FR2547309A1 - OIL COMPOSITION FOR WORKING METALS HAVING POLYETHERPOLYOL - Google Patents

Abstract

COMPOSITION OF OIL FOR WORKING METALS CONTAINING AS ESSENTIAL COMPONENTS, THE FOLLOWING COMPONENTS A, B AND POSSIBLY C; (A) ONE OR MORE LUBRICATING OIL COMPONENTS SUCH AS OILS, FATS, MINERAL OILS AND FATTY ACID ESTERS; (B) ONE OR MORE POLYETHERPOLYOLS COMPOUNDS SUCH AS POLYETHERPOLYOLS AND POLYETHERPOLYOL DERIVATIVES HAVING MOLECULAR WEIGHTS OF 300 TO 600000 AND OBTAINED BY ADDITION OF ALKYLENE OXIDES TO POLYALKYLENEIMINES; (C) ONE OR MORE COMPOUNDS SELECTED FROM ACIDIC PHOSPHORUS COMPOUNDS AND BORIC ACID.

Description

The present invention relates to a novel oil composition for the

  metal working and more particularly a metal working oil composition containing a lubricating oil component and a derivative

of particular polyetherpolyol.

  Commonly used metalworking oils are each obtained by adding lubricating oil additives, such as a lubricity additive, an extreme pressure additive, a rust protection agent and / or an antioxidant with a lubricating oil component, such as an oil, fat, mineral oil or fatty acid ester, and then converting the resulting mixture into an oil-in-water emulsion by means of an emulsifier. However, in the case of rolling of a metal, attempts have been made to increase, ie to speed up the rolling speed so as to obtain a higher production rate. based on the rapid progress that has been made in rolling mill facilities and technology in recent years. Reflecting such attempts, the The rolling properties, such as lubricity, circulating stability, working efficiency and ease of treatment of wastewater have become progressively more severe. There is thus a strong constant demand for the development of an oil. However, common rolling oils which make use of emulsifiers are subject to various disadvantages and are therefore unable to meet such requirements. Based on an emulsifier, the lubricating power for rolling is adjusted by changing the type and amount of the emulsifier so that the amount of oil to adhere to the rolls and each work piece, in other words, the amount deposited is increased or decreased. In the case of a rolling oil containing an emulsifier as described above, a problem arises because the deposited amount and the circulating stability of the emulsion show a mutually contradictory tendency, namely that the amount deposited on each workpiece is decreased and that the lubricating power is thus rendered insufficient if the stability of the emulsion is increased. If an attempt is made to increase the amount deposited, the emulsion becomes unstable and causes various problems when circulated for reuse. Accordingly, common rolling oils making use of In addition, further improvements are also desired with regard to the lubricity and work efficiency of other oils for working metal such as working oils. to the press and

cutting oils.

  the plaintiffs then undertook a search to find a solution to the inconveniences

  common metalworking oil of the emulsion type.

  The applicants have also succeeded in making improvements and in overcoming the aforementioned drawbacks by using a lubricating oil component which contains an oil, a fat or a wax having a melting point of 20 to 100 C, in combination with an agent. particular hydrophilic dispersant (an anionic, water-soluble polymeric compound) such that the lubricating oil component is suspended and stably dispersed in a solid form in water at a temperature below the melting point the resulting dispersion however, it becomes unstable when applied to each workpiece, ie at a temperature above the melting point. A patent application has already been filed for the above-mentioned invention (see Japanese Patent Application).

published under No. 147593/1980).

  The plaintiffs have continued their research and have now found a metalworking oil composition which can be successfully used for metalworking in severe shearing conditions which is to be expected in the case of metalworking. effective application of the oil composition as well as under conditions of high speeds and high pressures, which allow high speed speeds and large rolling reductions, and which allows machining of metals under cutting conditions severe and facilitates the implementation of the process because of the excellent stability in

circulation in liquid form.

  More particularly, the Applicants have now found that (1) the use of a lubricating oil component and a particular polyether polyol derivative optionally in combination with an acidic phosphorous acid or boric acid allows, because of the protective colloid function. of the polyether polyol derivative, a stable dispersion of the lubricating oil component in the form of large droplets in the water and hence the resulting dispersion has good circulating stability; (2) when the metalworking oil composition is fed to a work area and contacted with a metal workpiece, the oil droplets having large diameters form a thick and strong lubricating film on the work surface; said metal part; (3) When circulating and recirculating the oil for an extended period of time, large droplet diameters can be stably maintained despite the shear forces produced by a stirrer in a tank and by a feed and circulation pump; and (4) the combined use of boric acid or an organic or inorganic phosphorus compound of acidic nature which is commonly known as a compound having extreme pressure effects leads to the formation of a lubricating film on the metal part to be worked and allows as a result to obtain an even higher lubricating power -4 The invention has been completed on the basis of the findings described above Accordingly, it is proposed according to the invention a composition of metal working oil containing as essential components the following components (A) and (B): (A) one or more lubricating oil components selected from the group consisting of oils and fats, mineral oils and fatty acid esters ; and (B) one or more polyether polyol dispersant components (hereinafter referred to as "polyether polyol compound" for the sake of brevity) selected from the following groups (a) to (d): (a) polyether polyols and polyether polyol derivatives, having molecular weights of from 300 to 600,000 and obtained respectively by the addition of alkylene oxides to polyalkyleneimines and their derivatives containing from 6 to 200 nitrogen atoms; (b) polyolpolyether derivatives obtained respectively by the addition of alkylene oxides to a polyalkylenepolyamine and its derivatives; (c) polyolpolyether derivatives obtained respectively by the addition of alkylene oxides to alkyl and alkylaryl amines and their derivatives and having molecular weights of 200 to 100,000; and (d) polyether polyol derivatives obtained respectively by the addition of alkylene oxides to carboxylic acid amides and their derivatives and having

  molecular weights from 200 to 100,000.

