EP1835012B1 - Lubricant composition for cold working and cold working method using the same - Google Patents

Lubricant composition for cold working and cold working method using the same Download PDF

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Publication number
EP1835012B1
EP1835012B1 EP05819444.0A EP05819444A EP1835012B1 EP 1835012 B1 EP1835012 B1 EP 1835012B1 EP 05819444 A EP05819444 A EP 05819444A EP 1835012 B1 EP1835012 B1 EP 1835012B1
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EP
European Patent Office
Prior art keywords
cold working
mass
composition
carbonate
lubricating
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.)
Expired - Fee Related
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EP05819444.0A
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German (de)
English (en)
French (fr)
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EP1835012A4 (en
EP1835012A1 (en
Inventor
Keishi c/o SUMITOMO METAL INDUSTRIES LTD. MATSUMOTO
Yasunobu c/o SUMITOMO METAL INDUSTRIES LTD. MURAI
Masaki c/o SUMITOMO METAL INDUSTRIES LTD. NAKANE
Hidenori c/o SUMITOMO METAL INDUSTRIES LTD. OGAWA
Yasunari c/o YUSHIRO Chemical Ind. Co. Ltd. OSHIMOTO
Kazuyoshi c/o YUSHIRO Chemical Ind. Co. Ltd. OHASHI
Masahiko c/o YUSHIRO Chemical Ind. Co. Ltd. FUKUHARA
Yuji c/o YUSHIRO Chemical Ind. Co. Ltd. MISHIMA
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Nippon Steel Corp
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Nippon Steel Corp
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Publication date
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Publication of EP1835012A4 publication Critical patent/EP1835012A4/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/02—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 oxygen-containing compound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
    • B21J3/00—Lubricating during forging or pressing
    • 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
    • C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
    • C10M2201/0623—Oxides; Hydroxides; Carbonates or bicarbonates used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/064—Carbonyls
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/027—Neutral salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/064—Thiourea type 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/09—Heterocyclic compounds containing no sulfur, selenium or tellurium compounds in the ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106—Thiadiazoles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/41—Chlorine free or low chlorine content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/243—Cold working
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/245—Soft metals, e.g. aluminum
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/246—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/247—Stainless steel
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/32—Wires, ropes or cables lubricants

Definitions

  • the present invention relates to a lubricating composition for cold working and a method of cold working using such a composition. More particularly, it pertains to a lubricating composition which is free of chlorine compounds which may have problems with respect to carcinogenicity and generation of dioxin, which exhibits good lubricating and anti-seizure properties even in cold forging and cold pipe forming, both of which easily cause seizure and have severe lubricating requirements (such a type of working hereinafter referred to as "hard metalworking"), and which is compatible with the environment and less flammable, and a method of cold working using such a composition.
  • a lubricating composition which is free of chlorine compounds which may have problems with respect to carcinogenicity and generation of dioxin, which exhibits good lubricating and anti-seizure properties even in cold forging and cold pipe forming, both of which easily cause seizure and have severe lubricating requirements (such a type of working hereinafter referred to as "hard metalworking"),
  • an oilness agent such as a fat or fatty oil, a fatty acid, or an ester and/or an extreme pressure agent (EP agent) such as a sulfur-, chlorine-, or phosphorus-containing compound has been added to a lubricating oil for use in cold working such as cold forging in order to improve its lubricating action.
  • an extreme pressure agent such as a fat or fatty oil, a fatty acid, or an ester and/or an extreme pressure agent (EP agent) such as a sulfur-, chlorine-, or phosphorus-containing compound
  • E agent extreme pressure agent
  • chlorine-containing extreme pressure agents such as chlrorinated paraffins and chlorinated fatty acid esters are less expensive compared to other extreme pressure agents, have good lubricating properties, and are less flammable, so they are added to a lubricating composition which is used for hard metalworking such as cold forging.
  • chlorine compounds have the problems that they may be carcinogenic or generate dioxin.
  • a lubricant of the type for use in forging comprising an alkaline earth metal salt (a phenate, a carboxylate, or a sulfonate) with a high basicity dispersed in a base oil is proposed in JP H08-333594 A1 .
  • a lubricating oil comprising a base oil to which a petroleum sulfonate of high basicity and an extreme pressure agent such as a calcium salt of a phosphoric acid ester or a sulfurized fat or fatty oil are added is proposed in JP H08-34988 A1 .
