1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid amino esters, biocidal agents containing such esters, and methods of preparing them

1,3,5-Triazine-2,4,6-tris-alkylaminocarboxylic acid amino esters of the general formula (I): 1,3,5-triazine-2,4,6-tris[NH--(CH.sub.2).sub.n --CO--O--R.sup.1 ], in which R.sup.1 denotes the radical of an alkanolamine, can be employed as biocidal or biostatic compounds in aqueous systems, in particular in cooling lubricants.

The invention relates to 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic 
acid amino esters, biocidal and biostatic agents containing such amino 
esters and methods of preparing them. The abovementioned compounds are 
called "amino esters of the invention" below. 
The triazinetricarboxylic acids on which the amino esters of the invention 
are based, that is to say the 
2,4,6-tris(omega-carboxyalkylamino)-1,3,5-triazines, called 
1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acids below, are described 
in J. Prakt. Chemie, 23 (1963), pages 173 to 185, and in EP-B 0 046 139. 
EP-B 0 046 139 furthermore relates to the use of the triazinetricarboxylic 
acids mentioned and alkali metal and mono-, di- or triethanolammonium 
salts thereof as corrosion inhibitors in aqueous systems. EP-B 0 046 139 
furthermore describes the mono-, di- and triethanolammonium salts of these 
triazinetricarboxylic acids, which can be employed as corrosion inhibitors 
in aqueous systems; an analogous use of these compounds in aqueous 
systems, for example cooling liquids, cooling lubricants, paints or 
cleaning agents, is disclosed in EP-A 0 262 086. 
Biocidal or biostatic agents have to be added to aqueous systems of the 
abovementioned type for prevention of attack by bacteria, yeasts and/or 
fungi. Halogen-containing compounds and, for example, boric acid and 
reaction products of boric acid with alkanolamines have been used to date 
as agents which are suitable for this purpose, see Ullmanns Encyklopadie 
der technischen Chemie (Ullmann's Encyclopaedia of Industrial Chemistry), 
4th edition, Volume 8, Verlag Chemie, Weinheim 1974, pages 653-655. In 
other cases, formaldehyde or formaldehyde derivatives have been added as 
the biocide. However, for various reasons, halogen-containing compounds, 
boric acid and boric acid derivatives and also formaldehyde and 
derivatives thereof are undesirable. There is therefore an increasing need 
for biocidal agents which can be used in aqueous systems and are free from 
halogen-containing compounds, formaldehyde, formaldehyde derivatives, 
boric acid or boric acid derivatives. 
It has now been found that the amino esters of the invention display 
excellent biocidal or biostatic properties when used in aqueous systems of 
the above-mentioned type even in low concentrations. 
The invention accordingly relates to 
1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid amino esters of the 
general formula 
##STR1## 
in which n denotes a number in the range from 4 to 11 and R.sup.1 denotes 
a radical of an alkanolamine of the general formula 
EQU (R.sup.2).sub.3 N (II) 
in which at least one of the groups R.sup.2 is 
a) a hydroxyalkyl group having 2 to 4 carbon atoms, 
b) a hydroxyalkyl-oxyalkylene group having 4 to 6 carbon atoms or 
c) a dihydroxyalkyl group having 3 to 6 carbon atoms and, if less than 
three of the groups R.sup.2 have the above meaning, the other groups 
R.sup.2 are hydrogen. 
A preferred embodiment of the invention relates to amino esters of the 
general formula I in which n denotes the number 5. 
The alkanolamines of the general formula II contain primary, secondary or 
tertiary amino groups and free hydroxyl groups. In the reaction of 
alkanolamines containing primary or secondary amino groups with carboxylic 
acids, both amides and esters which are in equilibrium with one another 
can be formed, see "Surfactants in Consumer Products", editor J. Falbe, 
Springer-Verlag, Heidelberg 1987, page 96. For clarity, the reaction 
products of 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acids with 
alkanolamines to give compounds of the general formula I in which R.sup.1 
is the radical of an alkanolamine of the general formula II are shown here 
only as amino esters. However, it can readily be seen by the expert that 
the corresponding alkanolamides also fall under the 
1,3,5-triazine-2,4,6-tris-alkylcarboxylic acid derivatives thus defined. 
