WO2004092312A1 - Lubricant for water-miscible metal working oil - Google Patents

Abstract

A lubricant for water-miscible metal-working oils which comprises a polyether which is represented by the following general formula (1) and has an HLB of 6.1 to 16.0 and a weight-average molecular weight of 500 to 10,000; and a water-miscible metal working oil containing the lubricant. They have excellent lubricity in application not only to steel materials but to plastic metals such as aluminum. Even when diluted with water, they are stable and do not separate into phases. R1[{(OCH2CH2CH2CH2)m/(OA1)n}(OA2)p-OH]q (1) (In the formula, R1 represents a C1-24 residue; A1 and A2 each represents C2-4 alkylene; m is an integer of 1 or larger; n and p each is an integer of 0 or larger; q is an integer of 1 to 6; and {(OCH2CH2CH2CH2)m/(OA1)n} means random bonding when n is an integer of 1 or larger.)

Description

 Specification

 Lubricants for aqueous metalworking oils Technical field

 The present invention relates to a lubricant for aqueous metalworking oil. For details, see Polyether-based lubricants for metalworking oils, lubricant compositions for metalworking oils, and metalworking oils.

Background art

 Water-based metal processing oils such as cutting oil, rolling oil, drawing oil, press oil, forging oil, polishing oil for aluminum disc, polishing oil for silicon wafer, coolant for silicon wafer cutting, etc. are solution type, soluble type, and emulsion type. And so on.

 The properties required for these are lubricity, low foaming properties, stability in water dilution (stability of the diluent when diluted with water at the time of use), oil separation from other mineral oil-based processing oils, etc. It is.

 Polyethers have been used as lubricants in aqueous metalworking oils. These polyethers are block copolymers of ethylene oxide and propylene oxide, which are so-called pull-mouth nick type or reverse pluronic type (see, for example, US Pat. No. 4,414,121). (U.S. Pat. No. 4,636,321) or a random copolymer.

 The polyethylene oxide chains contained in these polyethers are introduced to increase the hydrophilicity and improve the stability of dilution with water, and these polyethers are usually used to improve lubricity. It has an average molecular weight of 00 or more. Summary of the Invention

An object of the present invention is to provide a lubricant for a water-based metal working oil which is excellent in lubricity not only for steel materials but also for plastic metals such as aluminum. Another object of the present invention is to provide a lubricant composition for an aqueous metalworking oil, comprising the above-mentioned lubricant and other additives, and having excellent lubricity.

 Still another object of the present invention is to provide an aqueous metalworking oil comprising water and the above-mentioned lubricant or the above-mentioned lubricant composition and having excellent lubricity, low foaming property, water dilution stability and oil separation property. It is to be.

 According to the present invention, the above object is achieved by an aqueous metalworking represented by the following general formula (1), comprising an HLB of 6.1 to 16.0 and a polyether (E) having a weight average molecular weight of 500 to 10,000. Achieved by oil lubricants (hereinafter abbreviated as lubricants).

R ¹ [{(OCH ₂ CH ₂ CH ₂ CH _m / (OA ¹ ) _n } (OA ² ) _p _OH] _q (1) wherein 1 ^ is 1 to 24 carbon atoms having 1 to 6 hydroxyl groups. A residue obtained by removing at least one hydroxyl group from the compound of formula (I); A ¹ is an alkylene group having 2 to 4 carbon atoms excluding 1,4-butylene group; A ² is an alkylene group having 2 to 4 carbon atoms; Is an integer of 1 or more with an average of 1 to 120; n and p are integers of 0 or 1 or more with an average of (n + p) of 1 to 200, and n and p are simultaneously 0. It is not; q is an integer of. 1 to 6; n is the time of one or more integer _{{(OC CHsCHsCHQ m / (OA} 1) n} denotes the random bond.

 The present invention is also a lubricating oil composition for an aqueous metallurgical oil comprising the above polyether (E) and other additives.

 The present invention also provides an aqueous metalworking oil comprising water, the above-mentioned lubricant, or the above-mentioned lubricant composition, wherein polyether (E) is contained in an amount of 0.01 to 95 based on the weight of the above-mentioned metalworking oil. It is an aqueous metalworking oil containing a weight percent. Detailed Disclosure of the Invention

In the general formula (1) of the present invention, R ¹ is a residue obtained by removing at least one, preferably all hydroxyl groups from a compound having 1 to 24 carbon atoms and having 1 to 24 carbon atoms.

R ¹ is a residue of a linear, branched or alicyclic mono- to hexa-valent aliphatic alcohol, a residue of a mono- to hexa-valent phenol, a mono- to hexa-valent aromatic group-containing aliphatic alcohol , A residue of a heterocyclic dihydric alcohol, a residue of a saccharide and a derivative thereof, and the like.

The following (el) to (e5) are examples of these alcohols and phenols.