  The present invention also provides a metal working oil composition containing the aforementioned components (A) and (B) in combination with one or more compounds selected from (C) phosphorus acids.

of acidic nature and boric acid.

  As the lubricating oil component which is the component (A) of the metalworking oil composition according to the invention, mention may be made, for example, of a mineral oil such as pin oil, machine oil, 11 'Turbine oil or cylinder oil, an animal or vegetable oil or fat such as whale oil, beef tallow, pork fat, rapeseed oil, castor oil, vegetable oil rice bran oil, palm oil or coconut oil, or an ester between a fatty acid obtained from beef tallow, coconut oil, coconut oil palm, castor oil or the like and a primary aliphatic alcohol containing from 1 to 22 carbon atoms, ethylene glycol, neopentyl alcohol, pentaerythritol or the like These components can be used individually In a different way, one can

  also use two of these components in combination.

  Of the components (B) of the invention, the polyether polyol or its derivative, which is component (a), may be prepared using a polyalkyleneimine having 6 to 200 nitrogen atoms or preferably 9 to 100 nitrogen atoms oi its derivative as a starting substance and an adjunct

an alkylene oxide.

  In this respect, it may be mentioned as polyalkylene.

  In addition, there may also be mentioned a polyalkyleneimine obtained by addition polymerizing ethyleneimine or propyleneimir with a substance containing an active hydrogen, such as alcohol, phenol or polyethyleneimine or a polypropyleneimine having from 6 to 200 nitrogen atoms. , amine, carboxylic acid or the like, so as to contain 6 to 200 carbon atoms or a polyalkyleneimine obtained by the ammonolysis or aminolysis of its corresponding dihaloalkane and having 6 to 200 nitrogen atoms. For example, a polyethyleneimine can be readily obtained by adding the ethyleneimine to a polyethylenepolyamine such as ethylenediamine, diethylenetriate triethylenetetramine, tetraethylenepentamine or pentaethylenehexamine or by polymerizing ethyleneimine

  commonly in the presence of an acid catalyst.

  It is preferable that the polyalkyleneimine contain at least 5 fragments each represented by the following formula (I), continuously in its molecule, that at least one of the fragments is a fragment represented by the formula (II)

  next and that the polyalkyleneimine contains an OH group and / or an NH group at at least one of its ends.

L 1 -CI-I 2 Bah -N

-CH 2 -CH 2-N /

CH -CHN /

-CE 2-CH 2-N /

CE 2-CH 2-

  (I) (II) Since the polyalkyleneimine described above has excellent chemical reactivity similar to ordinary amines, it is possible to obtain therefrom, by synthesis, a multiplicity of derivatives. Some representative examples of the polyalkyleneimines are indicated below. (a) reaction products with ketones; (b) reaction products with alkyls; (c) reaction products with thioisocyanates; (d) reaction products with each contain a double (e) reaction product with epihalohydrins or epihalohydrins; (f) reaction products with guanidines or ureas; and

  (g) Reaction products with ac, acyl acid anhydrides.

  aldehydes or isocyanate halides or compounds which actively bind; In practice, the polyalkyleneimines including the above-mentioned derivatives are those which have 6 to 200 nitrogen atoms, or preferably 9 to 100 nitrogen atoms, and which are obtained in the form of polyalkyleneimines, carboxylic acids or halides.

  using polyalkyleneimines or their derivatives.

  The alkylene oxides, which are intended to be added to the above-mentioned polyalkyleneimines, are ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like. It is preferable to copolymerize the propylene oxide and ethylene oxide at their

  copolymerization, they may be subjected to block copolymerization or random copolymerization.

  Propylene oxide or ethylene oxide may be added in advance to one of the polyalkyleneimines. It is more preferable to subject them to enbloc copolymerization. The resulting polyether polyol has a molecular weight in the range of 6000 to 600,000, preferably 10,000 to 300,000. Preferably, the polyether polyol contains ethylene oxide as the alkylene oxide. at a concentration of 3 to 80% by weight or more, and

  preferably 10 to 50% by weight relative to the polyether polyol.

  Such a polyether polyol can impart even better properties. In addition, the following compounds may be mentioned as polyether polyol derivatives: a) Reaction products each obtained by a reaction between a terminal hydroxyl group and a quantity

  equimolar of an epihalohydrin.

  Epichlorohydrin is generally used as epihalohydrin. This reaction allows the introduction of an epoxy group at one end because of the use of a difference in reactivity between an epoxy group and a halogen. b) Compounds which have each been obtained by cationizing nitrogen atoms contained in the fragments, in part or in whole, or by neutralizing the nitrogen atoms partially or wholly by an organic acid or a

mineral acid.

