WO2005095556A1 - 金属加工油 - Google Patents
金属加工油 Download PDFInfo
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- WO2005095556A1 WO2005095556A1 PCT/JP2005/005878 JP2005005878W WO2005095556A1 WO 2005095556 A1 WO2005095556 A1 WO 2005095556A1 JP 2005005878 W JP2005005878 W JP 2005005878W WO 2005095556 A1 WO2005095556 A1 WO 2005095556A1
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
- C10M111/02—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a non-macromolecular organic compound
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- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
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- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
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- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/02—Well-defined aliphatic compounds
- C10M2203/0206—Well-defined aliphatic compounds used as base material
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
- C10M2207/2825—Esters of (cyclo)aliphatic oolycarboxylic acids used as base material
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
- C10M2207/2835—Esters of polyhydroxy compounds used as base material
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
- C10M2207/401—Fatty vegetable or animal oils used as base material
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
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- 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
- C10M2223/041—Triaryl phosphates
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- 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
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/30—Anti-misting
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
Definitions
- the present invention relates to a metal working oil.
- Sharpness 1 In grinding, machining such as extending the life of tools used for machining, such as drills, end mills, cutting tools, and gantry, improving the surface roughness of workpieces, and thereby improving machining efficiency. For the purpose of improving productivity in the field, cutting oils for grinding are usually used.
- Cutting and grinding oils are used in the form of a water-soluble cutting oil that is used by diluting a surfactant and a lubricating component with water.
- Water-soluble water-soluble There are two main types: grinding fluids. In general, water-insoluble cutting and grinding fluids have excellent lubrication performance, and water-soluble cutting and grinding fluids have excellent cooling performance.
- Sharpening oils that are effective in improving processing efficiency 1 Grinding oils are also unfavorable from another aspect, and their typical problem is the effect on the environment. Oils, whether water-insoluble or water-soluble, gradually degrade during use and eventually become unusable. For example, in the case of a water-soluble oil agent, the stability of the liquid is reduced due to the generation of microorganisms, and the components are separated, or the sanitary environment is remarkably deteriorated and the use of the oil becomes impossible. In addition, in the case of water-insoluble oils, the acidic components generated by the progress of acidification cause corrosion of the metal material and a remarkable change in the viscosity, making it impossible to use them. In addition, the oil is attached to the chips and consumed, resulting in waste.
- oils discharged as waste require various treatments so as not to affect the environment.
- cutting and grinding fluids that have been developed with a priority on improving work efficiency use many chlorine compounds that can generate toxic dioxins during incineration. Removal processing is required. Therefore, chlorine compounds Grinding fluids that do not contain water are also being developed.
- Even grinding fluids that do not contain powerful harmful ingredients have the problem of affecting the environment due to the large amount of waste discharged. .
- water-soluble oils there is a possibility of contaminating the environmental waters, so it is necessary to perform advanced treatment at a high cost.
- the present invention has been made in view of such circumstances, and has properties as a water-insoluble oil agent for processing non-ferrous metals, and characteristics as an oil agent for grinding using a very small amount of oil supply system.
- An object of the present invention is to provide a metal working oil which is excellent in machining efficiency and can achieve a long working life of a tool.
- the present invention provides an ester oil having a kinematic viscosity at 40 ° C of 1 to
- a metal working oil characterized by containing 20 mm 2 Zs of hydrocarbon oil hereinafter referred to as “first metal working oil” and! ⁇ ⁇ ).
- the first metal-added oil becomes insoluble in non-ferrous metal-added oil.
- non-ferrous metals particularly aluminum
- the second metalworking oil has the above-described configuration, when used as a cutting oil IJ 'grinding oil with a trace amount of oil, a good oil mist can be formed, and Higher efficiency and longer tool life can be achieved.
- the hydrocarbon oil is at least one selected from white oil and polyolefin or a hydride power thereof.
- the water content of the first metalworking oil is preferably 200 to 20000 ppm.
- the present invention also provides a metal working oil (hereinafter, referred to as "second metal working oil") having an ester oil as a base oil and a water content of 200 to 20,000 ppm. .
- the second metal working oil can be used as a water-insoluble material for processing non-ferrous metals.
- welding of non-ferrous metals (particularly aluminum) to the tool and increase in resistance to kneading can be sufficiently suppressed, and it is possible to improve machining efficiency and extend tool life.
- the second metal working oil since the second metal working oil has the above-described configuration, it can form a good oil mist when used as a grinding oil in a very small amount of oil supply system. Higher efficiency and longer tool life can be achieved.
- the second metalworking oil contains ester oil that is more biodegradable than mineral oil and the like and water that does not affect the environment, it is also useful in reducing the burden on the environment. It is.
- the above-mentioned effect of the second metal working oil can be obtained by setting the water content within the above range while sufficiently suppressing phenomena such as generation of separated water and hydrolysis of ester oil. It is based on the knowledge of the present inventors that the excellent properties of water as an additive can be effectively used. This can be said to be an unexpected effect in view of the conventional technical common sense that, when ester oil is used, the water content is reduced as much as possible from the viewpoint of suppressing hydrolysis of the ester oil.
- first and second metal working oils further contain an oily agent and Z or an extreme pressure agent, respectively.
- the first and second metal working oils according to the present invention are suitably used for non-ferrous metal working. Further, the first and second metal working oils are suitably used for cutting, grinding, or rolling, and are also suitably used for metal working with a very small amount of oil agent supply system.
- the trace amount oil supply type metal processing refers to a metal processing in which a very small amount of oil, iZiooooo to iZioooooo, is reduced together with the compressed fluid to the grinding point in comparison with the amount of oil used in normal metal processing.
- Metalworking performed while More specifically, the ultra-small amount of oil supply system means that a very small amount of oil, usually at most 1 milliliter or less, is directed to a processing site (for example, cutting surface) along with a compressed fluid (for example, compressed air).
- a compressed fluid for example, compressed air
- a compressed fluid such as nitrogen, argon, helium, carbon dioxide, and water may be used alone, or some fluids may be used in combination.
- the oil is supplied after being misted, and therefore, when an oil having low stability is used, the oil adheres to the inside of a machine tool, a workpiece, a tool, a mist collector, or the like. This may cause stickiness, impair handling, and reduce work efficiency. Therefore, it is desirable that the oil agent used in the ultra-trace oil agent supply system be less sticky.
- the first and second metal working oils according to the present invention are both suitably used for metal working with a trace amount of oil agent supply method.
- the first metalworking oil is particularly preferred.
- the characteristics as a water-insoluble oil agent for processing non-ferrous metals and the characteristics as an oil agent for grinding using a very small amount of oil supply system are excellent, thereby improving the processing efficiency and improving the processing efficiency.
- a metal working oil capable of achieving a longer tool life is provided.
- FIG. 1 is an explanatory view showing an example of a machine tool suitably used in a very small amount of oil supply system cutting method 1 grinding method.
- the first metalworking oil that works in the present invention comprises (A) an ester oil and (B) a hydrocarbon oil having a kinematic viscosity at 40 ° C of ⁇ to 20 mm 2 Zs (hereinafter simply referred to as “(B) Hydrocarbon oils ”.
- the ester oil (A) may be a natural product (usually contained in natural fats and oils such as animals and plants) or a synthetic product.
- synthetic esters are preferred from the viewpoint of the stability of the obtained lubricating oil and the uniformity of the ester component. From the viewpoint of the effect on the environment, natural esters are preferred.
- the alcohol constituting (A) the ester oil may be a monohydric alcohol or a polyhydric alcohol, and the acid constituting the (A) ester oil may be a monobasic acid or a polybasic acid.
- the monohydric alcohol one having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms is used.
- Such an alcohol may be linear or branched. And it may be saturated or unsaturated.
- the alcohol having 1 to 24 carbon atoms include, for example, methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol, Straight or branched hexanol, straight or branched heptanol, straight or branched octanol, straight or branched nonanol, straight or branched decanol, straight chain Linear or branched dodecanol, linear or branched dodecanol, linear or branched tridecanol, linear or branched tetradecanol, linear or branched pentadecanol, Linear or branched hexadecanol, linear or
- polyhydric alcohol one having usually 2 to 10 valences, preferably 2 to 6 valences is used.
- Specific examples of the polyhydric alcohols having 2 to 10 include, for example, ethylene glycol, ethylene glycol, polyethylene glycol (3 to 15-mer of ethylene glycol), propylene Glycol, dipropylene glycol, polypropylene glycol (3 to 15 mer of propylene glycol), 1,3 propanediol, 1,2 propanediol, 1,3 butanediol, 1,4 butanediol, 2-methyl-1,2 Propanediol, 2-methyl 1,3-propanediol, 1,2-pentanediol, 1,3-pentanediol, 1
- Dihydric alcohols such as 1,4-pentanediol, 1,5-pentanediol, and neopentyl glycol; glycerin, polyglycerin (2 to 8 mer of glycerin, such as diglycerin, triglycerin, tetraglycerin, etc.), trimethylolalkane (trimethyl alcohol) Methylolethane, trimethylolpropane, trimethylolbutane, etc.) and their dimer to octamer, pentaerythritol and their dimer to tetramer, 1,2,4 butanetriol, 1,3,5 pentanetriol Polyhydric alcohols such as 1,2,6 hexanetriol, 1,2,3,4 butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adtol, arabitol, xylitol, mannitol;
- ethylene glycol propylene glycol
- neopentyl glycol glycerin
- trimethylonoleethane trimethylolpropane
- pentaerythritol sorbitan
- mixtures thereof neopentyldaricol, trimethylolethane, trimethylolpropane, pentaerythritol, a mixture thereof, and the like are most preferable because higher thermal stability can be obtained.
- the alcohol constituting the ester oil may be a monohydric alcohol or a polyhydric alcohol as described above.
- Polyhydric alcohols are preferred from the viewpoints of low points, improved properties, and quick handling in winter and cold regions, and improved properties.
- the effect of improving the finished surface accuracy of the workpiece and the effect of preventing the wear of the tool edge become greater in the grinding process.
- ester oil (A) a fatty acid having 2 to 24 carbon atoms is usually used as the monobasic acid, and the fatty acid may be linear or branched. It 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 preferably have 4 to 18 carbon atoms because lubricity and handleability are further improved.
