A water-soluble metal-working lubricant composition comprising as essential components thereof PA0 (a) one or more polyetherpolyols having molecular weights of 200 to 100,000 and obtained by adding alkylene oxides to either one or more of compounds selected from PA1 (1) polyalkylenepolyamines and derivatives thereof, PA1 (2) alkyl- and alkylaryl-amines and derivatives thereof and PA1 (3) carboxylic acid amides and derivatives thereof; and PA0 (b) one or more compounds selected from phosphoric acid compounds and boric acid. Incorporation of a specific polyetherpolyol compound together with phosphoric acid compound or boric acid serves as alternative to conventional liquid oil-base lubricant with mitigating drawbacks such as poor stability of emulsions, fouling of surfaces, difficulty in waste water, etc., which are inherent in conventional lubricants.

BACKGROUND OF THE INVENTION 
(i) Field of the Invention 
This invention relates to a novel, water-soluble, metal-working lubricant 
composition, and more specifically to a water-soluble metal-working 
lubricant composition which contains one or more of specific 
polyetherpolyols and their derivatives and one or more compounds selected 
from phosphoric acid compounds and boric acid and are useful as a 
lubricant upon working metals, e.g., upon plastic-working, cutting and 
grindworking metals or for similar purposes. 
(ii) Description of the Prior Art 
Liquid-like oil-base lubricants which have conventionally been employed for 
the plastic working, cutting and grinding of metals are applied to 
lubricating parts as they are. Besides, they are also emulsified in water 
to desired concentrations by means of emulsifiers such as surfactants and 
are applied as emulsions to the surfaces of workpieces upon working the 
workpieces. Namely, such liquid-like oil-base lubricants feature that 
their lubricating effects can be obtained by adhesion of droplets of the 
liquid-like oil-base lubricants emulsified by the surfactants or the like 
on the surfaces of the workpieces. Liquid-like oil-base lubricants which 
make use of water are particularly advantageous owing to their cooling 
effects for heat to be produced upon working workpieces, their economy 
derived from recirculated use of emulsions, and so on. On the other hand, 
they are also accompanied by various drawbacks with respect to control of 
emulsions, which include: 
(a) Poor stability of emulsions; 
(b) Inclusion of foreign matters such as metal powder, scum and the like, 
which occur during machining of metals, in emulsions; 
(c) Fouling of surfaces of workpieces due to such foreign matters; 
(d) Reduction to load resistant capacity due to reduced amounts of 
emulsified lubricant droplets adhered to surfaces of workpieces, which 
reduced amounts of emulsified lubricant droplets are induced to ensure 
stabilized emulsification; 
(e) Difficulty in treating waste water produced from emulsions; and 
(f) Corrosion and rust developed on workpieces, primarily due to used 
water. 
It is thus desired to develop a water-soluble lubricant which can provide 
beautiful surfaces without leaving any stains, which have tended to occur 
by lube-oils, on the surfaces of workpieces after completion of their 
working, and does not permit inclusion of foreign or fouled matters such 
as metal powder and deteriorated lubricants, in other words, does not hold 
such foreign and/or fouled matters in the lubricant system and is 
therefore free from fouling workpieces. Under the present circumstances, 
there has not yet been found any excellent lubricant which exhibits such 
advantageous effects. 
SUMMARY OF THE INVENTION 
The present invention provides a lubricant which can solve the 
above-mentioned drawbacks of conventional liquid-like oil-base lubricants 
and is soluble in water. It has been found that the above object can be 
attained without using any liquid-like oil-base lubricant if one makes use 
of a composition containing a specific polyetherpolyol or its derivative 
and a phosphoric acid compound or boric acid. 
Accordingly, the present invention provides a water-soluble metal-working 
lubricant composition comprising as essential components thereof (a) one 
or more polyetherpolyols having molecular weights of 200-100,000 and 
obtained by adding alkylene oxides to either one or more of compounds 
selected from (1) polyalkylenepolyamines and derivatives thereof, (2) 
alkyl- and alkylaryl-amines and derivatives thereof and (3) carboxylic 
acid amides and derivatives thereof, or derivatives thereof; and (b) one 
or more compounds selected from phosphoric acid compounds and boric acid. 
DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS 
As polyalkylenepolyamines (1) capable of yielding polyetherpolyols or their 
derivatives which are components (a) in compositions of this invention, 
may be mentioned ethylenediamine, diethylenetriamine, 
triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 
propylenediamine, butylenediamine, etc. As their derivatives, may also be 
mentioned N-alkylated compounds of the above compounds, each of which 
N-alkylated compounds contains an alkyl group having 4 to 22 carbon atoms, 
and derivatives of the N-alkylated compounds each of which derivatives 
contains up to 3 hydroxyl groups in place of the NH.sub.2 group or groups 
contained in the corresponding N-alkylated compound. As the alkyl- or 
alkylaryl-amines (2), may be mentioned mono- or di-alkylamines each of 
which contains 4 to 36 carbon atoms, cycloalkylamines each of which 
contains 3 to 6 carbon atoms, alkylarylamines each of which contains an 
alkyl group having 4 to 36 carbon atoms and containing at least one phenyl 
group. Furthermore, as carboxylic acid amides (3), may be mentioned fatty 
acid amides each of which contains 5 to 54 carbon atoms, polymeric acid 
amides such as dimeric acids and trimeric acids, and so on. 
As alkylene oxides to be added to these compounds (1) to (3), may be 
mentioned ethylene oxide, propylene oxide, butylene oxide, styrene oxide 
and the like. 
Among polyetherpolyols and their derivatives useful in the practice of this 
invention, it is preferable to use those obtained using alkylene oxides, 
which consist individually of ethylene oxide only or ethylene oxide and 
one or more of propylene oxide, butylene oxide and styrene oxide, and 
containing as added mole numbers per molecule 1 to 150 moles of ethylene 
oxide, 0 to 100 moles of propylene oxide, 0 to 100 moles of butylene oxide 
and 0 to 50 moles of styrene oxide. 
As phosphoric acid compounds which are components (b), the following 
compounds (i) to (v) may be mentioned. 
(i) phosphoric acid and phosphorous acid as well as thio compounds and 
ester compounds thereof; 
(ii) mono- and di-phosphoric acid esters containing respectively alkyl, 
alkylaryl and aryl groups which contain individually at least one hydroxyl 
group as well as thio compounds thereof; 
(iii) mono- or di-phosphonic acids which contain respectively alkyl groups 
containing 1 to 8 carbon atoms, alkylaryl groups and aryl group and thio 
compounds thereof, as well as derivatives thereof; 
(iv) mono- or di-phosphinic acids which contain respectively alkyl groups 
having 1 to 8 carbon atoms, alkylaryl groups and aryl group and thio 
compounds thereof, as well as derivatives thereof; and 
(v) mono-, di- and tri-phosphonic acids containing one or more nitrogen 
atoms. 
The following compounds may be mentioned as specific examples of the 
phosphoric acid compounds. As phosphoric acid compounds (i), may be 
mentioned by way of example phosphoric acid, phosphorous acid, mono- or 
di-phosphoric acid esters between aliphatic alcohols containing 1 to 8 
carbon atoms, alicyclic alcohols or aromatic alcohols and phosphoric acid 
as well as thio compounds of the mono- or di-phosphoric acid esters, and 
esters between the above alcohols and phosphorous acid and thio compounds 
of the esters. As an exemplary phosphoric acid compound (ii), may be 
mentioned 2-hydroxydipropyl phosphate. Illustrative of the phosphoric acid 
compounds (iii) may include phosphonic acids represented by the general 
formula: 
##STR1## 
wherein R.sub.0 and R'.sub.0 mean individually an alkyl group having 1 to 
8 carbon atoms, alkylaryl group or aryl group, for example, 
methylphosphonic acid containing 1 carbon atom, dimethylphosphonic acid to 
n-octylphosphonic acid containing 8 carbon atoms, di-n-octylphosphonic 
acid, 2-ethylhexylphosphonic acid, di-2-ethylhexylphosphonic acid, 
benzylphosphonic acid, dibenzylphosphonic acid, phenylphosphonic acid, 
diphenylphosphonic acid and hydroxyethanediphosphonic acid, as well as 
their thiophosphonic acids. Hydroxyethanediphosphonic compound is a 
compound represented by the following formula: 
##STR2## 
As exemplary phosphoric acid compounds (iv), may be mentioned phosphinic 
acids represented by the general formula: 
##STR3## 
wherein R.sub.0 and R'.sub.0 have the same meanings as defined 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 acids. As compounds (v), may for example by mentioned 
hexamethylphosphoric mono-(or di- )amide and 
nitrilotrismethylenephosphonic acid. Nitrilotrismethylenephosphonic acid 
is a compound represented by the following formula: 
##STR4## 
Although the mechanism of action achieved to the lubricity owing to the use 
of the polyetherpolyol and the acidic phosphoric acid or boric acid in 
accordance with this invention has not been fully elucidated, they seem to 
act probably in the following manner. Namely, when an aqueous solution 
containing the polyetherpolyol and boric acid or the phosphoric acid 
compound is supplied to a working part of a metal during the working of 
the metal, the polyetherpolyol forms a film, in which boric acid or the 
phosphoric acid compound is firmly adsorbed, over the working part of the 
metal owing to the strong adsorptive action of groups derived from the 
nitrogen atoms and at the same time, a still stronger film is formed owing 
to adsorption of boric acid or the phosphoric acid compound or reaction 
with the metal. As a result, the strong absorptive film of the 
polyetherpolyol serves, even under severe metal-working conditions, in 
much the same way as a strong oil film formed when a lube-oil is used. It 
is also believed that still better lubricity can be achieved when boric 
acid or the phosphoric acid compound is kept in contact with the metal, 
because an adsorbed film or reaction film is formed on the surface of the 
metal. 
