound 1 1 1__ is more preferably 8 or less, and further preferably 7 or less.
  • the lower limit of 1 to 11 min of the amine compound is not particularly limited, but from the viewpoint of the adhesion of the flux and the solubility in the base oil, 1 or more is preferable, 2 or more is more preferable, and 3 or more is further preferable.
  • the amine compound 1 to 1 !_ is, for example, preferably 1 to 10 in terms of the adhesion of the flux and the solubility in the base oil,
  • 1 to 1 1__ means 1 6 — 1 1 ⁇ 11 ⁇ ⁇ ⁇ It is an abbreviation for (hydrophilic/lipophilic balance) and is an index showing the balance between the hydrophilic group and the lipophilic group in the molecule of the surfactant. 1 to 1 1__ is calculated by the Griffin method.
  • hydrocarbon groups 23, 24, 25, 26, 27, 28, 29, or 30
  • the number of carbon atoms of the hydrocarbon group is preferably 8 to 24, more preferably 10 to 22 and further preferably 12 to 20.
  • the hydrocarbon group is, for example, an alkyl group such as octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, bentadecyl, hexadecyl, heptadecyl, octadecyl (stearyl), nonadecyl, eicosyl; octenyl, nonenyl.
  • alkyl group such as octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, bentadecyl, hexadecyl, heptadecyl, octadecyl (stearyl), nonadecyl, eicosyl; octenyl, nonenyl.
  • the hydrocarbon group may be of synthetic or natural origin.
  • the hydrocarbon group may be a naturally occurring mixed alkyl group or alkenyl group such as coconut alkyl, tallow alkyl, soybean alkyl and the like.
  • the naturally occurring hydrocarbon group (such as mixed alkyl or mixed alkenyl) includes a plurality of kinds of hydrocarbon groups having different carbon numbers.
  • coconut alkyl usually has a saturated or unsaturated straight-chain aliphatic hydrocarbon group having 12 to 16 carbon atoms as a main component
  • tallow alkyl usually has 16 to 18 carbon atoms.
  • the main component is the saturated or unsaturated linear aliphatic hydrocarbon group.
  • the main component of the naturally-occurring hydrocarbon group has a predetermined carbon number range (having 6 to 30 carbon atoms, more preferably 8 to 24, further preferably 10 to 22 and particularly preferably 12 to 20) Can be used as
  • [0017] is preferably 6 to 30 carbon atoms (more preferably 8 to 24 carbon atoms, further preferably 10 to 22 carbon atoms, and particularly preferably 12 to 20 carbon atoms).
  • the hydrocarbon group having 1 to 3 carbon atoms include methyl, ethyl, propyl and the like. From the point of flux adhesion, Is preferably a hydrogen atom.
  • the amine compound is a monoamine.
  • Formula ( ⁇ ) represents eight 1 and eight 2 each independently represent a single bond or Poriokishia alkylene group.
  • eight 3 represents a polyoxyalkylene group.
  • Eight polyoxyalkylene group in 1-8 3 is not particularly limited, and 1 to 1 1_ Snake is included in the above range is preferred. Examples thereof include polyoxyethylene, polyoxypropylene, polyoxyisopropylene, polyoxybutylene, polyoxy 1,2-butylene, polyoxy 2,3-butylene, polyoxypentylene and polyoxyoctylene.
  • Eight 1, eight 2, and eight 3 (eight 1-8 3) polyoxyalkylene group in the view of solubility and lubricity of the base oil, preferably, 1 to 6 carbon atoms (more preferred properly carbon A divalent group composed of a polymer chain of alkylene oxide having 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and more preferably a polymer chain of alkylene oxide having 2 to 3 carbon atoms. It is a constituent group (that is, polyoxyethylene, polyoxypropylene), and more preferably polyoxyethylene.
  • the 8 1 to 8 3 polyoxyalkylene groups may be the same or different. Further, the 8 1 to 8 3 polyoxyalkylene groups may be those in which alkylene oxides having different carbon numbers are bonded randomly or in blocks. For example, the polyoxyalkylene group of 8 1 to 8 3 is ethylene oxide. ⁇ 0 2020/175 595 1 1 ⁇ (: 170? 2020 /007892
  • It may be a compound in which a do (N) group and a propylene oxide (O) group are bonded randomly or in a block.
