EP0712925A2 - Schmierölzusammensetzung - Google Patents

Schmierölzusammensetzung Download PDF

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Publication number
EP0712925A2
EP0712925A2 EP95850199A EP95850199A EP0712925A2 EP 0712925 A2 EP0712925 A2 EP 0712925A2 EP 95850199 A EP95850199 A EP 95850199A EP 95850199 A EP95850199 A EP 95850199A EP 0712925 A2 EP0712925 A2 EP 0712925A2
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EP
European Patent Office
Prior art keywords
group
carbon atoms
mass
straight
branched
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP95850199A
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English (en)
French (fr)
Other versions
EP0712925A3 (de
Inventor
Shigetoshi Ogura
Katsumi Seki
Hideo Yokota
Junichi Shibata
Yoshitaka Natsume
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eneos Corp
Original Assignee
Nippon Oil Corp
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Filing date
Publication date
Application filed by Nippon Oil Corp filed Critical Nippon Oil Corp
Publication of EP0712925A2 publication Critical patent/EP0712925A2/de
Publication of EP0712925A3 publication Critical patent/EP0712925A3/de
Withdrawn legal-status Critical Current

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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
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • C—CHEMISTRY; METALLURGY
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    • C10M173/00—Lubricating compositions containing more than 10% water
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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
    • C10M129/04—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
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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
    • C10M129/16—Ethers
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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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    • 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
    • C10M133/08—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups
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    • C10M145/26—Polyoxyalkylenes
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    • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/046—Hydroxy ethers
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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
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    • 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
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    • 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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    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
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    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
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    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
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    • 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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    • C10N2040/241—Manufacturing joint-less pipes
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    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles

Definitions

  • This invention relates generally to lubricating oil compositions and particularly to such compositions which are useful in the production of rolled metal products of stainless steel, copper, aluminum, alloys thereof and the like.
  • Old conventional rolling lubricants typically were comprised of low-viscosity mineral oils and synthetic oils such as esters blended with various additives. These oils were soon shunned away because of their high flammability giving rise to fire hazards when used in high speed rolling.
  • Japanese Laid-Open Patent Publication No. 60-118790 discloses a water-soluble metal processing oil comprising salts or amides of acids such as carboxylic acid, sulfonic acid, naphthenic acid, an alkyleneglycol, a mineral or synthic oil or fat and oil, and water.
  • Such metal processing oil is laudable for being flame-retardant, but has a drawback in that it is not satisfactorily capable of cooling and subject to wide variation in viscosity depending upon the quantity of water used.
  • the present invention seeks to provide a lubricating oil composition suitable for use in the production of rolled metal products, which composition is substantially fire-proof, highly efficient in cooling, highly conducive to rolling performance, capable of retaining good surface gloss of rolled metal and filtering out abrasion dust or scum resulting from the rolling operation, with high storage stability and resistance to stain.
  • a lubricating oil composition which consists of a majority of nonflammable, cooling-efficient water and which comprises a selected oxygen-containing compound, a selected salt of fatty acid and water respectively blended in a specified range of quantities.
  • a lubricating oil composition which comprises (A) water added in the range of from 5 to 89.95 percent by mass; (B) an oxygen-containing compound added in the range of from 10 to 94.95 percent by mass and represented by the formula R1O-(R3-O) p -R (I) where R1 and R each independently are hydrogen or hydrocarbon groups of 1-18 carbon atoms, R3 is an alkylene group of 1-6 carbon atoms, p is an integer of 1-30; and (C) a salt of fatty acid added in the range of from 0.05 to 10 percent by mass and selected from the group consisting of (a) an alkaline metal salt of fatty acid of 6-22 carbon atoms, (b) a salt of fatty acid of 6-22 carbon atoms and an alkanol amine of 1-15 carbon atoms, and (c) a salt of fatty acid of 6-22 carbon atoms and a nitrogen-containing compound of the formula where R4 is a hydrocarbon
  • inventive lubricating oil composition finds extensive application not only in the cold-rolling of stainless steel, copper, aluminum and alloys thereof but also in the hot-rolling of aluminum and its alloys. There is no particular restriction as to the manner in which the inventive lubricant is applied. However, its prominent lubricating and cooling capabilities lead to a preferred mode of use in which the inventive lubricant is applied by means of jet spraying to or adjacent the nip between working rolls for rolling a metal substrate.
  • water as used herein as Component (A) designates all sorts of water ranging from hard water, soft water, drinking water, industrial water, ion-exchanged water to distilled water.
  • the lower limit of contents of this water is generally 5 percent by mass, preferably 15 percent by mass, more preferably 25 percent by mass based on the total amount of the resultant composition.
  • Its upper limit is generally 89.95 mass %, preferably 79.9 mass %, more preferably 69.8 mass % based on total composition. Amounts of water less than 5 percent by mass would result in reduced cooling capability of the oil composition, hence leading to seized metal during rolling, and amounts exceeding 89.95 percent by mass would result in reduced lubricity.
  • the oxygen-containing compound (B) according to the invention is represented by the formula R1O-(R3-O) p -R (2) where R1 and R each independently are hydrogen or hydrocarbon groups of 1-18 carbon atoms, R3 is an alkylene group of 1-6 carbon atoms, p is an integer of 1-30. R1 and R may be the same or different.
  • the hydrocarbon groups of 1-18 carbon atoms include an alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, straight or branched pentyl group, straight or branched hexyl group, straight or branched heptyl group, straight or branched octyl group, straight or branched nonyl group, straight or branched decyl group, straight or branched undecyl group, straight or branched dodecyl group, straight or branched tridecyl group, straight or branched tetradecyl group, straight or branched pentadecyl group, straight or branched hexadecyl group, straight or branched heptadecyl group and straight or branched octadecyl group;
  • R1 and R in the formula (I) each independently are preferably hydrogen, an alkyl or phenyl group 1-18 carbon atoms, or an alkylaryl group of 7-15 carbon atoms with a consideration given to compatibility of the two Components (B) and (A).
  • R3 in the formula (I) includes methylene group; methylmethylene group (ethylidene group) and ethylene group; ethylmethylene group (propylidene group), dimethylmethylene group (isopropylidene group), methylethylene group (propylene group) and trimethylene group; n-propylmethylene group (butylidene group), isopropylmethylene group (isobutylidene group), ethylmethylmethylene group, ethylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group and tetramethylene group; n-butylmethylene group (pentylidene group), sec-butylmethylene group, isobutylmethylene group (isopentylidene group), tetr-butylmethylene group, n-propylmethylmethylene group, isopropylmethylmethylene group, diethyl
  • R3 is preferably an alkylene group of 2-6 carbon atoms.
  • Oxygen-containing compounds (B) eligible for the purpose of the invention particularly from the point of view of compatibility with Component (A), i.e. water, are those represented by an embodiment of the formula (I) wherein R1 is hydrogen, straight or branched alkyl or phenyl group of 1-6 carbon atoms, or straight or branched alkylaryl group of 7-15 carbon atoms, R is hydrogen, R3 is an alkylene group of 2-6 carbon atoms, and p is an integer of 1-10.
  • oxygen-containing compounds (B) include (i) ethylene glycol, propylene glycol (inclusive of all isomers), butylene glycol (inclusive of all isomers), pentylene glycol (inclusive of all isomers) and hexylene glycol (inclusive of all isomers); (ii) polyglycols (exemplarily diglycol, triglycol and tetraglycol) derived from homopolymerization of one of the glycols (i); (iii) polyglycols (exemplarily polyoxyethyleneoxypropylene glycol) derived from random-, alternating-, or block-copolymerization of two or more of the glycols (i); (iv) monoalkylether compounds (having straight or branched alkyl groups of 1-6 carbon atoms) of glycols (i) and polyglycols (ii), (iii); (v) monophenylether compounds of glycols (i)-(iii); (
  • a copolymeric polyglycol having an ethylene glycol copolymerized with another alkylene glycol in a mole ratio of between 1-9 and 9-1, preferably between 2-8 and 8-2 as such polyglycol is readily comiscible with water.
  • oxygen-containing compounds (B) defined by the formula (I) are applicable for the purpose of the invention, there are some readily homogeneously soluble and others not so soluble with water when added in specified amounts appearing in the examples hereinafter given.
  • the lower limit of contents of the Component (B) in the inventive composition is generally 10, preferably 20, more preferably 30 percent by mass based on total composition, and the upper limit thereof is generally 94.95, preferably 84.9, more preferably 74.8 percent by mass based on total composition. Less than 10 mass % would lead to aggravated lubricating performance, while greater than 94.95 mass % would result in reduced surface gloss of a rolled metal product.