The water-soluble metal-working lubricant composition of this invention is 
prepared as a mixture of one or more of these polyetherpolyols and one or 
more of these polyetherpolyols and one or more of boric acid and the 
phosphoric acid compounds. It may also be formed into an aqueous solution 
by adding water thereto. In addition, it is also feasible to add, besides 
the above components, various known additives as needed, for example, an 
antioxidant, e.g., a phenolic antioxidant such as 2,4-di-t-butyl-p-cresol 
or an aromatic aminetype antioxidant such as phenyl-alpha-naphthylamine; a 
water-soluble thickener such as a polyethyleneglycol carboxylate; a 
water-soluble oilness agent, e.g., a metal salt, amine salt or sorbitan 
derivative of a carboxylic acid such as lauric acid, palmitic acid, oleic 
acid or stearic acid; a water-soluble rust and corrosion preventive; and 
so on. These various additives may each be added in a proportion of 0 to 
10% based on the whole amount of each water-soluble metal-working 
lubricant composition whenever necessary. 
As water-soluble rust and corrosion preventive, may for example be 
mentioned an inorganic compound such as chromate, nitrite, molybdate, 
tungstate, polyphosphate or the like; (1) a monoamine, diamine or amide as 
a sole compound or an ethoxyl compound, mono-basic acid salt, di-basic 
acid salt, naphthenate or phosphate thereof, or either one of the various 
salts exemplified above as inorganic compounds; (2) an alkali salt of an 
amino acid; (3) an imidazoline derivative; (4) a quaternary ammonium salt; 
or (5) an inorganic compound such as mercaptobenzotriazole. 
Furthermore, it is also possible to use sulfur or sulfur compound, which 
contains unpaired electrons, within the range of 1.2 to 4.0 wt % as a 
compound based on the whole composition in accordance with what end use 
would be made. As sulfur and sulfur compounds, may be mentioned by way of 
example elementary sulfur, sulfurous acid, mercaptans containing such 
hydrocarbon groups as aliphatic, alicyclic and aromatic hydrocarbon 
groups, sulfides (inclusive of thiophenes), and polysulfides such as 
disulfides and trisulfides. 
Besides, it is also feasible to use one or more of various known 
surfactants in a total amount of 20% or less based on the polyetherpolyols 
from the viewpoint of the stability of each composition upon mixing 
various additives therein. 
The water-soluble metal-working lubricant composition of this invention is 
used, whenever needed, by diluting it with water to a concentration of 100 
to 500,000 ppm or preferably 1,000 to 50,000 ppm upon its application. 
Application of an aqueous solution of the water-soluble metal-working 
lubricant composition of this invention to each working part may be 
effected by the spraying technique or immersion technique. When applied in 
such a way, the aqueous solution of the composition does not show any 
deterioration to its performance such as lubricity which deterioration is 
generally liable to occur due to inclusion of fouled matters and/or scum. 
Therefore, it may be repeatedly used by recirculating same. 
The thus-obtained water-soluble metal-working lubricant composition 
according to this invention has the following merits while still 
maintaining the high cooling effect with which lubricants making use of 
water and applied in the forms of emulsions are equipped: 
(1) It provides excellent lubricity upon working a metal, as it has, in the 
state of an aqueous solution, load resistant capacity either equal to or 
higher than conventional liquid-type lubricants even if it does not 
contain an oily, liquid-type lubricant such as mineral oil, beef tallow or 
fatty acid. 
(2) It can provide beautiful surfaces after working, because it does not 
contain any solid lubricants or oily, liquid-type lubricants. 
(3) The composition has strong adhesion to metal powder and fouled oil to 
be formed in the course of working a metal. These matters are thus 
rendered hydrophilic and are therefore prevented from resticking on the 
metal. In addition, the composition does not had interfacial activity. 
