JP4392154B2 - Metal processing oil - Google Patents

Description

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【表２】

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【表３】

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【発明の効果】
本発明のポリエーテル系金属加工油は鉱物油等の炭化水素との相溶性に優れ、潤滑性、粘度指数に優れるという効果を奏する。そのため、金属加工油として極めて好適である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyether-based metalworking oil. More specifically, the present invention relates to a polyether metalworking oil excellent in compatibility with a hydrocarbon base oil, lubricity and the like.
[0002]
[Prior art]
Lubricating properties are required for cutting oils, grinding oils, polishing oils, rolling oils, drawing oils, press oils, forging oils, and metal processing oils used for polishing and cutting silicon wafers. Conventionally, metal processing oils such as emulsion-based cutting oils and non-water-based cutting oils based on mineral oil are used as oil-based improvers such as fatty acid esters and fatty acids, and extreme pressure agents containing elements such as sulfur, chlorine, and neighbors. It has been added to improve lubricity. However, chlorine-based extreme pressure agents are difficult to use due to environmental problems such as ozone depletion and neighboring extreme pressure agents are eutrophied by wastewater. Furthermore, since the polyether having good lubricity has poor compatibility with hydrocarbon base oils such as mineral oil, it is difficult to make the product appearance uniform.
[0003]
[Problems to be solved by the invention]
An object of this invention is to provide the polyether type metalworking oil excellent in compatibility with a hydrocarbon type lubricating oil, lubricity, viscosity index property, etc.
[0004]
[Means for Solving the Problems]
  As a result of intensive studies in view of the above problems, the present inventors have reached the present invention.
  That is, the present invention comprises a polyether (E) and a hydrocarbon base oil which are represented by the following general formula (1), have an HLB of 6.0 or less and a weight average molecular weight of 500 to 30,000. It is metal processing oil containing -90 mass%.
R¹[-{(OCH₂CH₂CH₂CH₂)_m(OA)_n} -OH]_p     (1)
[Wherein R¹Is a residue obtained by removing a hydroxyl group from a branched monovalent saturated or unsaturated aliphatic alcohol having 4 to 24 carbon atoms, A is a 1,2-propylene group, and m and n are weight average molecular weights of (E) An integer greater than or equal to 1 that is 500 to 30,000, p is 1 It is. ]
[0005]
DETAILED DESCRIPTION OF THE INVENTION
R in the general formula (1)¹Is a residue obtained by removing all hydroxyl groups from a compound having 1 to 6 hydroxyl groups having 1 to 24 carbon atoms, a linear, branched or cyclic 1-6 valent alcohol residue, 1-6 valent Examples thereof include residues of phenols and residues of 1 to 6-valent araliphatic alcohols. That is, R¹Is R¹It is a residue obtained by removing all OH from [OH] p.
Specifically, a monohydric alcohol [R that forms a residue obtained by removing a hydroxyl group from a monohydric alcohol [R¹OH] includes linear or branched saturated aliphatic monools having 1 to 18 carbon atoms (methanol, ethanol, n- and i-propanol, butanol, pentanol, hexanol, heptanol, octanol, nonyl alcohol, decyl alcohol). , Undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, eicosyl alcohol, henecosyl alcohol, docosyl alcohol, tricosyl alcohol, tetracosyl Cis- or trans- unsaturated aliphatic hydrocarbon group (alcohol having alkenyl group or alkynyl group, for example, ethenyl alcohol, 1-, 2- and iso-propenyl alcohol, butenyl alcohol, pentynyl alcohol, hexenyl alcohol, heptenyl alcohol, nonenyl alcohol, decenyl alcohol, undecenyl alcohol, dodecenyl alcohol, tridecenyl alcohol, tetradecyl alcohol Cenyl alcohol, pentadecenyl alcohol, hexadecenyl alcohol, heptadecenyl alcohol, octadecenyl alcohol, nonadecenyl alcohol, eicosenyl alcohol, henecocenyl alcohol, dococenyl alcohol, Tricocenyl alcohol, tetracocenyl alcohol, etc.); and alicyclic monools having 4 to 24 carbon atoms (cyclopentanol, cyclohexanol, etc.).