 (e l) aliphatic alcohol

 (e l l) Monohydric alcohol

 (e111) Linear or branched aliphatic saturated monohydric alcohol having 1 to 24 carbon atoms: methanol, ethanol, propanol (n-propanol, isopropanol, etc.), butanol, pentanol, hexanol, heptanol, Octanol (n-octano mono, 2-ethylhexyl alcohol, etc.), nonyl alcohol, decyl alcohol, pendecyl alcohol, dodecyl alcohol, tridecyl alcohol (n-tridecyl alcohol, isotridecyl alcohol, etc.), tetradecyl Alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, eicosyl norecole, eicoschiolenorecole, docosiolenorecole Application Benefits Koshirua Rukonore, tetracosyl alcohol;

 (e 1 12) Linear or branched aliphatic unsaturated monohydric alcohol having 3 to 24 carbon atoms: alkenyl alcohol (1-, 2- or iso-prodyl alcohol, putininole alcohol, pentul alcohol) , Hexeninoleanolecole, Hepteninorea Nolecole, Octeninoleanolecole, Nonenyl alcohol, Deceninoleanolecole, Pendecenyl alcohol, Dodecenyl alcohol, Tridecenyl alcohol, Tetrade Cenyl alcohol, pentadecenyl alcohol, hexadecenyl alcohol, heptadeceninoleanolecole, octadeceninoleanorecole, nonadeceninole realeco, eicoseninoleanorecole, Heinecoseninoleanoreco nore, docoseninolea alcohol, tricosenyl alcohol , Alkynyl alcohol (pentulcohol, etc.).

 (e113) alicyclic monohydric alcohol having 4 to 24 carbon atoms:

 For example, cyclontanol and cyclohexanol.

(e12) Dihydric alcohol (e 121) Linear or branched aliphatic dihydric alcohol having 2 to 24 carbon atoms: anorecylene glycolone (ethylene glycol, propylene glycol, 1,3-1,1,4- or 1'2-butanediole) 1,6-pentanediol, 1,2- or 1,7-heptanediol, 1,2- or 1,8-octanediol, isobutylene glycolone, 3-methysole 1, 5-Pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-dimethinole 1,3-propanediol, 2-butynolee 2-ethynolee 1,3-propanediol, 2,5-dimethyl Hexane-1,2,5-diol, etc.);

 (e122) alicyclic dihydric alcohol having 4 to 18 carbon atoms:

 Cycloalkyleneglycol / re (1,4-cyclohexanediole, 1,4-cyclohexanedimethanol, etc.), hydrogenated bisphenols (hydrogenated bisphenol A, hydrogenated bisphenol F, etc.);

 (e 1 3) 3- to 6-valent anore

 (e 1 3 1) Linear or branched C3-24 trihydric aliphatic alcohols: glycerin, 1,2,3-butanetriol, 1,2,3_pentantriol, 2-methyl / ret 1,2,3-propanetriol, 2-methinole 2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4 —Hexanetriol, 4-propyl-1,3,4,5-heptantriol, 2,4-dimethinole 2,3,4-pentantriol, pentamethylglycerin, 1,2,4-butanetriol, 1 , 2,4-pentantriol, trimethyloloneethane, trimethylolpropane, etc.

 (e1 32) linear or branched C4 to C4 to C6 to C6 aliphatic alcohols and their intramolecular or intermolecular dehydrates;

 Pentaerythri tonole, dipentaerythrin tonole, sonorebitonore, mannitol, 1,5-, 3,6- or 1,4-sonolebitan, diglycerin, etc.

 (e 2) phenols

 (e21) monovalent phenols having 6 to 24 carbon atoms;

Phenol, anolequinolephenol (o, m or p-methinolephenol, 2, 3, 1, 2, 4-, 2, 5-, 3, 4- or 3,5-dimethylphenol, 2, 6 — Dimethinolephenol, o, m or p-ethynolephenol, ρ-n-butynolephenol, ρ-octylphenol, p-nonylphenol, monostyrylphenol, monobenzyl phenol, etc. .

 (e22) divalent to hexavalent phenols having 6 to 24 carbon atoms;

 Divalent phenols (catechol, resorcinol, hydroquinone, etc.), tri- to hexavalent phenols (trioxybenzene, tetraoxybenzene, hexoxybenzene, etc.), bisphenols (bisphenol A, bisphenol F, etc.) etc.

 (e 3) Aliphatic alcohol containing aromatic group

 (e31) an aralkyl alcohol having 7 to 24 carbon atoms;

 Benzyl alcohol, phenethyl alcohol and the like.

 (e32) a substituted aralkyl alcohol having 8 to 24 carbon atoms;

 o, m or p-methinolebenzinoreanorecole, -n-butinolefenetinorenorecole and the like.

 (e4) Heterocyclic dihydric alcohol:

 1, 4, 3, 6—Sorbide etc.

 (e5) sugars and derivatives thereof;

 Sucrose, glucose, mannose, funolectose, methinolegnolecoside, etc. Of these, preferred is (el), more preferred are (e 12) and (e 13), particularly preferred are those having 2 to 20 carbon atoms of (e 12), 1 3) having 3 to 18 carbon atoms, particularly preferably (e 1 2 1), (e 1 3 1) and (e 1 3 2) having 3 to 6 carbon atoms is there.

R ¹ is preferably a residue obtained by removing all hydroxyl groups from a dihydric or trihydric alcohol.

When the number of carbon atoms of R ¹ exceeds 24, since hydrophilicity of the (E) is insufficient, deteriorated water dilution stability of water-based metalworking fluids described below using (E) as or lubricants, separated after dilution May occur.

A ¹ in the general formula (1) is an alkylene group having 2 to 4 carbon atoms other than a 1,4-butylene group, and A ² is an alkylene group having 2 to 4 carbon atoms.