  As cationizing reagent, it is possible to use an alkyl halide or diethyl sulfate. It is possible to use an alkylarylsulphonic acid, acetic acid, hydrochloric acid or the like as an acid.

  however, an organic acid is preferred.

  c) Compounds each of which is obtained by carboxyalkylating or sulfating hydroxyl groups of

  terminal groups, in part or in whole; and salts of said compounds.

  d) Compounds each of which has been obtained by esterification with boric acid or phosphoric acid, hydroxyl groups of terminal groups, in part or

  In totality; and salts of said compounds.

  The esterification reaction, which is supposed to take place with boric acid, can be easily

  carried out through a dehydration reaction with boric acid or a reaction with boric anhydride.

  On the other hand, the esterification reaction, which is supposed to take place with phosphoric acid, can be carried out easily by means of a reaction with the pentoxide.

of phosphorus.

  Among the components (B), the polyether polyol compounds (b) to (d) are compounds known in the art. They can be prepared by processes known per se in the sector under consideration. Examples of polyalkylene polyamines and their derivatives which are useful raw materials in the preparation of the polyether polyol compounds (b), may include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine and their N-alkyl derivatives containing alkyl groups which have 4 to 22 carbon atoms, aminoethylethanolamine, as well as N-alkylpropylenediamines and N-alkylbutylenediamines containing alkyl groups which have from 4 to 22 carbon atoms. Further, examples of alkyl or alkylaryl amines and their derivatives (c ) may comprise mono or dialkyl amines containing 4 to 36 carbon atoms, cycloalkylamines containing 3 to 6 carbon atoms RBONE, alkylarylamines containing alkyl groups each having 4 to 36 carbon atoms and at least one phenyl group. Examples of carboxylic acid amides (d) are monocarboxylic acid amides, each containing 4 to 10 carbon atoms. 22 carbon atoms, and amides of polymerized acids such as dimer acids and

trimeric acids.

  It is also possible to improve the lubricating power additionally by the addition of an acid compound of phosphorus or boric acid as a compound (C) of the invention. Among said components (C), it is possible to use the following compounds as phosphorus acid compounds: (i) phosphoric acid and phosphorous acid as well as their thio analogs and ester derivatives; (ii) mono- and di-phosphoric acid esters, respectively containing alkyl, alkylaryl and aryl groups which individually contain at least one hydroxyl group as well as their thio analogs; (iii) mono- or di-phosphonic acids which contain, respectively, alkyl groups having from 1 to 8 carbon atoms, alkylaryl groups and an aryl group as well as their thio analogs, as well as their derivatives; (iv) mono- or di-phosphinic acids which contain, respectively, alkyl groups containing 1 to 8 carbon atoms, alkylaryl groups and an aryl group and their thio analogs, as well as derivatives thereof; (v) mono-, di- and triphosphonic acids which

  contain one or more nitrogen atoms.

  The following compounds may be mentioned as particular examples of the phosphorus acid compounds. Phosphorus acid compounds (i) may be exemplified by phosphoric acid, phosphorous acid, mono acid esters and the like. or di phosphoric acid between aliphatic alcohols containing 1 to 8 carbon atoms, alicyclic alcohols or aromatic alcohols and phosphoric acid as well as thio compounds of mono or di phosphoric acid esters, and esters between the aforementioned alcohols and phosphorous acid as well as the thio compounds of these esters As an example of an acidic compound of phosphorus

  (ii), there may be mentioned 2-hydroxydipropyl phosphate.

  Examples of the acidic compounds of phosphorus (iii) may include phosphonic acids represented by the general formula: R or POHO NOH or P-O wherein Ro and R 'individually denote an alkyl group having 1 to 8 carbon atoms, an alkylaryl group or an aryl group, for example, methylphosphonic acid containing 1 carbon atom, dimethylphosphonic acid to n-octylphosphonic acid containing 8 carbon atoms, di-n-octylphosphonic acid, benzylphosphonic acid, 2-ethylhexylphosphonic acid, di-2-ethylhexylphosphonic acid, dibenzylphosphonic acid, phenylphosphonic acid, diphenylphosphonic acid and hydroxyethanediphosphonic acid, as well as their thiophosphonic acid analogs. Hydroxyethane diphosphonic acid is a compound represented by the following formula:

O CH O

He 1 3 He

HO P P OH

OH H OH

  As examples of acidic compounds of phosphorus (iv), mention may be made of phosphinic acids represented by the general formula:

/ OH R

R-P or P -OH

OH R '

  wherein R and R 'are defined as specified above, for example, methylphosphinic acid containing 1 carbon atom, dimethylphosphinic acid to n-octylphosphinic acid containing 8 carbon atoms, di n-octylphosphinic acid, 2-ethylhexylphosphinic acid, di-2-ethylhexylphosphinic acid, benzylphosphinic acid, dibenzylphosphinic acid, phenylphosphinic acid and diphenylphosphinic acid, as well as their thiophosphinic acid analogs. phosphorus (v), mention may be made, for example, of mono (or di-) amide

  hexamethylphosphoric acid and nitrilotrismethylenephosphonic acid.

  Nitrilotrismethylenephosphonic acid is a compound represented by the following formula:

HO O O

/ P CH 2 N CH 2 -P OH

H 2 HO IH 2 b

HO P = O

  The metal working oil composition according to the invention can be prepared by mixing the aforementioned components. It is however preferable to limit their proportions in the following intervals, all based on the total composition: the lubricating oil component (A): 99.9 to 50% by weight (the percentages are simply indicated below for simplification by the% sign), in particular 99.9 to 70%, the polyether polyol compound (B): 0.1 to 3 %, in particular 0.1 to 10%, and the compound of

  phosphorus of acidic nature or boric acid (C): 0.1 to 70%, in particular 0.1 to 50%.