  • the lower limit of the sum of Components (A) and (B) should be 80 %, preferably 90 %, more preferably 95 % by mass based on total composition, and the upper limit should be 99.95 %, preferably 99.9 % and more preferably 99.8 % by mass based on total composition. Less than 80 mass % would result in poor surface finish of a rolled metal product, while more than 99.95 mass % would aggravate lubricity.
  • the Component (C), namely, a salt of fatty acid, used in the invention is selected from the group consisting of (a) an alkaline metal salt of fatty acid of 6-22 carbon atoms, (b) a salt of fatty acid of 6-22 carbon atoms and an alkanol amine of 1-15 carbon atoms, and (c) a salt of fatty acid of 6-22 carbon atoms and a nitrogen-containing compound of the formula where R4 is a hydrocarbon group of 1-24 carbon atoms, R5 is an ethylene or propylene group, q is an integer of 1-30, X is hydrogen, a hydrocarbon group of 1-24 carbon atoms or a group of the formula -(R6-O) r H where R6 is an ethylene or propylene group and r is an integer of 1-30.
  • Fatty acids in each of the listed salts (a), (b) and (c) may be saturated or unsaturated, of straight-chain or branched-chain, provided their carbon number remains in the range of 6-22.
  • Such fatty acids exemplarily include straight and branched saturated fatty acids such as hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid and docosanoic acid; and straight and branched unsaturated fatty acids such as hexenoic acid, heptenoic acid, octenoic acid, nonenoic
  • n-dodecanoic acid lauric acid
  • n-tridecanoic acid n-tetradecanoic acid
  • n-pentadecanoic acid n-hexadecanoic acid
  • palmitic acid n-heptadecanoic acid
  • n-octadecanoic acid stearic acid
  • n-dodecenoic acid n-tridecenoic acid
  • n-tetradecenoic acid n-pentadecenoic acid
  • n-hexadecenoic acid n-heptadecenoic acid
  • n-octadecenoic acid oleic acid
  • the basic component of the salt of fatty acid (a) is usually sodium or potassium.
  • the salt (a) may be formed from one or more of the above fatty acids and one or more of alkaline metals.
  • the basic component of the salt of fatty acid (b) includes monomethanol amine, dimethanol amine, trimethanol amine, monoethanol amine, diethanol amine, triethanol amine, mono-n-propanol amine, monoisopropanol amine, di-n-propanol amine, diisopropanol amine, tri-n-propanol amine, triisopropanol amine, monobutanol amine (inclusive of all isomers), dibutanol amine (inclusive of all isomers), tributanol amine (inclusive of all isomers), monopentanol amine (inclusive of all isomers), dipentanol amine (inclusive of all isomers), tripentanol amine (inclusive of all isomers), monohexanol amine (inclusive of all isomers), dihexanol amine (inclusive of all isomers), monoheptanol amine (inclusive of all is
  • the basic component of the salt of fatty acid (c) is a nitrogen-containing compound of the formula (II) where R4 is a hydrocarbon group of 1-24 carbon atoms.
  • This hydrocarbon group includes an alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, straight or branched pentyl group, straight or branched hexyl group, straight or branched heptyl group, straight or branched octyl group, straight or branched nonyl group, straight or branched decyl group, straight or branched undecyl group, straight or branched dodecyl group, straight or branched tridecyl group, straight or branched tetradecyl group, straight or branched pentadecyl group, straight or branched he
  • alkyl groups of 1-18 carbon atoms particularly preferred alkyl groups of 1-18 carbon atoms, alkenyl groups of 5-18 carbon atoms, and cyclohexyl groups or alkylcyclohexyl groups of 7-11 carbon atoms for reaction with the recited fatty acids to form their respective salts having a desired softening point conducive to the preparation of the inventive lubricant compositions.
  • R5 in the formula (II) is an ethylene group or a propylene group (methylethylene group); however, the former is preferred for ease of dissolution in water.
  • the designation "q” in the formula (II) is an integer of 1-30, preferably 3-20.
  • X in the formula (II) is hydrogen, a hydrocarbon group of 1-24 carbon atoms or a group of -(R6-O) r H.
  • the C1 ⁇ 24 hydrocarbon group is the same as deseribed for R4, of which are preferred C1 ⁇ 18 alkyl groups, C5 ⁇ 18 alkenyl groups, cyclohexyl groups or C7 ⁇ 11 alkylcyclohexyl groups.
  • R6 in the hydrocarbon formula is an ethylene or propylene (methylethylene) group, the former being preferred for better water solubility.
  • r is 1-30, preferably 3-20.
  • the nitrogen-containing compound of the formula (II) may be derived from reacting an ethylene or propylene oxide with monoamines of the formula (III) or diamines of the formula (IV).
  • One or more of the salts (a), (b) and (c) may be used for the component (C). These salts may be formed in situ in the reaction system by adding a selected fatty acid and a selected base separately. Alternatively, they may be pre-formed. In either case, however, the lower allowable limit of addition of the salts is 0.05, preferably 0.1, more preferably 0.2 mass % based on total composition and the upper allowable limit of the same is 10, preferably 5, more preferably 3 mass % based on total composition. Less than 0.05 mass % would lead to declined lubricating performance, while more than 10 mass % would make the salt less soluble in water and the resultant composition less glossy.
  • the component (C) is either completely dissolved or finely dispersed in a solution of components (A) and (B).
  • the lubricating oil compositions comprising specified amounts of components (A), (B) and (C), respectively, according to the invention may be readily put to use per se particularly in the manufacture of rolled metal products and may be, if desired, further added with suitable additives.
  • suitable additives exemplarily include: anion-based surface active agents such as sulfuric ester and sulfonate, and Nonion-based surface acitve agents such as polyoxyethylene compound; rust inhibitors such as sulfonate, phosphoric acid and phosphate, and boron compounds; antioxidants such as phenol-based, amine-based, sulfur-based, phosphorus-based and chlorine-based; nitrogen compounds such as benzotriazole, and corrosion inhibitors such as sulfur- and nitrogen-containing compound; antiseptics such as of phenol-based, formaldehyde donative compound and salicylamid-based compound; and silicone grease. These may be added in amounts of less than 10, preferably less than 5, more preferably less than 2 percent by mass based on the total
  • mineral oils or hydrocarbon-based synthetic oils are not eligible for addition to the inventive lubricant composition whether they be used for emulsion-type or water-soluble rolling oils.
  • non-eligible additives include paraffinic or naphthenic mineral oils derived from refining treatment of crude oil distillates such as by solvent-deasphalting, solvent-extraction, hydrocracking, solvent-dewaxing, contact dewaxing, hydrogenation, sulfur-washing, clay treatment and the like.
  • the inventive lubricating oil composition made up of the three components (A), (B) and (C) blended in the specified quantities may be stored as it is or with the component (A), i.e. water, added initially in an amount smaller than specified and later upon use supplemented to a desired level of dilution.
  • component (A) i.e. water
  • Paraffinic refined mineral oil (dynamic viscosity 7 mm/s @40°C) 84.4 mass % Butylstearate 15.0 mass % Alkenyl succinate 0.6 mass %
  • Paraffinic refined mineral oil (dynamic viscosity 7 mm/s @40°C) 49.4 mass % Dioctyl sebacate 50.0 mass % Alkenyl succinate 0.6 mass %