[0006]
Dihydric alcohols that form residues of dihydric alcohols [R¹(OH)₂] Is an aliphatic diol having 2 to 24 carbon atoms (for example, ethylene glycol, propylene glycol, 1,3-, 1,4- and 1,2-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2- and 1,8-octanediol, isobutylene glycol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-dimethyl-1,3 -Alkylene glycols such as propanediol, 2-butyl-2-ethyl-1,3-propanediol, and 2,5-dimethylhexane-2,5-diol; alicyclic diols having 4 to 18 carbon atoms (for example, , 1,4-cyclohexanediol, cycloalkylene glycol such as 1,4-cyclohexanedimethanol); hydrogenated bisphenols (For example, hydrogenated bisphenol A, hydrogenated bisphenol F); and heterocyclic diols (for example, 1,4,3,6-sorbide) and the like.
[0007]
3-6 valent alcohols that form residues of 3-6 valent alcohols [R¹(OH)_Three~₆] Is a trihydric alcohol having 3 to 24 carbon atoms (aliphatic triol, such as glycerin, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3- Propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl -3,4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, pentamethylglycerin, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolethane , Alkanetriols such as trimethylolpropane), 4 to 6-valent polyhydric alcohols having 5 to 24 carbon atoms (aliphatic polyols such as pentaerythrisol) Alkane polyols such as itolitol, sorbitol, mannitol, 1,5-, 3,6- and 1,4-sorbitan, diglycerin and intramolecular or intermolecular dehydrates; and sucrose, glucose, mannose, fructose, methylglucoside And saccharides thereof).
[0008]
Phenols that form residues obtained by removing hydroxyl groups from monovalent phenols [R¹OH] includes monohydric phenols having 6 to 24 carbon atoms, such as phenol, alkylphenol (o, m or p-methylphenol, m, p-dimethylphenol, 2,6-dimethylphenol, o, m or p. -Ethylphenol, pn-butylphenol, p-octylphenol and p-nonylphenol), monostyrylphenol and monobenzylphenol.
Phenols that form residues of 2-6 valent phenols [R¹(OH)₂] Includes C6-C24 divalent to hexavalent phenols. Examples of the phenols include monocyclic polyphenols [for example, divalent phenols (catechol, resorcin, hydroquinone, etc.), trioxybenzene, tetraoxybenzene, hexaoxybenzene, etc.], bisphenols (eg, bisphenol A, bisphenol F, etc.). Etc.).
[0009]
An araliphatic alcohol [R that forms a residue of a 1-6 valent araliphatic alcohol¹(OH)₁~₆] As aralkyl alcohols having 7 to 24 carbon atoms (benzyl alcohol, phenethyl alcohol, etc.), substituted aralkyl alcohols having 8 to 24 carbon atoms (o, m or p-methylbenzyl alcohol, pn-butylphenethyl alcohol, etc.) Etc.
[0010]
Among these, a linear, branched or cyclic 1-6 valent alcohol residue having 1 to 20 carbon atoms is preferable, and a linear or branched 1 to 3 valent carbon residue having 2 to 18 carbon atoms is more preferable. A residue of an aliphatic or alicyclic alcohol, particularly preferably a residual of a linear or branched monovalent saturated or unsaturated aliphatic alcohol having 4 to 18 carbon atoms in terms of good compatibility with hydrocarbons. It is a group. When the number of carbons exceeds 24, the viscosity index becomes worse.
[0011]
A in the general formula (1) is one or more alkylene groups having 2 to 4 carbon atoms excluding 1,4 butylene group. Examples of the alkylene group having 2 to 4 carbon atoms include ethylene group, 1,2- and 1,3-propylene group, 1,2- and 2,3-butylene group and isobutylene group. One or more of these may be used. Among these, preferred are an ethylene group, a 1,2-propylene group and a 1,2-butylene group, and particularly preferred are branched alkylene groups such as a 1,2-propylene group and a 1,2-butylene group. When the branched alkylene group is present in A, the compatibility with the hydrocarbon is improved.