  • each of 8 1 to 8 3 is a polyoxyalkylene group. In such a case, it has excellent flux adhesion
  • both 8 2 and 8 3 are polyoxyalkylene groups. In such a case, the flux adhesion is superior.
  • the amine compound is represented by the above general formula ().
  • 8 1 is an alkyl group or an alkenyl group having 6 to 30 carbon atoms, is a hydrogen atom,
  • And 8 1 and 8 2 are each independently a single bond or a polyoxyalkylene group
  • Eight 3 is a polyoxyalkylene group
  • 1- is an alkylene group having 1 to 8 carbon atoms
  • the amine compound is represented by the following general formula ( ⁇ ).
  • 01 1 and 01 2 each independently represent the average number of added moles of ethylene oxide of 0 or more.
  • the upper limit of 3 is not particularly limited, but may independently be, for example, 15 or less, 10 or less, 8 or less, or 7 or less.
  • ⁇ 1 1 to 3 are preferably set so that 1 to 11 _min of the amine compound falls within a predetermined range.
  • the content of the amine compound is, based on the total amount of the composition (100% by mass), preferably from 0.1% by mass or more, more preferably from 0.3% by mass or more, from the viewpoint of flux adhesion. It is preferably 0.5 mass% or more. From the viewpoint of metal workability (low friction), it is preferably 10% by mass or less, more preferably 7% by mass or less, further preferably 5% by mass or less, and particularly preferably 3% by mass or less. Further, the content of the amine compound is preferably from 0.01 to 10% by mass, more preferably from 0.01 to 10% by mass, and further preferably from 0.3 to 5% by mass from the viewpoint of flux adhesion. From the viewpoint of metal workability (low friction), it is more preferably 0.3 to 3 mass %, and from the viewpoint of particularly excellent flux adhesion and metal workability (low friction), 0.5 to 3% by mass. Mass% is more preferred.
  • the metalworking oil composition preferably comprises a base oil.
  • the base oil is not particularly limited, and any one can be appropriately selected and used from mineral oils and synthetic oils that have been conventionally used as base oils for metalworking oils. It is also a mixed oil that is a combination of two or more selected from mineral oils and synthetic oils. ⁇ 02020/175595 13 ⁇ (: 170? 2020 /007892
  • Examples of the mineral oil include atmospheric residual oils obtained by atmospheric distillation of crude oils such as paraffinic crude oil, intermediate base crude oil, and naphthenic crude oil; and these atmospheric residual oils obtained by vacuum distillation.
  • Distillate oil mineral oil obtained by subjecting the distillate oil to one or more purification treatments such as solvent degassing, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing and hydrorefining
  • natural gas Mineral oil GT L
  • GT L waxes obtained by isomerizing waxes (GT L waxes (G as To Liquids WAX)) produced by the Fischer-Tropsch method and the like.
  • mineral oils may be used alone or in combination of two or more.
  • Olefin homopolymer or olefin copolymer for example, ethylene _ a _ olefin copolymer, etc.
  • Olefin-based synthetic oil paraffin-based synthetic oil such as normal paraffin and isoparaffin
  • polyol ester dibasic acid ester (eg ditridecyl glutarate etc.), tribasic acid ester (eg trimellitic acid 2-ethylhexyl), phosphorus
  • ester synthetic oils such as acid esters
  • ether synthetic oils such as polyphenyl ether; polyalkylene glycols; alkylbenzenes; alkylnaphthalenes.
  • These synthetic oils may be used alone or in combination of two or more kinds.
  • the base oil is preferably a paraffin synthetic oil, and more preferably isoparaffin.
  • the kinematic viscosity of the base oil at 40° C. is preferably 0.5 to 10 mm 2 / s , more preferably 0.75 to 5 mm 2 / s , and further preferably 1 to 3 mm 2 / s. Is.
  • the kinematic viscosity at 40 ° is “1 3 [ ⁇ 2 2 8 3
  • the base oil used in one embodiment of the present invention has a high volatility, and thus "3 [ ⁇ 2 2 8 3 :2 0 Base oils whose kinematic viscosity and viscosity index at 100° are difficult to calculate by the measuring method based on 0.00 are preferable.