Typical examples of hydroxyalkyl groups having 2 to 4 carbon atoms which 
can form the group R.sup.2 are 2-hydroxyethyl, 1-methyl-2-hydroxyethyl, 
2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 4-hydroxybutyl and 
2-methyl-2-hydroxypropyl groups; typical examples of 
hydroxyalkyl-oxyalkylene groups having in each case 2 to 4 carbon atoms in 
the hydroxyalkyl and oxyalkylene radical are hydroxyethyl-oxyethylene, 
hydroxypropyloxyethylene, hydroxyethyl-diethyleneoxy, 
hydroxyethyloxypropylene and hydroxypropyl-oxypropylene groups, and 
typical examples of dihydroxyalkyl groups having 3 to 6 carbon atoms are 
2,3-dihydroxypropyl, 3,4-dihydroxybutyl, 1,3-dihydroxypropyl and 
1,3-dihydroxy-2-methyl- or -ethyl-propyl groups; and furthermore also 
hydroxyethyl-, hydroxypropyl- and hydroxybutyl-oxybutylene groups. 
Compounds of the general formula I in which R.sup.1 denotes a radical of an 
alkanolamine of the general formula II are obtainable by reaction of 
1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acids of the general 
formula 
EQU 1,3,5-triazine-2,4,6-tris[--NH--(CH.sub.2).sub.n --COOH] (III) 
in which n is as defined above, with alkanolamines of the general formula 
II by processes which are known per se. 
For many intended uses, it is not necessary for the amino esters of the 
invention to be isolated in bulk. Rather, it is sufficient for the amino 
esters of the invention to be prepared "in situ", for example in an excess 
of the alkanolamines of the general formula II, and if appropriate for the 
excess of alkanolamines to be neutralized with suitable acids which do not 
interfere with or under certain circumstances even promote the desired 
intended use. 
The reaction with a molar excess of the alkanolamines, based on the 
1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acids, is therefore 
preferred. The unreacted portion of the alkanolamines can be reacted with 
organic acids chosen from the group formed by straight-chain or branched, 
saturated or unsaturated fatty acids having 5 to 22 carbon atoms to 
establish a pH of 4.5 to 9.5. Examples of the fatty acids mentioned are 
pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic 
acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, 
tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic 
acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic 
acid, docosanoic acid, 10-undecenoic acid, 9c-dodecenoic acid, 
9c-tetradecenoic acid, 9c-hexadecenoic acid, 6c-octadecenoic acid, 
6t-octadecenoic acid, 9c-octadecenoic acid, 9t-octadecenoic acid, 
9c,12c-octadecadienoic acid, 9t,12t-octadecadienoic acid, 
9c,12c,15c-octadecatrienoic acid, 9c,11t,13t-octadecatrienoic acid, 
9c-eicosenoic acid, 5,8,11,14-eicosatetraenoic acid, 13c-docosenoic acid, 
13t-docosenoic acid, 4,8,12,15,19-docosapentaenoic acid, 
12-hydroxy-octadecanoic acid and 12 -hydroxy-9c-octadecenoic acid, c 
indicating a cis double bond and t a trans double bond, and 
technical-grade mixtures thereof. Fatty acids and fatty acid mixtures 
which are obtainable from renewable raw materials, in particular vegetable 
and/or animal fats and oils, for example caproic, caprylic, capric, 
lauric, myristic, palmitic, stearic, oleic, ricinoleic, linoleic, erucic 
and behenic acid, are also particularly suitable. 
The unreacted portion of the alkanolamines is preferably reacted with 
straight-chain or branched, saturated or unsaturated fatty acids having 5 
to 11 carbon atoms. If no stable solutions or emulsions are obtained in 
this manner, straight-chain or branched, saturated or unsaturated fatty 
acids having 12 to 22 carbon atoms can additionally be used to establish 
the desired hydrophilic/hydrophobic balance. 
Those amino esters of the general formula I which contain no secondary or 
tertiary amino functions are preferred. Secondary alkanolamines can form 
undesirable stable nitrosamines with nitrite ions. Under certain 
circumstances, tertiary alkanolamines can form secondary alkanolamines by 
dealkylation. In contrast, primary alkanolamines as a rule do not form 
stable nitrosamines, but rather are used as trapping agents for nitrite 
ions because of the rapid dissociation of the nitrosamines intermediately 
formed. If amino esters of the general formula I which are derived from 
secondary alkanolamines nevertheless are to be employed, it is preferable 
to use a mixture of compounds derived from primary and secondary 
alkanolamines, since formation of the unstable primary nitrosamines then 
takes place more rapidly than that of the secondary nitrosamines. 