  • a lubricating oil comprising a base oil in which a film strengthening agent such as a ZnDTP (zinc dialkyldithiophosphate) or sulfurized lard and a carbohydrate such as starch or its derivative are dispersed is proposed in JP H06-256784 A1 .
  • US 4,308,182 discloses lubricants comprising a carbonate and a hydroxide.
  • JP 2001 247887 A discloses lubricants comprising a fine calcium-containing solid powder and a chlorinated organic, organosulfur or organophosphorus compound.
  • JP 2004 083781 discloses lubricant compositions comprising one or more compounds containing a carbon atom having a bond to a sulphur atom and a bond to a nitrogen atom in one molecule and an alkali metal salt and/or an alkaline earth metal salt.
  • the present invention provides a lubricating composition for cold working and a method of cold working using such a composition in which the composition is free of chlorine compounds which may cause the problems of carcinogenicity and generation of dioxin, exhibits good lubricating and anti-seizure properties even in cold forging or cold pipe forming which easily cause seizure (namely, in hard metalworking), and is compatible with the environment and less flammable.
  • the lubricating composition which "is free of chlorine compounds” has a content of chlorine compounds of 0% by mass or greater than 0% by mass but not greater than 1% by mass based on the mass of the composition.
  • the present invention is based on the finding that a lubricating composition containing an alkali metal and/or alkaline earth metal carbonate (particularly one having a specific crystal structure) and an alkali metal and/or alkaline earth metal hydroxide in a certain proportion exhibits good anti-seizure and lubricating properties in the absence of a chlorine compound.
  • the temperature of the lubricating oil which is used may reach 150° C or higher.
  • the proportion of an alkali metal and/or alkaline earth metal carbonate in the composition By increasing the proportion of an alkali metal and/or alkaline earth metal carbonate in the composition, the proportion of a flammable material can be decreased, thereby causing the composition to be less flammable
  • a lubricating composition for cold working according to the present invention contains at least one carbonate selected from alkali metal carbonates and alkaline earth metal carbonates and at least one hydroxide selected from alkali metal hydroxides and alkaline earth metal hydroxides in a lubricating base oil selected from one or more of the group consisting of mineral oils, fats and fatty oils, and synthetic lubricating oils, and which has a content of chlorine compounds of 0% by mass or greater than 0% by mass but not greater than 1% by mass based on the mass of the composition.
  • the lubricating composition for cold working is characterized in that the content of the carbonate in the composition is from 15% by mass to 65% by mass while the content of the hydroxide is at least 0.01 parts by mass and at most 5 parts by mass per 100 parts by mass of the carbonate.
  • the lubricating composition for cold working can exhibit good lubricating and anti-seizure properties even in cold forging and cold pipe forming which have severe lubricating requirements and which tend to easily cause seizure (such as cold pilger mill rolling, for example).
  • the composition has low flammability.
  • the composition exhibits good lubricating performance without aid of a chlorine compound which is problematic with respect to carcinogenicity and generation of dioxin, so it is compatible with the environment.
  • the lubricating composition for cold working according to the present invention encompasses the following preferred embodiment.
  • the organosulfur compound is preferably at least one selected from the compounds having formulas (1) to (12): where x 1 is an integer from 2 to 4; where R 1 and R 2 are each -CH 3 or -C 2 H 5 and may be the same or different from each other. where x 2 is 1 or 2. where R 3 is -C(CH 3 ) 3 or -C 6 H 11 . where x 3 and x 4 are each an integer from 2 to 4 and may be the same or different from each other, and R 4 and R 5 are each -C 8 H 17 , -C 12 H 25 or -C(S)N(C 2 H 5 ) 2 and may be the same or different from each other.
  • R 6 and R 7 are each -CH 3 , -C 2 H 5 , -C 3 H 7 , -C 4 H 9 , -C 6 H 5 , or -CH 2 C 6 H 5 and may be the same or different from each other, and M is Na, K, or 1/2Ca.
  • R 8 is H or -CH 3
  • R 9 is -C 5 H 10 NH 2 or -CH(CH 3 )C 4 H 8 NH 2 .
  • R 10 , R 11 , R 12 , and R 13 are each -CH 3 , -C 2 H 5 , -C 3 H 7 , -C 4 H 9 , or -CH 2 CH(C 2 H 5 )C 4 H 9 and may be the same or different from each other, and x 5 is an integer from 1 to 4.
  • x 6 is an integer from 1 to 4.
  • R 14 and R 16 are each H, -CH 3 , or -C 2 H 5 and may be the same or different from each other
  • R 15 and R 17 are each -CH 3 , -C 2 H 5 , or -C 6 H 5 and may be the same or different from each other.