[0012]
M and n in General formula (1) are 1 or more integers from which the weight average molecular weight of polyether (E) becomes 500-30,000. The ratio of m to n (m / n) is preferably 5/95 to 45/55. That is (OCH₂CH₂CH₂CH₂) Content is (OCH₂CH₂CH₂CH₂) And (OA) is preferably 5 to 45 mol% of the total content.
In addition, (E) is an oxytetramethylene group (OCH₂CH₂CH₂CH₂Group) and other oxyalkylene groups (OA groups) are preferred because they have excellent flow characteristics at low temperatures. More preferably, 80% by mass or more of the oxytetramethylene groups constituting (E) are present in the random bond portion.
[0013]
P in the general formula (1) is an integer of 1 to 6, preferably 1 to 3, and particularly preferably 1 in the sense of good compatibility with hydrocarbons. When k exceeds 6, the lubrication performance is deteriorated.
[0014]
As a method for producing the polyether (E) represented by the general formula (1), R¹(OH)_pIn the presence of a catalyst, a compound having 1 to 6 carbon atoms having 1 to 24 carbon atoms represented by the following formula is preferably used: tetrahydrofuran (hereinafter referred to as THF) at a temperature of 30 to 120 ° C., preferably at a pressure of 0 to 0.6 MPa. It can be produced by adding alkylene oxides having 2 to 4 carbon atoms (hereinafter referred to as AO) randomly or in blocks.
[0015]
Conventionally known catalysts can be used for the above catalyst, but preferred ranges differ for THF addition and AO addition.
As a catalyst in the case of addition of THF alone or addition copolymerization with AO, for example, BF_Three, BCl_ThreeAlCl_Three, FeCl_Three, SnCl_ThreeLewis acids such as, and their complexes [eg BF_ThreeEther complex, BF_ThreeTetrahydrofuran complex (BF_ThreeTHF)]; H₂SO_Four, HClO_FourProtonic acid such as KClO_Four, NaClO_FourAlkali metal perchlorates such as Ca (ClO_Four)₂Mg (ClO_Four)₂Alkaline earth metal perchlorates such as Al (ClO_Four)_ThreeAnd other metal perchlorates other than those mentioned above.
Of these, preferably BF_ThreeEther complexes and BF_ThreeTetrahydrofuran complex (BF_Three• THF).
As the catalyst for adding AO alone, a known catalyst that is usually used may be used. In addition to the above-mentioned catalysts, alkali catalysts such as hydroxides [KOH, NaOH, CsOH, Ca (OH)] may be used.₂Alkali metal or alkaline earth metal hydroxide, etc.]; Oxide (alkali metal or alkaline earth metal oxide, such as K2O, CaO, BaO); Alkali metal (Na, K, etc.), and Hydrides (NaH, KH, etc.); amines such as triethylamine, trimethylamine and the like.
Of these, KOH, NaOH, CsOH, BF are preferred._ThreeEther complexes and BF_ThreeTetrahydrofuran complex (BF_Three• THF).
As AO to be added, A in the general formula (1) is an alkylene group having 2 to 4 carbon atoms. For example, ethylene oxide (hereinafter referred to as EO), propylene oxide (hereinafter referred to as PO), 1,2-butylene. Examples thereof include oxide, 2,3-butylene oxide, and isobutylene oxide. Of these, EO, PO, and 1,2-butylene oxide are preferable, and PO is particularly preferable. These may be used in combination, and the polymerization form may be random or block.
The added mole number (m) of THF is 3 to 100, and the added mole number (n) of AO is preferably 5 to 150, more preferably 4 to 20, and n is 6 to 50.
[0016]
The HLB value of the polyether (E) thus obtained is usually 6.0 or less, preferably 5.0 or less, more preferably 2 to 4. When the HLB value exceeds 6.0, the compatibility between the polyether (E) and hydrocarbons such as mineral oil and polybutene is deteriorated.
The HLB value is a value calculated by the Oda formula based on an organic conceptual diagram, and this calculation method is described in, for example, “Emulsification / Solubilization Technology” [Showa 51, Engineering Book Co., Ltd.]. For the organic and inorganic values for deriving the HLB values, see the inorganic base table described in "Organic Conceptual Diagram-Fundamentals and Applications-" [Sankyo Publishing Co., Ltd., 1984] (Reported value).