  It is possible to add to the metalworking oil composition according to the invention, apart from the abovementioned components, various additives known as required, for example, a surfactant, a

  prevention of rust, a lubricity agent, an extreme pressure additive, an antioxidant and the like.

  The various additives mentioned above may, whenever necessary, be added respectively to

  O to 5%, O to 2%, O to 20%, O to 3% and O to 5%.

  As surface-active agents, the following surfactants (1) to (14) may be mentioned by way of examples: (1) polyoxyethylene alkyls and alkylaryl ethers, each having 6 to 22 carbon atoms, and their salts carboxymethylated at the end of the chain; (2) polyoxyethylene polyoxypropylenealkyl and alkylaryl ethers, each having 6 to 22 carbon atoms; (3) oxyethyleneoxypropylene block polymers; (4) polyoxyethylene sorbitan esters of fatty acids having 10 to 18 carbon atoms; (5) polyethylene glycol esters containing 10 to 18 carbon atoms; (6) glycerol esters of mono fatty acids having 18 carbon atoms; (7) polyoxyethylenealkylamines containing 6 to 22 carbon atoms; (8) alkyl and alkylarylsulfonic acid salts containing 6 to 22 carbon atoms; (9) alkyl and alkylaryl sulfuric acid salts containing 6 to 22 carbon atoms; (10) salts of polyoxyethylenealkyl and polyoxyethylene alkyl ketyl ether sulfates containing from 6 to 22 carbon atoms; (11) fatty acid salts containing 6 to 22 carbon atoms; (12) alkylaminecarbonates containing 6 to 22 carbon atoms; (13) alkyl and alkylarylammonium salts containing 6 to 22 carbon atoms and derivatives thereof; and (14) ethylene oxide and propylene oxide adducts of ethylenediaminetetraacetic acid. Among said surfactants, agents

  Nonionic surfactants are particularly preferred.

  As examples of rust prevention agents, mention may be made of fatty acids such as alkenylsuccinic acids and their derivatives and oleic acid, esters such as sorbitan monooleates, and amines E and others. Examples of lubricity agents may include higher fatty acids such as oleic acid and stearic acid, fatty acid esters which are derivatives of the aforementioned fatty acids, diacids such as a dimer acid and the like. On the other hand, mention may be made of phosphorus compounds such as tricresyl phosphate and organometallic compounds such as zinc dialkyldithiophosphates as examples of additives

  As representative antioxidants, mention may be made of phenol compounds such as 2,4-di-t-butyl-p-cresol, aromatic amines such as phenyl-alphanaphthylamine, and the like.

  The metalworking oil composition according to the invention can be used simply by mixing the various components described above when actually using said metalworking oil composition or it can be used. prepare in advance as a thick solution with rising water content

  to about 80%, and then dilute it with water at the time of effective use of the metalworking oil composition.

  The metalworking oil composition according to the invention can be a metal working oil which provides relatively large droplets with a stable size distribution under stirring conditions such as when found in the presence of a high shear force, which provides high lubricity and exhibits small variations in quality over time as well as excellent circulating stability. In addition, the oil composition for working metals according to the invention has advantages such as those to be described below The polyether polyol compound: useful in the practice of the invention has by itself the ability to be rapidly adsorbed by liquid or solid particles of to render said liquid or solid particles hydrophilic, while by itself it has a low power of lowering the interfacial tension between the water As a result, the lubricating oil component is not emulsified. In comparison with common metal working oils using emulsifiers, the oil composition for metal working of the invention is thus advantageous because it develops the so-called good holding phenomenon, namely that it does not absorb fouled oil, which mixes during an actual rolling operation, and foreign matter, such as metal powder and the like, only to a small extent and still retain its high lubricating characteristics as a clean metal oil because of the function of the polyolpolyether compound described above. above, the metalworking oil composition according to the invention has the effect of making the work environment cleaner and the water treatment residue As a result, the metalworking oil composition of the invention provides an excellent characteristic which can result in a clean working environment, which none of the common rolling oils making use of emulsifiers can provide. had allowed to obtain. Although the mechanism of action obtained as a result of the use of the polyether polyol compound and the acidic phosphorus compound of acidic nature or boric acid according to the invention has not been fully elucidated, they seem to act probably as follows: That the polyether polyol compound which has been uniformly dissolved in a layer of water adsorbs droplets of the lubricating oil component, said droplets having been formed by mechanical shear forces, before said droplets begin to form. The polyether polyol compound then converts the oil droplets into larger droplets according to a kind of coagulation action. The resulting larger droplets are stably dispersed in the water by the protective action.

  colloidal, steric and electrical polyether polyol compound.

  This feature is different from that employed by the water-soluble anionic polymer compound of the aforementioned Japanese Patent Application No. 147593/1980, since said water-soluble anionic polymer compound has a weak visceral coagulation action. oil droplets and the lubricating oil component remains stabilized in the form of fine droplets due to the colloidal action

  protective and the fine oil droplets thus divided can not be reconstituted into larger droplets.