- Saturated fatty acids, unsaturated fatty acids having 4 to 18 carbon atoms and mixtures thereof are more preferred, and unsaturated fatty acids having 4 to 18 carbon atoms are more preferred.
- Fatty acids are even more preferred.
- Examples of the polybasic acid 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.
- ethanenic acid propanedioic acid, linear or branched butanedioic acid, linear or branched pentanedioic acid, linear or branched hexanedioic acid, linear Linear or branched heptane diacid, linear or branched octane diacid, linear or branched nonanniic acid, linear or branched decandioic acid, linear or branched pendecane Diacid, linear or branched dodecandioic acid, linear or branched tridecandioic acid, linear or branched tetradecandioic acid, linear or branched heptadecandioic acid, linear Or
- the acid constituting the (A) ester oil may be a monobasic acid or a polybasic acid, as described above. This is preferable because an ester contributing to the improvement of anti-sticking property is easily obtained.
- ester oil that can be used in the present invention include the following esters.
- the esters derived from natural products used in the present invention include palm oil, palm kernel oil, rapeseed oil, soybean oil, sunflower oil, and fatty acids that constitute glyceride by breeding and genetic engineering operations.
- Natural oils and fats such as vegetable oils such as high rapeseed rapeseed oil, rapeseed oil and oleic sunflower oil, and animal oils such as lard.
- esters derived from natural products triesters of fatty acids and glycerin (hereinafter, simply referred to as glycerin) are preferred from the viewpoint of the stability of lubricating oils.
- Triester wherein 40-98% by weight of the fatty acid is oleic acid.
- the content of oleic acid in the fatty acid constituting the triester is preferably at least 50% by mass, more preferably at least 50% by mass, since both lubricity and thermal oxidation stability can be achieved at a high level in a well-balanced manner.
- Is 60% by mass or more, more preferably 70% by mass or more, and the same point force is also preferably 95% by mass or less, more preferably 90% by mass or less.
- fatty acids constituting the triester (hereinafter referred to as "constituent fatty acids”)
- the ratio of formic acid and the ratio of linoleic acid and the like, which will be described later, are measured in accordance with the standard oil and fat analysis method established by the Japan Oil Chemists' Society, Section 2.4.2 “Fatty acid composition”.
- the fatty acid other than oleic acid is not particularly limited as long as lubricity and thermal stability are not impaired, but is preferably a fatty acid having 6 to 24 carbon atoms. is there.
- the fatty acid having 6 to 24 carbon atoms may be a saturated fatty acid or an unsaturated fatty acid having 1 to 5 unsaturated bonds.
- the fatty acid may be linear or branched. Further, the molecule may have one to three hydroxyl groups (—OH) in addition to the carboxyl group (one COOH).
- fatty acids include happroic acid, happuric acid, haptic acid, lauric acid, myristic acid, palmitic acid, stearic acid, araquinic acid, behenic acid, lignoceric acid, and lauroleic acid.
- fatty acids 1-60% by mass (more preferably 2% by mass) of the fatty acid constituting the triester, which is preferred by linoleic acid, in terms of compatibility between lubricity and heat stability. More preferably, 50% by mass, more preferably 4 to 40% by mass) is linoleic acid.
- 0.1 to 30% by mass (more preferably 0.5 to 20% by mass) of the constituent fatty acids is considered in terms of compatibility between lubricity and heat and acid stability.
- % By mass, more preferably 1 to 10% by mass is a fatty acid having 6 to 16 carbon atoms.
- the total unsaturation degree of the above triester is preferably 0.3 or less, more preferably 0.2 or less. If the total unsaturation of the triester is greater than 0.3, the lubricating oil of the present invention tends to have poor heat and acid stability.
- the total degree of unsaturation referred to in the present invention is measured by a similar apparatus and operating method in accordance with ISK1557- 1970 “Testing method for polyether for polyurethane” except that a triester is used instead of the polyether for polyurethane. Degree of total unsaturation to be obtained.
- the triester according to the present invention as long as the proportion of oleic acid in the constituent fatty acids satisfies the above-mentioned conditions, those obtained by synthesis may be used or the triester may be used.
- a natural oil such as a vegetable oil containing a ester may be used, it is preferable to use a natural oil such as a vegetable oil from the viewpoint of safety for the human body.
- rapeseed oil, sunflower oil, soybean oil, corn oil and canola oil are preferred, but sunflower oil, rapeseed oil and soybean oil are particularly preferred.
- many natural vegetable oils have a total unsaturation exceeding 0.3.
- the total unsaturation can be reduced by a treatment such as hydrogenation in the refining process.
- vegetable oil can be easily produced with low total unsaturation by the genetic recombination technique. For example if the total unsaturation degree is not more 0.3 or less and a high O maleic acid canola oils Orein acid as more than 70 wt%, high Orein acid soybean oil as 80 weight 0/0 or more of the high Orei down Acid sunflower oil, high oleic rapeseed oil and the like can be exemplified.
- the ester obtained when a polyhydric alcohol is used as the alcohol component may be a complete ester in which all of the hydroxyl groups in the polyhydric alcohol are esterified, and some of the hydroxyl groups are not esterified.
- a partial ester which remains as a hydroxyl group may be used.
- the organic acid ester obtained when a polybasic acid is used as the acid component may be a complete ester in which all of the carboxyl groups in the polybasic acid are esterified, or a part of the carboxyl group may be esterified. Alternatively, a partial ester that remains as a carboxyl group may be used.
- the iodine value of the (A) ester oil is preferably 0 to 80, more preferably 0 to 60, further preferably 0 to 40, still more preferably 0 to 20, and most preferably 0 to 10.
- the bronze value of the esternole is preferably 0 to 50 gBr / 100 g, more preferably 0 to 30 gB.
- r / 100 g more preferably 0 to 20 gBr / 100 g, most preferably 0 to LOgBr / 100 g
- the lubricating oil obtained tends to have more non-stickiness.
- the iodine value is measured by an indicator titration method in JI SK 0070 "Method for measuring acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable value of chemical products". Value.
- the bromine value refers to a value measured according to JIS K 2605 “Chemical product bromine value test method, electrometric titration method”.
- the (A) ester oil has a hydroxyl value of 0.01 to 300 mgKOHZg and a ken value of 100 to 500 mgKOHZg. H / g is preferred.
- the upper limit of the hydroxyl value of the ester for obtaining even higher lubricity is more preferably 200 mgKOH / g, most preferably 150 mgKOHZg, while the lower limit is more preferably.
- the upper limit of the saponification value of the ester oil is more preferably 400 mgKOHZg, while the lower limit is more preferably 200 mgKOH / g.
- the hydroxyl value is a value measured by an indicator titration method in JIS K 0070 "Method for measuring acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable value of chemical products".
- the saponification value is the value measured by the indicator titration method of JIS K 2503 “Aerospace Lubricating Oil Test Method”!
- the kinematic viscosity of the (A) ester oil is not particularly limited, but the kinematic viscosity at 40 ° C is preferably 300 mm 2 Zs or less, more preferably 200 mm 2 Zs or less, and still more preferably. It is 100 mm 2 Zs or less, particularly preferably 75 mm 2 Zs or less.
- the kinematic viscosity of the ester is preferably lmm 2 Zs or more, more preferably 3 mm 2 Zs or more, and further preferably 5 mm 2 Zs or more.
- the pour point and viscosity index of (A) the ester oil are not particularly limited, but the pour point is preferably 10 ° C or lower, more preferably -20 ° C or lower. It is desirable that the viscosity index be 100 or more and 200 or less.
- the hydrocarbon oil (B) in the first metal working oil is not particularly limited as long as it has a kinematic viscosity at 40 ° C. of l to 20 mm 2 Zs. Either may be used, and some may be a mixture of two or more of these!
- the mineral oil for example, a lubricating oil fraction obtained by distilling a crude oil under normal pressure and reduced pressure is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, Paraffinic mineral oil or naphthenic mineral oil refined by appropriately combining refining treatments such as sulfuric acid washing and clay treatment are exemplified.
- the synthetic oil include propylene oligomer, polybutene, polyisobutylene, an oligomer of ⁇ -olefin having 5 to 20 carbon atoms, and a co-oligomer of ethylene and ⁇ -olefin having 5 to 20 carbon atoms.
- polyolefins or hydrides thereof monoalkylbenzenes
- Alkylbenzenes such as monoalkylnaphthalene, dialkylnaphthalene, and polyalkylnaphthalene
- alkylnaphthalenes such as monoalkylnaphthalene, dialkylnaphthalene, and polyalkylnaphthalene.
- the polyolefin is a copolymer of olefin monomers having different structures
- the monomer ratio and monomer arrangement in the copolymer there is no particular restriction on the monomer ratio and monomer arrangement in the copolymer, and random copolymers, alternating copolymers, and block copolymers are not particularly limited. Any of polymers may be used.
- the olefin monomer may be any one of OC olefin, internal olefin, linear olefin, and branched olefin.
- white oil and polyolefin or a hydride thereof are preferred from the viewpoints of oil mist resistance and biodegradability.
- White oil is also referred to as liquid paraffin and refers to mineral oil that has been highly refined by sulfuric acid treatment or hydrogenation treatment or the like. More specifically, those that meet the provisions of JIS K 2231 “Liquid paraffin”, that is, the score of the corrosion test (100 ° C, 3 hours) is 1 or less, and the color (Saybolt) is +30 or more In the sulfuric acid color test, a white oil is a color that shows the same color as the standard color solution or a lighter color than that of the standard color solution, and no yellow crystals (nitronaphthalene) remain in the nitronaphthalene test.
- ⁇ -olefin oligomers having 5 to 20 carbon atoms or hydrides thereof are preferred.
- 1 Ottaten oligomer hydride, 1-decene oligomer hydride and 1-decene oligomer hydride Particularly preferred are hydrides of dodecene oligomers.
- the polyolefin used in the present invention can be produced by a conventionally known method. Specifically, for example, it can be produced by a thermal reaction without a catalyst, and an organic peroxide catalyst such as benzoyl peroxide;
- Friedel-Crafts catalysts such as aluminum chloride, titanium tetrachloride, aluminum tin chloride tin halide, boron fluoride; Ziegler catalysts such as organic chloride aluminum tetrachloride, organic aluminum titanium tetrachloride; Known catalysts such as aluminoxane zirconocene-based, ionic compound zirconocene-based, etc. meta-open catalysts; Lewis acid complex-type catalysts such as aluminum chloride monobasic, boron fluoride monobasic, etc.