[0017]
The weight average molecular weight (Mw) of (E) is 500 to 30,000, preferably 700 to 10,000, and more preferably 800 to 5,000. If it is less than 500, the lubricity of metalworking oil will fall, and if it exceeds 30,000, kinematic viscosity of metalworking oil will become high too much. The weight average molecular weight is measured by gel permeation chromatography (GPC) (column: TSKgel G2000, G3000, G4000HXL, solvent: THF). The same applies to the following.
[0018]
The polyether-based metal processing oil of the present invention is made of polyether (E), but polyether (E) may be a mixture of different compositions, molecular weights, etc., and if necessary, hydrocarbon System oil may be added.
Hydrocarbon oils include solvent refined oil, paraffin mineral oil, naphthene mineral oil, alkyl (10 to 100 carbon atoms) benzene, alkyl (10 to 100 carbon atoms) naphthalene, poly-α-olefin (2 to 50 carbon atoms). , Polybutene (weight average molecular weight 200 to 4000), polyisobutene (weight average molecular weight 200 to 4000) and the like. Preference is given to solvent refined oils, paraffinic mineral oils, naphthenic mineral oils and polybutenes. The kinematic viscosity (measured in accordance with JIS K 2283) of these hydrocarbon oils is preferably 1 to 520 mm2 / s at 40 ° C.
The blending ratio of the polyether-based metalworking oil and the hydrocarbon-based oil may be arbitrary, but the mass ratio of the polyether-based metalworking oil / hydrocarbon-based oil is preferably 5/95 to 95/5, more preferably 10 / 90 to 90/10, particularly preferably 20/80 to 80/20. The mixed oil can exhibit the features of both polyether and hydrocarbon.
In addition, if necessary, other polyether [oxytetramethylene group (OCH in the general formula (1)₂CH₂CH₂CH₂And the like). Its content is less than 90% by weight.
[0019]
Furthermore, if necessary, one or more kinds selected from detergent dispersants, antioxidants, oiliness agents, extreme pressure agents, metal deactivators, rust inhibitors, antifoaming agents, viscosity index improvers, and pour point depressants. It is preferable that the additive is added to form a metalworking oil composition.
[0020]
As the detergent / dispersant, neutral or basic sulfonates (eg, petroleum sulfonic acids such as calcium petroleum sulfonate (normal salt) and basic barium sulfonate, and positive or negative alkyl sulfonate (aromatic carbon number 5 to 36) substituted aromatic sulfonic acids) Basic metal salts, etc.]; neutral or basic phenates [e.g., alkyl (C1-C36) phenol, alkyl (C1-C36) phenol sulfide, alkyl (C1-36) phenol aldehyde condensate Positive or basic metal salt, etc.]; neutral or basic phosphonate, thiophosphonate; alkyl (C1-C36) substituted salicylate; alkyl (C5-C36) methacrylate or methacrylate and polar group Monomers including (amine, amide, imide, hydroxyl, carboxyl, nitrile, etc.) (Molar ratio 99/1 to 10/90) copolymer [for example, alkyl (carbon number 1 to 36) methacrylate-vinylpyrrolidinone copolymer (weight average molecular weight: 1,000 to 100,000), alkyl (carbon number) 1-36) Methacrylate-diethylaminoethyl methacrylate copolymer (weight average molecular weight: 1,000-100,000), alkyl (carbon number 1-36) methacrylate-polyethylene glycol-methacrylate copolymer (weight average molecular weight: 1, N-substituted alkenyl (carbon number 5 to 36) succinimide (eg N-tetraethylenepentamine polyisobutenyl succinimide etc.); high molecular weight amide [eg polystearamide (weight) Average molecular weight: 1,000-100,000) etc.]. The amount of the cleaning dispersant used is preferably 15% by mass or less based on the metal processing oil. Hereinafter, the amount of the additive is a value based on the metal processing oil.