According to another aspect, the invention thus relates to amino esters of 
the general formula I which are free from secondary or tertiary amino 
functions and thus cannot form stable nitroso compounds or which, if the 
analogous compounds of the general formula I containing secondary or 
tertiary amino functions are present at the same time, prevent the 
formation of stable nitroso compounds. 
Biocidal or biostatic mixtures of monocarboxylic acid alkanolamides and 
amino esters of the general formula I and if appropriate alkanolammonium 
salts of the monocarboxylic acids and/or of the 
1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acids can also be prepared 
by the process of the invention. 
The abovementioned biocidal and biostatic mixtures can be prepared by 
mixing the individual components. However, they are expediently prepared 
by preparing the alkanolamides in situ from the monocarboxylic acids and 
the 1,3,5-triazine-tris-alkylaminocarboxylic acids of the general formula 
III, in which n is as defined above, with alkanolamines of the general 
formula II, in which R.sup.2 is as defined above, preferably in an excess 
of the alkanolamines. 
Primary alkanolamines or mixtures of primary and secondary alkanolamines 
are preferably used. 
Preferably, 10 to 50 mol, in particular 10 to 30 mol, of the alkanolamines 
of the general formula II and 0.5 to 5 mol of the monocarboxylic acids are 
reacted per mol of the 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic 
acids. 
The amino esters of the invention are prepared at a temperature in the 
range from 100.degree. to 180.degree., in particular 130.degree. to 
180.degree. C. 
Straight-chain or branched, saturated or unsaturated fatty acids having 3 
to 22, in particular 12 to 22, carbon atoms are preferably used as the 
monocarboxylic acids and are reacted in a first stage with the 
alkanolamines to give the corresponding amino esters or alkanolamides, 
which is followed by addition and reaction of the 
1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acids with the excess of 
alkanolamines present to give the amino esters of the invention in a 
second stage. This reaction can also be carried out in a different 
sequence or in a single stage, but under certain circumstances less 
pronounced biocidal or biostatic properties of the mixture are then 
obtained. 
Monocarboxylic acids which are furthermore used are preferably 
ether-carboxylic acids of the general formula 
EQU R.sup.3 -(O--C.sub.m H.sub.2m).sub.q --O--CH.sub.2 --COOH (III) 
in which 
R.sup.3 denotes a straight-chain or branched alkyl or alkenyl group having 
9 to 18 carbon atoms, 
m denotes the number 2 and/or 3 and 
q denotes a number in the range from 0 to 100, preferably from 0 to 20. 
The reaction here can be carried out in any desired sequence, but also in a 
single stage. 
Monocarboxylic acids which are likewise used are preferably 
arylsulphonamidocarboxylic acids of the general formula 
EQU (R.sup.4)aryl--SO.sub.2 --N(R.sup.5)--R.sup.6 --COOH (Va) 
in which 
R.sup.4 denotes hydrogen or a methyl or a ethyl group or several groups, 
R.sup.5 denotes hydrogen or a methyl, ethyl, beta-cyanoethyl or 
hydroxymethyl group, R.sup.6 denotes an alkylene group having 4 to 6 
carbon atoms and aryl denotes a phenyl, naphthyl or anthracenyl radical, 
alkylsulphonamidocarboxylic acids of the general formula 
EQU R.sup.7 --SO.sub.2 --NR.sup.8 --CH.sub.2 --COOH (Vb) 
in which R.sup.7 denotes a straight-chain or branched alkyl group having 12 
to 22 carbon atoms and R.sup.8 denotes hydrogen or the group --CH.sub.2 
--COOH, and/or half-esters or half-amides of the general formula Vc 
EQU R.sup.9 --OOC--R.sup.10 --COOH (Vc) 
in which 
R.sup.9 is the radical of an alkanolamine of the general formula II and 
R.sup.10 is an o-phenylene, vinylene or 1,2-ethylene radical. Here also, 
the reaction can be carried out in any desired sequence, but also in a 
single stage. It has not yet been possible to determine whether the 
sulphonamidocarboxylic acids of the general formula Va or Vb are reacted 
with the alkanolamines of the general formula II to give 
sulphonamidocarboxylic acid aminoalkyl esters, to give 
sulphonamidocarboxylic acid alkanolamides or to give mixtures thereof. For 
simplicity, these reaction products are always called alkanolamides here. 