  • the content of the base oil is not particularly limited, but based on the total amount of the composition (100% by mass), it is preferably 50.0 to 99.99% by mass in terms of annealing and drying properties, More preferably, it is from 7.0 to 99.9 mass%, and even more preferably from 900 to 99 mass%.
  • the metalworking oil composition may include at least one friction modifier selected from ( ⁇ 31) alcohol having 6 to 30 carbon atoms and (02) alkylglycerol because of its excellent annealing property.
  • the friction modifier may be used in combination of two or more selected from ( ⁇ 31) alcohol having 6 to 30 carbon atoms and (02) alkyl glycerol.
  • the metalworking oil composition contains both ( ⁇ 1) alcohol having 6 to 30 carbon atoms and ( ⁇ 2) alkylglycerol because it is excellent in metalworkability (low friction).
  • the mass ratio thereof is preferably 10: 90 to 90: 10
  • the alcohol having 6 to 30 carbon atoms a monovalent aliphatic saturated alcohol and a monovalent aliphatic unsaturated alcohol are preferable, and they may be linear or branched.
  • the number of carbon atoms of the alcohol is more preferably 8 to 26, further preferably 10 to 20 and particularly preferably 12 to 18 ⁇ 0 2020/175 595 15 ⁇ (: 170? 2020 /007892
  • Examples of —valent saturated aliphatic alcohols include octanol (capryl alcohol), 2-ethylhexanol, decanol, dodecanol (lauryl alcohol), tetradecanol (myristyl alcohol), hexadecanol (cetyl alcohol), octane.
  • Decanol stearyl alcohol, isostearyl alcohol, behenyl alcohol and the like can be mentioned.
  • Examples of the monovalent aliphatic unsaturated alcohol include octenol, decenool, dodecenol, tetradecenol, hexadecenol, octadecenol (oleyl alcohol), and linoleyl alcohol.
  • oleyl alcohol is preferable in terms of solubility in base oil and lubricity.
  • the alcohol having 6 to 30 carbon atoms may be used alone or in combination of two or more.
  • Alkyl glycerol is a mono- or di-ether compound of alcohol and glycerin (alkyl glyceryl ether).
  • alkyl glycerol a mono- or diether compound of an alcohol having 6 to 30 carbon atoms and glycerin is preferable, and a monoether compound of an alcohol having 6 to 30 carbon atoms and glycerin is more preferable.
  • the number of carbon atoms of the alcohol having 6 to 30 carbon atoms which constitutes the alkyl glycerol is more preferably 8 to 26, further preferably 10 to 20 and particularly preferably 1 in terms of lubricity and flux adhesion. It is 2 to 18.
  • specific examples of the alcohol having 6 to 30 carbon atoms which constitutes the alkyl glycerol those exemplified as the above-mentioned ((31) C 6 to 30 alcohols can be preferably used.
  • alkyl glycerol are table below _ general formula (III).
  • alkyl glycerol examples include glyceryl monostearyl ether (batyl alcohol), glyceryl monocetyl ether (chimyl alcohol)
  • Monooleyl glyceryl ether (ceracyl alcohol), monobehenyl glyceryl ether, mono-2-ethylhexyl glyceryl ether, monoisostearyl glyceryl ether, monocapryl glyceryl ether, mono isodecyl glyceryl ether and the like.
  • monostearyl glyceryl ether (batyl alcohol), glyceryl monocetyl ether (chimyl alcohol), and monooleyl glyceryl ether (ceracyl alcohol) are preferable from the viewpoint of lubricity and flux adhesion, and monooleyl glyceryl ether (ceracyl alcohol) is preferable. Kill alcohol) is more preferable.
  • the alkyl glycerol may be used alone or in combination of two or more.
  • the total content of the (0 1) alcohol having 6 to 30 carbon atoms and the ( ⁇ 2) alkyl glycerol is not particularly limited, but the lubricity and the total content of the composition (100 mass%) are used as the basis. From the viewpoint of flux adhesion, it is preferably 0.001 to 30% by mass, more preferably 0.001 to 20% by mass, and further preferably 0.1 to 10% by mass.