- the desired polyolefins can be produced by homopolymerizing or copolymerizing the above-mentioned olefins using a medium.
- the polyolefin obtained by such a method generally has a double bond carbon as described above in the first metal working oil as described above. It is preferable to use, as a base oil, a hydride of so-called polyolefin obtained by hydrogenating phenol.
- a base oil a hydride of so-called polyolefin obtained by hydrogenating phenol.
- the use of polyolefin hydrides tends to improve the thermal oxidation stability of metalworking oils.
- the hydride of polyolefin can be obtained, for example, by hydrogenating polyolefin with hydrogen in the presence of a known hydrogenation catalyst and saturation of the double bond present in polyolefin.
- the polymerization of the olefin and the hydrogenation of the polymer can be performed, and the polymerization of the olefin and the double existing in the polymer can be performed without passing through two steps. It is also possible to complete the bond hydrogenation in one step.
- a kinematic viscosity at 40 ° C of a hydrocarbon oil is a previously described 20 mm 2 Zs less, good Mashiku 15 mm 2 Zs less, more preferably 10 mm 2 Zs less, more preferably 5 mm 2 Zs or less. If the kinematic viscosity exceeds 20 mm 2 Zs, the oil mist-forming properties will be reduced, resulting in insufficient machining efficiency and tool life in the trace amount oil supply system, and insufficient biodegradability.
- the kinematic viscosity at 40 ° C of (B) a hydrocarbon oil and the previously described lmm 2 Zs or more, preferably 2 mm 2 Zs or more, more preferably 3 mm 2 Zs or more. If the kinematic viscosity is lmm 2 Zs, the oil agent tends to be excessively misted, the mist scattered in the atmosphere increases, and a sufficient amount of oil agent is supplied in the micro oil supply system! It is impossible to suppress the increase in welding or working resistance in non-ferrous metal working, and in any case, working efficiency and tool life become insufficient.
- the content of the hydrocarbon oil (B) in the first metal working oil is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass, based on the total amount of the metal working oil. % Or less. If the content is more than 70% by mass, the oil misting properties will be reduced, and the machining efficiency and tool life will tend to be reduced when used for grinding with very small amounts of oil supply.
- the content of the hydrocarbon oil (B) is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more based on the total amount of the metalworking oil. And particularly preferably at least 20% by mass. If the content force is less than ⁇ % by mass, it becomes impossible to suppress the increase in welding or working resistance in non-ferrous metal working, and the working efficiency and tool life tend to decrease.
- the first metalworking oil according to the present invention may be composed of (A) an ester oil and (B) a hydrocarbon oil, but may further contain another base oil.
- base oils include polyethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene glycol, polyethylene glycol monoether, polypropylene glycolone monoether, polyoxyethylene polyoxypropylene glycolone ether, polyethylene Polyglycols such as glycol ether, polypropylene glycol ether, and polyoxyethylene polyoxypropylene glycol diether; monoalkyl diphenyl ether, dialkyl diphenyl ether, monoalkyl triphenyl ether, dialkyl triphenyl ether, tetraphenyl ether , Monoalkyl tetraphenyl ether, dialkyl tetraphenyl ether, pentaphenyl ether Hue such les - Noreeteru; silicone oil; Pafunoreo port Etenore etc
- the content of the base oil other than the components (A) and (B) in the first metal working oil is preferably 65% by mass or less, more preferably 50% by mass, based on the total amount of the metal working oil. %, More preferably 30% by mass or less, even more preferably 20% by mass or less, particularly preferably 10% by mass or less.
- the water content of the first metalworking oil is not particularly limited, but is preferably 20000 ppm or less, more preferably ⁇ m or less, further more preferably 5000 ppm or less from the viewpoint of storage stability and rust prevention. It is.
- the water content is preferably 200 ppm or more, more preferably 300 ppm or more, and still more preferably. Is at least 400 ppm, more preferably at least 500 ppm.
- the water content in the present invention means a water content measured by Karl Fischer coulometric titration in accordance with JIS K2275.
- water When water is added to the first metalworking oil to adjust the water content, tap water, industrial water, ion-exchanged water, distilled water, which may be hard water or soft water, may be used. Water, alkali ion water, etc. can be used arbitrarily.
- the second metalworking oil according to the present invention has (A) an ester oil as a base oil and a water content of S200 to 20000 ppm.
- the specific examples and preferred embodiments of the (A) ester oil in the second metal working oil are the same as those in the case of the (A) ester oil in the first metal working oil. I do.
- the water content of the second metal working oil working on the present invention is 200 to 20000 ppm. That is, the water content of the second metalworking oil must be 20000 ppm or less, preferably 100 ppm or less, more preferably 5000 ppm or less from the viewpoint of storage stability and rust prevention. Further, in order to prevent welding and increase in the resistance of kamitsu work, and to achieve excellent calorie efficiency and tool life, the water content needs to be 200 ppm or more, preferably 300 ppm or more, more preferably 300 ppm or more. It is preferably at least 400 ppm, more preferably at least 500 ppm.
- the water content in the present invention means a water content measured by Karl Fischer coulometric titration in accordance with JIS K 2275.
- the water to be added may be either hard water or soft water, such as tap water, industrial water, ion-exchanged water, or distilled water. And alkaline ionized water can be optionally used.
- the second metalworking oil that works in the present invention may be (A) an ester oil that has a water content within a range of 200 to 20,000 ppm, or may have another base oil described later. Oils and additives may be further included.
- the content of (A) ester oil is preferably 30% by mass or more, more preferably 30% by mass, based on the total amount of metalworking oil. Is at least 50% by mass, more preferably at least 70% by mass, particularly preferably at least 80% by mass.
- the content is less than 30 mass%, the oil mist-forming properties will be reduced, and when used for cutting 'processing with a trace amount of oil supply method, the processing efficiency and tool life will increase due to the increase in welding or processing resistance. Tends to be insufficient, and biodegradability tends to decrease.
- the second metalworking oil further contains (A) a base oil other than the ester oil
- the base oil may be a mineral oil or a synthetic oil, or may be a mixture of two or more thereof.
- the mineral oil for example, a lubricating oil fraction obtained by atmospheric distillation and vacuum distillation of crude oil is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, Paraffinic mineral oil or naphthenic mineral oil refined by appropriately combining refining treatments such as sulfuric acid washing and clay treatment are exemplified.
- the synthetic oil include propylene oligomer, polybutene, polyisobutylene, an oligomer of ⁇ -olefin having 5 to 20 carbon atoms, and a co-oligomer of ethylene and ⁇ -olefin having 5 to 20 carbon atoms.
- the content of the other base oil in the second metal working oil is preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less, based on the total amount of the metal working oil. It is even more preferably at most 20% by mass, particularly preferably at most 10% by mass.
- the first and second metal working oils according to the present invention contain (C) an oily agent because they can prevent welding and increase in working resistance to achieve better working efficiency and tool life. It is preferable to do so.
- the oil agent include (C-1) an alcohol oil agent, (C-2) a carboxylic acid agent, (C 3) an unsaturated carboxylic acid sulfate, and (C 4) a compound represented by the following general formula (1).
- Compound, ( C5) a compound represented by the following general formula (2), (C6) a polyoxyalkylene conjugate, (C7) an ester oil agent, (C8) a hydric carbyl ether of a polyhydric alcohol, (C — 9) Amin oily agents.
- R 1 represents a hydrocarbon group having 1 to 30 carbon atoms
- a represents an integer of 1 to 6
- b represents an integer of 0 to 5.
- R 2 represents a hydrocarbon group having 1 to 30 carbon atoms
- c represents an integer of 1 to 6
- d represents an integer of 0 to 5.
- the alcoholic agent may be a monohydric alcohol or a polyhydric alcohol! Alcohols having 1 to 40 carbon atoms are more preferable, and monohydric alcohols having 1 to 40 carbon atoms are more preferable, because they can achieve better working efficiency and tool life by preventing welding and increase in working resistance. And most preferably an alcohol having 8 to 18 carbon atoms. Specifically, examples of the alcohol constituting the ester of the base oil can be given. These alcohols may be linear or branched, and may be saturated or unsaturated, but preferably have a point force saturation for preventing stickiness.
- the (C-2) carboxylic acid oil agent may be a monobasic acid or a polybasic acid.
- a monovalent carboxylic acid having 1 to 40 carbon atoms is preferable, and more preferably a monovalent carboxylic acid having 5 to 25 carbon atoms, because it can prevent welding and increase in processing resistance to achieve more excellent processing efficiency and tool life.
- Carboxylic acids most preferably carboxylic acids having 5 to 20 carbon atoms.
- examples of the carboxylic acid constituting the ester as the base oil can be given. These carboxylic acids are linear However, it may have a branch or may be saturated or unsaturated, but is preferably a saturated carboxylic acid from the viewpoint of preventing stickiness!
- Examples of the sulfide of the unsaturated carboxylic acid (C3) include, among the carboxylic acids of the above (C2), unsaturated sulfides. Specific examples include sulfuric acid sulphate of oleic acid.
- examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R 1 include, for example, a linear or linear hydrocarbon group having 1 to 30 carbon atoms. Branched alkyl group, cycloalkyl group having 5 to 7 carbon atoms, alkylcycloalkyl group having 6 to 30 carbon atoms, linear or branched alkenyl group having 2 to 30 carbon atoms, aryl group having 6 to 10 carbon atoms, and carbon atom 7 And alkylaryl groups having up 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 30 carbon atoms is more preferable.
- a linear or branched alkyl group of LO most preferably a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a linear or branched propyl group, and a linear or branched butyl group.
- the substitution position of the hydroxyl group is arbitrary, but when it has two or more hydroxyl groups, it is preferable that the substitution is made with an adjacent carbon atom.
- a is preferably an integer of 1 to 3, and more preferably 2.
- b is preferably an integer of 0 to 3, and more preferably 1 or 2.
- Examples of the compound represented by the general formula (1) include p-tert-butyl catechol.
- examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R 2 include R 1 in the general formula (1)
- the substitution position of the hydroxyl group is arbitrary, but when it has two or more hydroxyl groups, it is preferable that the hydroxyl group is substituted with an adjacent carbon atom.
