WO2012132053A1 - 塑性加工用潤滑剤組成物 - Google Patents
塑性加工用潤滑剤組成物 Download PDFInfo
- Publication number
- WO2012132053A1 WO2012132053A1 PCT/JP2011/070744 JP2011070744W WO2012132053A1 WO 2012132053 A1 WO2012132053 A1 WO 2012132053A1 JP 2011070744 W JP2011070744 W JP 2011070744W WO 2012132053 A1 WO2012132053 A1 WO 2012132053A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- branched
- linear
- mass
- carbon atoms
- Prior art date
Links
Images
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
- C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
-
- 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
- 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
- C10M2207/26—Overbased carboxylic 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
-
- 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
Definitions
- the present invention relates to a lubricant composition for plastic working.
- a metal plastic working lubricant a composition in which a sulfur base compound, a chlorine compound, a phosphate ester, or the like is blended with a lubricant base oil is known.
- the above components are appropriately combined according to the required performance.
- chlorinated compounds have been used as effective when difficult to machine stainless steel sheets.
- plastic processing lubricants non-chlorine plastic processing lubricants
- plastic working lubricants those containing zinc dithiophosphate in addition to the above-described sulfur compounds and phosphate esters have been proposed (see, for example, Patent Documents 1 to 3).
- plastic processing lubricants such as those described in Patent Documents 1 to 3 described above do not necessarily have sufficient performance. I can't say that. In particular, in some difficult processing conditions, it is difficult to obtain sufficient workability such as seizure is likely to occur.
- This invention is made
- the present invention provides a zinc dithiophosphate represented by the following general formula (1) in an amount of 0.1 to 40% by mass and a sulfur-based extreme pressure agent of 30 to 70% by mass based on the total amount of the composition. % And an organic acid salt of 10 to 60% by mass.
- R 1 and R 2 may be the same or different and each represents a linear or branched alkyl group having 1 to 18 carbon atoms.
- the lubricant composition for plastic working of the present invention is an environmentally friendly lubricant composition that does not contain a chlorine compound, and is formed by press forming, bending forming, drawing, etc. on steel plates, stainless steel plates, surface-treated steel plates, aluminum alloy plates, etc. When performing plastic working such as molding and ironing, a remarkable effect is exhibited in that good lubricity is exhibited.
- the lubricant composition for plastic working according to the present embodiment is based on the total amount of the composition, and 0.1 to 40% by mass of zinc dithiophosphate represented by the following general formula (1) and 30 to 30% of the sulfur-based extreme pressure agent. 70% by mass and 10 to 60% by mass of organic acid salt.
- R 1 and R 2 may be the same or different and each represents a linear or branched alkyl group having 1 to 18 carbon atoms. From the viewpoint of improving workability, the carbon number of R 1 and R 2 is preferably 2 to 12, more preferably 3 to 10, and most preferably 4 to 8.
- the alkyl group represented by R 1 and R 2 may be linear or branched, but is more preferably branched.
- the content of zinc dithiophosphate represented by the general formula (1) is 0.1% by mass or more and 40% by mass or less based on the total amount of the composition. From the viewpoint of cost-effectiveness commensurate with workability and content, the content is preferably 0.3 to 30% by mass, more preferably 0.7 to 25% by mass, and even more preferably 1 to 20% by mass.
- the zinc content derived from zinc dithiophosphate is preferably 0.01 to 4% by mass, and 0.03 to 3% by mass based on the total amount of the composition. % Is more preferable, and 0.05 to 2% by mass is more preferable.
- sulfur-based extreme pressure agent dihydrocarbyl polysulfide, sulfurized ester (including sulfurized fats and oils) and sulfide mineral oil are preferably used.
- the dihydrocarbyl polysulfide is a sulfur compound generally called polysulfide or sulfurized olefin, and specifically means a compound represented by the following general formula (2).
- R 3 -S a -R 4 (2) [In the formula (2), R 3 and R 4 may be the same or different, each having a linear or branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, Represents an alkylaryl group having 7 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, and a represents an integer of 2 to 6, preferably an integer of 2 to 5. ]
- R 3 and R 4 in the general formula (2) are more preferably each independently a branched alkyl group having 3 to 18 carbon atoms derived from ethylene or propylene, and is derived from ethylene or propylene.
- a branched alkyl group having 6 to 15 carbon atoms is particularly preferable.
- sulfurized ester examples include so-called sulfurized fats and oils obtained by sulfurizing animal and vegetable fats and oils such as beef tallow, pork tallow, fish fat, rapeseed oil, and soybean oil, and unsaturated fatty acids (oleic acid, linoleic acid, or the above). (Including fatty acids extracted from animal and vegetable fats and oils) and various alcohols obtained by sulfurizing unsaturated fatty acid esters obtained by any method and mixtures of animal and vegetable oils and unsaturated fatty acid esters by any method And sulfided with
- Sulfided mineral oil refers to mineral oil dissolved in elemental sulfur.
- the mineral oil used in the sulfide mineral oil according to the present invention is not particularly limited, and specifically, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation is solvent desorbed and solvent extracted. , Hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, washing with sulfuric acid, paraffinic mineral oil, naphthenic mineral oil, etc. purified by appropriately combining purification treatments such as clay treatment.
- dihydrocarbyl polysulfide and sulfurized ester are preferable from the viewpoint of improving processability.
- the content of the sulfur-based extreme pressure agent is 30 to 70% by mass based on the total amount of the composition, and is preferably 33 to 67% by mass from the viewpoint of cost-effectiveness commensurate with workability and blending amount. More preferably, 64% by mass, and even more preferably 40-60% by mass.
- the sulfur content derived from the sulfur-based extreme pressure agent is preferably 5 to 25% by mass, more preferably 7 to 23% by mass, and 8 to 22% by mass. Is more preferable, and 10 to 21% by mass is particularly preferable.
- organic acid salt sulfonate, phenate, salicylate, and a mixture thereof are preferably used.