  • the metalworking oil composition may contain (0 3) other friction modifiers in addition to the above-mentioned ( ⁇ 1) alcohol having 6 to 30 carbon atoms and (02) alkylglycerol.
  • any one of the known friction modifiers conventionally used as the friction modifier for metal working oils can be appropriately selected and used.
  • the organic dithiophosphate salt is preferably zinc dialkyldithiophosphate, and more preferably secondary zinc zinc dialkyldithiophosphate.
  • the content of the organic dithiophosphate is based on the total amount of the composition (100 mass %), and is preferably 0.05 to 20 mass %.
  • molybdenum-based friction modifiers examples include molybdenum dithiocarbamate (IV!00), molybdenum dithiophosphate (IV!00), and amine salts of molybdate. These may be used alone or in combination of two or more.
  • the content of molybdenum atoms derived from the molybdenum-based friction modifier is, based on the total amount of the composition, preferably 30 to 400 mass.
  • ashless friction modifiers include ester friction modifiers such as partial ester compounds obtained by the reaction of fatty acids with aliphatic polyhydric alcohols.
  • the fatty acid is preferably a fatty acid having a linear or branched hydrocarbon group having 6 to 30 carbon atoms, and the hydrocarbon group has more preferably 8 to 24 carbon atoms, and further preferably 10 to 2 carbon atoms. It is 0.
  • the aliphatic polyhydric alcohol is a dihydric or higher and hexavalent or lower alcohol, and examples thereof include ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, and sorbitol. These may be used alone or in combination of two or more.
  • the content of the ashless friction modifier is not particularly limited, it is preferably 0.011 to 8.0% by mass based on the total amount of the composition (100% by mass).
  • the content of the friction modifier is not particularly limited, but based on the total amount of the composition (100% by mass), preferably 0.001 to 30% by mass, more preferably 0.01 to 2%. O mass%, more preferably 0.1 to 10 mass%.
  • the total content of component (8) (amine compound), component (M) (base oil), and component ( ⁇ (friction modifier)) in the metalworking oil composition is The total amount of the composition (100% by mass) is preferably 90 to 99.999% by mass, and more preferably 95 to 99.999% by mass. It is particularly preferable that the content is 99 to 99.9% by mass. ⁇ 0 2020/175 595 18 ⁇ (: 170? 2020 /007892
  • the metalworking oil composition may contain other additives as long as the effects of the present invention are not impaired.
  • Such other additives include, for example, antioxidants, oiliness agents, extreme pressure agents, antirust agents, metal deactivators, defoamers, viscosity index improvers, antistatic agents, wettability improvers. Etc. These additives may be used alone or in combination of two or more kinds.
  • any one of known antioxidants conventionally used as an antioxidant for metalworking oils can be appropriately selected and used.
  • amine-based antioxidants can be used.
  • Examples of the amine-based antioxidant include diphenylamine and C3 to C2.
  • Diphenylamine-based antioxidants such as alkylated diphenylamine having 0 alkyl group; Naphthylamine, phenyl Naphthylamine, carbon Naphthylamine-based antioxidants such as naphthylamine; and the like.
  • phenolic antioxidants examples include 2, 6-Gie 16 "1:-Phtylphenol, 2, 6-Gee” “_ _Putyl 4-Methylphenol (0M), 2, 6-Gee ⁇ "1: _Putyl 4-ethylphenol, isooctyl 3-(3, 5 -di ⁇ "1: -Putyl 4-hydroxyphenyl” Probionate, octadecyl 3-(3, 5 -Di I 6 "1: -Putyl 4-hydroxyphenyl) Propionate and other monophenol antioxidants; 4, 4, -methylenebis (2, 6-di I 6 "1: _Putylphenol", 2, 2, -methylenebis (4-ethyl-6) — ⁇ “1: _Putylphenol” and other diphenol-based antioxidants; Hindered phenol-based antioxidants and the like.
  • sulfur-based antioxidants examples include dilauryl 3,3'-thiodipropionate and the like. ⁇ 0 2020/175 595 19 ⁇ (: 170? 2020 /007892
  • molybdenum-based antioxidants examples include molybdenum trioxide and/or molybdenum amine complex obtained by reacting molybdic acid with an amine compound.
  • Examples of the phosphorus-based antioxidant include phosphite and the like.