  • a method of cold working characterized by subjecting a material to be worked to cold working using the above-described lubricating composition for cold working is also provided.
  • This method makes it possible to perform cold working satisfactorily on the material to be worked due to good anti-seizure and lubricating properties of the lubricating composition for cold working which is used.
  • a method of cold working according to the present invention can perform cold working satisfactorily on a material to be worked which is a stainless steel, a high alloy steel, aluminum, copper, titanium, nickel, or an alloy thereof.
  • Figure 1 is an explanatory view schematically showing a testing machine used in an ironing test.
  • a lubricating composition for cold working according to the present invention contains an alkali metal and/or alkaline earth metal carbonate (hereinafter referred to simply as “carbonate”) and an alkali metal and/or alkaline earth metal hydroxide (hereinafter referred to simply as a “hydroxide”) in a lubricating base oil and has a content of chlorine compounds of 0% by mass or greater than 0% by mass but not greater than 1% by mass based on the mass of the composition.
  • the carbonate and hydroxide are present in the base oil in dispersed state, but they may partly be dissolved therein.
  • the "lubricating base oil” is selected from one or more of the group consisting of mineral oils, fats and fatty oils, and synthetic lubricating oils.
  • the mineral oils include kerosene, light oil, spindle oil, machine oil, neutral oil, turbine oil, cylinder oil, and liquid paraffin.
  • the fats and fatty oils include beef tallow, lard, rapeseed oil, coconut oil, palm oil, and rice bran oil, as well as hydrogenated oils of these.
  • the synthetic oils include fatty acids derived from the above-described fats and fatty oils, esters of a fatty acid and an alcohol, poly(alpha-olefins) such as polybutene, polyols such as polyethylene glycol and polyol esters, polyethers or polyesters, and higher alcohols.
  • the "lubricating base oil” may be constituted by one or more oils.
  • the content of the lubricating base oil in the lubricating composition for cold working is not limited, but it is preferably in the range of from 1% to 90%, more preferably from 5% to 80%, even more preferably from 10% to 70%, and most preferably from 10% to 60% by mass based on the mass of the composition (total mass of all the constituents constituting the composition).
  • the "alkali metal” includes lithium, sodium, and potassium
  • the “alkaline earth meal” includes magnesium, calcium, and barium.
  • Specific examples of the carbonate include lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, and barium carbonate. Of these, from consideration as an alternative to a chlorine compound which is inexpensive, sodium carbonate and calcium carbonate are preferred since they are inexpensive and make it possible to stably provide a lubricating composition.
  • One or more carbonates may be used.
  • the crystal structure of the carbonates is not limited to a specific form.
  • possible crystal structures include vaterite, calcite, and amorphous. It is preferable to use a carbonate which is amorphous in crystal structure since a lubricating composition for cold working having improved anti-seizure property can be obtained. Two or more carbonates having different crystal structures may of course be used.
  • the mean particle diameter of the carbonates is not limited either, but it is preferably not greater than 0.5 micrometers (and usually at least 0.001 micrometers), and more preferably not greater than 0.3 micrometers and even more preferably not greater than 0.1 micrometers.
  • the reason why the mean particle diameter is preferably not greater than 0.5 micrometers is that it is possible to obtain a lubricating composition for cold working having improved anti-seizure property.
  • the content of the carbonates is from 15% to 65% by mass based on the mass of the composition, thereby providing a lubricating composition for cold working having both good lubricity and good anti-seizure property, and making it possible for the lubricating composition to have a sufficiently increased flash point.
  • alkali metal and “alkaline earth metal” in the above-described hydroxide include the same metal species as listed above for each of these classes with respect to the carbonates.
  • the particular alkali metal and/or alkaline earth metal constituting the hydroxide may be the same as or different from the particular alkali metal and/or alkaline earth metal constituting the carbonate.
  • Specific examples of the hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide.
  • One or more hydroxides may be used.
  • the content of the hydroxides when expressed as parts by mass per 100 parts by mass of the carbonate, is at least 0.01 parts by mass and not greater than 5 parts by mass. It is preferably in the range of from 0.05 to 5 parts by mass, and more preferably from 0.05 to 4 parts by mass, and most preferably from 0.09 to 3.5 parts by mass. If the content of the hydroxides exceeds 5 parts by mass, sufficient anti-seizure property cannot be obtained.
  • the content of the hydroxides can be determined by a common titration method such as neutralization titration with an acid.