- c is preferably an integer of 1 to 3, and more preferably 2.
- d is preferably an integer of 0 to 3, and more preferably 1 or 2.
- Examples of the compound represented by the general formula (2) include 2,2 dihydroxynaphthalene and 2,3 dihydroxy. Sinaphthalene can be mentioned.
- Examples of the (C 6) polyoxyalkylene compound include compounds represented by the following general formula (3) or (4).
- R 3 and R 5 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms
- R 4 represents an alkylene group having 2 to 4 carbon atoms
- e represents a number average. Represents an integer such that the molecular weight is 100-3500.
- A represents a residue obtained by removing some or all of the hydrogen atoms of a hydroxyl group of a polyhydric alcohol having 3 to 10 hydroxyl groups
- R 6 represents an alkylene group having 2 to 4 carbon atoms
- R 7 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms
- f represents an integer having a number average molecular weight of 100 to 3500
- g represents the hydroxyl group of A. Represents the same number as the number.
- At least one of R 3 and R 5 is preferably a hydrogen atom.
- Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R 3 and R 5 include the same as the examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R 1 in the general formula (1). I can mention it, and the examples of good things are the same.
- e is preferably an integer having a number average molecular weight of 300 to 2,000, and more preferably an integer having a number average molecular weight of 500 to 1500.
- polyhydric alcohol having 3 to 10 hydroxyl groups constituting A include glycerin, polyglycerin (a dimer to tetramer of glycerin, for example, diglycerin, , Triglycerin, tetraglycerin), trimethylolalkane (trimethylolethane, trimethylolpropane, trimethylolbutane) and their dimer to tetramer, pentaerythritol, dipentaerythritol, 1,2,4 butanetriol 1,3,5 pentanetriol, 1,2,6 hexanetriol, 1,2,3,4 butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adtol, arabitol, xylitol, mannitol Polyhydric alcohols such as toll, idylitol, talitol, dulcitol,
- glycerin polyglycerin, trimethylolalkane, and dimer to tetramer thereof, pentaerythritol, dipentaerythritol, sorbitol, or sorbitan are preferable.
- Examples of the alkylene group having 2 to 4 carbon atoms represented by R 6 are the same as the examples of the alkylene group having 2 to 4 carbon atoms represented by R 4 in the general formula (3). be able to.
- Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R 7 are the same as the examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R 1 in the general formula (1). And preferred examples are the same. at least one of preferably be hydrogen atom instrument all of the g-number of R 7 is more preferably water atom.
- f is preferably an integer having a number average molecular weight of 300 to 2,000, and more preferably an integer having a number average molecular weight of 500 to 1500.
- the alcohol constituting the ester oil agent may be a monohydric alcohol or a polyhydric alcohol, and the carboxylic acid may be a monobasic acid or a polybasic acid.
- ester referred to here is distinguished from the triester which is an essential component of the first and second metal working oils. In the following description, the former is referred to as “ester oily agent” for convenience.
- Examples of the monohydric alcohol and the polyhydric alcohol constituting the (C-7) ester oily agent include monohydric alcohol and polyhydric alcohol, and the acid constituting the ester oily agent is a monobasic acid. But it may be a polybasic acid!
- the monohydric alcohol generally has 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 24 carbon atoms.
- alcohols are used, and such alcohols may be linear or branched, and may be saturated or unsaturated.
- the alcohol having 1 to 24 carbon atoms include, for example, methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol, Straight or branched hexanol, straight or branched heptanol, straight or branched Branched octanol, linear or branched nonanol, linear or branched decanol, linear or branched pendanol, linear or branched dodecanol, linear or branched Tridecanol, linear or branched tetradecanol, linear or branched pentadecanol, linear or branched hexadecanol, linear or branched heptadecanol, Linear or branched octadecanol, linear or branched nonadenicol,
- polyhydric alcohol one having usually 2 to 10 valence, preferably 2 to 6 valent is used.
- polyhydric alcohols having 2 to 10 include, for example, ethylene glycol, ethylene glycol, polyethylene glycol (3 to 15-mer of ethylene glycol), propylene glycol, dipropylene glycol, and polypropylene glycol (propylene glycol glycol).
- ethylene glycol propylene glycol
- neopentyl glycol glycerin
- trimethylonoleethane trimethylolpropane
- pentaerythritol sorbitan
- mixtures thereof neopentyldaricol, trimethylolethane, trimethylolpropane, pentaerythritol, a mixture thereof, and the like are most preferable because higher thermal stability can be obtained.
- the alcohol constituting the ester oily agent may be a monohydric alcohol or a polyhydric alcohol as described above.
- Polyhydric alcohols are preferred from the viewpoints of achieving high efficiency and tool life, and having a low pour point, and further improving the handleability in winter and cold regions.
- esters of polyhydric alcohols In grinding, the finished surface accuracy of the workpiece is improved and the effect of preventing wear of the tool edge is further increased.
- the acids constituting the ester oily agent as the monobasic acid, a fatty acid having 2 to 24 carbon atoms is usually used, and the fatty acid may be linear or branched, and may be saturated or unsaturated. It may be unsaturated or unsaturated.
- saturated fatty acids having 3 to 20 carbon atoms, and 3 to 3 carbon atoms Preferred are unsaturated fatty acids having 4 to 18 carbon atoms, unsaturated fatty acids having 4 to 18 carbon atoms, and unsaturated fatty acids having 4 to 18 carbon atoms, which are preferred by 22 unsaturated fatty acids and mixtures thereof. Saturated fatty acids having 4 to 18 carbon atoms are more preferred from the viewpoint of more preferable stickiness prevention properties.
- 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.
- ethanenic acid propanedioic acid, linear or branched butanedioic acid, linear or branched pentanedioic acid, linear or branched hexanedioic acid, linear Linear or branched heptane diacid, linear or branched octane diacid, linear or branched nonanniic acid, linear or branched decandioic acid, linear or branched pendecane Diacid, linear or branched dodecane diacid, linear or branched Tridecandioic acid, linear or branched tetradecandioic acid, linear or branched heptadecandioic acid, linear or branched hex
- ester oily agent used in the (C-7) ester oily agent is optional and not particularly limited.
- ester oily agent usable in the present invention include the following esters. it can.
- C-7-6 Mixed esters of polyhydric alcohols with monobasic acids and mixtures of polybasic acids
- a polyhydric alcohol is used as the alcohol component
- a complete ester in which all of the hydroxyl groups in the polyhydric alcohol are esterified may be used, or a part of the hydroxyl groups may be left unesterified without being esterified.
- the remaining partial ester may be used.
- a polybasic acid is used as the carboxylic acid component
- a complete ester in which all of the carboxyl groups in the polybasic acid are esterified may be used, or a part of the carboxyl group may not be esterified and remain as a carboxyl group. However, it may be a partial ester.
- the total carbon number of the ester oil agent is not particularly limited, the total carbon number is preferably 7 or less in order to prevent welding and increase in processing resistance to achieve better processing efficiency and tool life.
- the above ester is preferred. 9 or more esters are more preferred. 11 or more esters are most preferred.
- esters having a total carbon number of 60 or less are preferred, esters with a total carbon number of 45 or less are more preferred, and esters with a total carbon number of 26 or less are preferred in that they do not increase the occurrence of sting or corrosion and are compatible with organic materials.
- Esters of 24 or less are more preferred.
- Esters of 22 or less are most preferred.
- polyhydric alcohol constituting the hydrocarbyl ether of the (C-8) polyhydric alcohol one having usually 2 to 10 valency, preferably 2 to 6 valency is used.
- polyhydric alcohol having 2 to 10 include, for example, ethylene glycol, diethylene glycol, polyethylene glycol (3 to 15-mer of ethylene glycol), propylene glycol, dipropylene glycol, and polypropylene glycol (propylene glycol).
- ethylene glycol diethylene glycol, polyethylene glycol (3 to 10 mer of ethylene glycol), propylene glycol, dipropylene glycol, polypropylene glycol (3 to 10 mer of propylene glycol), 1,3-propanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerin, diglycerin, triglycerin, Trimethylolalkanes (trimethylolethane, trimethylolpropane, trimethylolbutane, etc.) and their dimer to tetramer, pentaerythritol, dipentaerythritol, 1,2,4 butanetriol, 1,3,5 pentanetriol , 1, 2, 6 hexanetriol, 1, 2, 3, 4 butane tetrol, sorbitol, sorbitan, sorbi
- Alcohol and mixtures thereof are preferred. Even more preferred are ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylonoleethane, trimethylolpropane, pentaerythritol, sorbitan, and mixtures thereof. Among these, glycerin is most preferable because it can prevent welding and increase the resistance of kamuna work, thereby achieving better kamune efficiency and tool life.
- hydric carbyl ether of the polyhydric alcohol (C8) those in which a part or all of the hydroxyl groups of the above-mentioned polyhydric alcohol has been converted to the hydric carbyl ether can be used. From the viewpoint of preventing welding and increase in working resistance to achieve better working efficiency and tool life, a polyhydric alcohol obtained by partially hydrocarbyl etherifying hydroxyl groups (partially etherified product) is preferable.
- the carbyl group at the mouth is defined as an alkyl group having 1 to 24 carbon atoms, an alkyl group having 2 to 24 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, and an alkylcyclo group having 1 to 6 carbon atoms. It represents a hydrocarbon group having 1 to 24 carbon atoms such as an alkyl group, an aryl group having 6 to 10 carbon atoms, an alkyl aryl group having 7 to 18 carbon atoms, and an arylalkyl group having 7 to 18 carbon atoms.
- alkyl group having 1 to 24 carbon atoms examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a linear or branched group.
- alkenyl group having 2 to 24 carbon atoms examples include a vinyl group, a linear or branched probe group, a linear or branched butenyl group, a linear or branched pentenyl group, and a straight or branched pentenyl group.
- Examples of the cycloalkyl group having 5 to 7 carbon atoms include a cyclpentyl group, a cyclohexyl group, and a cycloheptyl group.
- Examples of the alkylcycloalkyl group having L1 include a methylcyclopentyl group, a dimethylcyclopentyl group (including all structural isomers), a methylethylcyclopentyl group (including all structural isomers), and ge.