  • the content of the antioxidant is not particularly limited, but based on the total amount of the composition (100 mass%), preferably 0.001 to 1 mass%, more preferably 0.05 to 0 mass%. 0.8% by mass, more preferably 0.01 to 0.5% by mass.
  • oiliness agents include aliphatic saturated and unsaturated monocarboxylic acids such as stearic acid and oleic acid; polymerized fatty acids such as dimer acid and hydrogenated dimer acid; ricinoleic acid, 12-hydroxystearic acid and the like.
  • Hydroxy fatty acids such as lauryl alcohol and oleyl alcohol; aliphatic saturated and unsaturated monoamines such as stearylamine and oleylamine; aliphatic acids such as lauric acid amide and oleic acid amide Saturated and unsaturated monocarboxylic acid amides; partial esters of polyhydric alcohols such as glycerin and sorbitol with aliphatic saturated or unsaturated monocarboxylic acids; and the like. These may be used alone or in combination of two or more.
  • the content of the oiliness agent is not particularly limited, but is preferably 0.01 to 10 mass% based on the total amount of the composition (100 mass %), and more preferably 0.01. It is about 5.0% by mass, more preferably about 0.1% to 3.0% by mass.
  • Examples of the extreme pressure agent include sulfur-based compounds such as sulfurized olefins, dialkyl polysulfides, diarylalkyl polysulfides and diaryl polysulfides, phosphorus-based compounds other than phosphites (for example, phosphate esters). (For example, tricresyl phosphate (c)), thiophosphoric acid ester, phosphoric acid ester amine salt, phosphorous acid ester amine salt, and the like). These may be used alone or in combination of two or more.
  • the content of the extreme pressure agent is not particularly limited, but is preferably 0.01 to 10 mass% based on the total amount of the composition (100 mass %), and more preferably 0.01. To 5.0 mass%, and more preferably from 0.1 to 3.0 mass%. ⁇ 0 2020/175 595 20 (: 170? 2020 /007892
  • Examples of the anticorrosion agent include, for example, metal sulfonates, alkylbenzene sulfonates, dinonylnaphthalene sulfonates, organic phosphorous acid esters, organic phosphoric acid esters, organic sulfonic acid metal salts, organic phosphoric acid metal salts, and alkenyl succinates.
  • Examples include acid esters, polyhydric alcohol esters, and benzotriazole compounds. These may be used alone or in combination of two or more.
  • the content of the antirust agent is not particularly limited, but is preferably 0.01 to 10.0 mass%, more preferably 0.05 to 5.0 mass% based on the total amount of the composition (100 mass%). %, and more preferably 0.1 to 3.0% by mass.
  • Examples of the metal deactivator include benzotriazole compounds, tolyl triazole compounds, thiadiazole compounds, imidazole compounds, pyrimidine compounds and the like. These may be used alone or in combination of two or more.
  • the content of the metal deactivator is not particularly limited, but is based on the total amount of the composition (100% by mass), preferably 0.001 to 5.
  • O mass% is more preferable, and 0.01 mass% to 3.0 mass% is more preferable, and 0.1 mass% to 1.0 mass% is still more preferable.
  • Examples of the defoaming agent include silicone oil, fluorosilicone oil, and fluoroalkyl ether. These may be used alone or in combination of two or more.
  • the content of the defoaming agent is not particularly limited, but is based on the total amount of the composition (100% by mass), preferably 0.01% to 0.50% by mass, and more preferably 0.01 to ⁇ . It is 0.30 mass%, and more preferably 0.1 to 0.20 mass%.
  • Examples of the viscosity index improver include polymethacrylate, dispersion-type polymethacrylate, olefin-based copolymer (for example, ethylene-propylene copolymer, etc.), dispersion-type olefin-based copolymer, styrene-based copolymer Examples thereof include a combination (for example, a hydrogenated copolymer of styrene). These may be used alone or in combination of two or more.
  • the content of the viscosity index improver is not particularly limited, it is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass based on the total amount of the composition (100% by mass). %, ⁇ 2020/175595 21 21 (: 170? 2020/007892
  • Examples of the wettability improver include an oxygen-containing compound having a carbon number of 14 or more, an oxygen number of 2 or more, and having at least one of a hydroxyl group, an ether bond and an ester bond.