  • the content of the hydroxides when expressed as % by mass based on the mass of the composition, is greater than 0% and less than 5%, preferably in the range of from 0.05% to 4%, and more preferably from 0.05% to 3%, even more preferably from 0.05% to 2%, and most preferably from 0.1% to 1% by mass.
  • the carbonates and the hydroxides may be obtained by a chemical reaction, or they may be commercially available products. Commercially available products of these compounds can be obtained in powder form. It is also possible to obtain these compounds in the form of a solution or dispersion containing an alkali metal and/or alkaline earth metal carbonate and hydroxide uniformly dissolved or dispersed in an appropriate medium (an inorganic solvent or an organic solvent, and particularly an oil for use as a lubricating base oil).
  • an appropriate medium an inorganic solvent or an organic solvent, and particularly an oil for use as a lubricating base oil.
  • a lubricating composition for cold working according to the present invention is free of chlorine compounds.
  • the expression "chlorine compound” indicates any inorganic or organic compound containing one or more chlorine atoms. Specific examples of such a compound include chlorine-containing extreme pressure agents such as chlorinated paraffin and chlorinated fats and fatty oils, chlorinated solvents such as carbon tetrachloride, trichloroethylene, and methylene chloride, chlorine-containing fluorinated solvents such as chlorofluorocarbons, and inorganic chlorine compounds such as ammonium chloride.
  • a lubricating composition for cold working according to the present invention which "is free of chlorine compounds" ideally has 0% content of chlorine-containing compounds. However, it encompasses a composition containing a slight amount of a chlorine-containing compound due to contamination by unavoidable impurities or similar reason.
  • the present invention does not exclude a lubricating composition for cold working containing chlorine compounds in an amount of greater than 0% and not greater than 1% by mass based on the mass of the composition.
  • the content of the chlorine compound is preferably at most 0.5%, more preferably at most 0.1%, even more preferably at most 0.01%, and most preferably at most 0.001% by mass.
  • a lubricating composition according to the present invention may further include at least one metal salt selected from alkali metal or alkaline earth metal sulfonates, salicylates, phenates, and carboxylates. As a result, it becomes possible to provide the lubricating composition with detergent dispersant activity.
  • alkali metal and “alkaline earth metal” for the metal salt include the same metal species as listed above for each of these classes.
  • the particular "alkali metal” and “alkaline earth metal” constituting the metal salt may be the same as or different from the particular alkali metal and/or alkaline earth metal constituting the carbonate and/or hydroxide.
  • the "sulfonates” include alkali metal salts and alkaline earth metal salts of a sulfonic acid such as petroleum sulfonate, an alkyl-aromatic sulfonic acid such as alkylbenzenesulfonic acid, an alkyl sulfonic acid, or polyisobutenylsulfonic acid.
  • the "salicylates” include alkali metal salts and alkaline earth metal salts of a salicylic acid such as an alkylsalicylic acid.
  • the "phenates” include alkali metal salts and alkaline earth metal salts of a phenol such as phenol or an alkylphenol.
  • the “carboxylates” include alkali metal salts and alkaline earth metal salts of a carboxylic acid such as maleic polybutene, a fatty acid, or a carboxyl-modified acrylic resin.
  • a carboxylic acid such as maleic polybutene, a fatty acid, or a carboxyl-modified acrylic resin.
  • One or more metal salts may be used.
  • the metal salt such as an alkali metal and/or alkaline earth metal salt of a sulfonate, salicylate, phenate or carboxylate can be prepared by blowing carbon dioxide into a system which is a solution of the corresponding acid, i.e., a sulfonic acid, a salicylic acid, a phenol, or a carboxylic acid dissolved in a base oil and which contains an alkali metal and/or alkaline earth metal hydroxide (and/or oxide) added to the solution.
  • the alkali metal and/or alkaline earth metal hydroxide is used in an excess amount.
  • the resulting metal salt contains an alkali metal and/or alkaline earth metal carbonate and in some cases unreacted alkali metal and/or alkaline earth metal hydroxide, so it becomes a basic salt.
  • the base number of the metal salt depends on the amount of the alkali metal and/or alkaline earth metal hydroxide added to the system, and a metal salt having a high base number of 100 mg-KOH/g may be formed in some cases.
  • the base number of the metal salt which is used in the present invention is not limited.
  • a lubricating composition for cold working according to the present invention contains a metal salt such as a sulfonate and the metal salt contains an alkali metal and/or alkaline earth metal carbonate and/or hydroxide
  • the amount of the carbonate and/or hydroxide contained in the metal salt is included in the amount of the "carbonate" and/or "hydroxide" described above as essential constituents in the composition according to the present invention.