[0021]
Antioxidants include phenolic antioxidants (eg 2,4-dimethyl-6-tert-butylphenol, 4,4-butylidenebis (6-tert-butylmetacresol), etc.); amine antioxidants (eg monooctyl) Diphenylamine, dioctyldiphenylamine and the like); dialkyl (carbon number 1 to 36) zinc dithiophosphate; diallyl (carbon number 2 to 36) zinc dithiophosphate; organic sulfide; organic selenide and the like. The amount of the antioxidant used is preferably 2% by mass or less.
[0022]
Oils and fats such as lard oil; long-chain fatty acids having 8 to 36 carbon atoms (octylic acid, lauric acid, palmitic acid, oleic acid, stearic acid, etc.) and their fatty acids and monohydric and polyhydric alcohol esters; carbon Examples include higher alcohols of several 8 to 36 (octyl alcohol, lauryl alcohol, palmityl alcohol, oleyl alcohol, stearyl alcohol, etc.) and esters thereof. The amount of the oily agent used is preferably 15% by mass or less.
[0023]
As extreme pressure agents, lead soap (lead naphthenate, etc.); sulfur compounds (sulfurized fatty acid esters, sulfide palm oil, sulfurized terpene, dibenzyl disulfide, etc.); chlorine compounds (chlorinated paraffin, chloronaphthazanate, etc.); phosphorus Compound (tricresyl phosphate, tributyl phosphate, tricresyl phosphite, n-butyl di-n-octyl phosphinate, di-n-butyl dihexyl phosphonate, di-n-butyl phenyl phosphonate, dibutyl phosphoramidate, amine dibutyl Phosphate, etc.). The amount of the extreme pressure agent used is preferably 10% by mass or less.
[0024]
Examples of the metal deactivator include benzotriazole, mercaptobenzothiazole, N, N′-disalicylidene-1,2-diaminopropane, alizarin and the like. The amount of the metal deactivator used is preferably 2% by mass or less.
[0025]
Examples of rust inhibitors include aliphatic carboxylic acids having 6 to 36 carbon atoms (caprylic acid, lauric acid, nonanoic acid, decanoic acid, oleic acid, etc.), alkali metal salts, amine salts; alkenyl succinic acids having 6 to 36 carbon atoms. (Octenyl succinic acid, dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, etc.) and alkali metal salts, amine salts; dibasic acids having 6 to 24 carbon atoms (azelaic acid, dodecanedioic acid sebacate, Dimer acids, etc.) and alkali metal salts, amine salts; aromatic carboxylic acids (benzoic acid, p-tertbutylbenzoic acid, nitrobenzoic acid, etc.) and alkali metal salts, amine salts; (alkyl phosphorus having 8 to 18 carbon atoms) Acid ester salt; (cyclo) alkylamine (C1-C36) or heterocyclic amine (C4-C36) alkylene oxide (C2-C4) ( -10 mol) adducts (eg, cyclohexylamine EO 2 mol adduct, cyclohexylamine PO 2 mol adduct, morpholine EO 1 mol adduct, morpholine PO 1 mol adduct, etc.); petroleum sulfonates; alkyl (C 1-36) naphthalene sulfonic acid Salts and sorbitan esters (for example, sorbitan laurate, sorbitan stearate, etc.), the above-mentioned aliphatic carboxylic acids, alkenyl succinic acids, dibasic acids, amines and amides of ammonia, etc. Preferably it is 5 mass% or less.
[0026]
Examples of the antifoaming agent include polyorganosiloxane (for example, polydimethylsiloxane). The amount of antifoaming agent used is preferably 0.1% by mass or less.
[0027]
As the viscosity index improver, polyalkyl (1 to 18 carbon atoms) methacrylate or polyalkyl (1 to 18 carbon atoms) acrylate having a weight average molecular weight of 20,000 to 1,500,000; Mw of 5,000 to 300, 000 polyisobutylene; Mw of 10,000 to 300,000 polyalkyl (8 to 12 carbon atoms) styrene; olefin (2 to 12 carbon atoms) copolymer [eg ethylene-propylene (molar ratio 5/95 to 95) / 5) copolymer, styrene-isoprene (molar ratio 5/95 to 95/5) copolymer hydrogenated product, etc.]. The amount of the viscosity index improver used is preferably 15% by mass or less.