- Positive components of these organic acid salts include alkali metals such as sodium and potassium; alkaline earth metals such as magnesium, calcium and barium; ammonia, alkylamines having 1 to 3 carbon atoms (monomethylamine, dimethyl) Amines, trimethylamines, monoethylamines, diethylamines, triethylamines, monopropylamines, dipropylamines, tripropylamines), alkanolamines having 1 to 3 carbon atoms (monomethanolamine, dimethanolamine, trimethanolamine, Monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine etc.) such as amine, zinc, etc. But an alkali metal or alkaline earth metals are preferred, calcium is particularly preferred.
- the positive component of the organic acid salt is an alkali metal or
- the total base number of the organic acid salt is preferably 50 to 500 mgKOH / g, more preferably 100 to 470 mgKOH / g, and most preferably 150 to 420 mgKOH / g. If the total base number of the organic acid salt is less than 100 mgKOH / g, the processability tends to be insufficient. On the other hand, the organic acid salt with a total base number exceeding 500 mgKOH / g is usually very difficult to manufacture. Are difficult to achieve, respectively.
- the total base number referred to here is JIS K2501 “Petroleum products and lubricants-Neutralization number test method”. The total base number [mgKOH / g] by the perchloric acid method measured according to the above.
- the sulfonate produced by any method can be used.
- alkali metal salts, alkaline earth metal salts, amine salts and mixtures of alkyl aromatic sulfonic acids obtained by sulfonating alkyl aromatic compounds having a molecular weight of 100 to 1500, preferably 200 to 700 are used. it can.
- alkyl aromatic sulfonic acid here, generally, a sulfonated alkyl aromatic compound of a lubricating oil fraction of mineral oil, a petroleum sulfonic acid such as so-called mahogany acid, which is produced as a by-product during white oil production, and a detergent Sulfurized alkylbenzene having linear or branched alkyl groups obtained by by-production from the raw material alkylbenzene production plant or alkylating polyolefin to benzene, or alkylnaphthalene such as dinonylnaphthalene And synthetic sulfonic acids such as those obtained by sulfonation of
- the above alkyl aromatic sulfonic acid and an alkali metal base such as an alkali metal oxide or hydroxide
- an alkaline earth metal base such as an alkaline earth metal oxide or hydroxide
- So-mentioned So-called neutral (normal salt) sulfonates obtained by react
- So-called carbonate overbased (superbasic) sulfonates obtained by: neutral (normal salt) sulfonates with alkali metal bases, React with potassium earth bases or amines and boric acid compounds such as boric acid or boric anhydride, or carbonate overbased (superbasic) sulfonates and boric acid compounds such as boric acid or boric anhydride. And so-called borate overbased (superbasic) sulfonates produced by reacting; and mixtures thereof.
- an alkali metal base an alkali metal oxide or Hydroxides
- alkaline earth metal bases alkaline earth metal oxides, hydroxides, etc.
- neutrals obtained by reacting with the amines mentioned above ammonia, alkylamines, alkanolamines, etc.
- Phenates neutral phenates and excess alkali metal bases, alkaline earth metal bases or amines obtained by heating in the presence of water, so-called basic phenates; neutral phenates in the presence of carbon dioxide So-called carbonate overbasic (super salt) obtained by reacting with metal base, alkaline earth metal base or amine Phenates; neutral phenates react with alkali metal bases, alkaline earth metal bases or amines and boric acid compounds such as boric acid or boric anhydride, or carbonate overbased (superbasic) phenates And so-called borate overbased (superbasic) phenates produced by reacting boric acid compounds such as boric acid or boric anhydride with boric acid or boric acid, and mixtures thereof.
- boric acid compounds such as boric acid or boric anhydride with boric acid or boric acid, and mixtures thereof.
- alkali metal base alkali metal oxide
- hydroxides alkaline earth metal bases (such as alkaline earth metal oxides and hydroxides) or the above-described amines (such as ammonia, alkylamines and alkanolamines).
- So-called basic salicylate obtained by heating neutral salicylate and excess alkali metal base, alkaline earth metal base or amine in the presence of water; neutral salicylate in the presence of carbon dioxide gas
- So-called carbonate persalts obtained by reacting with alkali metal bases, alkaline earth metal bases or amines
- neutral salicylates can be reacted with alkali metal bases, alkaline earth metal bases or amines and boric acid compounds such as boric acid or boric anhydride, or carbonate overbased (super (Basic) metal salicylates and so-called borate overbased (superbasic) salicylates produced by reacting boric acid compounds such as boric acid or boric anhydride; and mixtures thereof.
- organic acid salt calcium sulfonate, amine sulfonate, sodium sulfonate, calcium phenate, and calcium salicylate are preferable, and calcium sulfonate, calcium phenate, and calcium salicylate are particularly preferable.
- the content of the organic acid salt is 10 to 60% by mass, preferably 20 to 57% by mass, and preferably 25 to 53% by mass based on the total amount of the composition from the viewpoint of processability and cost-effectiveness corresponding to the content. Is more preferable, and 30 to 50% by mass is even more preferable.
- the content of the positive component of the organic acid salt is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, and 3 to 11% by mass. Further preferred is 4 to 8% by mass.
- the lubricant composition for plastic working according to this embodiment may be composed of zinc dithiophosphate represented by the above general formula (1), a sulfur-based extreme pressure agent, and an organic acid salt, A lubricating base oil may be contained.
- a lubricating base oil mineral oil and synthetic hydrocarbon oil are suitable.
- mineral oil for example, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, catalytic dewaxing, hydrogenation.
- mineral oil for example, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, catalytic dewaxing, hydrogenation.
- examples thereof include paraffinic mineral oil or naphthenic mineral oil that is refined by appropriately combining purification treatments such as purification, sulfuric acid washing, and clay treatment.
- The% Cp of the mineral oil is preferably from 40 to 80, more preferably from 45 to 75, and most preferably from 50 to 70, from the viewpoint of improving workability.
- % Cp here refers to “Standard Test Method for Calculation Distribution and Structural Group of Petroleum Oils of Meet-by-M” as defined in ASTM D-3238. .
- synthetic oils include propylene oligomer, polybutene, polyisobutylene, 1-octene oligomer, 1-decene oligomer, ethylene and propylene co-oligomer, ethylene and 1-octene co-oligomer, and ethylene.