  In connection with the fact that one obtains in every case a clean working oil, ie which avoids the inclusion of fouling materials (phenomenon of good conservation or holding) as a result of the prevention of a decrease of the protective action of the high molecular weight compound against oil droplets and the prevention of their surface tension by the high molecular weight compound as well as the cleaning action of the high molecular weight compound with respect to said fouling materials, it is assumed that the phosphorus compound of acidic nature or boric acid have the effect of

to increase the above effects.

  The invention will be described hereinafter with reference to the following examples intended to illustrate the invention in more detail without in any way limiting it in its scope and spirit.

EXAMPLE 1

  The oil compositions for working the metals having respectively the formulations shown in the tables, namely Table IA in Table IC, are prepared and their seizing strengths are measured. The results of the tests are shown in Table II. this subject, all

  the designations of% in the tables are for% by weight.

Table I-A

  (%) Composition Lubricating oil component Polyether Compound Oil antioxidant for tallow Polyol fatty acid forming (Note: 3) beef work derived from tallow (Note: 1) a salt of polyether polyol beef metals (Note: 2) Product of the invention

1 96 2 (1) 1 I

2 96.5 2 (2) 0.5 1

3 96.8 2 (3) 0.1 1

(4) 0.1

4 9 l 2 (1) 5 1

(3) I

86 2 (1) 10 (1) 1

6 96.3 2 (2) 0.5 (2) 0.2 1

7 91 2 (3) 2 (3) 2 1

(4) 2

8 86 2 (1) 5 (3) I I

(3) 5

Table I-B

  (%) Composition Lubricating oil component Polyether Compound Antioxyda oil for Oil Stearate Polyol acid forming (Note: 3 Oleyl octyl mineral work (Note: 1) a metal salt (polyether spherical oil) polyol (Note: 2 ) Product of 1 invention

9 73.5 20 5 (1) 0.5

69 20 5 (4) 5

It 68 20 5 * (2) 3

(3) 3

12 64 20 5 (1) 5

(4) 5

13 71.6 20 5 (1) 2 (1) 0.4

14 67 20 5 (4) 5 (3) 2

65.5 20 5 (2) 4 (3) 0.5

(3) 4

16 72.7 20 5 (1) 0.1 (2) 0.2

(4) I

Table I-C

  (%) Composition Lubricating oil component Polyether Compound Oil antioxidant for Polyol tetraoleate oil forming (Note 3) Mineral work of pentaery (Note: 1) A salt of metals (Polyethylene glycol thritol oil) Polyol (Note: 2) Product of the invention

17 74 20 (1) 5

18 78.8 20 (3) 0.2

19 69 20 (2) 10

74 20 (2) 4

(4) 1

21 77.9 20 (1) I (1) 0.1

22 73.95 20 (2) 5 (3) 0.05

23 75.9 20 (2) 3 (3) 0.1 1

24 78.45 20 (2) 0.25 (2) 0.05 1

(4) 0.25

  19 - Comparative product nl: Lubricating oil component: Beef tallow Fatty acids derived from beef tallow Emulsifier (Note: 4) Antioxidant (Note: 3) 10 Comparative product n 2: Lubricating oil component: Beef tallow Fatty acids derived from tallow Beef Extreme Pressure Additive (Note: 5 Emulsifier (Note: 4) Antioxidant Comparative Product N 03: Lubricating Oil Component: Mineral Oil (Cylinder Oil) 20 Pentaerythritol Tetraoleate Emulsifier (Note: 4) Antioxidant (Note: 3) Product Comparative No. 4: Lubricating Oil Component: Mineral Oil (Cylinder Oil) Pentaerythritol Tetraoleate Extreme Pressure Additive (Note: 5 Emulsifier (Note: 4) Antioxidant (Note: 5) 30 Comparative Product No. 5: Lubricating Oil Component: Mineral Oil (Pin Oil) Octyl Stearate Oleic Acid Emulsifier (Note: 4) Antioxidant (Note: 3) Comparative Product No. 6: Lubricating Oil Component: Mineral Oil (Pin Oil))

(%) 95

(%) 94

(%) 77 20

(%) 76 20

) 72 20

(%) 71

  Octyl stearate 20 Oleic acid 5 Ermulsifier (Note: 4) 2 Antioxidant (Note: 3) 1 Extreme pressure additive (Note: 5) 1 Note 1: Polyether polyols:: 0 (1) Polyether polyol obtained by addition to a polyethyleneimine, ethylene oxide in an amount of 20% with respect to polyethyleneimine and conversion of the resulting adduct into a glycolic acid salt, and having a molecular weight of 50,000; (2) a polyether polyol obtained by the addition to a polyethyleneimine of a 1: 1 (by weight) mixture of ethylene oxide and propylene oxide in an amount of 50% with respect to the polyethyleneimine and having a molecular weight of 150,000; (3) a polyether polyol obtained by adding, to a polyethyleneimine, a 1: 1 (by weight) mixture of ethylene oxide and butylene oxide in an amount of 60% relative to the polyethyleneimine; and (4) a polyether polyol obtained by addition, a polyalkylene (ethylene: propylene = 4: 1) imine, a 3: 1 mixture (weight ratio) of ethylene oxide and propylene oxide in an amount of 30% with respect to the polyalkyleneimine and

  having a molecular weight of 200,000.

  Note 2: Compounds forming a polyether polyol salt: (1) phosphoric acid; (2) triphenylphosphinic acid; and

  (3) zinc diethyldithiophosphate.