A ¹ and A ² may be the same or different. A ¹ is an ethylene group, 1, 2 - or 1, 3-propylene group, 1, 2 or 2, 3-butylene group, include Isopuchiren group, if A ¹ there are a plurality may be used in combination of two or more of these. Also the A ² include 1, 4 Buchiren group in addition to those listed in A ^1, if there A ^ plurality may be used in combination of two or more thereof.

Among A ¹ and A ² , preferred are an ethylene group, 1,2-propylene group and 1,2-butylene group, more preferred are an ethylene group and 1,2-propylene group, and particularly preferred is water. An ethylene group is used from the viewpoint of improving dilution stability. Water soluble when at least a part of the A ¹ or A ² is an ethylene group (E) is above improvement. In the general formula (1), a compound in which A ² is an ethylene group is preferable. M, n, p and q in the general formula (1) are selected from the following ranges so that the weight average molecular weight (hereinafter abbreviated as Mw) of (E) is from 500 to 10,000. In addition, since (E) in the present invention usually has a molecular weight distribution, m, n, p and q in the general formula (1) have many combinations within the above range, and (E) May be a mixture thereof or one kind.

 m is an integer of 1 or more, preferably 1 to 120, and more preferably 1 to 30, with an average of 1 to 120, preferably 1 to 30, and more preferably 1 to 14.

 n and p are 0 or 1 or more, preferably 0 or 1 to 200, more preferably 0, in which the average of (n + p) is 1 to 200, preferably 2 to 57, more preferably 2 to 16. Or an integer from 1 to 40.

 When n is 0, p is 1 to 200. When p is 0, n is 1 to 200, and n and p are never 0 at the same time.

 n is preferably 0 to 14, more preferably 2 to 14 on average. p is preferably 0 to 44, more preferably 0 to 12, and particularly preferably 0. In the general formula (1), n or p is preferably 0.

 mZn is preferably 0.1 to 4 and more preferably 0.2 to 3 from the viewpoint of water dilution stability.

/ (m + n) is preferably 0 to 3, more preferably 0 to 0.2, from the viewpoint of water dilution stability. m / (m + n + p) is preferably 0.05 to 0.8, and more preferably 0.1 to 0.7, from the viewpoint of water dilution stability.

 q is an integer of 1 to 6, preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 to 3 in terms of good water dilution stability. If q exceeds 6, lubricity will deteriorate.

 The Mw (measured by gel permeation chromatography) of (E) is from 500 to 10,000, preferably from 700 to 7,000, more preferably from 800 to 6,000, particularly preferably from 1,000. ~ 5,000. If the Mw of (E) is less than 500, the lubricating properties are insufficient, and if it exceeds 10,000, the kinematic viscosity is too high and the handling properties in compounding and the like deteriorate.

Also, the polyether (E) requires that (OCH ₂ CH ₂ CH ₂ CH and (OA ¹ ) in the formula (1) be a random bond, otherwise, the flow of (E) at low temperature Insufficient mobility and poor handling of lubricant.

 The HLB of (E) is 6.1 to L6.0, preferably 6.3 to 13.8, and more preferably 8 to 13. If the HLB is less than 6.1, the hydrophilicity of (E) is insufficient, the stability in water dilution is poor, and separation may occur after dilution. If it exceeds 16. 0, lubricity deteriorates.

 The HLB in the present invention is the HLB of the Oda method, which can be calculated from the ratio of the organic value to the inorganic value of the compound, and is described in “Introduction to New Surfactants” [1996, Sanyo Chemical Industries, Ltd. ] It is calculated by the calculation method described on page 197.

 The assault point of (E) is preferably higher from the viewpoint of water dilution stability, but is preferably 5 to 60 ° C in view of lubricity. The cloud point in the present invention is a temperature at which a 2% by weight aqueous solution of (E) is heated and cloudiness is visually observed.

(E) is usually liquid at ordinary temperature, and preferably has a kinematic viscosity of 5 to 1,000 mm ² / s at 40 ° C. The kinematic viscosity can be measured according to JIS K 2283 (hereinafter, the kinematic viscosity is measured in the same manner).

 (E) can be produced by the following method.

(i) In the above (el) to '(e5), in the presence of a catalyst, tetrahydrofuran (hereinafter abbreviated as THF) and at least one alkylene oxalate having 2 to 4 carbon atoms other than THF A random addition reaction of an amide (hereinafter abbreviated as AO), and then, if necessary, adding one or more AOs having 2 to 4 carbon atoms.

 (ii) In the case of a polyether in which n in formula (1) is 0, polyoxytetramethylene glycol (hereinafter referred to as (el) to (e5)) is prepared by homopolymerizing THF alone in the presence of a catalyst. , Abbreviated as PTMG) and adding one or more AOs having 2 to 4 carbon atoms in the presence of a catalyst.

 The temperature of the addition reaction in (i) and (ii) is preferably 30 to 120 ° C, and the pressure is preferably 0 to 0.6 MPa.

 AO used for the addition reaction includes ethylene oxide (EO), propylene oxide (PO), 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide and the like.

 As the catalyst, a conventionally known catalyst can be used, but preferred types of the catalyst differ between the THFZAO random addition reaction and the AO addition reaction.

 Examples of the catalyst for the THFZAO random addition reaction include the following.