The abovementioned sulphonamidocarboxylic acids are known, for example, 
from DE-C 28 40 112 and DE-A 33 04 164. 
Excess alkanolamine contained in the resulting reaction mixture can then be 
reacted with fatty acids having 3 to 22, preferably 3 to 11, carbon atoms, 
ethercarboxylic acids of the general formula IV, in which R.sup.3, m and q 
are as defined above, and/or aryl- or alkyl-sulphonamidocarboxylic acids 
of the general formula Va or Vb, in which R.sup.4, R.sup.5, R.sup.6, 
R.sup.7, R.sup.8 and R.sup.9 are as defined above, to establish a pH in 
the range from 4.5 to 9.5. 
It is preferable to carry out all the reactions such that the reaction 
mixture is always kept liquid. This is achieved, for example, with the 
preferred large excess of alkanolamines. 
Finally, the fungicides described below can also be added to the reaction 
mixture after the reaction, preferably in an amount of 1 part by weight of 
fungicides per 10 to 100 parts by weight of the amino esters of the 
general formula I, in which R.sup.1 and n are as defined above, contained 
in the biocidal or biostatic mixture. 
An excess of alkanolamines present after the reaction described above is 
completely or partly neutralized, as mentioned above, to establish a 
suitable pH range and with the formation of further contents of 
alkanolamides or alkanolammonium salts. 
Examples of straight-chain or branched, saturated or unsaturated fatty 
acids having 3 to 22 carbon atoms are propanoic acid, the abovementioned 
fatty acids having 5 to 22 carbon atoms and technical-grade mixtures 
thereof. The reaction products of the alkanolamines with the 
monocarboxylic acids furthermore can serve as anti-corrosion agents in the 
aqueous systems. 
Preferred examples of alkanolamines of the general formula II, in which 
R.sup.2 is as defined above, which can be used according to the invention 
are mono-, di- and triethanolamine, mono-, di- and tripropanolamine, 
mono-, di- and triisopropanolamine, 2-amino-1-butanol, 
2-(2'-aminoethoxy)-ethanol, 2-amino-2-methyl-1-propanol and 
2-amino-2-ethyl-1,3-propanediol; as already mentioned, alkanolamines 
having primary amino groups or mixtures thereof with alkanolamines having 
secondary amino groups are particularly preferred. 
Secondary alkanolamines which, in addition to having a single hydroxyalkyl, 
hydroxyalkyl-oxyalkylene or dihydroxyalkyl group according to the 
definitions given above for R.sup.2, are substituted by an alkyl group 
having 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, i-propyl, 
n-butyl, i-butyl, pentyl, cyclopentyl, hexyl or cyclohexyl, furthermore 
are also preferred. 
Such secondary monoalkanol-monoalkylamines are commercially available; 
typical representatives are methyl-hydroxyethyl-amine, 
n-butyl-hydroxyethylamine and cyclohexyl-hydroxyethyl-amine and the 
correspondingly substituted hydroxypropyl derivatives. Some of the 
compounds of the general formula I derived from these 
monoalkanolmonoalkylamines have pronounced fungicidal properties which 
render the addition of other fungicides to improve the biostatic 
properties superfluous. 
Examples of alkylene groups having 4 to 6 carbon atoms which can form the 
radical R.sup.6 are butylene, pentylene, hexylene, 2-methyl-propylene, 
2-methyl-butylene, 3-methyl-butylene, 2,2-dimethylpropylene and 
2,2-dimethylbutylene groups. 
Examples of alkyl groups having 12 to 22 carbon atoms which can form the 
radical R.sup.7 are the dodecyl, tridecyl, tetradecyl, pentadecyl, 
hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl and 
docosyl group. 
The biocidal or biostatic action of the amino esters of the general formula 
I used according to the invention extends to bacteria, yeasts and fungi. 
The limits between a biocidal and a biostatic action merge here. Either 
the biocidal (germ-destroying) or the biostatic (growth inhibiting) action 
predominates, depending on the amount used and the duration of the action. 