- Tylcyclopentyl group (including all structural isomers), methylcyclohexyl group, dimethylcyclohexyl group (including all structural isomers), methylethylcyclohexyl group (including all structural isomers) Form), getylcyclohexyl group (including all structural isomers), methylcycloheptyl group, dimethylcycloheptyl group (including all structural isomers), methylethylcycloheptyl group (all ), A getylcycloheptyl group (including all structural isomers), and the like.
- Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group.
- Examples of the alkylaryl group having 7 to 18 carbon atoms include a tolyl group (including all structural isomers), a xylyl group (including all structural isomers), and an ethylfuryl group (including all structural isomers).
- Linear or branched propylphenyl group (including all structural isomers), linear or branched butylphenyl group (including all structural isomers), linear or branched Pentylphenyl group (including all structural isomers), linear or branched hexylphenyl group (including all structural isomers), linear or branched heptylphenyl group (including all structural isomers) Different Including sex. ), A linear or branched octylphenyl group (including all structural isomers), a linear or branched noylphenyl group (including all structural isomers), a linear or branched decylphenyl group. (Including all structural isomers), linear or branched pentadecylphenyl group (including all structural isomers), linear or branched dodecylphenol group (including all structural isomers) Body).
- Examples of the arylalkyl group having 7 to 12 carbon atoms include a benzyl group, a phenyl group, a phenyl propyl group (including isomers of propyl group), a butyl butyl group (including isomers of butyl group). ), A phenylpentyl group (including an isomer of a pentyl group), a phenylhexyl group (including an isomer of a hexyl group), and the like.
- straight-chain or branched alkyl having 2 to 18 carbon atoms can be achieved because it is possible to prevent welding and increase the resistance of katsumi and to achieve better katsu-e efficiency and tool life.
- straight-chain or branched alkenyl groups having 2 to 18 carbon atoms are preferred, and straight-chain or branched alkyl groups and oleyl groups having 3 to 12 carbon atoms (residues excluding hydroxyl group and oleyl alcohol power) Is more preferred
- a monoamine is preferably used as the (C-9) amine oily agent.
- 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 monoamine, 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.
- Primary monoamines are preferred because they can achieve improved processing efficiency and tool life.
- Examples of the hydrocarbon group bonded to the nitrogen atom of the monoamine include an alkyl group, an aryl group, a cycloalkyl group, an alkylcycloalkyl group, an aryl group, an alkylaryl group, and an arylalkyl group.
- An alkyl group or an alkyl group is preferable, since usable welding and increase in working resistance can be prevented to achieve better working efficiency and tool life.
- the alkyl group and the alkyl group may be straight-chain or branched-chain, but have better machining efficiency and tool life by preventing welding and increase in machining resistance. In view of achieving the above, a linear one is preferred.
- Preferable examples of the monoamine used in the present invention include, for example, hexylamine (including all isomers), heptylamine (including all isomers), octylamine (all isomers) ), Norlamine (including all isomers), decylamine (including all isomers), pendecylamine (including all isomers), dodecylamine (including all isomers), tridecylamine (including all isomers) Isomers), tetradecylamine (including all isomers), pentadecylamine (including all isomers), hexadecylamine (including all isomers), heptadecylamine (all Octadecylamine (including all isomers), nonadecylamine (including all isomers), icosylamine (including all isomers), hen Cosylamine (including all isomers), docosylamine (including all isomers), tricosylamine (
- primary monoamines having 12 to 24 carbon atoms are preferred because primary monoamines having 12 to 24 carbon atoms are preferred because they can prevent welding and increase in machining resistance to achieve better machining efficiency and tool life. Primary monoamines are more preferred. Primary monoamines having 16 to 18 carbon atoms are more preferred.
- oily agents (C-1) to (C-9) may be used, and a mixture of two or more kinds may be used.
- the (C-2) carboxylic oil agent and the (C-9) amine oil agent are selected because they can prevent welding and increase in processing resistance to achieve better processing efficiency and tool life.
- One or a mixture of two or more is preferable.
- the content of the oil agent is not particularly limited, but from the viewpoint that it is possible to achieve excellent machining efficiency and tool life by preventing welding and increase in machining resistance, the amount is based on the total amount of metal working oil. It is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more. From the viewpoint of stability, the content of the oil agent is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less, based on the total amount of the metal working oil.
- the first and second metal working oils according to the present invention are capable of achieving higher working efficiency and tool life by preventing welding and increase in working resistance.
- Pressure agent It is preferred to have.
- the synergistic action of these agents prevents welding and increases in working resistance, thereby achieving better working efficiency and tool life.
- the first and second metal working oils can be used as lubricating oil for parts other than the machined part of the machine tool as described later, but in this case, (C) an oil agent must be contained. Desired,.
- Examples of the (D) extreme pressure agent include a (D-1) sulfur compound and a (D-2) phosphorus compound described below.
- the (D-1) sulfur-containing compound is not particularly limited as long as the properties of the metalworking oil are not impaired, but dinodicarbyl polysulfide, sulfide ester, sulfide mineral oil, zinc dithiophosphate Preferred are di-conjugated compounds, dithio-potassium zinc rubinate conjugates, molybdenum dithiophosphate conjugates, and dithio-potassium molybdenum diphosphate.
- the dihydrocarbyl polysulfide is a sulfur compound generally called polysulfide or sulfided sulfide, and specifically means a compound represented by the following general formula (5).
- R 8 and R 9 may be the same or different and each may be a linear or branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon number.
- R 8 and R 9 in the general formula (5) specifically, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, tert- butyl group, Straight or branched pentyl group, straight or branched hexyl group, straight or branched heptyl group, straight or branched octyl group, straight or branched noel group, straight or branched decyl group, Straight-chain or branched undecyl group, straight-chain or branched dodecyl group, straight-chain or branched tridecyl group, straight-chain or branched tetradecyl group, straight-chain or branched pentadecyl group, straight-chain or branched hexadecyl group A straight-chain or branched heptadecyl group, a straight-chain or branched oc
- R 8 and R 9 in the general formula (5) an alkyl group having 3 to 18 carbon atoms derived from propylene, 1-butene or isobutylene cap, or an aryl group having 6 to 8 carbon atoms. These groups are preferably an alkylaryl group or an arylalkyl group.
- Examples of these groups include an isopropyl group and a branched hexyl group derived from a propylene dimer (all branched Isomer), a branched nonyl group derived from propylene trimer (including all branched isomers), a branched dodecyl group derived from propylene tetramer (including all branched isomers) Pentadecyl group derived from propylene pentamer (including all branched isomers), branched octadecyl group derived from propylene hexamer (including all branched isomers) Including isomers ), Sec-butyl group, tert-butyl group, 1-butene dimer, branched octyl group (including all branched isomers), isobutylene dimer Branched octyl group (including all branched isomers), branched dodecyl group derived from 1-
- R 8 and R 9 in the above general formula (5) are separately selected from ethylene because they can prevent welding and increase in working resistance to achieve better working efficiency and tool life.
- the propylene force is also a derived C 3-18 branched alkyl group, and it is particularly preferable that the ethylene or propylene force is also a derived C 6-15 branched alkyl group. preferable.
- sulfur ester examples include animal and vegetable fats such as beef tallow, lard, fish fat, rapeseed oil, and soybean oil; unsaturated fatty acids (such as those extracted from oleic acid, linoleic acid, and the above animal and vegetable fats and oils).
- unsaturated fatty acid esters obtained by reacting various kinds of alcohols with unsaturated fatty acids; and those obtained by sulfurating a mixture thereof by an arbitrary method.
- Sulfur mineral oil refers to mineral oil in which elemental sulfur is dissolved.
- the mineral oil used in the sulfur oil mineral oil according to the present invention is not particularly limited. Specifically, specifically, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation is used. Paraffinic mineral oil, naphthenic mineral oil, etc., which are refined by appropriately combining purification processes such as solvent removal, solvent extraction, hydrocracking, solvent dewaxing, solvent dewaxing, hydrorefining, sulfuric acid washing, and clay treatment. .
- the elementary sulfur may be in any form such as a lump, a powder, and a molten liquid.However, if powdered or molten liquid is used, it can be efficiently dissolved in a base oil. Is preferred. It should be noted that liquid sulfur in liquid form is not Has the advantage that the melting operation can be carried out in a very short time because it is mixed with water.It must be handled at a temperature higher than the melting point of elemental sulfur, requiring special equipment such as heating equipment, It is not always easy to handle, for example, it involves danger. On the other hand, powdered elemental sulfur is particularly preferable because it is inexpensive and easy to handle, and the time required for dissolution is sufficiently short. Further, the sulfur content in the sulfur oil mineral oil according to the present invention is not particularly limited, but is usually preferably 0.05 to 1.0% by mass, more preferably 0.1 mass%, based on the total amount of the sulfur oil. It is 1 to 0.5% by mass.
- the zinc dithiophosphate conjugate, the dithiophosphate zinc rubinate, the molybdenum dithiophosphate compound and the dithiophosphate molybdenum conjugate are respectively represented by the following general formula (6)
- R 11 R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 2 °, R 21 , R 22 , R 23 , R 24 and R 25 may be the same or different and each represents a hydrocarbon group having 1 or more carbon atoms, and X 1 and X 2 each represent an oxygen atom or a sulfur atom.
- R 10, R 11 R 12 , R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21, R 22, R 23, R 24 and Specific examples of the hydrocarbon group represented by R 25 include a methyl group, an ethyl group, a propyl group (including all branched isomers), a butyl group (including all branched isomers), Pentyl group (including all branched isomers), hexyl group (including all branched isomers), heptyl group (including all branched isomers), octyl group (including all branched isomers) ), Nonyl group (including all branched isomers), decyl group (including all branched isomers), pendecyl group (including all branched isomers), dodecyl group (including all branched isomers) Tridecyl group (including all branched isomers), tetradecyl group (including all branched
- (D-2) phosphorus conjugate examples include phosphate esters, acidic phosphate esters, amine salts of acidic phosphate esters, chlorinated phosphate esters, and phosphite esters. And phosphorothionate, and a metal salt of a Lynch compound represented by the following general formula (10) or (11).
- Examples of these phosphorus compounds include esters of phosphoric acid, phosphorous acid or thiophosphoric acid with alkanols, polyether alcohols, and derivatives thereof.
- X 3 , X 4 and X 5 may be the same or different and each represent an oxygen atom or a sulfur atom, and at least two of X 3 , X 4 and X 5 are oxygen atoms , R 26 , R 27 , and R Represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, which may be the same or different.