Lewis acids, and complexes _{thereof; BF Q, BC 1 3,} A 1 C 1 ", F e C l 3, S nC 1 3, BF 3 - etherate, BF ₃ 'THF complex (hereinafter, BF _3' THF Abbreviation).

Protonic _{acid; H 2 S0 4, HC 10} 4 mag.

Perchlorates of alkali _{metals; KC 10 4, N a C} 10 4 mag.

Alkaline earth metal perchlorates; C a (C 1 O ₄ ) ₂ , Mg (C 10 ₄ ) _{2 and the} like. Other metal perchlorates; A 1 (C 10 ₄ ) _{3 and the} like.

Of these, BF ₃ 'ether complex and BF ₃ ' THF are preferred.

Examples of the catalyst for the AO addition reaction include the following in addition to the above catalysts. Hydroxide of alkaline metal or alkaline earth metal; KOH, NaOH, CsOH, Ca (OH) _{2 and the} like.

Oxides of alkali metals or alkaline earth metals; K ₂₀ , C a O, B a〇 and the like. Alkaline metal and its hydrides; Na, K, Na a, ΚΗ, etc.

Amines; triethylamine, trimethylamine and the like. Preferred among these KOH, Na OH, C s OH , BF 3 ' ether complex body, BF _3' is THF.

 The lubricant composition for a water-based metal working oil of the present invention (hereinafter abbreviated as a lubricant composition) comprises the above (E) and other additives.

 Other additives include aliphatic ruponic acids having 8 to 22 carbon atoms and / or salts thereof (F), other polyethers (G), antioxidants (H), extreme pressure additives (I), One or more types selected from the group consisting of a fire retardant (J) and an antifoaming agent (K).

 Examples of (F) include the following compounds (F1) to (F3).

 (F 1) Aliphatic monocarboxylic acid

 (F 11) Saturated aliphatic monocarboxylic acid

 For example, octylic acid (caprylic acid, isooctylic acid), nonanoic acid, decanoic acid (potassic acid and the like), pendecanoic acid, dodecanoic acid (lauric acid and the like) and the like are preferable. Acids, more preferred are caprylic acid and nonanoic acid.

 (F 1 2) Unsaturated aliphatic monocarboxylic acid

 For example, lindelic acid, maccodic acid, myristoleic acid, palmitooleic acid, oleic acid, erlic acid, etc. are mentioned, and oleic acid is preferred.

 (F 2) Aliphatic dicarboxylic acid

 Examples thereof include ω-dicarboxylic acid (eg, azelaic acid, sebacic acid, dodecandioic acid, etc.) and alkenyl succinic acid (eg, octeyl succinic acid, dodecenyl succinic acid, pentadecenyl succinic acid, etc.), and are preferred. Is alkenyl succinic acid, especially dodecenyl succinic acid and pentadecenyl succinic acid.

 (F 3) Salt of the above monocarboxylic acid or dicarboxylic acid

 Examples of the salt include an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an aliphatic amine salt, and a salt of an aliphatic amine with an AO adduct.

Examples of the salt include (F1) and (F2) neutralized products with a neutralizing agent. Examples of neutralizing agents include alkali metal hydroxides (sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, etc.); and alkaline earth metal hydroxides (calcium hydroxide, magnesium hydroxide). Etc.); ammonia; aliphatic amines [charcoal Alkyl or alkenylamines having a prime number of 1 to 10 or more (laurylamine, oleylamine, etc.), heterocyclic amines having 3 to 10 carbon atoms (such as morpholine), and alkanol groups having 2 to 10 carbon atoms Mono-, di-, or trial-form ethanol (monoethanolamine, triethanolamine, isopropanolamine, N-dimethylaminoethanolamine, etc.)]; AO adducts of these amines, etc. However, two or more of these may be used in combination.

 Examples of the AO adduct of the above-mentioned amine include, for example, AO of alkyl monoamine having an alkyl group having 1 to 10 or more carbon atoms (e.g., methylamine, ethylamine, getylamine, propylamine, butylamine, hexahexylamine, octynoleamine). AO adducts of alkylene diamines having 2 to 18 or more carbon atoms in the alkylene group (ethylenediamine, propylenediamine, hexylenediamine, octylenediamine, decylenediamine, dodecylenediamine, etc.); A polyalkylene polyamine having a prime number of 4 to 18 or more, an alkylene group of 2 to 6 carbon atoms, and an amine number of preferably 3 to 7 (ethylenediamine, triethylenetetramine, tetraethylenepentamine , Pentaethylene hexamine, hexae A O adduct of polyethylene polyamines) such Renheputamin like. AO includes those having 2 to 4 carbon atoms, for example, EO and PO (preferably PO). The number of moles of AO added is preferably 0.5 to 2 moles, more preferably 1 to 2 moles per N atom of amine. ~ 2 moles. When the amount is 0.5 to 2 mol, the oil separating property of the aqueous metal working oil becomes good.

 Among the neutralizing agents, preferred are aliphatic amines and their AO adducts, more preferred are AO adducts, particularly preferred are triethanolamine, PO 2 to 8 mole adducts of ethylenediamine, and especially 4 It is a molar adduct, a 3 to 8 molar adduct of PO of methylentriamine, especially a 5 molar adduct.

 Incidentally, the dicarboxylate includes a monosalt of dicarboxylic acid.

 The lubricant composition of the present invention is preferable because it contains (F) because foaming of the metal working oil when diluted with water is suppressed.