If a fungicide is also used in addition to the amino esters of the 
invention, synergistic effects occur, that is to say the actions mutually 
intensify each other. Examples of fungicides are pyrithione and 
derivatives thereof, N-alkyl- or N-aryl-, in particular 
N-cyclohexyldiazenium dioxide salts, for example with potassium, 
aluminium, tin or copper as the metal component (Ullmanns Encyklopadie der 
technischen Chemie (Ullmann's Encyclopaedia of Industrial Chemistry), 4th 
edition, Volume 17, Verlag Chemie, Weinheim 1979, page 369), phenols, 
cresols, 1,2-benzisothiazolin-3-one and derivatives thereof and also 
2-methyl- and 2-octyl-4-isothiazolin-3one, halogen-free compounds being 
preferred. Fungicides which are water-soluble and stable to alkali 
furthermore are preferably employed. 
According to another preferred embodiment of the invention, pyrithione or 
derivatives thereof and/or N-alkyl- or N-aryl-, in particular 
N-cyclohexyl-diazenium dioxide salts, for example with potassium, 
aluminium, tin or copper as the metal component, are used as the 
fungicides. Pyrithione is the abbreviated name for 2-pyridinethiol 
1-oxide, which is in tautomeric equilibrium with 
1-hydroxy-2-pyridinethione. Possible derivatives of pyrithione are the 
ammonium, sodium, magnesium and zinc salts and 2,2'-dithiobis(pyridine 
1,1'-dioxide), the disulphide of pyrithione. Under certain circumstances, 
the anion of pyrithione can be precipitated by heavy metals. In contrast, 
the abovementioned N-alkyl- and N-aryl-diazenium dioxide salts also have 
complexing properties, in addition to fungicidal properties. A mixture of 
pyrithione or derivatives thereof and the abovementioned N-alkyldiazenium 
dioxide salts is therefore preferably used. However, it is also possible 
to employ only pyrithione or derivatives thereof, the fungicidal action 
being retained in the absence of significant amounts of heavy metals. 
Since combinations of the fungicides mentioned with the amino esters 
according to the invention display synergistic effects, very small amounts 
thereof are sufficient for the use according to the invention in aqueous 
systems. 
The aqueous systems which can be prepared according to the invention 
comprise 0.05 to 0.40% by weight of the amino esters of the general 
formula I and 0.0001 to 0.2% by weight, preferably 0,001 to 0.1, in 
particular 0.001 to 0.02% by weight of fungicides, based on the total 
formulation. 
Uses in virtually any desired aqueous or water-containing systems are 
possible, for example in metalworking liquids, coolants for cooling 
circulations, cleaning agents, hydraulic fluids, cosmetics and paints. For 
use in cosmetics, these are preferably brought to a pH in the range from 
4.5 to 7.0 by the process described above. In contrast, cooling lubricants 
are preferably brought to a pH in the range from 7.5 to 9.5. 
The amino esters of the general formula I are used in particular in cooling 
lubricants. 
Cooling lubricants are aqueous liquids which are used for cooling and 
lubrication, for example, during drilling, grinding, milling, turning, 
cutting, sawing, abrading and thread cutting or during rolling or drawing 
of metals. These can be classified into three groups, according to the 
mineral oil content: 
a) synthetic cooling lubricants which are free from mineral oil, 
b) semi-synthetic cooling lubricants which comprise about 10 to 60% by 
weight of mineral oil and 
c) cooling lubricants which comprise about 60 to 80% of mineral oil. 
mineral oil. 
The cooling lubricant furthermore can comprise polyglycols. Instead of 
mineral oils, it is also possible to use naturally occurring or synthetic 
fatty acid esters, for example rape oil or ester oils. 
Further additives, such as corrosion inhibitors, copper passivators, 
antiwear agents, emulsifiers, carriers, precipitating agents, 
oxygen-trapping agents, complexing agents or foam prevention agents, can 
be added to all three types of cooling lubricants. 