  Note 3: Emulsifier: Polyoxyethylene phenyl ether (Amphipathic Index = 7.6) Note 4: Antioxidant: 2,4-Di-tert-Butyl-p-Cresol Note 5 Extreme Pressure Additive: Triphenyl Phosphite (Test Method ) Measurement of galling resistance loads is performed in accordance with ASTM D-3233 Test of Pressure Resistance Load (Falex Test) The preparation of each test sample is carried out by diluting each oil composition to the work of the metals with water at a concentration of 3% and then mixing the resulting product at 10,000 rpm in a homogenizer. The deposit of each test sample is carried out by applying the mixed solution as indicated above on a rotating spindle which is centrally disposed in a fixed block, at a spray rate of 50 ml / u (at a pressure of 0.5 Pa) and at a

  50 C dispersion using a gear pump.

  (Results) ## STR1 ## 1-h * 11 o Ln kt> W W F U Ln: t CJ n O> -J -J -J O -J o o CD

CD r; 0.

  ## EQU2 ## Wo -4 -J w D - <j <-OCOO CD tJ DO '-JU) WO VD q W Xo DW Uo has OOW 9 a O% DM 1 O "O Pl CD O CDC) ah O to 4 F t - * 9 jteea <o 41 4 1 jo CD O PJ ri FJ P Jo <Pw 0îl> jr, l HH (Dt (D (, he xo, 0 PJ H HD PJ HH l Lj wio P) H ti (DI tct O? D LQ ul (D nr (4 o Lfl -t NI

2547309 23

EXAMPLE 2

  With regard to the metal working oil compositions prepared in Example 1, their seizing charges are measured. The results are collected.

in Table III.

  (Test Method) Measurement of seizure loads in accordance with Japanese Self Defense Force Provisional Standard NDS XXK 2740, Resistance Test Method

  of an Oil Film (Test Method of Four Soda Balls).

  The preparation of each test sample is carried out by diluting each metalworking oil composition with water to a concentration of 3%, and then mixing the resulting product at 10,000 rpm in a homogenizer. Deposition of each test sample applying the aforementioned mixed solution upwardly through a centrally formed space between three points of contact of three steel test balls which are secured by a retaining member to a steel ball. the position of which is maintained above the above-mentioned three balls, with a flow rate of 0.5 l / min (a pressure of 0.5 105 Pa) and a temperature of 50 ° C. for the sample in solution by means of 'a pump

with gears.

(Results)

Table III

  Oil Composition for Seizing Charge Metal Working (Pa) (a Product of the Invention

  11 12 13 14 15 16 17 18 19 20 21 22 23 24

  , 5 10.5 11.5 11.0 11.5 12.0 12.5 11.5 9.0 8.5 8.5 9.5 9.5 9.5 9.0 9.5 9.0 8.5 8.0 8.5 8.5 9.5 9.5 8.5

  He He He He II He ll '; It is not possible to compare it with the 11 11 11 Comparative product n

7.0 8.0 5.5 6.0

, -5 6.0

he

II I, I '

II 1 II

EXAMPLE 3

  Test of Ease of Wastewater Treatment To each test solution (1 t prepared in the same manner as in Example 2, 3 g of aluminum sulphate is added. The resulting mixture is stirred for 2 min. by adding Ca (OH) 2 to bring its pH to 7.0 The stirring thus prepared is continued for a further 10 minutes. After allowing the resulting mixture to stand for 30 minutes, the supernatant is collected to measure its COD. (chemical oxygen demand, consistent with the K Mn 04 method.) The results are shown in

Table IV.

Table IV

  Composition of oil for working metal COD (ppm) Product of the invention n Comparative product n

  11 12 13 14 15 16 17 18 19 20 21 22 23 24

  222 216 195 128 292 311 365 195 229 320 395 420 211 265 190 180 244 316 410 298 255 301 425 266

1,980 2,210 2,560 1,870 2,200 2,110

EXAMPLE 4

  Metal working oil compositions having the formulations shown in the following Tables from Table V-A to Table V-Co were prepared. Their seizure resistance charges were measured in the same manner as in US Pat.

  Example 1 The results are shown in Table VI.

(Compositions)

Table V-A

  (%) Product of Lubricating Oil Component Polyether Compound Antioxidant Invention Fatty Acid Polyol Fatty (Note: 3) N Beef Derived from Tallow (Note: 1) Polyether Polyol Beef Salt (Note: 2)

96 2 (1) 1 I

26 94 2 (2) 3 I

27 92 2 (3) 5

28 96.4 2 (4) 0.2 1

(5) 0.2

29 94.5 2 (6) 2 (1) 0.5 1

9 l 2 (7) 5 (2) 1 1

31 94 2 (1) 1 (3) 1 1

(3) 1

32 86 2 (5) 5 (4) 1 1

(8) 5

Table V-B

  (%) Product of Lubricating Oil Component Polyether Compound Antioxidant The Invention Oil Polyol Tétraoléate Forming (Note: 3) Mineral N of Pentaéry (Note: 1) A Salt of (Polyethylene Threaded Polyether Cylinder) Polyol (Note: 2)