When the number of carbon atoms in (F) is 8 or more, the lubricant composition does not easily increase the metal content, and when the number of carbon atoms is 22 or less, foaming is small even when diluted with water. No.

 Monocarboxylic acid (salt) [Hereinafter, carboxylic acid (salt) represents a carboxylic acid and / or a salt thereof. ] And dicarboxylic acid (salt) are preferably used in combination from the viewpoint of lubricity, preferably monocarboxylic acid (salt) dicarboxylic acid (salt) = 100 to 5/0 to 95〜, more preferably 100 to 100 : L 0Z0 ~ 90.

 The equivalence ratio of porphyric acid / proportion in the mixture of porphyric acid and porphyrate is preferably 0 to 50/50 to 100, more preferably 0 to 3θΖ70 to 100.

 In the case of using porphyric acid salt, porphyric acid salt may be added as it is, but porphyric acid and a neutralizing agent are separately added, and neutralized in the compounding step to form a carboxylate. You may. Preferred is a method of neutralizing in the compounding step.

 When an aliphatic amine or its AO adduct is used as a neutralizing agent, the equivalent ratio of carboxylic acid / neutralizing agent is preferably 1 / 0.8 to 3, more preferably 1 / 0.9 to 2. However, when the carboxylic acid is in excess, the excess carboxylic acid usually acts not only as a foam-suppressing effect but also as an oily component.

 Conversely, when the neutralizing agent is in excess, the excess aliphatic amine or its AO adduct acts as an antioxidant component in the lubricant composition and is not included in the content of (F). It is included in the content of the protective agent (J).

 When a small amount of neutralized water (preferably less than 5% based on the weight of (E)) is produced in the method of neutralization in the compounding step, the water is also a component of the lubricant composition of the present invention. include.

 The content ratio of (F) to (E) is usually from 0.03 to 10, preferably from 0.03 to 5.0, more preferably from 0.06 to 1.2, particularly preferably from 0.1 to 1.0, by weight. 1. It is 0.

 If the ratio of (F) is 0.03 or more, the processed metal is less likely to be formed and the lubricity tends to be improved. On the other hand, when the value is 5 or less, the oil separating property of the aqueous metal working oil is good. In the present invention, (F) does not include sulfur and / or nitrogen atom-containing carboxylic acids (salts) used as extreme pressure additives described below.

The other polyether (G) is a polyether other than (E) of the present invention, One T fine 04/003741

12

Polyethers having a Mw of 500 to 300,000, which has been used as a lubricant, are mentioned.

 (G) includes non-ionic polyethers (G 1) and ionic polyethers (G 2).

 (G1) includes, for example, polyethylene glycol, an EO adduct of a C1-C24 monohydric alcohol, and an EO // PO random or block adduct of a C1-C24 monohydric alcohol. EOZPO / EO block copolymers (for example, the term “pull nick” described in US Pat. No. 4,414,121 and US Pat. No. 4,636,321). ), POZEOZPO block copolymer (what is referred to as “reverse pull-mouth nick”), terminal alkoxylated product or terminal acylated product of these polyethers or (E), and the like.

 Examples of (G2) include anion products of the above (G1), for example, sulfates of polyoxyalkylene compounds (as described in US Pat. No. 3,950,258), phosphorus Acid esters (as described in U.S. Pat. No. 3,945,930), carboxyetherified compounds and the like.

 The added amount of (G) is preferably 90% or less based on the weight of (E) in the lubricant composition (hereinafter, unless otherwise specified,% represents% by weight), more preferably 60%. Or less, particularly preferably 30% or less.

 Examples of the antioxidant (H) include phenolic antioxidants [eg, 2,4-dimethyl-6-tert-butylphenol, 4,4-butylidenebis (6-tert-butylmethcresol), etc.]; Inhibitors (eg, phenyl a-naphthylamine, phenyl-β-naphthylamine, etc.); dialkyl (1 to 36 carbon atoms) zinc dithiophosphate; diaryl (2 to 36 carbon atoms) zinc dithiophosphate; organic sulfide; organic Selenide and the like. The amount of the antioxidant (Η) is preferably 2% or less, more preferably 0.0001 to 1%, based on the weight of the polyether (Ε) in the lubricant composition.

Extreme pressure additives (I) include: Suzuishi Ken (lead naphthenate etc.); Sulfur compounds (sulfurized fatty acids such as oleic sulfide, sulfided fatty acid esters, sulfided palm oil, terminated sulfide, dibenzyl disulfide, carbon number) 8-24 alkylthiopropionic acids An amine salt or an alkali metal salt of an amine, an amine salt or an alkali metal salt of an alkylthioglycolic acid having 8 to 24 carbon atoms, etc.); a chlorine compound (a chlorinated stearic acid, a chlorinated paraffin, a chloronaphthazanthate, etc.); Phosphorus compounds (tricresyl phosphate, tripty / rephosphate, tricresinolephosphite, n-butylyl-n-octynolephosphinate, di-n-butynolehexynolephosphonate, di-n-butyl phosphine Enyl phosphonate, dibutyl phosphoramidate, amine dibutyl phosphate, etc.). The amount of the extreme pressure additive (I) added is preferably 10% or less, more preferably 5% or less, based on the weight of the polyether (E) in the lubricant composition.