Examples of corrosion inhibitors are organic acids and salts and esters 
thereof, for example benzoic acid, p-tert-butylbenzoic acid, disodium 
sebacate, triethanolamine laurate, isononanoic acid, the triethanolamine 
salt of p-toluenesulphonamidocaproic acid, sodium N-lauroylsarcosinate or 
nonylphenoxyacetic acid, or polycarboxylic acids; nitrogen-containing 
substances, for example fatty acid alkanolamides, imidazolines, 
oxazolines, triazoles, triethanolamine, fatty amines, N-acylsarcosines or 
inorganic nitrites or nitrates; phosphorus-containing substances, for 
example amine phosphates, phosphonic acids, phosphonates, 
phosphonocarboxylic acids, phosphinocarboxylic acids or inorganic 
phosphates, such as NaH.sub.2 PO.sub.4, and sulphur-containing substances, 
for example salts of petroleumsulphonates or alkylbenzenesulphonates, or 
heterocyclic compounds which contain one sulphur atom or more in the ring. 
Copper passivators which can be used are, for example, benzotriazoles, 
methylene-bis-benzotriazoles, such as sodium-2-mercaptobenzotriazole, 
thiadiazoles, for example 2,5-dimercapto-1,3,4-thiadiazole derivatives, or 
tolyltriazoles. 
Antiwear agents can be AW(antiwear) or EP(extreme pressure) additives, for 
example substances containing sulphur, phosphorus or halogen, such as 
sulphurated fats and olefins, tritolyl phosphate and mono- and diesters of 
phosphoric acid, addition products of ethylene oxide and/or propylene 
oxide with polyhydroxy compounds, which are optionally partly esterified 
with fatty acids, chloroparaffins or ethoxylated phosphate esters, 
chlorine-free compounds being preferred. 
Examples of emulsifiers are ether-carboxylic acids, fatty acid 
alkanolamides, sodium petroleum-sulphonates, mono- or diesters or -ethers 
of polyethylene glycols, polypropylene glycols or mixed 
polyethylene/polypropylene glycols or fatty acid soaps. 
Carriers which can be used are, for example, poly(meth)acrylic acid and its 
salts, hydrolysed polyacrylonitrile, polyacrylamide and copolymers 
thereof, ligninsulphonic acid and salts thereof, starch and starch 
derivatives, cellulose, alkylphosphonic acids, 
1-amino-alkyl-1,1-diphosphonic acids and their salts, polymaleic acids and 
other polycarboxylic acids, ester oils, naturally occurring or synthetic 
fatty acid esters, for example rape oil, or alkali metal phosphates. 
Examples of precipitating agents are alkali metal phosphates or alkali 
metal carbonates. 
Examples of oxygen-trapping agents are alkali metal sulphates, morpholine 
and hydrazine. 
The amino esters of the formula I according to the invention themselves 
have complexing properties. However, it is also possible to add other 
complexing agents, for example phosphonic acid derivatives, 
nitrilotriacetic acid or ethylenediamine-tetraacetic acid and salts 
thereof. Furthermore, the N-alkyl- and N-aryldiazenium dioxide salts 
optionally to be employed as fungicides also have complexing properties, 
to which reference has already been made. 
Examples of foam prevention agents are distearylsebacic acid diamide, 
distearyladipic acid diamide or ethylene oxide and/or propylene oxide 
addition products of such amides, fatty alcohols and ethylene oxide and/or 
propylene oxide addition products thereof, naturally occurring and 
synthetic waxes, silicone compounds, silicic acid derivatives and 
pyrogenic silicon dioxide. 
Typical cooling lubricants in the context of the invention are, for 
example, those which comprise 
a) amino esters of the general formula I, 
b) fungicides, 
c) water, 
d) if appropriate mineral oil, 
e) if appropriate emulsifiers and/or further auxiliaries, 
f) if appropriate corrosion inhibitors, 
the lubricants comprising the amino esters in an amount of 0.05 to 0.40% by 
weight and the fungicides in an amount of 0.0001 to 0.2% by weight, 
preferably 0.001 to 0.1, in particular 0.001 to 0.02% by weight, based on 
the total amount of cooling lubricant. 
Cooling lubricants which comprise, as emulsifiers and/or further 
auxiliaries, 
a) ether-carboxylic acids of the general formula IV, in which R.sup.3, m 
and q are as defined above, in the form of their alkanolamides and/or 
alkanolammonium salts with alkanolamines of the general formula II, in 
which R.sup.2 is as defined above, 
b) fatty acid alkanolamides based on straight-chain or branched, saturated 
or unsaturated fatty acids having 12 to 22 carbon atoms and amines of the 
general formula II, 
c) aryl- and alkylsulphonamidocarboxylic acids of the general formula Va or 
Vb, in which R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are as defined 
above, in the form of their alkanolamides and/or alkanolammonium salts 
with alkanolamines of the general formula II, in which R.sup.2 is as 
defined above, 
d) straight-chain or branched, unsaturated or saturated carboxylic acids 
having 5 to 22, preferably 5 to 11, carbon atoms to establish a pH in the 
range from 7.5 to 9.5 or 
e) straight-chain or branched fatty alcohols having 12 to 18 carbon atoms, 
are particularly advantageous. 