Therefore, it is possible to avoid emulsification and inclusion of fouled 
oil, thereby making it possible to keep the surface or each workpiece 
clean and during working, to maintain the environment clean. 
(4) It facilitates treatment of waste water, because it does not use such 
emulsifiers as those employed in oily, liquid-type lubricants. 
(5) It is safer from the viewpoint of hazard prevention, since it is used 
as an aqueous solution. 
When it is desired to use water for such reasons as placement of importance 
on cooling or prevention of oil vapor, the composition of this invention 
can be used more effectively for example in the fields of plastic working 
of metals, cutting of metals, grind-working of metals, etc. Furthermore, 
it may be possible to expand the application fields of the composition of 
this invention to such working fields where general lubricants are 
employed due to possible generation of heat or possible application of 
heat. 
In addition, the composition of this invention showed excellent effects 
toward maintaining the surfaces of workpieces and when applied in actual 
machining, keeping the environment clean, owing to its re-adhesion 
preventory effect for metal powder and fouled oil produced in the course 
of working metals. The readhesion preventory effect has been brought about 
owing to the conversion of such metal powder and fouled oil into 
hydrophilic matters, which conversion has in turn been materialized owing 
to the strong adhesion of the composition of the present invention. 
As has been described above, the present invention has excellent features 
and has a great value from the viewpoint of commercial utility. 
The invention will next be described with reference to Examples. 
The following metal-working lubricant compositions were used in the 
Examples. Besides, the following compounds or substances were also used 
respectively as polyolethers, phosphoric acid compounds, an emulsifier, an 
antioxidant, an extreme-pressure additive, water-soluble rust preventives, 
water-soluble oilness agents, sulfur compounds containing unpaired 
electrons, and surfactants: 
Polyetherpolyols 
(1) A polyetherpolyol obtained by adding, to ethylenediamine, 5 moles of 
propylene oxide and then adding 15 moles of ethylene oxide; 
(2) A polyetherpolyol obtained by adding 10 moles of ethylene oxide to 
N-lauryltriethylenetetramine; 
(3) A polyetherpolyol obtained by adding 15 moles of ethylene oxide to 
N-coconutalkyldiethylenetriamine; 
(4) A polyetherpolyol obtained by adding 2 moles of butylene oxide to 
N-octylpropylenedimaine, followed by an addition of 8 moles of ethylene 
oxide; 
(5) A polyetherpolyol obtained by adding 5 moles of ethylene oxide to 
laurylamine; 
(6) A polyetherpolyol obtained by adding 3 moles of propylene oxide to 
oleylbutylamine, followed by an addition of 12 moles of ethylene oxide; 
(7) A polyetherpolyol obtained by adding 6 moles of ethylene oxide to 
cyclohexylamine; 
(8) A polyetherpolyol obtained by adding 18 moles of ethylene oxide to the 
amide of a polymeric acid (dimeric acid/polymeric acids of trimeric acid 
and up=8/2) of oleic acid; and 
(9) A polyetherpolyol obtained by adding 3 moles of propylene oxide to the 
amide of a polymeric acid (dimeric acid/polymeric acids of trimeric acid 
and up=7/3) of fatty acids derived from toll oil, followed by a further 
addition of 20 moles of ethylene oxide. 
(10) A polyetherpolyol obtained by adding 15 moles of ethylene oxide to the 
amide of coconut fatty acid. 
Phosphoric acid compounds 
(1) Phosphoric acid; 
(2) Butylphosphonic acid; 
(3) Boric acid; 
(4) Dibutylthiophosphonic acid; and 
(5) Butyl acid phosphate. 
Emulsifier 
Polyoxyethylenenonyl phenyl ether (HLB=7.8) 
Antioxidant 
2,4-Di-t-butyl-p-cresol 
Extreme-pressure additive 
Triphenyl phosphite. 
Water-soluble rust preventives 
(1) The amine salt of butyl laurate; 
(2) Sodium N-coconutalkyl-betaiminodipropionate (80 parts) and 
benzotriazole (20 parts); and 
(3) Sodium (beef tallow) alkenylsuccinate. 
Water-soluble oilness agents 
(1) The sodium salts of fatty acids derived from beef tallow; and 
(2) The butylamine salts of polymeric fatty acids derived from beef tallow 
(dimeric acid/polymeric acids of trimeric acid and up=7/3). 
Sulfur compounds containing unpaired electrons 
(1) Dilauryl sulfide; 
(2) Butyl mercaptan; and 
(3) Dipropyl disulfide. 