 Examples of the protective agent (J) include aliphatic carboxylic acid amides having 14 to 36 carbon atoms (such as myristic acid amide, palmitic acid amide, and oleyl amide); and alkenyl succinamides having 6 to 36 carbon atoms. N, N, N, N, N, N, N 1-disalicylidene-1,2-diaminopropane; arizarin; aliphatic amines mentioned as the neutralizing agent described above, and AO adducts thereof.

 Of (J), preferred are AO adducts of aliphatic amines, particularly preferred are triethanolamine, PO 2 to 8 mol adducts of ethylenediamine, particularly 4 mol adducts, and 3 to 8 mol adducts, especially 5 mol adducts.

 The aliphatic carboxylic acid amide having 14 to 36 carbon atoms and the amide of alkenyl succinic acid having 6 to 36 carbon atoms also have a function as an oiliness improver.

 The amount of the protective agent (J) to be added is preferably 50% or less, more preferably 1 to 40%, based on the weight of the polyether (E) in the lubricant or composition. The amount of) also includes the excess aliphatic amine described above.

Examples of the antifoaming agent (K) include polyorganosiloxanes (for example, polydimethylsiloxane). The addition amount of the antifoaming agent (K) is preferably not more than 100 ppm, more preferably not more than 100 ppm based on the weight of the polyether (E) in the lubricant composition. 10 to 500 p.

 The lubricant composition of the present invention preferably contains an aliphatic carboxylic acid having 8 to 22 carbon atoms and / or a salt thereof (F) as another additive. Further, the lubricant composition of the present invention also preferably contains, as other additives, one or more selected from the group consisting of antioxidants, extreme pressure additives, antioxidants and defoamers. .

 The lubricant composition of the present invention preferably does not contain a hydrocarbon-based oil (mineral oil, animal and vegetable oil, etc.). It is preferable to not contain a hydrocarbon-based oil since deterioration due to spoilage is small even when water is added and stored as an aqueous metal-based oil for a long period of time.

 The percentage (%) of (E) / (F) / (G) to (K) based on the weight of the lubricant composition of the present invention is usually 10 to 99/1 to 90/0 to 50, preferably 50-909-80-1-30, more preferably 60-90 / 9-30 / 1-10. The aqueous metalworking oil of the present invention contains water and the above-described lubricant or lubricant composition, and usually contains polyether (E) in an amount of 0.01 to 95%, preferably 0.01 to 95% based on the weight of the aqueous metalworking oil. Is contained at a concentration of 0.2 to 90%, more preferably 10 to 85%, particularly preferably 30 to 60%.

 In addition, the aqueous metalworking oil of the present invention contains the lubricant composition in an amount of usually 0.01 to 99%, preferably 0.3 to 95%, more preferably 12 to 88, based on the weight of the aqueous metalworking oil. %, Particularly preferably 30 to 80%.

 The concentration of (E) in the water-based metal working oil is determined when the water-based metal working oil is transported or stored, or when the water-based metal working oil is used as a drawing oil, press oil, rolling oil, forging oil, etc. Preferably it is 5 to 90%, more preferably 10 to 60%.

 Also, when water-based metal working oil is used as cutting oil, grinding oil, polishing oil for aluminum disk, polishing oil for silicon wafer and coolant for silicon wafer cutting, not only (E) but also (F) is included. It is particularly preferred that, prior to use, the weight concentration of (E) is 0.5-3%, especially 1-2%, and the concentration of (F) is 0.1-2%, especially 0.2. Preferably it is diluted with water to ~ 2%.

The aqueous metalworking oil of the present invention can be produced by blending the above-mentioned lubricant or lubricant composition as it is with water. Each component may be separately blended with water, and the blending order is not particularly limited.

 The aqueous metal working oil of the present invention may be in any form of a solution type, a soluble type, or an emulsion type. From the viewpoint of the appearance stability of the aqueous metal working oil over time, a solution type or a solution type is preferred. It is.

 When the solution type or soluble type metal working oil of the present invention is used as a cutting oil, it can be used by supplying the diluent to the metal to be cut and the cutting tool.

 The water-based metalworking oils of this study have excellent lubricity not only for steel and iron, but also for plastic metals such as aluminum and aluminum alloys. That is, the water-based metal working oil of the present invention includes aluminum, aluminum alloy, iron and

Preferred for machining Z or steel. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. Hereinafter, parts means parts by weight.

 (1) Mw measurement conditions;

 Measuring equipment: LC8 1 20 manufactured by Tosoh Corporation

 Eluent: THF

 Flow rate: 0.6 (ml / min)

 Column: TSKg e l S u er H4000, H3000, H2000 Reference substance: polyethylene glycol

 (2) Cloud point measurement method;

 A 2% by weight aqueous solution of (E) was heated, and the temperature at which white turbidity was visually observed was measured. Above the cloud point, the aqueous solution is transparent, and the higher the cloud point, the better the water dilution stability.