Other particularly advantageous cooling lubricants comprise, as fungicides, 
pyrithione or derivatives thereof and/or N-alkyldiazenium dioxide salts. 
The cooling lubricants can be prepared by mixing the individual components 
together. If the cooling lubricants are to have a content of fatty acid 
alkanolamides, it is preferable for the amino esters of the general 
formula I to be prepared in the manner described above in the form of 
their mixtures with the fatty acid alkanolamides. This process furthermore 
offers the advantage that exclusively liquid reaction mixtures are 
obtained, which can be further processed without extra measures, for 
example comminution or dissolving in suitable solvents. 
The invention is described in more detail below with the aid of 
particularly preferred embodiment examples. 
Examples 1 to 12 show the preparation of derivatives, used according to the 
invention, of 2,4,6-tris-(omega'-carboxypentylamino)-1,3,5-triazine, 
called triazinecarboxylic acid for short below, which is commercially 
obtainable or can be obtained by reaction of cyanuric chloride with the 
sodium salt of 6-aminohexanoic acid in accordance with EP-B 0 046 139. 
The triazinecarboxylic acid can be used as the commercially available 
product or in the form of the commercially available aqueous product. In 
the following examples, a solid product containing about 50% by weight of 
water was employed.

EXAMPLE 1 
75 g (0.714 mol) of diethanolamine were stirred with 25 g (0.0267 mol) of 
triazinecarboxylic acid. After a reaction time of several hours at 
150.degree. to 160.degree. C., 10 g of water were distilled off. 
The final acid number was 10 mg of KOH/g. 
90 g of a clear, medium-viscosity liquid were obtained. 
EXAMPLE 2 
75 g (1.230 mol) of monoethanolamine were stirred with 25 g (0.0267 mol) of 
triazinecarboxylic acid at 60.degree. C. and the mixture was heated to 
140.degree. to 143.degree. C. After a reaction time of 10 hours, 18 g of 
water were distilled off. 
The final acid number was 12 mg of KOH/g. 
A white, solid product was obtained. 
EXAMPLE 3 
863 g (9.697 mol; 31.5 mol per mol of triazinecarboxylic acid) of 
2-amino-1-butanol were stirred with 287 g (0.307 mol) of 
triazinecarboxylic acid at 60.degree. C. and the mixture was heated to 
145.degree. C. After a reaction time of 20 hours, 150 g of water were 
distilled off. 
The final acid number was 10 mg of KOH/g. 
1000 g of a clear, low-viscosity liquid were obtained. 
EXAMPLE 4 
375 g (3.571 mol; 26.7 mol per mol of triazinecarboxylic acid) of 
2-(2'-aminoethoxy)-ethanol were stirred with 125 g (0.134 mol) of 
triazinecarboxylic acid at 60.degree. C. and the mixture was heated to 
145.degree. C. After a reaction time of 16 hours, 73 g of water were 
distilled off. 
The final acid number was 7 mg of KOH/g. 
427 g of a white, pasty product were obtained. 
EXAMPLE 5 
228 g (2.171 mol; 7.1 mol per mol of triazinecarboxylic acid) of 
2-(2'-aminoethoxy)-ethanol and 627 g (7.045 mol; 23.1 mol per mol of 
triazinecarboxylic acid) of 2-amino-1-butanol were stirred with 285 g 
(0.304 mol) of triazinecarboxylic acid at 60.degree. C. and the mixture 
was heated to 145.degree. C. After a reaction time of 16 hours, 140 g of 
water were distilled off. 
The final acid number was 13 mg of KOH/g. 
1000 g of a clear, medium-viscosity liquid were obtained. 
EXAMPLE 6 
833 g (8.424 mol; 31.5 mol per mol of triazinecarboxylic acid) of AMP 90 
were heated to 60.degree. C. and stirred with 250 g (0.267 mol) of 
triazinecarboxylic acid, and the mixture was heated to 140.degree. to 
145.degree. C. After a reaction time of 20 hours, 240 g of water were 
distilled off. 