- Poly ⁇ -olefins such as co-oligomers with 1-decene or their hydrides; isoparaffins; alkylbenzenes such as monoalkylbenzene, dialkylbenzene, and polyalkylbenzene; alkylnaphthalenes such as monoalkylnaphthalene, dialkylnaphthalene, and polyalkylnaphthalene These can be used alone or in combination of two or more.
- the lubricant composition for plastic working according to this embodiment may further contain one or more of a phosphorus-based extreme pressure agent, an oily agent, and an antioxidant.
- the lubricant composition for plastic working according to the present embodiment may further contain a phosphorus extreme pressure agent because high processing efficiency and an improvement effect of tool life are obtained.
- a phosphorus extreme pressure agent include phosphoric acid esters, acidic phosphoric acid esters, amine salts of acidic phosphoric acid esters, chlorinated phosphoric acid esters, phosphorous acid esters, and phosphorothioates.
- these phosphorus compounds include esters of phosphoric acid, phosphorous acid or thiophosphoric acid and alkanols, polyether type alcohols, or derivatives thereof.
- phosphoric acid esters Among the above-mentioned phosphorus-based extreme pressure agents, phosphoric acid esters, acidic phosphoric acid esters, and amine salts of acidic phosphoric acid esters are preferable because higher processing efficiency and tool life improvement effects can be obtained.
- the content of the phosphorus-based extreme pressure agent is arbitrary, but from the viewpoint of improvement in processing efficiency and improvement in tool life, it is preferably 1% by mass or more, more preferably 2% by mass or more, based on the total amount of the composition. Preferably it is 3 mass% or more. Further, from the viewpoint of improving the tool life, it is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less, based on the total amount of the composition.
- the lubricant composition for plastic working according to the present embodiment preferably contains an oiliness agent from the viewpoint of further improving the working efficiency and tool life.
- oiliness agents include alcohols, carboxylic acids, sulfides of unsaturated carboxylic acids, compounds represented by the following general formula (3), compounds represented by the following general formula (4), polyoxyalkylene compounds, esters, Mention may be made of hydrocarbyl ethers of dihydric alcohols and amines.
- R 5 represents a hydrocarbon group having 1 to 30 carbon atoms
- c represents an integer of 1 to 6, and b represents an integer of 0 to 5.
- R 6 represents a hydrocarbon group having 1 to 30 carbon atoms
- d represents an integer of 1 to 6
- e represents an integer of 0 to 5.
- examples of the monohydric alcohol include linear alcohols having 3 to 18 carbon atoms, branched alcohols having 3 to 18 carbon atoms, cycloalkyl alcohols having 5 to 10 carbon atoms, and alkylcycloalkyl alcohols. .
- linear or branched propanol including n-propanol, 1-methylethanol, etc.
- linear or branched butanol n-butanol, 1-methylpropanol, 2-methyl
- pentanol including n-pentanol, 1-methylbutanol, 2-methylbutanol, 3-methylbutanol, etc.
- linear or branched hexanol including n-hexanol, 1-methylpentanol, 2-methylpentanol, 3-methylpentanol, etc.
- linear or branched heptanol n-heptanol, 1-methylhexanol, 2-methylhexanol) , 3-methylhexanol, 4-methylhexanol, 5-methylhexanol, 2,4-dimethylpentanol, etc.
- Chain or branched octanol including n-octan
- polyhydric alcohols having 2 to 8 hydroxyl groups are preferably used.
- dihydric alcohol examples include ethylene glycol, 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, , 4-pentanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl- 2-propyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,
- trihydric or higher alcohols include trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di- ( Pentaerythritol), tri- (pentaerythritol), glycerin, polyglycerin, 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol glycerin condensate, polyvalent alcohols such as adonitol, arabitol, xylitol, mannitol, xylose, arabinose Ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, genti North, sugars such as mele
- neopentyl glycol trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythritol, di- (pentaerythritol), tri- (penta Hindered alcohols such as erythritol are preferred.
- saturated monohydric alcohols having a branched chain are preferably used from the viewpoint of processability.
- a so-called partial ester in which a part of the hydroxyl group is esterified may be used.
- the carboxylic acid may be a monobasic acid or a polybasic acid. In view of higher processing efficiency and tool life, monovalent carboxylic acids having 1 to 40 carbon atoms are preferred, more preferred are carboxylic acids having 5 to 25 carbon atoms, and most preferred are 5 to 20 carbon atoms. Carboxylic acid. These carboxylic acids may be linear or branched and may be saturated or unsaturated, but are preferably saturated carboxylic acids from the standpoint of stickiness prevention.
- a fatty acid having 2 to 24 carbon atoms is usually used as the monobasic acid.
- the fatty acid may be linear or branched, and may be saturated or unsaturated.
- saturated fatty acids having 3 to 20 carbon atoms, unsaturated fatty acids having 3 to 22 carbon atoms, and mixtures thereof are particularly preferable from the viewpoint of improving processing efficiency and tool life and handling, and having 4 to 18 carbon atoms.
- Saturated fatty acids, unsaturated fatty acids having 4 to 18 carbon atoms and mixtures thereof are more preferable, unsaturated fatty acids having 4 to 18 carbon atoms are more preferable, and saturated fatty acids having 4 to 18 carbon atoms are further preferable from the viewpoint of stickiness prevention. preferable.
- polybasic acid examples include dibasic acids having 2 to 16 carbon atoms and trimellitic acid.
- the dibasic acid having 2 to 16 carbon atoms may be linear or branched, and may be saturated or unsaturated.
- ethanedioic acid propanedioic acid, linear or branched butanedioic acid, linear or branched pentanedioic acid, linear or branched hexanedioic acid, linear Or branched heptanedioic acid, linear or branched octanedioic acid, linear or branched nonanedioic acid, linear or branched decanedioic acid, linear or branched undecanedioic acid Acid, linear or branched dodecanedioic acid, linear or branched tridecanedioic acid, linear or branched tetradecanedioic acid, linear or branched hept
- Examples of the unsaturated carboxylic acid sulfide include unsaturated sulfides of the carboxylic acid (B) described above. Specific examples include sulfides of oleic acid.
- examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R 5 include, for example, a linear or branched alkyl group having 1 to 30 carbon atoms, carbon number 5 A cycloalkyl group having 7 to 7 carbon atoms, an alkylcycloalkyl group having 6 to 30 carbon atoms, a linear or branched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, And arylalkyl groups having 7 to 30 carbon atoms.