33 78.5 20 (1) 0.5 I

34 77 20 (2) 1

(6) 1

73 20 (3) 5

(4) 1

36 76.5 20 (5) 2 (1) 0.5 1

37 73 20 (7) 5 (2) 1 1

38 75 20 (1) I (3) 1 1

(8) 2

39 71 (3) 2 (4) 2 1

(6) 4

73 20 (4) 5 (3) 1 1

Table V-C

  (%) Product of Lubricating Oil Component Polyether Compound Antioxidant The Invention Oil Stearate Polyol Acid Forming (Note: 3) N Oleyl Oleyl Mineral (Note: 1) Polyol (polyether spindle oil) salt (Note: 2)

41 72 20 5 (1) 2

42 73 20 5 (2) 0.5

(4) 0.5

43 72.5 20 5 (3) I (1) 0.5

44 70 20 5 (5) 3 (2) 1

71.5 20 5 (6) 2 (3) 0.5

46 72.5 20 5 (7) 1 (4) 0.5

47 '70 20 5 (8) 4

48 73 20 5 (4) 1

  The following compositions are used as comparative products: Comparative product No. 7: Lubricating oil component: Beef tallow Fatty acids derived from beef tallow Emulsifier (Note: 4) Antioxidant (Note: 3) Comparative product No. 8: Oil component lubricant: Mineral oil (oil cylinders) Pentaerythritol tetraoleate 15 Emulsifier (Note: 4) Antioxidant (Note: 3) Comparative product n 9: Lubricating oil component: Mineral oil (pin oil) 20 Octyl stearate Oleic acid Emulsifier (Note : 4) Antioxidant (Score: 3)

(%) 95

(%) 77 20

(%) 72 20

  Note 1: Polyether polyol compounds: (1) A polyether polyol compound obtained by the addition of 5 moles of ethylene diamine propylene oxide, followed by the addition of 10 moles of ethylene oxide; (2) a polyether polyol compound obtained by adding 10 moles of ethylene oxide to N-lauryltriethylenetetramine; (3) a polyether polyol compound obtained by adding 2 moles of butylene oxide to N-octylpropylenediamine, followed by addition of 8 moles of ethylene oxide; (4) a polyether polyol compound obtained by the addition of 5 moles of ethylene oxide to laurylamine; (5) a polyether polyol compound obtained by adding 3 moles of propylene oxide to oleylbutylamine, followed by addition of 12 moles of ethylene oxide; (6) a polyether polyol compound obtained by adding 6 moles of ethylene oxide to cyclohexylamine; (7) a polyether polyol compound obtained by adding 18 moles of ethylene oxide to the amide of a polymeric acid (dimer acid / polymeric acids consisting of trimer acid and more polymerized acids than the latter = 8/2 ) derived from oleic acid (8) a polyether polyol compound obtained by the addition of 3 moles of propylene oxide to the amide of a polymeric acid E (dimeric acid / polymeric acids consisting of trimer acid and 1 acid more polymerized than the latter = 7/3) derived from fatty acids drawn oil, followed by an additional addition of 20 moles

of ethylene oxide.

  Note 2: Phosphorus compounds of acidic nature or boric acid (1) phosphoric acid; (2) butylphosphonic acid; (3) boric acid; and

* (4) hydroxyethanedisulfonic acid.

Note 3:

  Antioxidant: 2,4-di-t-butyl-β-cresol.

  Note 4: Emulsifier: Polyoxyethylenenonyl phenyl ether (Amphipathic Index: 7.8) (Results) I o rt o Pl P.

r 1 Fi-.

  I-h oj 1-I o iz H. F rt <I H D P ,. o 4 I i ww WWWWWWWWN r N> 1 NO, XD OD I CO 4 wo m co mt in W in J b> b> a i N 4 'jd> d <a db -4 4 bs * <t UI 1 v DJOO J Ua O 3 t DK OQ O -V 30 OJ N) c OWO 'Wo O vo <b 20 ov P tv Dc o <oe, I oo O r 1 Wr il p'PJO PO F -l Pl' OP QJ I (DDO Ca ert <Pl 10 FP) CD Lnm (D It (a> in q P) tr H t D ói w CD l ru 1 -O O t> 0 C 31 -

EXAMPLE 5

  With respect to the metalworking oil compositions of Example 4, their seizing charges were measured in the same manner as in Example 2.

are shown in Table VII.

Table VII -

  Composition of Oil for Working with Metals Product of the Invention n Comparative Product No.

  26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48

Grab load (Pa)

9.0 105

8.5 "

8.0 8.5 9.5

, 5 "

11.5 "

11.0 "

8.0 "

7.5 o 7.5 8.5 "

9.0 "

9.0 "

9.0 8.5 "

8.0 "

8.0 "

9.0 "

9.0 o 9.0 "

9.0 "

7.5 "

7.5 "

8.0 "

, 5 "

, 0

32 2547309

EXAMPLE 6

Testing adherent quantities

  Each metalworking oil composition is diluted with water to a concentration of 3% and then heated to a temperature of 60 ° C. It is then stirred at 100,000 rpm for 60 minutes in a vacuum. Homogenizer, thus preparing a test sample The sample is deposited by heating a steel plate (50 x 150 x 0.2 mm) cleaned on its surface at a temperature of 150 ° C. and then spraying the test sample for 2 seconds with a spray rate of 500 ml / min (1110 Pa pressure) by means of a gear pump. The adhering amount is measured by subjecting the test plate to steel which is coated with the test sample, extracted with a solvent.