  • the content of the metal salt is preferably from 1 to 50 parts, more preferably 1 to 40 parts, and even more preferably 5 to 30 parts by mass, expressed as the mass of the metal salt per 100 parts by mass of the carbonate.
  • the metal salt contains a carbonate and/or hydroxide, the mass of the carbonate and/or hydroxide in the salt is excluded from the mass as the metal salt itself.
  • a lubricating composition according to the present invention may further contain an organosulfur compound having a carbon atom to which a sulfur atom and a nitrogen or oxygen atom are bonded in order to further improve the lubricity of the composition.
  • Preferred examples of the organosulfur compounds are those of the preceding formulas (1) to (12), which make it possible to ensure that a lubricating composition having further improved lubricity is obtained.
  • One or more organosulfur compounds may be used.
  • the content of the organosulfur compound is not limited, but it is preferably from 0.1% to 50%, more preferably from 1% to 40%, and even more preferably from 5% to 30% by mass based on the mass of the composition. When the content is within the above-described range, it is possible to obtain a lubricating composition having further improved lubricity.
  • a lubricating composition for cold working according to the present invention may include, if necessary, various additives which are added to conventional oils for plastic working, in addition to the above-described constituents.
  • additives include oiliness agents such as hindered esters and alkylamines; extreme pressure agents including organosulfur compounds such as polysulfides and sulfurized fats and fatty oils; organophosphorous compound such as phosphate and phosphite esters and acidic phosphate and phosphite esters; organometallic salts such as zinc dithiophosphate and molybdenum dithiocarbamate; solid lubricants such as graphite and molybdenum sulfide; antioxidants, antirust agents, and anticorrosive agents.
  • Use of sold lubricants such as graphite and molybdenum sulfide is preferably avoided as much as possible since they may adversely affect the working environment.
  • a lubricating composition for cold working according to the present invention is free of chlorine compounds, optional additives when they are used should be other than chlorine compounds. However, as long as no disadvantageous effect is produced, the present invention does not exclude the use of a chlorine compound as an optional additive used in a slight amount.
  • a lubricating composition for cold working according to the present invention is in the form of a liquid or gel at room temperature (about 25°C).
  • the composition preferably has a flash point, measured with a Cleveland open-cup flash point tester in accordance with JIS K2265, of 150°C or higher, more preferably 170°C or higher, and even more preferably 200°C or higher.
  • a flash point measured with a Cleveland open-cup flash point tester in accordance with JIS K2265, of 150°C or higher, more preferably 170°C or higher, and even more preferably 200°C or higher.
  • the lubricating composition can be used safely even in cold working under severe conditions which cause the lubricating composition to have a high temperature.
  • the material to be worked is not limited.
  • the material to be worked includes stainless steel, high alloy steel, aluminum, copper, titanium, nickel, and alloys of these.
  • the shape of the material to be worked is not limited, and it may be a bar or rod or a block. Alternatively, it is conceivable to perform working on hot-forged shapes (such as gears and shafts).
  • the product produced by cold working is also not limited. Some specific examples of cold worked products include metal tubes and pipes, metal wires, metal rods or bars, and billets.
  • cold working examples include plate rolling, pipe or tube rolling, rolling of bar steels (shape steels, bars, and wire rods), drawing, forging, and the like.
  • Particularly preferred cold working is cold forging or cold pipe forming.
  • the conditions and method for cold working such as cold forging or cold pipe forming are not limited, and cold working can be carried out using a known apparatus under conditions which are appropriately set.
  • Carbonate dispersions Nos. 1 to 5 shown in Table 1 were prepared by dispersing the indicated alkali metal or alkaline earth metal carbonate and hydroxide, and a metal sulfonate (calcium or sodium salt of an alkylbenzenesulfonic acid) in a mineral oil (purified mineral oil manufactured by Nippon Oil Corporation) such that each constituent had the indicated content.
  • Table 1 also indicates the mean particle diameter and crystal structure of each alkali metal or alkaline earth metal carbonate which was used as well as the appearance of the dispersions. In each dispersion, the metals of the carbonate and hydroxide were the same.
  • Each of the lubricating compositions for cold working of Examples 1 to 18 and Comparative Examples 1 and 2 were prepared by dispersing a carbonate dispersion selected from the above-described No.1 to No. 5 and an organosulfur compound selected from the following No. 1 to No. 12 in a mineral oil (purified mineral oil manufactured by Nippon Oil Corporation) such that each constituent had the content indicated in Table 2 or 3.