- a linear or branched alkyl group having 1 to 30 carbon atoms is preferable, a linear or branched alkyl group having 1 to 20 carbon atoms is more preferable, and a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable.
- the substitution position of the hydroxyl group is arbitrary, but when it has two or more hydroxyl groups, it is preferably substituted with an adjacent carbon atom.
- c is preferably an integer of 1 to 3, more preferably 2.
- b is preferably an integer of 0 to 3, more preferably 1 or 2.
- Examples of the compound represented by the general formula (3) include p-tert-butylcatechol.
- examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R 6 include 1 carbon atom represented by R 1 in the general formula (2).
- examples of the hydrocarbon groups of ⁇ 30 can be mentioned, and examples of preferable ones are also the same.
- the substitution position of the hydroxyl group is arbitrary, but when it has two or more hydroxyl groups, it is preferably substituted with an adjacent carbon atom.
- d is preferably an integer of 1 to 3, and more preferably 2.
- e is preferably an integer of 0 to 3, more preferably 1 or 2.
- Examples of the compound represented by the general formula (4) include 2,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene.
- Examples of the polyoxyalkylene compound include compounds represented by the following general formula (5) or (6).
- R 7 O— (R 8 O) f —R 9 (5) [In Formula (5), R 7 and R 9 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, R 8 represents an alkylene group having 2 to 4 carbon atoms, and f is a number average molecular weight. Represents an integer such that becomes 100-3500.
- A-[(R 10 O) g -R 11 ] h (6) [In Formula (6), A represents a residue obtained by removing part or all of the hydrogen atoms of a hydroxyl group of a polyhydric alcohol having 3 to 8 hydroxyl groups, and R 10 represents an alkylene group having 2 to 4 carbon atoms. R 11 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, g represents an integer having a number average molecular weight of 100 to 3500, and h represents the number of hydrogen atoms removed from the hydroxyl group of A. Represents the same number. ]
- R 7 and R 9 is preferably a hydrogen atom.
- the hydrocarbon group having 1 to 30 carbon atoms represented by R 7 and R 9 are the same as the examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R 5 in the general formula (3). Examples of preferred ones are also the same.
- Specific examples of the alkylene group having 2 to 4 carbon atoms represented by R 8 include an ethylene group, a propylene group (methylethylene group), and a butylene group (ethylethylene group).
- f is preferably an integer such that the number average molecular weight is 300 to 2,000, more preferably an integer such that the number average molecular weight is 500 to 1,500.
- the alcohol constituting the ester may be a monohydric alcohol or a polyhydric alcohol
- the carboxylic acid may be a monobasic acid or a polybasic acid.
- the monohydric alcohol and polyhydric alcohol those similar to the monohydric alcohol and polyhydric alcohol exemplified in the description of the alcohol as the oily agent can be used.
- the alcohol constituting the ester oily agent may be a monohydric alcohol or a polyhydric alcohol, but it is possible to achieve better processing efficiency and tool life, and a low pour point.
- Polyhydric alcohols are preferred from the standpoints that products are easier to obtain and handleability in winter and cold regions is improved. Trivalent alcohol is particularly preferable. Further, when an ester of a polyhydric alcohol is used, the processability improvement and the continuous processability effect become greater.
- the acid constituting the ester oily agent may be a monobasic acid as a carboxylic acid shown as the oily agent, or a polybasic acid.
- the alkyl group of the carboxylic acid may be linear or branched and may be saturated or unsaturated, but is preferably linear or unsaturated.
- a polyhydric alcohol When a polyhydric alcohol is used as the alcohol component, it may be a complete ester in which all the hydroxyl groups in the polyhydric alcohol are esterified, or a partial ester in which some of the hydroxyl groups are not esterified and remain as hydroxyl groups. Good. Further, when a polybasic acid is used as the carboxylic acid component, it may be a complete ester in which all the carboxyl groups in the polybasic acid are esterified, or a part of the carboxyl group is not esterified and remains as a carboxyl group. It may be a partial ester.
- the total number of carbon atoms of the ester oil-based agent is not particularly limited, but from the viewpoint of improving processing efficiency and tool life, an ester having a total carbon number of 7 or more is preferable, an ester of 9 or more is more preferable, and an ester of 11 or more is preferable. Most preferred. Further, from the viewpoint of not increasing the occurrence of stain and corrosion, and compatibility with organic materials, an ester having a total carbon number of 60 or less is preferred, an ester of 45 or less is more preferred, an ester of 26 or less is more preferred, 24 or less esters are more preferred, and 22 or less esters are most preferred.
- the polyhydric alcohol constituting the hydrocarbyl ether of the polyhydric alcohol is the same as the polyhydric alcohol of the alcohol compound according to the present invention.
- ethylene glycol propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan, and mixtures thereof.
- glycerin is most preferable from the viewpoint of improving the processing efficiency and the tool life.
- hydrocarbyl ether of the polyhydric alcohol one obtained by converting a part or all of the hydroxyl groups of the polyhydric alcohol into a hydrocarbyl ether can be used. From the viewpoint of improving processing efficiency and tool life, a product obtained by hydrocarbyl etherifying a part of hydroxyl groups of a polyhydric alcohol (partially etherified product) is preferable.
- the hydrocarbyl group here means an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an alkylcycloalkyl group having 6 to 11 carbon atoms, carbon Represents a hydrocarbon group having 1 to 24 carbon atoms such as an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms, and an arylalkyl group having 7 to 18 carbon atoms.
- a linear or branched alkyl group having 2 to 18 carbon atoms and a linear or branched alkenyl group having 2 to 18 carbon atoms are preferable.
- 3-12 linear or branched alkyl groups and oleyl groups (residues obtained by removing hydroxyl groups from oleyl alcohol) are more preferred.
- Monoamine is preferably used as the amine.
- the carbon number of the monoamine is preferably 6 to 24, more preferably 12 to 24.
- the carbon number here means the total number of carbon atoms contained in the moamine, and when the monoamine has two or more hydrocarbon groups, it represents the total number of carbon atoms.