[0028]
As pour point depressants, polyalkyl (6 to 24 carbon atoms) methacrylate; naphthalene-chlorinated paraffin condensation product; ethylene-vinyl acetate (molar ratio 5/95 to 95/5) copolymer; polyacrylamide; vinyl carboxy Examples thereof include a rate (carbon number 1 to 36) -dialkyl (carbon number 1 to 36) fumarate (molar ratio 5/95 to 95/5) copolymer. These pour point depressants all have a weight average molecular weight of 1,000 to 100,000. The amount of the pour point depressant used is preferably 1% by mass or less.
[0029]
The total content of the above additives is preferably 20% by mass or less in the metalworking oil. Moreover, these additives may use 2 or more types together.
[0030]
Moreover, emulsifiers, such as surfactant, may be mix | blended with these as needed, and it can dilute and use 10 to 100 times with water. The amount of the emulsifier added is the amount added to the base oil (polyether-based metalworking oil or polyether-based metalworking oil / hydrocarbon-based mixture of metalworking oil) unless otherwise specified. %.
[0031]
As emulsifiers, Na and K salts of sulfonic acids (alkylbenzenesulfonic acid, petroleum sulfonic acid, alkylnaphthalenesulfonic acid, etc.), fatty acids (lauric acid, palmitic acid, myristic acid, oleic acid, castor oil fatty acid, etc.) Na, K Salts, monoethanolamine, diethanolamine, triethanolamine, and the like, PEG esters obtained by esterifying these fatty acids and polyethylene glycol, and alcohols having 8 to 24 carbon atoms (octyl alcohol, decyl alcohol, dodecyl alcohol, tridecyl alcohol, tetra Decyl alcohol, hexadecyl alcohol, oleyl alcohol, stearyl alcohol, etc.) non-ionic active agent, sorbitan fatty acid ester and these ethylene oxides added with ethylene oxide Nonionic surfactants such as the like. The amount of emulsifier used is usually 30% or less.
[0032]
The polyether-based metal processing oil of the present invention can be used for cutting oil, rolling oil, grinding oil, polishing oil, forging oil, press oil, drawing oil, mold release oil, silicon wafer cutting, and the like.
[0033]
【Example】
The present invention will be described in detail by the following examples, but the present invention is not limited thereto.
[0034]
The test method is as follows.
(1) Kinematic viscosity and viscosity index
The measurement was made according to JIS K 2283.
(2) Compatibility
Spindle oil [SYC spindle oil manufactured by Cosmo Oil. The same shall apply hereinafter. ] Was evaluated by measuring the critical temperature.
The critical temperature was 0 ° C. to 85 ° C., and the metal processing oils of Examples and Comparative Examples and the above hydrocarbons were mixed in a test tube at a mass ratio of 30/70, and the temperature at which they were separated was measured.
(3) Lubricity
Using a vibration friction and wear tester (SRV tester), evaluation was made by observing the friction coefficient in point contact between a steel ball and a flat steel disk and the wear scar diameter on the steel ball.
<Lubricity test conditions>
Frequency: 50Hz
Vibration width: 2mm
Load: 200N, 300N, 500N
Time: 10 minutes
Temperature: 30 ° C
Friction coefficient: Average value for 10 minutes
Wear diameter (mm): 10 mm steel ball (SUJ-2)
Oil film breakage: Friction coefficient (μ) variation was observed.
○: Stable, △: Slight fluctuation, × Large fluctuation
In addition, unless otherwise specified, the part in a sentence represents a mass part.
[0035]
Example 1
Isotridecanol [Kyowa Hakko Kogyo Co., Ltd. trade name “Tridecanol” in a glass autoclave. The same shall apply hereinafter. 200 parts (1.0 mol), 468 parts (6.5 mol) of tetrahydrofuran (THF) and 7.9 parts of BF 3 · THF were charged, and 580 parts (10.0 mol) of PO 580 (10.0 mol) were added in an amount of 35 to 50 It was dripped at 10 degreeC over 10 hours. Then, it reacted at 50 degreeC for 5 hours, and cooled. Further, after adding 4.8 parts of 48% NaOH aqueous solution, an adsorption treatment agent [Kyoward 600 and Kyoward 1000 manufactured by Kyowa Chemical Industry Co., Ltd.]. The same shall apply hereinafter. ], Filtered, and dehydrated under reduced pressure at 30 mmHg or less to obtain 1120 parts (a1) of a random adduct of isotridecanol in THF 6.5 mol / PO 10.0 mol.