  • the “oxygen number” refers to the total number of oxygen atoms in the molecule.
  • Preferable oxygen-containing compounds include, for example, sorbitan carboxylic acid esters, acetylene glycol-based compounds (for example, acetylene glycol or its ethylene oxide adduct (Mix adduct)), polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl Examples include ether.
  • Specific oxygen-containing compounds include sorbitan monooleate; sorbitandiolate; sorbitan trioleate; sorbitan monostearate; sorbitan distearate; sorbitan tristearate; sorbitan monolaurate; 2, 4, 7, 9, -Tetramethyl-5-decyne-4,7-diol; 2,4,7,9-Tetramethyl-5-decyne _4,7-diol ⁇ 1.3 mol adduct; 3,6-Dimethyl-4-octyne-3, 6-diol, 3,5-dimethyl-1-hexyne-3-ol; trioxyethylene oleyl ether and the like.
  • the content of the wettability improver is selected in the range of 0.01 to 3 mass% based on the total amount of the composition (100 mass%).
  • the preferable content of the wettability improver is 0.03 mass% or more, more preferably 0.05 mass% or more, and further preferably 0.1 mass% or more.
  • the upper limit of the preferable content of the wettability improver is 2.5% by mass or less, more preferably 2.0% by mass or less, and further preferably 1.5% by mass or less.
  • the friction coefficient measured under the conditions described in the examples below is preferably 0.2 or less, more preferably 0.14 or less, and It is preferably 0.12 or less. It can be said that the lower the coefficient of friction is, the better the metalworking oil composition is (the low frictional property). ⁇ 2020/175595 22 22 (: 170? 2020/007892
  • the metalworking oil composition of the present invention is capable of imparting good flux adhesion to the surface of a metal article after metalworking, and is therefore suitable for processing metal parts used in a brazing process using flux. Used for. As an example, it is more preferably used for metal working of a metal material such as an aluminum material or an aluminum alloy material, and further preferably used for metal working of an aluminum fin material or an aluminum alloy fin material.
  • the method for producing the metalworking oil composition of the present invention is not particularly limited. For example, it is produced by mixing the following components: () amine compound, (M) base oil, ( ⁇ friction modifier, and (mouth) other additives.
  • the production method of one embodiment is: Compound (component (8)), at least one base oil selected from mineral oil and synthetic oil (component (M)), and, if necessary, selected from alcohol having 6 to 30 carbon atoms and alkyl glycerol. Mixing with at least one friction modifier (component (O)).
  • Specific embodiments of the component (), the component (8), the component ( ⁇ , the component (mouth) are the same as those described in the above “1. Metalworking oil composition”.
  • the above component (8), the component (Mitsumi), ingredient ( ⁇ , and ingredient (mouth) may be mixed by any method, and the order and method of blending are not limited.
  • One form of the present invention provides a metal working method, wherein metal working is performed using a metal working oil composition.
  • the metalworking method of the embodiment includes working a metal material in the presence of the metalworking oil composition described above.
  • the metal material is not particularly limited and includes non-ferrous metal materials such as iron, aluminum or aluminum alloy.
  • the method of the present invention is preferably aluminum or aluminum. ⁇ 0 2020/175595 23 23 (: 170? 2020 /007892
  • It is preferably used for processing a plate or foil of a aluminum alloy.
  • the type of metal processing is not particularly limited, but for example, forging, extrusion, rolling, drawing, rolling, pressing (shearing, punching, fine blanking, bending, deep drawing, corrugated, corrugated (Corrugated) processing, spatula drawing, high-energy high-speed processing (electric discharge forming in liquid, explosive forming, electromagnetic forming, high-speed forging), and other metal working such as plastic working.
  • the metalworking oil composition of the present invention can impart good flux adhesion to the surface of a metal material, and therefore includes a step of attaching a flux and brazing in a step after metalworking. It is preferably used for processing metal parts.
  • the metal article is a heat exchanger component, and the method of the present embodiment is used for processing a heat exchanger component.
  • the metal material is preferably an aluminum material or an aluminum alloy material, more preferably an aluminum material or an aluminum alloy material.
  • the metal working is punching of aluminum fin material or corrugating of aluminum fin material.