- any of a primary monoamine, a secondary monoamine, and a tertiary monoamine can be used, but a primary monoamine is preferable from the viewpoint of improving processing efficiency and tool life.
- any of an alkyl group, alkenyl group, cycloalkyl group, alkylcycloalkyl group, aryl group, alkylaryl group, arylalkyl group, etc. can be used. From the viewpoint of improving efficiency and tool life, an alkyl group or an alkenyl group is preferable.
- the alkyl group and alkenyl group may be linear or branched, but are preferably linear from the viewpoint of improving processing efficiency and tool life.
- preferred monoamines include hexylamine (including all isomers), heptylamine (including all isomers), octylamine (including all isomers), nonylamine (all Including isomers), decylamine (including all isomers), undecylamine (including all isomers), dodecylamine (including all isomers), tridecylamine (including all isomers) , Tetradecylamine (including all isomers), pentadecylamine (including all isomers), hexadecylamine (including all isomers), heptadecylamine (including all isomers), octadecyl Amines (including all isomers), nonadecylamine (including all isomers), icosylamine (including all isomers), heicosylamine (including all isomers) All isomers), docosylamine (including all isomers), tricosylamine (including all isomers), tri
- primary monoamines having 12 to 24 carbon atoms are preferable, primary monoamines having 14 to 20 carbon atoms are more preferable, and primary monoamines having 16 to 18 carbon atoms are preferable from the viewpoint of improving machining efficiency and tool life.
- Grade monoamines are more preferred.
- only one kind selected from the above oil agents may be used, or a mixture of two or more kinds may be used.
- the content of the oily agent is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less, based on the total amount of the composition. If the amount is too large, an effect commensurate with the amount added cannot be obtained.
- the lubricant composition for plastic working according to the present embodiment further contains an antioxidant.
- an antioxidant By adding an antioxidant, it is possible to prevent stickiness due to alteration of the constituent components, and to improve thermal and oxidation stability.
- antioxidants examples include phenolic antioxidants, amine-based antioxidants, and those used as other food additives.
- any phenolic compound used as an antioxidant for lubricating oils can be used, and is not particularly limited, but for example, an alkylphenol compound is preferable.
- any amine-based compound used as an antioxidant for lubricating oils can be used, and is not particularly limited.
- phenyl- ⁇ -naphthylamine, Np-alkyl Phenyl- ⁇ -naphthylamine and p, p′-dialkyldiphenylamine are preferred, and specific examples include 4-butyl-4′-octyldiphenylamine, phenyl- ⁇ -naphthylamine, octylphenyl- ⁇ -naphthylamine, dodecylphenyl. - ⁇ -naphthylamine and mixtures thereof.
- an antioxidant used as a food additive can also be used, and partially overlaps with the above-mentioned phenolic antioxidant.
- DBPC 2,6-di-tert-butyl-p-cresol
- ascorbic acid vitamin C
- fatty acid ester of ascorbic acid tocopherol
- vitamin E 3,5-di-tert-butyl-4-hydroxyanisole, 2-tert-butyl-4- Hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, 1,2-dihydro-6-ethoxy-2,2,4-tri Chirukinorin (ethoxyquin)
- 2- (1,1-dimethyl) -1,4-benzenediol TBHQ
- antioxidants those used as phenolic antioxidants, amine antioxidants, and food additives are preferable. Furthermore, when importance is attached to biodegradability, those used as the above-mentioned food additives are more preferable.
- the content of the antioxidant is not particularly limited, but in order to maintain good heat / oxidation stability, the content is preferably 0.01% by mass or more based on the total amount of the composition, more preferably 0.05. % By mass or more, most preferably 0.1% by mass or more. On the other hand, since the effect cannot be expected even if it is added more, the content is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 3% by mass or less.
- the lubricant composition for plastic working according to the present embodiment may contain conventionally known additives other than those described above.
- additives include extreme pressure agents other than the above-mentioned phosphorus-based extreme pressure agents and sulfur-based extreme pressure agents; wetting agents such as diethylene glycol monoalkyl ether; acrylic polymers, paraffin wax, microwax, slack wax, polyolefin wax.
- Film formers such as fatty acid amine salts; solid lubricants such as graphite, fluorinated graphite, molybdenum disulfide, boron nitride, polyethylene powder; amines, alkanolamines, amides, carboxylic acids, carboxylates, Corrosion inhibitors such as sulfonate, phosphoric acid, phosphate, partial ester of polyhydric alcohol; metal deactivators such as benzotriazole and thiadiazole; antifoaming agents such as methylsilicone, fluorosilicone and polyacrylate; alkenyl Succinimide, benzylamine, polyalkke Ashless dispersants such as propylamine polyaminoamide; and the like.
- the content when these known additives are used in combination is not particularly limited, but is added in such an amount that the total content of these known additives is 0.1 to 10% by mass based on the total amount of the composition. It is common.
- the plastic working lubricant composition according to the present embodiment may contain a chlorine-based additive such as a chlorine-based extreme pressure agent as described above, but it improves safety and reduces the burden on the environment. From the viewpoint, it is preferable that no chlorine-based additive is contained.
- the chlorine concentration is preferably 1000 ppm by mass or less, more preferably 500 ppm by mass or less, still more preferably 200 ppm by mass or less, and 100 ppm by mass or less, based on the total amount of the composition. It is particularly preferred.
- the lubricant composition according to this embodiment is used for plastic working of metal materials.
- it is preferably used for difficult-to-work materials such as steel plates, stainless steel plates, surface-treated steel plates, aluminum alloy plates, and titanium alloys.
- it is preferably used in difficult processing conditions such as press molding, bending molding, pultrusion molding, ironing molding and forging.
- Example 1 to 28, Reference Example 1, Comparative Examples 1 to 12 lubricant compositions having the compositions shown in Tables 1 to 6 were prepared using the following components, respectively.
- A2 Zinc dithiophosphate having a structure represented by the general formula (1), wherein R 1 and R 2 are linear (pri-) alkyl groups having 4 or 5 carbon atoms (zinc content: 10% by mass) )
- A3 Zinc dithiophosphate having a structure represented by the general formula (1), wherein R 1 and R 2 are branched (sec-) alkyl groups having 12 carbon atoms (zinc content: 7.5% by mass) )
- A4 Zinc dithiophosphate having a structure represented by the general formula (1) and R 1 and R 2 being a branched chain (pri-) alkyl group having 18 carbon atoms (zinc content: 11% by mass)
- B1 Sulfurized ester (sulfurized oil) (sulfur content 28% by mass)
- B2 Di-t-nonyl polys
- D5 Polyalphaolefin (kinematic viscosity at 40 ° C.