[0036]
Example 2
A glass autoclave was charged with 130 parts (1.0 mol) of 2-ethylhexyl alcohol, 504 parts (7.0 mol) of THF, and 7.9 parts of BF3 · THF, and 580 parts (10.0 mol) of PO from a pressure dropping funnel. The solution was added dropwise at 35 to 50 ° C. over 10 hours. Then, it reacted at 50 degreeC for 5 hours, and cooled. Further, 4.8 parts of 48% NaOH aqueous solution was added, treated with an adsorption treatment agent, filtered, dehydrated under reduced pressure at 30 mmHg or less, and then 1100 parts of 2-ethylhexyl alcohol in THF 7.0 mol / PO 10.0 mol random adduct. (A2) was obtained.
[0037]
Example 3
A glass autoclave was charged with 200 parts (1.0 mol) of isotridecanol, 504 parts (7.0 mol) of THF, and 7.9 parts of BF3 · THF, and 580 parts (10.0 mol) of PO from a pressure dropping funnel. The solution was added dropwise at 35 to 50 ° C. over 10 hours. Thereafter, it was aged at 50 ° C. for 5 hours and cooled. Furthermore, after adding 4.8 parts of 48% NaOH aqueous solution, it processed with the adsorption processing agent, filtered, and dehydrated under reduced pressure below 30 mmHg. Among 1220 parts of THF 7.0 mol / PO 10.0 mol random adduct of isotridecanol obtained, 642 parts (0.5 mol) and 2.27 parts of KOH were charged into a glass autoclave, and PO116 was added from a pressure dropping funnel. Part (2.0 mol) was added dropwise at 105 ° C. over 5 hours. Then, it was made to react at 130 degreeC for 5 hours, and it cooled. After further treatment with an adsorption treatment agent, filtration, and dehydration under reduced pressure at 30 mmHg or less, 689 parts (a3) of isotridecanol in THF 7.0 mol / PO 10.0 mol random / PO 4.0 mol block adduct was obtained.
[0038]
Example 4
30 parts of (a1) and 70 parts of spindle oil were mixed to obtain 100 parts (a4) of a mixture of (a1) and spindle oil.
[0039]
Example 5
30 parts of (a1) and 70 parts of polybutene [Nisshi Polybutene LV-25E manufactured by Nippon Petrochemical Co., Ltd.] were mixed to obtain 100 parts (a5) of a mixture of (a1) and polybutene.
[0040]
Comparative Example 1
Into a glass autoclave, 200 parts (1.0 mol) of isotridecanol and 3.3 parts of KOH were charged, and 1102 parts (19.0 mol) of PO was dropped from a pressure-resistant dropping funnel at 105 ° C. over 33 hours. Then, it was made to react at 130 degreeC for 10 hours, and was cooled. Further, after treatment with an adsorption treatment agent, filtration, and dehydration under reduced pressure at 30 mmHg or less, 1184 parts (b1) of a PO 19.0 mol adduct of isotridecanol (b1) was obtained.
[0041]
Comparative Example 2
A glass autoclave was charged with 146 parts (1.0 mol) of 2,2,4-trimethyl-1,3-pentanediol and 3.3 parts of KOH, and 1154 parts of PO (19.9 mol) were added at 105 ° C. from a pressure-resistant dropping funnel. The solution was added dropwise over 33 hours. Then, it was made to react at 130 degreeC for 10 hours, and was cooled. Furthermore, after treating with an adsorption treating agent, filtering, and dehydrating under reduced pressure at 30 mmHg or less, 1230 parts (b2) of a PO, 19.9 mol adduct of 2,2,4-trimethyl-1,3-pentanediol was obtained.