- X 7 , X 8 and X 9 may be the same or different and each represent an oxygen atom or a sulfur atom, and at least three of X 6 , X 7 , X 8 or X 9 are oxygen a atom, a charcoal hydrocarbon group R 29, R 3 0 and R 31 Yogu hydrogen atom or 1 to 30 carbon atoms which may be the same or different.
- examples of the phosphoric acid ester include tributyl phosphate, tripentyl phosphate, trihexynolephosphate, triheptinolephosphate, trioctynolephosphate, trinolephosphate, tridecylphosphate, tridecylphosphate and tridecylphosphate.
- Tridecyl phosphate tridodecyl phosphate, tritridecyl phosphate, tritetradecyl phosphate, tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl phosphate, trioctadecyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresinole Phosphate, trixyleninole phosphate, cresyl diphenyl phosphate, xylen diphenyl phosphate, etc .;
- Examples of the acidic phosphoric acid ester include monobutyl acid phosphate, monopentyl acid phosphate, monohexinorea acid phosphate, monoheptinorea acid phosphate, monooctyl acid phosphate, mono-nole acid phosphate, monodecyl acid phosphate and monounacid acid phosphate.
- Decyl acid phosphate monododecyl acid phosphate, monotridecyl acid phosphate, monotetradecyl acid phosphate, monopentadecyl acid phosphate, monohexadecyl acid phosphate, monoheptadecyl acid phosphate, monooctadecyl acid phosphate, monooleyl Acid phosphate, dibutyl acid phosphate, dipentyl acid phosphate, Le acid phosphate, diheptyl acid phosphate, di-O-lipped Le acid phosphate Hue Dinodecyl acid phosphate, didecyl acid phosphate, didecyl acid phosphate, didodecyl acid phosphate, ditridecyl acid phosphate, ditetradecyl acid phosphate, dipentadecyl acid phosphate, dihexadecyl acid phosphate, dihepta acid Phosphate, dioc
- acidic phosphate ester amine salts include the acidic phosphate esters methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, getylamine, dipropylamine, dibutylamine, dipentylamine, dipentylamine, dipentylamine and dipentylamine.
- Salts with amines such as hexylamine, diheptylamine, octylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, etc .
- Phosphorus chlorinated Examples of the acid esters include tris' dichloro mouth propyl phosphate, tris' chloroformate phosphate, tris' chloroformate phenol phosphate, and polyoxyanoleylene'bis (Chloroanolequinole)] phosphate and the like;
- phosphites examples include dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite, dino-phosphite, didecyl phosphite, didecyl phosphite, and didodecyl phosphite.
- Dioleyl phosphite diphenyl phosphite, dicresyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinole phosphite, tridecyl phosphite, tridecyl phosphite Decyl phosphite, tridodecyl phosphite, trioleyl phosphite, triphenyl phosphite, tritaresyl phosphite, etc .;
- Phosphorothionates include tributylphosphorothionate, tripentylphosphorothionate, trihexylphosphorothionate, triheptylphosphorothionate, trioctylphosphorothionate, and trinonylphosphorothionate.
- Tridecylphosphorothionate Tridenedecylphosphorothionate, tridodecylphosphorochonate, tritridecylphosphorothionate, tritetradecylphosphorothionate, tripentadecylphosphorothionate, trihexadecylphosphorothionate Acetate, triheptadecylphosphorothionate, trioctadecylphosphorothionate, trioleylphosphorothionate, triphenylphosphorothionate, tricresylphosphorothionate, trixylphosphorothionate, Cresyl dihue
- a metal salt of the general formula (10) or (11) Rini ⁇ compounds represented by a hydrocarbon group having 1 to 30 carbon atoms represented by R 2 6 to R 31 in the formula
- Specific examples include an alkyl group, a cycloalkyl group, an alkyl group, an alkylcycloalkyl group, an aryl group, an alkylaryl group, an arylalkyl group and the like.
- alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a pendecyl group, a dodecyl group, and a tridecyl group.
- alkyl groups such as tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group (the alkyl groups may be linear or branched).
- Examples of the cycloalkyl group include cycloalkyl groups having 5 to 7 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
- Examples of the above alkylcycloalkyl group include a methylcyclopentyl group, a dimethylcyclopentyl group, a methylethylcyclopentyl group, a getylcyclopentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylethylcyclohexyl group.
- a C6 to C11 alkylcycloalkyl group such as an alkyl group to a cycloalkyl group
- a group getyl cyclohexyl group, methylcycloheptyl group, dimethylcycloheptyl group, methylethylcycloheptyl group, and getylcycloheptyl group.
- the substitution position is also arbitrary).
- alkenyl group examples include a butyr group, a pentenyl group, a hexenyl group, Alkenyl groups such as heptenyl group, otathenyl group, nonenyl group, decenyl group, pendecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecyl group, octadecyl group, etc.
- the group may be linear or branched, and the position of the double bond is also arbitrary.).
- Examples of the aryl group include aryl groups such as a phenyl group and a naphthyl group.
- Examples of the alkylaryl group include, for example, a tolyl group, a xylyl group, an ethylphenol group, a propylphenol group, a butylphenol group, a pentylphenol group, a hexylphenyl group, a heptylphenol group, C7-C18 alkylaryl groups such as octylphenol, norphenol, decylphenol, undecylphenyl, dodecylphenyl, etc.
- the alkyl group may be linear or branched. And the position of substitution on the aryl group is also arbitrary).
- Examples of the above arylalkyl group include C7 to C12 carbon atoms such as benzyl, phenyl, phenylpropyl, phenylbutyl, phenylpentyl, and phenylhexyl.
- Reel alkyl groups (these alkyl groups may be linear or branched).
- hydrocarbon group having 1 to 30 carbon atoms represented by R 26 to R 31 is preferably an alkyl group or Ariru group having 6 to 24 carbon atoms having 1 to 30 carbon atoms, more preferably carbon An alkyl group having 3 to 18 carbon atoms, more preferably an alkyl group having 4 to 12 carbon atoms.
- R 26, R 27 and R 28 represents a Yogu each a hydrogen atom or the hydrocarbon group which may be the same or different, Of R 26, R 27 and R 28, 1 to 3 amino is the carbonized It is more preferable that one or two hydrogen groups are the above-mentioned hydrocarbon groups, and it is even more preferable that two of them are the above-mentioned hydrocarbon groups.
- R 29 , R 3 and R 31 may be the same or different and each represent a hydrogen atom or the above-mentioned hydrocarbon group, and one to three of R 29 , R 3 ° and R 31 Is preferably the above-mentioned hydrocarbon group. It is more preferable that one or two are the above-mentioned hydrocarbon groups. It is further preferable that two are the above-mentioned hydrocarbon groups.
- Rini ⁇ of the general formula (10) at least two, all the oxygen atoms of the force X 3 to X 5 is required to be an oxygen atom of X 3 to X 5 Is preferred! / ,. [0147] Further, in Rini ⁇ of the general formula (11), all of the force x 6 ⁇ x 9 at least three is required to be an oxygen atom of X 6 to X 9 It is preferably an oxygen atom.
- Examples of the phosphorus conjugate represented by the general formula (10) include phosphorous acid and monothiophosphorous acid; the above-mentioned phosphoric acid monoester having one hydrocarbon group having 1 to 30 carbon atoms; Monothiophosphorous acid monoester; the above-mentioned phosphite diester having two hydrocarbon groups having 1 to 30 carbon atoms, the monothiophosphoric acid diester; the above-mentioned triphosphorous acid having three hydrocarbon groups having 1 to 30 carbon atoms Esters, monothiophosphorous triesters; and mixtures thereof.
- phosphite monoester and phosphite diester are more preferable, and phosphite diester is more preferable.
- Examples of the phosphorylated compound represented by the general formula (11) include phosphoric acid and monothiophosphoric acid; the above-mentioned phosphoric acid monoester and monothiophosphoric acid having one hydrocarbon group having 1 to 30 carbon atoms. Monoester; the above-mentioned phosphoric acid diester having two hydrocarbon groups having 1 to 30 carbon atoms and monothiophosphoric acid diester; the above-mentioned phosphoric acid triester having three hydrocarbon groups having 1 to 30 carbon atoms and monothiophosphoric acid triester; And mixtures thereof.
- phosphoric diesters which are preferably phosphoric monoesters and phosphoric diesters, are more preferred.
- Examples of the metal salt of the phosphorus compound represented by the general formula (10) or (11) include a salt obtained by neutralizing a part or all of the acidic hydrogen of the phosphorus compound with a metal base.
- Examples of the strong metal base include metal oxides, metal hydroxides, metal carbonates, and metal chlorides.
- Specific examples of the metal include alkali metals such as lithium, sodium, potassium, and cesium.
- Examples include metals, alkaline earth metals such as calcium, magnesium and norm, and heavy metals such as zinc, copper, iron, lead, nickel, silver and manganese. Of these, alkaline earth metals such as calcium and magnesium and zinc are preferred.
- the metal salt of the phosphorus compound has a different structure depending on the valency of the metal or the number of OH groups or SH groups in the phosphorus compound. Therefore, the structure is not limited at all. For example, lmol zinc oxide When 2 mol of phosphoric acid diester (having one OH group) is reacted with a compound having the structure represented by the following formula (12), it is considered that the main component is obtained. It is considered. [0152] [Formula 9]
- a mixture of two or more of these can also be used.
- phosphate ester and acidic phosphoric acid are preferred because they can prevent welding and increase in koji kneading resistance to achieve more excellent processing efficiency and tool life.
- Esters, and amine salts of acidic phosphate esters are preferred.
- the metal working oil of the present invention can be applied to uses other than metal working as described later.
- the metal working oil of the present invention when used as a sliding surface oil for machine tools, Preferably contains an acidic phosphoric acid ester or an amine salt of an acidic phosphoric acid ester.
- a phosphate ester is preferred.
- at least one kind selected from acidic phosphate esters and amine salt of acidic phosphate esters is combined with phosphate esters. It is preferable to use them.