- E1 Acid phosphate (mixture of mono n-octyl acid phosphate and di n-octyl acid phosphate (phosphorus content: 11.6% by mass))
- E2 Ester: Glycerol trioleate
- E3 Fatty acid: Oleic acid
- E4 Antioxidant: 2,6-di-tert-butyl-p-cresol (DBPC)
- E5 Chlorinated paraffin (chlorine content, 50% by mass)
- FIG. 1 is a schematic cross-sectional view showing the configuration of a burring tester used in this test.
- a burring tester shown in FIG. 1 includes a support 1 having a hollow inside, a die 2 disposed on the support 1, a die cushion 3 provided in a hollow portion of the support 1, a die 2 and a punch 5 provided above the die 2.
- the test first, using a waste impregnated with the lubricant composition, 1 to 2 g / m 2 on both surfaces of the test piece 6 (material SUS304, outer diameter 80 mm, inner diameter 4 mm, thickness 2 mm).
- the lubricant composition was applied so that Next, a test piece 6 and a steel ball 7 (material SUJ2, diameter 15 mm) are placed on the die 2, and the steel ball 7 is pressed from the upper side by the punch 5 while being held by the wrinkle pressing member 4, and the die cushion 3 And the test piece 6 was squeezed.
- the test temperature at this time is 100 ° C.
- the ironing ratio ((thickness of test piece 6 before deformation ⁇ thickness of deformed portion after squeezing) / thickness of test piece 6 before test) is 62.5%.
- the processing speed was 10 mm / s. The presence or absence of seizure and adhesion between the test piece 6 and the steel ball 7 was observed visually.
- Evaluation criteria for the presence or absence of seizure are as follows. S: No burn-in at all A: No burn-in but slight cloudiness on the surface B: Slight burn-in C: There is burn-in on the entire surface.
- the evaluation criteria for the presence or absence of adhesion are as follows. S: There is no adhesion. A: There is no adhesion, but there is some cloudiness on the surface. B: There is some adhesion. C: Adhesion is on the entire surface. The results obtained are shown in Tables 1-6.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
Description
R3-Sa-R4 (2)
[式(2)中、R3及びR4は同一でも異なっていてもよく、それぞれ炭素数3~20の直鎖状又は分枝状のアルキル基、炭素数6~20のアリール基、炭素数7~20のアルキルアリール基あるいは炭素数7~20のアリールアルキル基を表し、aは2~6の整数、好ましくは2~5の整数を表す。]
本実施形態に係る塑性加工用潤滑剤組成物は、高い加工効率及び工具寿命の向上効果が得られることからリン系極圧剤をさらに含有してもよい。リン系極圧剤としては、具体的には、リン酸エステル、酸性リン酸エステル、酸性リン酸エステルのアミン塩、塩素化リン酸エステル、亜リン酸エステル及びフォスフォロチオネート等が挙げられる。これらのリン化合物は、リン酸、亜リン酸又はチオリン酸とアルカノール、ポリエーテル型アルコールとのエステルあるいはその誘導体が挙げられる。
本実施形態に係る塑性加工用潤滑剤組成物は、加工効率及び工具寿命がより高められる点から、油性剤を含有することが好ましい。油性剤としては、アルコール、カルボン酸、不飽和カルボン酸の硫化物、下記一般式(3)で表される化合物、下記一般式(4)で表される化合物、ポリオキシアルキレン化合物、エステル、多価アルコールのハイドロカルビルエーテル及びアミンなどを挙げることができる。
R7O-(R8O)f-R9 (5)
[式(5)中、R7及びR9は各々独立に水素原子又は炭素数1~30の炭化水素基を表し、R8は炭素数2~4のアルキレン基を表し、fは数平均分子量が100~3500となるような整数を表す。]
A-[(R10O)g-R11]h (6)
[式(6)中、Aは、水酸基を3~8個有する多価アルコールの水酸基の水素原子の一部又は全てを取り除いた残基を表し、R10は炭素数2~4のアルキレン基を表し、R11は水素原子又は炭素数1~30の炭化水素基を表し、gは数平均分子量が100~3500となるような整数を表し、hはAの水酸基から取り除かれた水素原子の個数と同じ数を表す。]
また、本実施形態に係る塑性加工用潤滑剤組成物は、酸化防止剤を更に含有していることが好ましい。酸化防止剤の添加により、構成成分の変質によるべたつきを防止することができ、また、熱・酸化安定性を向上させることができる。
また、本実施形態に係る塑性加工用潤滑剤組成物は、上記した以外の従来公知の添加剤を含有することができる。かかる添加剤としては、例えば、上記したリン系極圧剤及び硫黄系極圧剤以外の極圧剤;ジエチレングリコールモノアルキルエーテル等の湿潤剤;アクリルポリマー、パラフィンワックス、マイクロワックス、スラックワックス、ポリオレフィンワックス等の造膜剤;脂肪酸アミン塩等の水置換剤;グラファイト、フッ化黒鉛、二硫化モリブデン、窒化ホウ素、ポリエチレン粉末等の固体潤滑剤;アミン、アルカノールアミン、アミド、カルボン酸、カルボン酸塩、スルホン酸塩、リン酸、リン酸塩、多価アルコールの部分エステル等の腐食防止剤;ベンゾトリアゾール、チアジアゾール等の金属不活性化剤;メチルシリコーン、フルオロシリコーン、ポリアクリレート等の消泡剤;アルケニルコハク酸イミド、ベンジルアミン、ポリアルケニルアミンアミノアミド等の無灰分散剤;等が挙げられる。これらの公知の添加剤を併用する場合の含有量は特に制限されないが、これらの公知の添加剤の合計含有量が組成物全量基準で0.1~10質量%となるような量で添加するのが一般的である。