[0042]
Comparative Example 3
A glass autoclave was charged with 74 parts (1.0 mol) of n-butanol and 1.1 parts of KOH, and a mixture of 224.4 parts (5.1 mol) and 226.2 parts (3.9 mol) of PO from a pressure-resistant dropping funnel. Was added dropwise at 110 ° C. over 15 hours. Then, it was made to react at 130 degreeC for 10 hours, and was cooled. After cooling, it was treated with an adsorption treatment agent, filtered, and dehydrated under reduced pressure at 30 mmHg or less to obtain 475 parts (b3) of n-butanol EO 5.1 mol / PO 3.9 mol random adduct.
[0043]
Comparative Example 4
4.8 parts are used instead of 1.1 parts KOH, 915.2 parts (20.8 moles) are used instead of 224.4 parts EO, 916.4 parts (15.8 moles) are used instead of 226.2 parts PO. ) Was used in the same manner as in Comparative Example 3 to obtain 1800 parts (b4) of n-butanol random adduct of EO 20.8 mol / PO 15.8 mol.
[0044]
Comparative Example 5
In Comparative Example 3, 3.8 parts were used instead of 1.1 parts of KOH, 1281.8 parts (22.1 mol) were used instead of 226.2 parts of EO, EO was not used, and the temperature was 105 ° C. 1220 parts (b5) of a PO22.1 mol adduct of n-butanol was obtained in the same manner as in Comparative Example 3 except that the reaction solution was added dropwise over a period of time and then reacted at 130 ° C. for 5 hours.
[0045]
Comparative Example 6
The spindle oil was the metal working oil (b6) of Comparative Example 3.
[0046]
Comparative Example 7
Polybutene [Nisshi Polybutene LV-25E manufactured by Nippon Petrochemical Co., Ltd.] was used as the metal working oil (b7) of Comparative Example 7.
[0047]
Test example
The main items (weight average molecular weight, HLB, kinematic viscosity at 40 ° C., kinematic viscosity at 100 ° C., viscosity of the hydraulic working oils of the metal working oils a1 to a5 and b1 to b7 of the above examples and comparative examples are shown below. Tables 1 and 2 show the physical properties of the index, the friction coefficient under the load of 200N, 300N and 500N representing the lubricity, the wear scar diameter and the oil film breakage, and the critical temperature at which the lubricating oil representing compatibility with hydrocarbons is separated. Shown in
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Examples 6-9, Comparative Examples 8-14
In the formulation based on Table 3, a water-soluble processing oil was obtained and the lubricity of a 5% aqueous solution was measured.
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[Table 1]

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[Table 2]

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[Table 3]

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【The invention's effect】
The polyether-based metalworking oil of the present invention is excellent in compatibility with hydrocarbons such as mineral oil, and has the effect of being excellent in lubricity and viscosity index. Therefore, it is extremely suitable as a metal processing oil.

Claims (4)

5 to 90% by mass of the polyether (E) and hydrocarbon base oil represented by the following general formula (1) and having an HLB of 6.0 or less and a weight average molecular weight of 500 to 30,000 Metal processing oil.
_{^{R 1 [- {(OCH 2}} CH 2 CH 2 CH 2) m (OA) n} -OH] p (1)
[Wherein R ¹ is a residue obtained by removing a hydroxyl group from a branched monovalent saturated or unsaturated aliphatic alcohol having 4 to 24 carbon atoms, A is a 1,2-propylene group, and m and n are (E) An integer of 1 or more with a weight average molecular weight of 500 to 30,000, p is 1 It is. ] The content of the _{(OCH 2 CH 2 CH 2 CH} 2) is _{(OCH 2 CH 2 CH 2 CH} 2) and (OA) content of the total amount from 5 to 45 mol% in a claim 1 metalworking oil according to the . The metalworking oil according to claim 1 or 2, wherein the bond of (OCH ₂ CH ₂ CH ₂ CH ₂ ) and (OA) includes a random bond. Furthermore, at least one selected from the group consisting of detergent dispersants, antioxidants, oil agents, emulsifiers, extreme pressure agents, metal deactivators, rust inhibitors, antifoaming agents, viscosity index improvers and pour point depressants. The metalworking oil according to any one of claims 1 to 3, comprising an additive.