  In this respect, several types of

  metalworking oil compositions among the products of the invention used in Examples 4 and 5 for use in the test of the present example on adherent amounts.

  The results are listed in Table VIII.

Table VIII

  Oil Composition for Adherent Amount Metal Working (g / m 2) Product of Invention No. 25 1.5

28 1.3

32 1.2

33 1.3

36 1.2

39 1.1

42 1.2

44 1.4

48 1.3

Comparative Product No. 7 0.9

8 0.8

9 0.6

Claims (11)

claims   A metalworking oil composition containing as essential components the following components: (A) and (B): (A) one or more lubricating oil components selected from the group consisting of oils and fats, mineral oils and esters fatty acids; and (B) one or more polyether polyol dispersant components selected from the following groups (a) to (d): (a) polyether polyols and polyether polyol derivatives having molecular weights of 300 to 600,000 and obtained respectively from addition of alkylene oxides to polyalkyleneimines and derivatives thereof containing from 6 to 200 nitrogen atoms: (b) polyolpolyether derivatives obtained respectively by the addition of alkylene oxides to a polyalkylenepolyamine and its derivatives; (c) polyolpolyether derivatives obtained respectively by the addition of alkylene oxides to alkyl and alkylaryl amines and their derivatives and having molecular weights of 200 to 100,000; and (d) polyether polyol derivatives obtained respectively by the addition of alkylene oxides to carboxylic acid amides and their derivatives and having   molecular weights from 200 to 100,000.   A metalworking oil composition according to claim 1, characterized in that in component (B) each of the polyalkyleneimines is a polyethyleneimine which contains continuously, in its molecule, at least five fragments individually represented by the following formula (I): -CH 2 -CH 2 -NN (I)   at least one of said five fragments being a fragment represented by the following formula (II): CH 2 -CH 2 -N I -CH 2 -CH 2 -N, (II) -C 2-CH 2-Ns 34 2547309   has OH and / or NH 2 groups on at least one of its   ends, and contains 6 to 100 nitrogen atoms.   3 Composition of metal working oil according to claim 1 characterized in that in the component (B), each of the compounds selected from polyalkylenepolyamine and its derivatives contains OH groups   and / or NH 2 on at least one of its ends and 2 to 100 nitrogen atoms.   Metal working oil composition according to Claim 1, characterized in that in component (B) each of the alkyl and alkylaryl amines contains 4 to 22 carbon atoms.   A metalworking oil composition according to claim 1, characterized in that in component (B) each of the carboxylic acid amides is a carboxylic acid amide containing from 4 to 22 carbon atoms.   carbon, or a polymerized acid amide such as the corresponding dimer acid or trimer acid.   Metal working oil composition according to Claim 1, characterized in that in the component (B) each alkylene oxide is ethylene oxide or a mixture of ethylene oxide and ethylene oxide. one or more compounds selected from the group consisting of propylene oxide, butylene oxide and styrene oxide. 7 Oil composition for metalworking according to   according to any one of the preceding claims, characterized in that the amount of alkylene oxide amounts to 3 to 60% by weight of component (B).   8 Oil composition for metalworking according to   any of the preceding claims, characterized by the fact that   components other than the lubricating oil component (s) represent 0.1 to 20% by weight of the total composition.   9 A metalworking oil composition containing as essential components the following components (A), (B) and (C): _ 35 2547309   (A) one or more lubricating oil components selected from the group consisting of oils and fats, mineral oils and fatty acid esters; (B) one or more polyether polyol dispersant components selected from the following groups (a) to (d): (a) polyether polyols and polyether polyol derivatives having molecular weights of 300 to 600,000 and obtained respectively from addition of alkylene oxides to polyalkyleneimines and derivatives thereof containing 6 to 200 nitrogen atoms; (b) polyolpolyether derivatives obtained respectively by the addition of alkylene oxides to a polyalkylenepolyamine and its derivatives; (c) polyolpolyether derivatives obtained respectively by the addition of alkylene oxides to alkyl and alkylaryl amines and their derivatives and having molecular weights of 200 to 100,000; and (d) polyether polyol derivatives obtained respectively by the addition of alkylene oxides to carboxylic acid amides and their derivatives and having molecular weights of 200 to 100,000, and   (C) one or more compounds selected from acid phosphorus compounds and boric acid.   A metalworking oil composition according to claim 9, characterized in that in component (C) each of the acidic phosphorus compounds is any of the following compounds (i) to (v): (i) phosphoric acid and phosphorous acid as well as their thio analogs and ester derivatives; (ii) mono and di phosphoric acid esters, respectively containing alkyl, alkylaryl and aryl groups which individually contain at least one hydroxyl group as well as their thio analogues; (iii) mono- or di-phosonic acids which contain, respectively, alkyl groups containing 1 to 8 carbon atoms, alkylaryl groups and an aryl group and their thio analogs, as well as derivatives thereof; 36 2547309   (iv) mono- or di-phosphinic acids which contain, respectively, alkyl groups having 1 to 8 carbon atoms, alkylaryl groups and an aryl group and thio analogs thereof, as well as derivatives thereof; and (v) mono-, di- and tri-phosphonic acids which   contain one or more nitrogen atoms.   Metal working oil composition O according to Claim 9 or 10, characterized in that the component (C) is present in a proportion of 0.1 to 50% by weight. weight with respect to the component (B).