実施例1~28、参考例1、比較例1~12においては、それぞれ以下の成分を用いて、表1~6に示す組成を有する潤滑剤組成物を調製した。
(A)成分:亜鉛ジチオフォスフェート(「亜鉛含有量」は希釈油等を含んだ状態での値を意味する。)
A1:一般式(1)で表される構造を有し、式中のR1及びR2が炭素数6の分岐鎖型(sec-)アルキル基である亜鉛ジチオフォスフェート(亜鉛含有量9.3質量%)
A2:一般式(1)で表される構造を有し、R1及びR2が炭素数4又は5の直鎖型(pri-)アルキル基である亜鉛ジチオフォスフェート(亜鉛含有量10質量%)
A3:一般式(1)で表される構造を有し、R1及びR2が炭素数12の分岐鎖型(sec-)アルキル基である亜鉛ジチオフォスフェート(亜鉛含有量7.5質量%)
A4:一般式(1)で表される構造を有し、R1及びR2が炭素数18の分岐鎖型(pri-)アルキル基である亜鉛ジチオフォスフェート(亜鉛含有量11質量%)
(B)成分:硫黄系極圧剤(「硫黄含有量」は希釈油等を含んだ状態での値を意味する。)
B1:硫化エステル(硫化油脂)(硫黄含有量28質量%)
B2:ジ-t-ノニルポリサルファイド(t-ノニル基はプロピレンの3量体から誘導されたもの;1分子中の平均硫黄原子数4.6;硫黄含有量38質量%)
B3:硫化ラード(硫黄含有量19質量%)
(C)成分:有機酸塩(「Ca、Na含有量」は希釈油等を含んだ状態での値を意味する。)
C1:カルシウムスルホネート(塩基価403mgKOH/g Ca含有量15%)
C2:ナトリウムスルホネート(塩基価165mgKOH/g Na含有量11%)
C3:カルシウムフェネート(塩基価302mgKOH/g Ca含有量10%)
C4:カルシウムサリシレート(塩基価274mgKOH/g Ca含有量15%)
C5:カルシウムスルホネート(塩基価101mgKOH/g Ca含有量18%)
C6:カルシウムスルホネート(塩基価51mgKOH/g Ca含有量13%)
(D)炭化水素油
D1:鉱油(40℃における動粘度94mm2/s、%Cp=67)
D2:鉱油(40℃における動粘度101mm2/s、%Cp=51)
D3:鉱油(40℃における動粘度95mm2/s、%Cp=78)
D4:鉱油(40℃における動粘度96mm2/s、%Cp=44)
D5:ポリαオレフィン(40℃における動粘度98mm2/s)
その他の添加剤
E1:酸性リン酸エステル(モノn-オクチルアシッドホスフェートとジn-オクチルアシッドホスフェートの混合物(リン含有量:11.6質量%))
E2:エステル:グリセリントリオレート
E3:脂肪酸:オレイン酸
E4:酸化防止剤:2,6-ジ-tert-ブチル-p-クレゾール(DBPC)
E5:塩素化パラフィン(塩素分、50質量%)
実施例1~28、参考例1、比較例1~12の各潤滑剤組成物を用いて、以下に示すバーリング試験を実施した。
図1は本試験に用いたバーリング試験機の構成を示す模式断面図である。図1に示したバーリング試験機は、内部が中空になっている支持体1と、支持体1上に配置されたダイス2と、支持体1の中空部に設けられたダイクッション3と、ダイス2の上方に配置されたしわ押さえ部材4と、ダイス2の上方に設けられたパンチ5とを備える。
試験に際しては、まず、潤滑剤組成物を含侵させたウエスを用いて、試験片6(材質SUS304材、外径80mm、内径4mm、厚さ2mm)の両面に、1~2g/m2となるように潤滑剤組成物を塗布した。次に、ダイス2上に試験片6及び鋼球7(材質SUJ2、直径15mm)を配置し、これらをしわ押さえ部材4で保持しながら、パンチ5により上側から鋼球7を押しつけるとともにダイクッション3を上昇させて、試験片6をしごいた。このときの試験温度は100℃、しごき率((変形前の試験片6の厚さ-しごいた後の変形部の厚さ)/試験前の試験片6の厚さ)は62.5%、加工速度は10mm/sとした。そして、試験片6と鋼球7の間での焼き付き及び凝着の有無を、それぞれ目視にて観察した。
焼付きの有無の評価基準は以下の通りである。
S:焼き付きが全く無い
A:焼き付きないが表面に若干の曇りあり
B:焼き付きがややある。
C:焼き付きが全面にある。
また、凝着の有無の評価基準は以下の通りである。
S:凝着が全く無い。
A:凝着ないが表面に若干の曇りあり
B:凝着がややある。
C:凝着が全面にある。
得られた結果を表1~6に示す。
Claims (1)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201180069702.XA CN103443259B (zh) | 2011-03-29 | 2011-09-12 | 塑性加工用润滑剂组合物 |
JP2013507034A JP5668135B2 (ja) | 2011-03-29 | 2011-09-12 | 塑性加工用潤滑剤組成物 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011-072537 | 2011-03-29 | ||
JP2011072537 | 2011-03-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012132053A1 true WO2012132053A1 (ja) | 2012-10-04 |
Family
ID=46929862
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/070744 WO2012132053A1 (ja) | 2011-03-29 | 2011-09-12 | 塑性加工用潤滑剤組成物 |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP5668135B2 (ja) |
CN (1) | CN103443259B (ja) |
WO (1) | WO2012132053A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014181286A (ja) * | 2013-03-19 | 2014-09-29 | Jx Nippon Oil & Energy Corp | 塑性加工用潤滑油組成物 |
JP2018039914A (ja) * | 2016-09-07 | 2018-03-15 | Jxtgエネルギー株式会社 | 金属加工油組成物 |
JP2018538424A (ja) * | 2015-11-04 | 2018-12-27 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンHenkel AG & Co. KGaA | 脂肪酸および脂肪酸グリセリドに基づく粉末潤滑剤ならびにその使用 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014145052A (ja) * | 2013-01-30 | 2014-08-14 | Yokohama National Univ | 塑性加工用潤滑剤組成物 |
CN104818103B (zh) * | 2015-03-23 | 2021-03-23 | 重庆电讯职业学院 | 汽车用低碳钢件冷挤压成形润滑剂及其制备方法 |
CN105567392B (zh) * | 2015-12-23 | 2018-03-02 | 南京科润新材料技术有限公司 | 一种拉拔润滑油 |
CN106635302A (zh) * | 2016-09-21 | 2017-05-10 | 广西大学 | 一种625合金冷冲压润滑剂组合物 |
CN107523404B (zh) * | 2017-08-16 | 2020-06-26 | 李静 | 水基防锈金属冷锻润滑剂及其制备方法 |
CN109666530B (zh) * | 2017-10-13 | 2021-11-19 | 中国石油化工股份有限公司 | 一种轴承加工专用的冷辗扩油组合物 |
CN108441279B (zh) * | 2018-04-11 | 2020-11-17 | 江苏捷达油品有限公司 | 一种双组分的高润滑性防锈乳化油及其制备方法和应用 |