- the metalworking oil of the present invention may contain either (D-1) the sulfur conjugate or (D-2) the phosphorus conjugate, or may contain both. There may be. From the viewpoint of preventing welding and increase in working resistance to achieve better working efficiency and tool life, (D-2) phosphorous compound or (D-1) sulfur compound and (D-2) Contains both phosphorus compounds More preferably, it contains both (D-1) the sulfur-containing compound and (D-2) the phosphorus-containing compound.
- the content of the extreme pressure agent is optional, but from the viewpoint that it is possible to achieve better machining efficiency and tool life by preventing welding and increase in machining resistance, the metal working oil It is more preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.05% by mass or more. In order to prevent abnormal wear, the content of extreme pressure agent is preferably 15% by mass or less, more preferably 10% by mass or less, based on the total amount of metalworking oil. % Is still more preferred.
- the first and second metal working oils that work on the present invention it is possible to prevent welding and increase in working resistance to achieve more excellent working efficiency and tool life.
- It preferably contains an organic acid salt.
- the 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 norm; ammonia; alkylamines having an alkyl group having 1 to 3 carbon atoms (monomethyl).
- Amines such as methanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, etc.
- zinc such as the power of these
- the alkali metal or ⁇ alkaline earth metal preferably tool calcium are particularly preferred.
- the positive component of the organic acid salt is an alkali metal or an alkaline earth metal, higher lubricity tends to be obtained.
- the sulfonate those produced by any method can be used.
- an alkali metal salt of an alkyl aromatic sulfonic acid obtained by sulfonating an alkyl aromatic compound having a molecular weight of 100 to 1500, preferably 200 to 700, alkaline earth Metal salts, amine salts and mixtures thereof can be used.
- the alkyl aromatic sulfonic acid referred to herein is generally a sulfonated alkyl aromatic compound of a lubricating oil fraction of mineral oil, a petroleum sulfonic acid such as so-called mahoganic acid, which is a by-product of white oil production, and a detergent.
- Alkoxybenzene having a linear or branched alkyl group obtained by alkylating polyolefin to benzene, which is a by-product from an alkylbenzene production plant that is a raw material for benzene, is sulfonated.
- alkyl aromatic sulfonic acid and a base of an alkali metal such as an oxide or hydroxide of an alkali metal
- a base of an alkaline earth metal such as an oxide or hydroxide of an alkaline earth metal
- So-called neutral (normal salt) sulfonate obtained by reacting the above-described amines (ammonia, alkylamine alkanol, noramine, etc.); neutral (normal salt) sulfonate, excess alkali metal base, alkaline earth
- basic sulfonate obtained by heating a base of a class of metals or an amine in the presence of water
- a neutral (normal salt) sulfonate in the presence of carbon dioxide gas to form a base of an alkali metal, a base of an alkaline earth metal or So-called carbonate overbased (ultrabasic) sulfonate
- a carbonate overbased (ultrabasic) phenate and a boric acid or boric acid anhydride a boric acid or boric acid anhydride.
- Basic phenates; and mixtures thereof.
- salicylate examples include, in the presence or absence of elemental sulfur, an alkylsalicylic acid having 1 to 2 alkyl groups having 4 to 20 carbon atoms, and an alkali metal base (alkali base).
- alkaline earth metal bases alkaline earth metal oxides and hydroxides
- amines ammonia, alkylamine alkanolamines, etc.
- a neutral salicylate obtained by heating a neutral salicylate and an excess of an alkali metal base, an alkaline earth metal base or an amine in the presence of water; a so-called basic salicylate;
- a so-called carbonate persalt obtained by reacting a neutral salicylate with an alkali metal base, alkaline earth metal base or amine in the presence Neutral (ultrabasic) salicylates; neutral salicylates are 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.
- (Ultrabasic) a so-called overbased (ultrabasic) salicylate produced by reacting a metal salicylate with a boric acid or a
- the base number of (E) the organic acid salt is preferably from 50 to 500 mgKOHZg, more preferably from 100 to 450 mgKOHZg.
- the base number of the organic acid salt is less than 100 mgKOH, g, the lubricating effect of the organic acid salt added tends to be insufficient.
- the organic acid salt having a base value of more than OOmgKOH / g is Usually, it is not preferable because it is very difficult to manufacture and it is difficult to obtain.
- the base number used here is the base number [mgKOHZg] determined by the perchloric acid method measured in accordance with Section 7 of JIS K2501 “Testing Methods for Neutralization Value of Petroleum Products and Lubricating Oils”.
- the content of the organic acid salt (E) is preferably 0.1 to 30 based on the total amount of the metal working oil. %, More preferably 0.5 to 25% by mass, even more preferably 1 to 20% by mass.
- the content of the organic acid salt is less than the lower limit, the effect of improving the processing efficiency and tool life due to the prevention of welding and increase in processing resistance by the added casket tends to be insufficient.
- the stability of the metalworking oil tends to decrease, and precipitates tend to form.
- the organic acid salt may be used alone or in combination with the organic acid salt and other additives.
- Sulfur compounds which are preferred to use an organic acid salt in combination with the above extreme pressure agent, from the viewpoint of preventing welding and increase in resistance of kamitsu work and thereby achieving better processing efficiency and tool life, It is particularly preferable to use a combination of three kinds of phosphorus compounds and organic acid salts.
- the first and second metal working oils working on the present invention further contain (F) an antioxidant.
- F Stickiness due to the deterioration of the constituents can be prevented by the addition of the anti-irridating agent, and the stability of the heat-irridation can be improved.
- antioxidants examples include phenol-based antioxidants, amine-based antioxidants, zinc dithiophosphate-based antioxidants, and other additives used as food additives. Are mentioned.
- any phenolic compound used as an antioxidant in lubricating oils can be used, and is not particularly limited.
- One or more alkylphenol compounds selected from the compounds represented by 14) and the general formula (15) are preferred.
- R represents an alkyl group having 1 to 4 carbon atoms, and represents a hydrogen atom or 1 carbon atom.
- R 4 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, the following general formula (i) or (ii):
- R 35 represents an alkylene group having 1 to 6 carbon atoms
- R 36 represents an alkyl group or an alkenyl group having 1 to 24 carbon atoms.
- R represents an alkylene group having 1 to 6 carbon atoms, represents an alkyl group having 1 to 4 carbon atoms, and R 39 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- K represents 0 or 1.
- R 4 "and R 4 may be the same or different and each represent an alkyl group having 1 to 4 carbon atoms
- R 41 and R 43 may be the same or different and each represents hydrogen
- R 44 and R 45 may be the same or different
- Each represents an alkylene group having 1 to 6 carbon atoms
- A is an alkylene group having 1 to 18 carbon atoms or the following general formula (iii):
- R 46 and R 47 may be the same or different and each represents an alkylene group having 1 to 6 carbon atoms.
- any amine-based compound used as an antioxidant in lubricating oils can be used, and is not particularly limited.
- p, p'-dialkyldifluoro-amine represented by the following general formula (17) Medium strength One or two or more aromatic amines selected are preferred.
- R 48 represents a hydrogen atom or an alkyl group.
- R 49 and R & may be the same or different and each represents an alkyl group.
- amine-based antioxidants include 4-butyl-4'-octyldiphenylamine, phenyl-2-naphthylamine, octylphenyla-naphthylamine, and dodecylamine.
- Ruf-ru a naphthylamine and mixtures thereof.
- zinc dithiophosphate-based antioxidant used in the present invention include zinc dithiophosphate represented by the following general formula (14).
- R 51 , R 52 , R 53 and R 54 each represent a hydrocarbon group which may be the same or different.
- an antioxidant used as a food additive can also be used, and a force partially overlapping with the above-mentioned phenol-based antioxidant, for example, 2,6 ditertbutyl — P-Talesol (DBPC), 4,4,1-methylenebis (2,6-di-tert-butylphenol), 4,4,1-bis (2,6-di-tert-butylphenol), 4,4, -thiobis (6— tert-butyl o-cresol, ascorbic acid (vitamin C), fatty acid ester of ascorbic acid, tocopherol (vitamin E), 3,5-di-tert-butyl 4-hydroxysol, 2-tert-butyl-4 -Hydroxydinol, 3-tert-butyl-4-hydroxynininol, 1,2 dihydric amide 1,6 ethoxy-1,2,2,4 trimethylquinoline (ethoxyquin), 2- (1,1-dimethyl) -1,4 benzenediol (DBPC), 4,4,
- antioxidants those used as phenol-based antioxidants, amine-based antioxidants, and the above-mentioned food additives are preferable.
- the content of the antioxidant (F) is not particularly limited, but the content is 0.01% based on the total amount of metalworking oil in order to maintain good heat and acid resistance.
- the content is more preferably 0.05% by mass or more, and most preferably 0.1% by mass or 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.
- first and second metal working oils that work on the present invention can contain conventionally known additives other than those described above.
- strong additives include extreme pressure agents other than the above-mentioned phosphorus compounds and sulfur compounds (including chlorine-based extreme pressure agents); wetting agents such as diethylene glycol monoalkyl ether; acrylic polymers, paraffin wax, micro wax, Film forming agents such as slack wax and polyolefin wax; water displacing agents such as fatty acid amine salts; solid lubricants such as graphite, fluorinated graphite, molybdenum disulfide, boron nitride, and polyethylene powder; amines, alkanolamines, amides, Corrosion inhibitors such as carboxylic acid, carboxylate, sulfonate, phosphoric acid, phosphate and partial ester of polyhydric alcohol; metal deactivators such as benzotriazole and thiadiazole; methyl silicone, fluorosilicon
- the first and second metalworking oils according to the present invention may contain a chlorine-based additive such as a chlorine-based extreme-pressure agent as described above, but may improve safety and protect the environment. From the viewpoint of reducing the load, it is preferable not to contain a chlorine-based additive.
- the chlorine concentration is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, more preferably 200 mass ppm or less, more preferably 100 mass ppm or less, based on the total amount of metalworking oil. It is particularly preferred that the concentration be less than ppm.
- the kinematic viscosities of the first and second metal working oils according to the present invention are not particularly limited.
- the kinematic viscosity at 40 ° C is 200 mm 2 Zs or less. Is more preferably 100 mm 2 Zs, more preferably 75 mm 2 Zs, and most preferably 50 mm 2 Zs.
- the lower limit value is preferably lmm 2 Zs, a more preferably 3 mm 2 Zs, most preferably 5 mm 2 Zs.
- first and second metal working oils according to the present invention are excellent in working efficiency such as working efficiency, tool life, and handling property, they are widely used in the metal working field. Can be suitably used.