  • One aspect of the present invention provides a brazing method comprising contacting a surface of a metal article having a metalworking oil composition with a flux for brazing. Since the metalworking oil composition of the present invention can impart good flux adhesion to the surface of a metal article after metalworking, the metalworking oil composition used in the brazing process using flux (for example, heat exchange). It is preferably used for the processing of ware parts.
  • the surface of the metal article coated with the metalworking oil composition of the present invention is excellent in the flux-printing property, and the defective joint between the components due to the dropping of the flux in the brazing process is suppressed. Further, when a brazing process using a flux is performed after metal working using the metal working oil composition of the present invention, the cleaning treatment of the metal parts before applying the flux can be omitted or simplified, resulting in excellent manufacturing efficiency.
  • Brazing is performed by, for example, contacting the surface of a metal article with flux and then ⁇ 02020/175595 24 24 (: 170? 2020 /007892
  • the flux is not particularly limited, and any flux can be appropriately selected and used from the flux materials conventionally used in brazing of metal materials such as aluminum materials or aluminum alloy materials.
  • the flux may be used alone or in combination of two or more kinds.
  • the flux is an aluminum brazing flux.
  • One embodiment of the present invention is a brazing method comprising brazing an aluminum brazing flux in contact with the surface of a metal article having the metalworking oil composition deposited thereon.
  • the aluminum brazing flux is not particularly limited, and known ones can be used.
  • potassium tetrafluoroaluminate ⁇ 8 4 alone or ⁇ 8 4 and potassium hexafluoroaluminate ([ ⁇ 3 8 I 6 ) or potassium pentafluoroaluminate ( ⁇ 2 Potassium fluoroaluminate consisting of a mixture with Hachijo 5 ); Potassium fluoride; Aluminum fluoride; Lithium fluoride; Sodium fluoride; Potassium fluoroaluminate-cesium complex (non-reactive cesium-based flux); Cesium acid (non-reactive cesium-based flux); potassium fluorofluorozellese (reactive zinc substitution flux) such as potassium trifluorozinese (KZ n F 3 ) and potassium tetrafluorozinese (K 2 Z n F 4 ); Examples include cesium fluorozyere (reactive zinc substitution flux).
  • the fluoride-based flux may be used alone or in combination of two or more kinds.
  • the flux may be brought into contact with the surface of the metal article in the form of a flux liquid dispersed in a solvent such as water or an organic solvent, optionally together with a binder.
  • the solvent examples include water alone and a mixture of water and an organic solvent, and water is preferably used alone.
  • binder examples include (meth)acrylic resins such as methacrylic acid-alkyl methacrylate ester-based copolymers; polyvinyl alcohol; polyethylene oxide; water-based polyester resins; methyl cellulose; water-based epoxy resins.
  • the blending amount of the binder is not particularly limited, but is, for example, 0 to 15% by mass, preferably 0.1 to 10% by mass, and more preferably 0.3 to 4% by mass based on the total amount of the flux liquid. It is% by mass.
  • the blending amount of the flux is not particularly limited, but is, for example, 2 to 50% by mass, preferably 5 to 50% by mass, more preferably 10 to 40% by mass based on the total amount of the flux liquid. %. ⁇ 0 2020/175 595 26 ⁇ (: 170? 2020 /007892
  • the method of bringing the flux into contact is not particularly limited, and includes, for example, immersing and showering.
  • the brazing method is not particularly limited, and a conventionally known brazing method using flux and brazing conditions can be used.
  • One form of the invention provides a method of making a metal article.
  • the method for manufacturing a metal article according to this embodiment has the following step (1).
  • Step (1) A metal processing step in which a metal material is processed using the above metal processing oil composition.
  • the method for producing a metal article according to this embodiment may further include the following step (2).
  • Step (2) After the step (1), with the composition remaining on a part of the surface of the metal material, a flux is brought into contact with the surface of the metal material to perform brazing treatment. Attaching process.
  • brazing treatment in the step (1) is as described in “4. Brazing method” above.
  • the metal article is a component for a heat exchanger.
  • the metal material is preferably an aluminum material or an aluminum alloy material, and more preferably an aluminum material or an aluminum alloy material.
  • the metal working is punching aluminum fin material or corrugating aluminum fin material.