CN109536250B (zh) * | 2018-11-02 | 2021-09-14 | 欧陆宝(天津)新材料科技有限公司 | 一种环保可降解的铝及其合金拉拔工艺润滑剂及制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002285181A (ja) * | 2001-03-22 | 2002-10-03 | Nippon Oil Corp | 塑性加工用潤滑油組成物 |
JP2007119680A (ja) * | 2005-10-31 | 2007-05-17 | Toyota Boshoku Corp | 金属材料加工用の潤滑油 |
JP2008055426A (ja) * | 2005-11-22 | 2008-03-13 | Toyota Boshoku Corp | 金属材料のプレス加工方法 |
JP2008195765A (ja) * | 2007-02-09 | 2008-08-28 | Toyota Boshoku Corp | 金属材料プレス加工用の潤滑油とそれを用いた金属材料のプレス加工方法 |
JP2009209239A (ja) * | 2008-03-03 | 2009-09-17 | Nippon Oil Corp | 塑性加工用潤滑油組成物 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4485390B2 (ja) * | 2005-03-11 | 2010-06-23 | トヨタ紡織株式会社 | 金属材料加工用の潤滑油 |
-
2011
- 2011-09-12 CN CN201180069702.XA patent/CN103443259B/zh active Active
- 2011-09-12 WO PCT/JP2011/070744 patent/WO2012132053A1/ja active Application Filing
- 2011-09-12 JP JP2013507034A patent/JP5668135B2/ja active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002285181A (ja) * | 2001-03-22 | 2002-10-03 | Nippon Oil Corp | 塑性加工用潤滑油組成物 |
JP2007119680A (ja) * | 2005-10-31 | 2007-05-17 | Toyota Boshoku Corp | 金属材料加工用の潤滑油 |
JP2008055426A (ja) * | 2005-11-22 | 2008-03-13 | Toyota Boshoku Corp | 金属材料のプレス加工方法 |
JP2008195765A (ja) * | 2007-02-09 | 2008-08-28 | Toyota Boshoku Corp | 金属材料プレス加工用の潤滑油とそれを用いた金属材料のプレス加工方法 |
JP2009209239A (ja) * | 2008-03-03 | 2009-09-17 | Nippon Oil Corp | 塑性加工用潤滑油組成物 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014181286A (ja) * | 2013-03-19 | 2014-09-29 | Jx Nippon Oil & Energy Corp | 塑性加工用潤滑油組成物 |
JP2018538424A (ja) * | 2015-11-04 | 2018-12-27 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンHenkel AG & Co. KGaA | 脂肪酸および脂肪酸グリセリドに基づく粉末潤滑剤ならびにその使用 |
US10975324B2 (en) | 2015-11-04 | 2021-04-13 | Henkel Ag & Co. Kgaa | Powder lubricant based on fatty acids and fatty acid glycerides and use thereof |
JP2018039914A (ja) * | 2016-09-07 | 2018-03-15 | Jxtgエネルギー株式会社 | 金属加工油組成物 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2012132053A1 (ja) | 2014-07-24 |
JP5668135B2 (ja) | 2015-02-12 |
CN103443259A (zh) | 2013-12-11 |
CN103443259B (zh) | 2015-10-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5668135B2 (ja) | 塑性加工用潤滑剤組成物 | |
JP5566037B2 (ja) | 極微量油剤供給式アルミニウム加工用油剤組成物 | |
EP1741771A1 (en) | Metalworking fluid | |
WO2008032504A1 (fr) | Procédé de découpage/meulage avec lubrification en quantité minimale, et composition d'huile pour un découpage/meulage avec lubrification en quantité minimale | |
JP2008163115A (ja) | 金属加工油組成物 | |
US8058217B2 (en) | Metal working fluid | |
JP2005290161A (ja) | 金属加工油 | |
JP6002523B2 (ja) | 潤滑剤組成物およびそれを用いた成形方法 | |
JP2002105476A (ja) | 潤滑油組成物 | |
JP2019137748A (ja) | 潤滑油用添加剤組成物及び潤滑油組成物 | |
JP5462993B2 (ja) | 金属加工油組成物 | |
JP5638431B2 (ja) | 金属加工用潤滑油組成物 | |
JP4599078B2 (ja) | 金属加工油組成物 | |
JP5283529B2 (ja) | アルミニウム加工用潤滑油組成物 | |
JP2005307200A (ja) | 潤滑油組成物 | |
JP5089179B2 (ja) | 極微量油剤供給式切削・研削加工方法 | |
JP5380408B2 (ja) | 金属加工油及び金属加工方法 | |
JP2005187647A (ja) | 工作機械用潤滑油及び工作機械の潤滑方法 | |
JP2008088428A (ja) | 金属加工用潤滑油組成物 | |
JP2014145052A (ja) | 塑性加工用潤滑剤組成物 | |
JP2009286823A (ja) | 切り屑吸引式切削・研削加工用油剤組成物 | |
JP6232194B2 (ja) | 塑性加工用潤滑油組成物 | |
WO2023190158A1 (ja) | 潤滑油組成物 | |
JP2008248990A (ja) | 転がり案内面の潤滑方法 | |
JP2006249370A (ja) | 金属加工油組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11862065 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2013507034 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1301005474 Country of ref document: TH |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 11862065 Country of ref document: EP Kind code of ref document: A1 |