Surfactants 
(1) Polyoxyethylenenonyl phenyl ether (HLB=12.5); 
(2) Sorbitan monooleate/polyoxyethylenesorbitan monolaurate (HLB=16.7)=1/4 
(by weight ratio); and 
(3) Oxyethylene-oxypropylene block polymer (the weight percentage of 
ethylene oxide in the whole molecules is 40 and the block polymer has a 
molecular weight of about 2,250). 
TABLE 1 
__________________________________________________________________________ 
Composition* (wt %) 
Invention Product 
Sulfur 
Water- Water- Compound 
Phosphoric 
Soluble Soluble Containing 
Polyether- 
Acid Oilness Rust Unpaired 
polyol Compound 
Agent Preventive 
Electrons 
Surfactant 
Compound No. 
Compound No. 
Compound No. 
Compound No. 
Compound No. 
Compound No. 
(Concentration) 
(Concentration) 
(Concentration) 
(Concentration) 
(Concentration) 
(Concentration) 
__________________________________________________________________________ 
1 
1 (40) 1 (10) 
2 
2 (40) 2 (10) 
3 
3 (40) 3 (10) 
4 
4 (40) 4 (10) 
5 
5 (40) 5 (10) 
6 
6 (40) 1 (20) 
7 
7 (40) 2 (20) 
8 
8 (40) 3 (20) 
9 
9 (40) 4 (20) 
10 
10 (40) 5 (20) 
11 
1 (60) 1 (30) 
12 
2 (60) 2 (30) 1 (10.0) 
13 
3 (60) 3 (30) 2 (10.0) 
14 
4 (60) 4 (30) 1 (8.0) 
15 
5 (60) 5 (30) 2 (8.0) 
16 
6 (60) 1 (5) 1 (5.0) 
17 
7 (60) 2 (5) 2 (5.0) 
18 
8 (60) 3 (5) 1 (3.0) 
19 
9 (60) 4 (5) 2 (3.0) 1 (5.0) 
20 
10 (60) 5 (5) 1 (2.0) 2 (5.0) 
21 
1 (30) 1 (3) 2 (2.0) 3 (5.0) 
22 
2 (30) 2 (3) 1 (1.0) 1 (3.0) 1 (2.0) 1 (1.0) 
23 
3 (30) 3 (3) 2 (1.0) 2 (3.0) 2 (2.0) 2 (1.0) 
24 
4 (30) 4 (3) 1 (3.0) 3 (3.0) 3 (2.0) 3 (1.0) 
25 
5 (30) 5 (3) 2 (3.0) 1 (2.0) 1 (1.5) 1 (2.0) 
26 
6 (30) 1 (5) 1 (4.0) 2 (2.0) 2 (1.5) 2 (2.0) 
27 
7 (30) 2 (5) 2 (4.0) 3 (2.0) 3 (1.5) 3 (2.0) 
28 
8 (30) 3 (5) 1 (5.0) 1 (10.0) 
1 (3.0) 1 (3.0) 
29 
9 (30) 4 (5) 2 (5.0) 2 (10.0) 
3 (3.0) 3 (3.0) 
30 
10 (30) 5 (5) 1 (3.0) 3 (10.0) 
3 (3.0) 3 (3.0) 
__________________________________________________________________________ 
*The remainders are water. 
______________________________________ 
Comparative product No. 1: 
Lube-oil component: 
Beef tallow 95% 
Fatty acids derived from beef tallow 
2 
Emulsifier 2 
Antioxidant 1 
Comparative product No. 2: 
Lube-oil component: 
Beef tallow 94% 
Fatty acids derived from beef tallow 
2 
Extreme-pressure additive 
1 
Emulsifier 2 
Antioxidant 1 
Comparative product No. 3: 
Lube-oil component: 
Mineral oil (cylinder oil) 
77% 
Pentaerythritol tetraoleate 
20 
Emulsifier 2 
Antioxidant 1 
Comparative product No. 4: 
Lube-oil component: 
Mineral oil (cylinder oil) 
76% 
Pentaerythritol tetraoleate 
20 
Extreme-pressure additive 
1 
Emulsifer 2 
Antioxidant 1 
Comparative product No. 5: 
Lube-oil component: 
Mineral oil (spindle oil) 
72% 
Octyl stearate 20 
Oleic acid 5 
Emulsifier 2 
Antioxidant 1 
Comparative product No. 6: 
Lube-oil component: 
Mineral oil (spindle oil) 
71% 
Octyl stearate 20 
Oleic acid 5 
Extreme-pressure additive 
1 
Emulsifier 2 
Antioxidant 1 
______________________________________