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Paper (AREA)
EP95850199A 1994-11-21 1995-11-10 Schmierölzusammensetzung Withdrawn EP0712925A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP311169/94 1994-11-21
JP31116994A JP3406407B2 (ja) 1994-11-21 1994-11-21 圧延用潤滑剤組成物

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EP0712925A2 true EP0712925A2 (de) 1996-05-22
EP0712925A3 EP0712925A3 (de) 1996-07-31

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
US10519391B2 (en) 2017-08-17 2019-12-31 Dane Bush Gun lubricant

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* Cited by examiner, † Cited by third party
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CN102239240B (zh) * 2008-09-30 2013-08-28 国际壳牌研究有限公司 润滑脂组合物

Family Cites Families (6)

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Publication number Priority date Publication date Assignee Title
US3580847A (en) * 1967-06-16 1971-05-25 Wyandotte Chemicals Corp Hydraulic fluid
US4243537A (en) 1978-08-08 1981-01-06 Aluminum Company Of America Synthetic metal working lubricant
US4452712A (en) 1983-01-20 1984-06-05 Aluminum Company Of America Metalworking with an aqueous synthetic lubricant containing polyoxypropylene-polyoxyethylene-polyoxypropylene block copolymers
SE452627B (sv) * 1986-05-13 1987-12-07 Berol Suisse Sa Forfarande vid mekanisk bearbetning av metaller i nervaro av ett vattenbaserat kylsmorjmedel samt koncentrat av kylsmorjmedlet
US4830768A (en) 1988-02-22 1989-05-16 Aluminum Company Of America Metalworking lubricant composition containing propoxylated fatty alcohol
JP2812964B2 (ja) * 1988-10-31 1998-10-22 出光興産株式会社 水−グリコール型作動液

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10519391B2 (en) 2017-08-17 2019-12-31 Dane Bush Gun lubricant

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KR100423478B1 (ko) 2004-06-14
TW294716B (de) 1997-01-01
EP0712925A3 (de) 1996-07-31
JPH08143890A (ja) 1996-06-04
KR960017828A (ko) 1996-06-17

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