 (3) HLB calculation method

"Introduction to New Surfactants" [1996, Sanyo Chemical Industries, Ltd.] Calculated by the calculation method described on page 97. Examples 1 to 4, 7 and Comparative Example 1 A glass-coated stainless steel autoclave equipped with a heating / cooling device, a stirrer, a pressure dropping funnel, a nitrogen purge tube, and a thermometer, and the aliphatic alcohol of the number of parts shown in Table 1 or Table 2 And THF and BF ₃ · THF were charged, and EO of the number of parts [in () in moles] shown in Tables 1 and 2 was dropped from the pressure-resistant dropping funnel over 10 hours while maintaining the temperature at 35 to 50 ° C. After aging at 50 ° C for 5 hours, it was cooled. In addition, 48 weight of the number of copies shown in Tables 1 and 2. After adding / oNaOH aqueous solution to neutralize the catalyst, low volatile components were distilled off at 120 ° C under a reduced pressure of 30 mmHg or less. After that, the catalyst residue is adsorbed using an adsorption treatment agent (Kyowa Chemical Industry Co., Ltd. “Kyonode 600” and “Kyoichi Word 1000”), filtered, and dehydrated under reduced pressure (130 ° C, 30 mmHg or less) , 1 hour, and so on.) After that, polyethers (E1) to (E4) and (E7) and comparative polyether (E, 1) were obtained, and these were used in Examples 1 to 4, The lubricants of 7 and Comparative Example 1 were used. Examples 5, 6 and 8

 A polyether was prepared by random AO addition reaction in the same manner as in Example 1 except that the charged amounts of THF and EO were the amounts shown in Table 1 or Table 2, and after purification, the same autoclave as in Example 1 was used. Then, the polyether and potassium hydroxide were charged in the amounts shown in Table 1, dehydrated under reduced pressure, and the EO of the number of parts shown in Table 1 [in the parentheses, the molar ratio] was increased from 130 ° C to 130 It was dropped over time. Then, it was further aged at 130 ° C for 5 hours and cooled. Thereafter, purification was performed in the same manner as in Example 1 to obtain polyethers (E5), (E6) and (E8), which were used as the lubricants in Examples 5, 6, and 8. Example 9

1,000 parts of PTMG (1.0 mol; “PTMG 1000” manufactured by Mitsubishi Chemical Corporation; PTMG with Mw of about 1,000) and 0.4 parts of KOH were charged, dehydrated under reduced pressure, and then withdrawn from a pressure-resistant dropping funnel. 2 Ι, 01 2 parts (23 mol) was dropped at 150 ° C over 10 hours. Thereafter, the mixture was aged for 10 hours until the pressure was equilibrated at 150 ° C, and cooled. After that, purification was performed in the same manner as in Example 1, and PTMG-1000 EO 2 1,950 parts (E 9) of 3 moles of kamo with a block were obtained and used as the lubricant of Example 9. Comparative Example 2

 In the same autoclave as in Example 1, 76 parts (1 mol) of propylene glycol and 4.0 parts of OH were charged, and after dehydration under reduced pressure, 682 parts (29 mol) of PO 1 were added from a pressure-resistant dropping funnel at 105 ° C for 10 minutes. It was dropped over time. After aging for 8 hours at 130 ° C until the pressure was equilibrated, 1,188 parts (27 moles) of EO was added dropwise from the pressure dropping funnel at 130 ° C over 8 hours. After that, it was aged for 5 hours until the pressure became equilibrium at the same temperature, and cooled. Thereafter, purification was carried out in the same manner as in Example 1 to obtain 2,800 parts (£, 2) of an adduct of 29 mol of PO and 27 mol of EO of propylene dalicol, which was used as a lubricant of Comparative Example 2.

Tables 1 and 2 show the yields, Mw, HLB and cloud point of (E1) to (E9) and (E, 1) to (E, 2).

Example

1 2 3 4 5 6 Polyether E 1 E 2 E 3 E 4 E 5 E β

1,4-butane 90 90 90 90 90 90 Gionolle (1) (1) (1) (1) (1) (1) LA

 Glycerin

 Da

 M

 Propylene

 Ma

 Glycol

 Was

 Is THF 216 1008 792 504 1512 2016

 (3) (14) (11) (7) (21) (28)

D

 , So

 EO 176 880 1100 1408 440 440

 Λ (4) (20) (25) (32) (10) (10)

Ά

 0

 PO

 With

 Addition

 Anti

_{BF 3 · 3.2 12.8 12.8 12.8 12.8} 17.0 response

 THF

48% 1.9 7.4 7.4 7.4 7.4 9.8 Aqueous solution

220 220th stage EO

 (5) (5) AO

Addition

 KOH 1.2 1.4 Reaction yield (parts) 460 1880 1883 1902 2150 2628

Mw 500 2150 2180 2200 2490 3040

HLB 11.7 9.9. 11.7 14.3 7.4 6,5 Cloud point () 21 21 34 46 13 10 Example Comparative example

7 8 9 1 2 Small litter E 7 8 Ε 9 Ε '1 E' 2

1,4-butane 90 90

 Diol (1) (i.o)

 La

 Glycerin 92

 Da (1)

 M

 Also propylene 76 was glycol (1)

 PTMG-1000

 B THF 1152 1512 1512

 ¾ on UUUQ

 (16) (21) (21)

 (1)

 ヅ

 EO 1760 1760 352 1188

A (40) (40) (8) (27) 0

 With PO 1682 Add (29) Anti

 Response B Fa ■ 19.1 12.8 12.8

 THF

48 NaOH 11.0 7.4 7.4 Aqueous solution

EO 5720 1012

 Step

 (130) (23)

AO

Addition

 KOH 5.6 0.4

Amount obtained (parts) 2850 8630 1950 1860 2800

Mw 3300 9990 2100 2150 3240

HLB 12.4 15.6 10.7 5,9 10.5 Cloud point (in) 39> 70 25 None 58 Examples 10 to 21 and Comparative Examples 3 to 6

 Components other than water were blended based on the blending ratios (parts) shown in Table 3 below, and then thoroughly mixed at room temperature to obtain a lubricating oil composition.