  • Tables 2 and 3 include the content of the alkali metal or alkaline earth metal carbonate, its crystal structure and mean particle diameter, and the content of the alkali metal or alkaline earth metal hydroxide relative to the amount of the alkali metal or alkaline earth metal carbonate.
  • the figures with an asterisk in Table 3 indicate that the figures are outside the scope of the present invention.
  • a water-insoluble type lubricating oil (primarily comprising 15% of fatty acid esters and 70% of a sulfurized fat and fatty oil) was used.
  • a steel pipe having dimensions of 21.5 mm in outer diameter, 16.04 mm in inner diameter, and 750 mm in length (made of SUS 304) was used as a material to be worked.
  • the pipe had previously been subjected to solution treatment and then surface roughening by pickling.
  • the laboratory drawing machine had a drawing die with an inner diameter of 17.5 mm and a plug of the semi-floating type having an outer diameter of 13.2 mm in its straight portion.
  • the reduction of area of a pipe which had been subjected to cold drawing with the laboratory drawing machine was 35.6%.
  • the testing machine T had a die 1 (a female-shaped cemented carbide tool having a diameter of 20.85 mm) placed on a pedestal 7, a steel ball 4 (a male-shaped tool made of SUJ 2 (bearing steel) having a diameter of 19 mm), and a press 5 placed above the die 5 and capable of a vertical stroke.
  • a material (blank) to be worked which was used was a test plate 2 (made of SUS 304, thickness of 2.0 mm, disk shaped) having a hole 6 with a diameter of 10 mm formed at the center.
  • Each of the lubricating compositions for cold working of Examples 1 to 18 and Comparative Examples 1 to 3 was applied in an adequate amount to both surfaces of such a test plate 2.
  • the test plate 2 was then secured at the center of the die 1 with a blank holder 3.
  • the steel ball 4 was then placed on the center hole 6 of the test plate 2. This placement was carried out such that the axes of the die 1, the test plate 2, the ball 4, and a cylinder rod 8 of the press 5 were in alignment.
  • the lubricating compositions of Examples 1 to 18 had a high flash point in the range of 150 - 260° C, so it could be confirmed that these lubricating compositions could be used safely even for cold working under severe working conditions in which the temperatures of the compositions became high.

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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)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Lubricants (AREA)
  • Forging (AREA)
  • Metal Extraction Processes (AREA)
EP05819444.0A 2004-12-24 2005-12-26 Lubricant composition for cold working and cold working method using the same Expired - Fee Related EP1835012B1 (en)

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JP2004374557A JP4611014B2 (ja) 2004-12-24 2004-12-24 冷間塑性加工用潤滑剤組成物及びそれを用いた冷間塑性加工方法
PCT/JP2005/023750 WO2006068270A1 (ja) 2004-12-24 2005-12-26 冷間塑性加工用潤滑剤組成物及びそれを用いた冷間塑性加工方法

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US20090247433A1 (en) * 2006-06-15 2009-10-01 Nidec Corporation Method of preventing lubricant from deteriorating, lubricant, and dynamic-pressure bearing device
CN101498634B (zh) * 2008-10-09 2010-10-27 中国航空工业第一集团公司北京航空材料研究院 一种用于钛合金丝材的冷顶锻试验装置的夹具
JP5689088B2 (ja) * 2012-03-23 2015-03-25 新日鐵住金株式会社 冷間ピルガ圧延用潤滑剤組成物
US10160926B2 (en) * 2016-11-25 2018-12-25 Hyundai Motor Company Axle oil composition having enhanced fuel efficiency and low viscosity
WO2020191112A1 (en) * 2019-03-18 2020-09-24 Texas Tech University System Buckling-assisted manufacturing of microscopic metallic tubes and related devices
CN110790725A (zh) * 2019-11-14 2020-02-14 太平洋联合(北京)石油化工有限公司 一种含噻二唑基团的润滑油添加剂的制备方法
JP7190213B2 (ja) 2020-12-16 2022-12-15 スギムラ化学工業株式会社 塑性加工用潤滑剤組成物

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WO2006068270A1 (ja) 2006-06-29
JP4611014B2 (ja) 2011-01-12
BRPI0519409B1 (pt) 2015-11-17
EP1835012A4 (en) 2012-06-06
EP1835012A1 (en) 2007-09-19
BRPI0519409A2 (pt) 2009-01-20
ES2805345T3 (es) 2021-02-11

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