- metal working as used herein is not limited to the grinding process, but broadly refers to all metal working.
- first and second metal working oils according to the present invention can be applied to metal lubrication by a normal lubrication system, but since they exhibit a more remarkable effect, they can be used in a micro oil supply system. (MQL) It is preferable to use it as a processing oil!
- metal working include cutting, grinding, rolling, forging, pressing, drawing, rolling, and the like.
- first and second metal working oils are very useful for applications such as cutting, grinding, and rolling.
- the material of the workpiece to which the first and second metal working oils according to the present invention are applied is not particularly limited.
- the metal working oil of the present invention is suitable as an oil for processing non-ferrous metals. It is a very good oil for processing aluminum or aluminum alloys.
- first and second metal working oils according to the present invention may be used as lubricating oils other than machined parts of machine tools such as oils for sliding surfaces, oils for bearings, oils for hydraulic equipment, and the like. This is possible, and is therefore very useful in that it can save space and energy in machine tools.
- the sliding surface oil agent according to the present invention refers to the lubrication used for the guide mechanism of the two-plane sliding motion that comes into contact with the components provided in the machine tool used for the grinding IJ 'grinding process.
- oils For example, a machine tool that transports a workpiece to a grinding tool by arranging the workpiece on a table that can be moved on a bed and moving the table In this case, the sliding surface between the table and the bed is lubricated by the sliding surface oil. Further, in a machine tool in which a cutting / grinding tool is fixed on a table movable on a bed and the table is moved to move the tool toward a workpiece, a slide between the table and the bed is used. The moving surface is lubricated by the sliding surface oil.
- Such oils for sliding surfaces are required to have friction characteristics such as a low friction coefficient on the sliding surfaces and a high stick-slip prevention property! If stick-slip occurs on a sliding surface such as a machining table of a machine tool, the frictional vibration is transferred to the workpiece as it is, resulting in reduced machining accuracy or reduced tool life due to the vibration. Occurs.
- the first and second metal working oils according to the present invention can sufficiently prevent these phenomena when used as an oil agent for a sliding surface. Is preferably further contained.
- lubrication methods such as oil lubricant lubrication and mist bearing lubrication for the lubrication of the bearing portion, and the first and second oil compositions according to the present invention can be used for both.
- Oil bearing lubrication refers to a lubrication method in which lubricating oil is supplied to the bearing portion in a liquid state to ensure smooth sliding of the portion, and cooling of the bearing portion by the lubricating oil can be expected.
- a lubricating oil for bearing lubrication is required to be less likely to be thermally degraded because it is used in a higher temperature portion, that is, to be excellent in heat resistance. Processing oil can also be used for such oil bearing lubrication.
- Mist bearing lubrication refers to a lubrication method in which lubricating oil is atomized by a mist generator, and the mist oil is supplied to the bearing portion with the expectation of air or the like to ensure smooth sliding of the portion.
- lubricating oils for mist lubrication are required to be less susceptible to thermal degradation because they are used at higher temperatures, that is, to be excellent in heat resistance. Processing oil can be used for such mist bearing lubrication.
- the hydraulic equipment performs the operation and control of the machine by hydraulic pressure
- the hydraulic pressure control part that controls the operation of the machinery uses hydraulic oil that is expected to have lubrication, sealing, and cooling effects.
- Hydraulic oil is used to compress lubricating oil to a high pressure with a pump, generate oil pressure, and operate equipment.
- the lubricating oil is required to have high lubricity, high oxidation stability, and thermal stability, and the first and second metal working oils can be used for such hydraulic oils.
- the oil preferably further contains a phosphorus conjugate to further improve the lubricity.
- FIG. 1 is an explanatory diagram showing an example of a machine tool suitably used in the ultra-trace oil supply type cutting method 1 grinding method.
- the machine tool shown in FIG. 1 includes a table 2 movable on a bed 1 in the direction of an arrow, and a tool 11 supported by a support means 10 and rotatable in the direction of an arrow.
- the oil supply tank 12 contains the oil agent of the present invention, and when the workpiece 3 disposed on the table 2 is to be cut and ground, the compressed air sent from the compressed air introduction unit 18 is used for grinding. At the same time, the mist-like oil agent of the present invention is supplied from the processing oil agent supply section 13 toward the kafune portion.
- the oil agent of the present invention stored in the oil supply tank 12 is supplied to the sliding surface 16 between the bed 1 and the table 2 from the sliding surface oil agent supply unit 14, and is also supplied to the bearing oil agent supply unit 15.
- the lubricating oil is supplied to the bearing between the support means 10 and the tool 11 to lubricate the sliding surface 16 and the bearing 17.
- the oil agent of the present invention accommodated in oil supply tank 12 is supplied to a hydraulic device provided in a machine tool, and the oil agent of the present invention is hydraulically actuated. Use as oil.
- Examples 1 to 21 and Comparative Examples 1 and 2 metal working oils having the compositions shown in Tables 1 to 6 were prepared using the base oils and the additives described below, respectively. Tables 1 to 6 also show the kinematic viscosity and water content of the obtained metalworking oil at 40 ° C. Table 7 shows the fatty acid composition and total unsaturation of base oil A4.
- A1 Triester of trimethylolpropane and oleic acid (kinematic viscosity at 40 ° C .: 46 mm 2 / s)
- A2 Diester of neopentyl glycol and oleic acid (kinematic viscosity at 40 ° C: 24 mm 2 / s ⁇ )
- A3 diester of isodecyl alcohol and adipic acid (kinematic viscosity at 40 ° C: 14m m 2 / Roh s ⁇ )
- A4 High oleic rapeseed oil (kinematic viscosity at 40 ° C: 39mm 2 Zs)
- a tapping test was performed by using a very small amount of oil supply system (MQL) or a normal oil supply system.
- MQL oil supply system
- tapping tests were performed using the metal working oil and the comparative standard oil (DIDA: diisodecyl adipate) alternately under the following conditions, and the tapping energy in each case was measured. did.
- Metalworking oil sprayed under the condition of compressed air 0.2MPa, oil composition 25mlZh
- Metalworking oil and DIDA Sprayed directly on the machined part without using compressed air under the condition of 4.3mLZ.
- the tapping energy efficiency (%) was calculated from the measured value of the tapping energy according to the following equation. Tables 1 to 6 show the results. In the table, the higher the value of tapping energy efficiency, the higher the lubricity Means that.
- Tapping energy efficiency (%) (Tapping energy when using DIDA) / (Tapping energy when using oil composition)
- each metal working oil was discharged from the MQL supply port under the conditions of compressed air of 0.2 MPa and an oil composition of 25 ml Zh, and the oil was misted and placed on a glass Petri dish placed at a position corresponding to the processing point. The amount of collected oil mist was measured. Tables 1 to 6 show the obtained results.
- Example 1 Example 2 Example 3 Example 4
- Example 5 (Amount of collected mist [mg / h]) 2]
- Example 6 Example 7
- Example 8 Example 8
- Example 10 (Amount of collected mist [mg / h]) 3] Example 9 Example 10 Example 11 Example 12
- Example 16 (Amount of collected mist [mg / h]) 4] Example 13 Example 14 Example 15 Example 16
- Examples 22 to 36 and Comparative Examples 3 to 8 the following base oils and carotenoids were used, and the water contents were adjusted to obtain the compositions and water contents shown in Tables 8 to 13.
- Metal working oil was prepared. Tables 8 to 13 show the compositions of metalworking oils so that the sum of the base oil and additives and the water content would be 100% by mass. Tables 8 to 13 also show the kinematic viscosities of the obtained metalworking oils at 40 ° C.
- the fatty acid composition and total unsaturation of the base oil A4 are as shown in Table 7 above.
- A5 Mixed ester of triester of trimethylolpropane and oleic acid and diester of neopentyl glycol and oleic acid (kinematic viscosity at 40 ° C: 32 mm 2 Zs)
- A3 diester of isodecyl alcohol and adipic acid (kinematic viscosity at 40 ° C: 14m m 2 / Roh s ⁇ )
- A4 High oleic rapeseed oil (kinematic viscosity at 40 ° C: 39mm 2 Zs)
- a tapping test was performed by using a very small amount of oil supply system (MQL) or a normal oil supply system.
- MQL oil supply system
- Metalworking oil sprayed under the condition of compressed air 0.2MPa, oil composition 25mlZh
- the tapping energy efficiency (%) was calculated from the measured value of the tapping energy according to the following equation. Tables 8 to 13 show the results. In the table, the higher the value of tapping energy efficiency, the higher the lubricity.
- Tapping energy efficiency (%) (Tapping energy when using DIDA) / (Tapping energy when using oil agent composition).
- Example 30 Example 31 Example 32 Example 33
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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)
- Health & Medical Sciences (AREA)
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- Lubricants (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/547,355 US20080026967A1 (en) | 2004-03-31 | 2005-03-29 | Metal Working Fluid |
EP05727451.6A EP1741771A4 (en) | 2004-03-31 | 2005-03-29 | METALWORKING FLUID |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004106112A JP2005290161A (ja) | 2004-03-31 | 2004-03-31 | 金属加工油 |
JP2004-106112 | 2004-03-31 | ||
JP2004106128A JP4599078B2 (ja) | 2004-03-31 | 2004-03-31 | 金属加工油組成物 |
JP2004-106128 | 2004-03-31 |
Publications (1)
Publication Number | Publication Date |
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WO2005095556A1 true WO2005095556A1 (ja) | 2005-10-13 |
Family
ID=35063760
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2005/005878 WO2005095556A1 (ja) | 2004-03-31 | 2005-03-29 | 金属加工油 |
Country Status (3)
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US (1) | US20080026967A1 (ja) |
EP (1) | EP1741771A4 (ja) |
WO (1) | WO2005095556A1 (ja) |
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US8030255B2 (en) | 2006-06-08 | 2011-10-04 | Nippon Oil Corporation | Lubricating oil composition |
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JP2021147507A (ja) * | 2020-03-19 | 2021-09-27 | 出光興産株式会社 | 金属加工油組成物 |
Also Published As
Publication number | Publication date |
---|---|
EP1741771A4 (en) | 2013-11-13 |
US20080026967A1 (en) | 2008-01-31 |
EP1741771A1 (en) | 2007-01-10 |
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