  • a method for manufacturing a heat exchanger using the above method metal working method and/or brazing method, or metal article manufacturing method.
  • the amine compound can be used as a flux adhesion improving agent which is added to a solution such as a base oil and adheres to the surface of a material such as a metal material to give good flux adhesion to the surface of the material. ..
  • Specific embodiments of the amine compound are as described as "component (8): amine compound” incorporated in the above "metalworking oil composition”.
  • the flux adhesion improving agent may be adhered to the surface of the metal component, and then the flux may be brought into contact with the brazing step.
  • the flux adhesion improver is a solution of the above () amine compound in a base oil.
  • the base oil the same as the “component (B): base oil” blended in the above “metalworking oil composition” can be used.
  • the concentration of the flux adhesion promoter in the base oil can be, for example, 0.2 to 10% by mass.
  • Root temperature typically show from about 1 0 ° ⁇ about 3 5 ° ⁇ . Unless otherwise specified,% means mass percent.
  • the kinematic viscosity at 40° ⁇ was measured according to I 3 [ ⁇ 2 2 8 3 :200
  • test oil was applied to both surfaces of the test piece, and the test piece was immersed in the stirring flux solution for about 10 seconds. The flux coverage on the surface of the test piece after being taken out from the flux solution was measured. The test was performed at room temperature.
  • a test piece eight 3003 — 1 to 124 (1 0 0 0 1 1 0 0 0 1 thickness 0.40 It was used.
  • a flux solution (“1_-7” manufactured by Morita Kagaku Kogyo Co., Ltd.) was dissolved in ion-exchanged water so that the flux concentration was 20% by mass.
  • Min: Coverage is 60% or more and less than 90%
  • the test oil was applied to the test piece, and the friction coefficient was measured by the reciprocating friction test shown below.
  • Test piece Aluminum plate 8 1 050— (Thickness 1 0 0! 0 0 0 0 Ball material: 3 II” 2 (Diameter: 1/2 inch)
  • the sample was kept in a constant temperature bath heated to 0 ° C for 5 minutes, and the presence or absence of stains on the aluminum cup surface after evaporation of the test oil was evaluated according to the following criteria.
  • Antioxidant 0390 (2, 6-Gee I 6 “1:-Putyl 4-methylphenol)
  • Examples 6 to 11 (Table 2) and Examples 22 to 31 (Table 4) containing both an alcohol having 6 to 30 carbon atoms and an alkyl glycerol were more excellent in metal workability (low friction). It was From Table 2 and Table 4, Examples 6 to 11 (Table 2) and Examples 22 to 3 1 (Table 4) containing both an alcohol having 6 to 30 carbon atoms and an alkyl glycerol showed metal workability (low friction). It was excellent in sex.
  • the flux adhesion was further improved as compared with the case of blending (Comparison between Examples 16 and 17 and Example 21; Comparison between Examples 26 and 27 and Example 31).
  • the metalworking oil composition of the present invention can impart good flux adhesion to the surface of a metal article after metalworking, it can be applied to a metal part used in a brazing process using a flux. Suitable for processing.

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PCT/JP2020/007892 2019-02-28 2020-02-27 金属加工油組成物 WO2020175595A1 (ja)

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WO2023112842A1 (ja) * 2021-12-15 2023-06-22 出光興産株式会社 潤滑油基油および潤滑油組成物

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JPH08176581A (ja) * 1994-12-22 1996-07-09 Kobe Steel Ltd アルミニウム及びアルミニウム合金板の低温成形用潤滑剤
JPH08337787A (ja) * 1995-06-13 1996-12-24 Cosmo Sogo Kenkyusho:Kk 金属加工油組成物
JP2002088390A (ja) * 2000-07-10 2002-03-27 Yushiro Chem Ind Co Ltd 鋼板用水溶性冷間圧延油
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JP7566595B2 (ja) 2020-11-24 2024-10-15 出光興産株式会社 水溶性金属加工油組成物
WO2023112842A1 (ja) * 2021-12-15 2023-06-22 出光興産株式会社 潤滑油基油および潤滑油組成物
JP2023088623A (ja) * 2021-12-15 2023-06-27 出光興産株式会社 潤滑油基油および潤滑油組成物

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