 Here, 4 mol of triethanolamine, ethylenediamine (PO) and 5 mol of diethylenetriamine (PO) were used as neutralizing agents for carboxylic acid, but the excess equivalent was a protective agent (J).

 To these lubricating oil compositions, water in the number of parts shown in Table 3 was further added and sufficiently mixed at room temperature to obtain aqueous metal working oils of Examples 10 to 21 and Comparative Examples 3 to 6. Table 3 shows the appearance of these metalworking oils.

The evaluation criteria for the appearance are as follows.

〇: Transparent uniform

X: separated into two layers

Table 3

Table 4 shows the results of evaluating the water dilution stability and lubricity of these aqueous metalworking oils by the following measurement methods. ' <Adjustment of test solution>

 The aqueous metalworking oils of Examples and Comparative Examples were further diluted 20 times with water to prepare test liquids. Water dilution stability>

The test solution was placed in a 10 OmL glass graduated cylinder with a stopper, and the appearance after 1 day at 25 ° C was visually judged according to the following criteria.

 〇: Transparent uniform

 Δ: slight turbidity

X: Lubricity that separates into two layers>

 Using a ball-on-disk type friction and wear tester (Fress Player FPR-2000, manufactured by Les Power Co., Ltd.), the coefficient of friction of the test solution at point contact (load 100 g) between a steel ball and a flat steel plate or aluminum plate It was evaluated by measuring the oil film breakage.

The test conditions are as follows.

Rotation speed: 20 rpm

Turning radius: 15 mm

Temperature: 30 ° C

Time: 5 minutes

Coefficient of friction (): Average value for 5 minutes

 The evaluation criterion for oil slick breakage was determined as follows by observing the fluctuation of μ within the measurement time and determining the magnitude of the fluctuation width of μ.

 Ο: Fluctuation range of μ 0.025

 : Fluctuation range of 0.025-0.040

X: fluctuation range of μ> 0.040 Table 4

産業上の利用可能性

Industrial applicability

 The lubricant for aqueous metal working oil of the present invention includes cutting oil, rolling oil, drawing oil, press oil, forging oil, polishing oil for aluminum disk, polishing oil for silicon wafer, and coolant for silicon wafer cutting. It is extremely effective as a lubricant for processing oils.

Claims

The scope of the claims 1. Represented by the following general formula (1), HLB of 6.1 to 16.0 and 500 to 1 A lubricant for water-based metal oil containing polyether (E) having a weight average molecular weight of 000. _{^{R 1 [{m / (OA}} 1) (OA 2) p (OCH.CH.CH ^ H.) - OH] q (1) [ in the formula, carbon atoms R ¹ has 1 to 6 hydroxyl groups 1 A residue obtained by removing at least one hydroxyl group from a compound having from 24 to 24; A ¹ is an alkylene group having 2 to 4 carbon atoms excluding a 1,4-butylene group; A ² is an alkylene group having 2 to 4 carbon atoms M is an integer of 1 or more with an average of 1 to 120; n and p are integers of 0 or 1 or more with an average of (n + p) of 1 to 200, and n and p are simultaneously 0. Q is an integer of 1 to 6; when n is an integer of 1 or more, {(OCH ₂ CH ₂ CH ₂ CH _m / (OA ¹ ) _n } indicates a random bond.] 2. 2. The lubricant according to claim 1, wherein in the general formula (1), n or p is 0. 3. The lubricant according to claim 1 or 2, wherein in the general formula (1), R ¹ is a residue obtained by removing all hydroxyl groups from a dihydric or trihydric alcohol. 4. The lubricant according to any one of claims 1 to 3, wherein the lubricant is an AS ethylene group in the general formula (1). 5. The lubricant according to any one of claims 1 to 4, wherein m / (m + n + p) in the general formula (1) is 0.05 to 0.8. 6. A lubricant composition for an aqueous metalworking oil, comprising the polyether (E) according to any one of claims 1 to 5 and other additives. 7. The lubricant composition according to claim 6, wherein the other additive is an aliphatic carboxylic acid having 8 to 22 carbon atoms and / or a salt thereof (F). 8. The lubricant composition according to claim 7, wherein (F) / (E) is 0.03 to 5.0 by weight. 9. Any one of claims 6 to 8 containing, as another additive, at least one selected from the group consisting of an antioxidant, an extreme pressure additive, an antioxidant and an antifoaming agent. The lubricant composition described in the above. 10. The lubricant composition according to any one of claims 6 to 9, wherein the lubricant composition does not contain a hydrocarbon-based oil as another additive. 1 1. A water-based metal comprising water and the lubricant according to any one of claims 1 to 5, or the lubricant composition according to any one of claims 6 to 10. A water-based metalworking oil, comprising a polyether (E) in an amount of 0.01 to 95% by weight based on the weight of the metalworking oil. 1 2. The aqueous metalworking oil according to claim 11, which is of a solution type or a solution type. 1 3. The water-based metal working oil according to claim 11 or 12 for processing aluminum, aluminum alloy, iron, Z or steel.