The final acid number was 15 mg of KOH/g. 
843 g of an almost clear, high-viscosity product were obtained. 
EXAMPLE 7 
990 g (8.319 mol; 23.6 mol per mol of triazinecarboxylic acid) of AEPD were 
heated to 60.degree. C. and stirred with 330 g (0.353 mol) of 
triazinecarboxylic acid, and the mixture was heated to 140.degree. to 
145.degree. C. After a reaction time of 16 hours, 320 g of water were 
distilled off. 
The final acid number was 10 mg of KOH/g. 
1000 g of a clear, high-viscosity liquid were obtained. 
EXAMPLE 8 
375 g (5.000 mol; 37.4 mol per mol of triazinecarboxylic acid) of 
monoisopropanolamine were heated to 60.degree. C. and stirred with 125 g 
(0.134 mol) of triazinecarboxylic acid, and the mixture was heated to 
140.degree. C. After a reaction time of 16 hours, 74 g of water were 
distilled off. 
The final acid number was 12 mg of KOH/g. 
426 g of a clear, low-viscosity liquid were obtained. 
EXAMPLE 9 
750 g (5.034 mol; 18.9 mol per mol of triazinecarboxylic acid) of 
triethanolamine were heated to 60.degree. C. and stirred with 250 g (0.267 
mol) of triazinecarboxylic acid, and the mixture was heated to 140.degree. 
to 145.degree. C. After a reaction time of 16 hours, 130 g of water were 
distilled off. 
The final acid number was 6 mg of KOH/g. 
870 g of a clear, medium-viscosity liquid were obtained. 
EXAMPLE 10 
1st stage 
130 g (1.238 mol; 4.8 mol per mol of triazinecarboxylic acid) of 
2-(2'-aminoethoxy)-ethanol and 370 g (4.157 mol; 16.2 mol per mol of 
triazinecarboxylic acid) of 2-amino-1-butanol were reacted with 190 g 
(0.674 mol; 2.6 mol per mol of triazinecarboxylic acid) of olein at 
145.degree. C. After a reaction time of 10 hours, 12 g of water were 
distilled off. 
678 g of a liquid product having an acid number of 7 mg of KOH/g were 
obtained. 
2nd stage 
678 g of the liquid from the first stage were heated to 60.degree. C. and 
stirred with 240 g (0.256 mol) of triazinecarboxylic acid, and the mixture 
was heated to 140.degree. to 150.degree. C. After a reaction time of 10 
hours, 138 g of water were distilled off. 
The final acid number was 14 mg of KOH/g. 
780 g of a clear, medium-viscosity product were obtained. 
EXAMPLE 11 
130 g (1.238 mol) of 2-(2'-aminoethoxy)-ethanol, 370 g (4.157 mol) of 
2-amino-1-butanol, 174 g (0.497 mol) of sulphonamidocarboxylic acid and 
240 g (0.256 mol) of triazinecarboxylic acid were reacted at 145.degree. 
C. After a reaction time of 12 hours, 143 g of water were distilled off. 
771 g of a medium-viscosity, clear, liquid product having a final acid 
number of 25 mg of KOH/g were obtained. 
EXAMPLE 12 
130 g (1.238 mol) of 2-(2'-aminoethoxy)-ethanol, 370 g (4.157 mol) of 
2-amino-1-butanol, 106 g (0.148 mol) of ether-carboxylic acid and 240 g 
(0.256 mol) of triazinecarboxylic acid were reacted at 145.degree. C. 
After a reaction time of 13 hours, 137 g of water were distilled off. 
709 g of a clear, medium-viscosity product having a final acid number of 20 
mg of KOH/g were obtained. 
Comparison Examples 1 to 3 and Examples 13 to 19 
A number of the amino esters thus prepared were formulated with water, 
spindle oil and further additives stated in each case, and in some 
examples with fungicides, to give mixtures which give cooling lubricants 
in a dilution with water of 1:20 to 1:80. 
Furthermore, mixtures without biocides were formulated in Comparison 
Examples 1 and 2, and a mixture with a boric acid-alkanolamine 
condensation product as a biocidal agent were formulated in Comparison 
Example 3. 
Data in % below always relate to parts by weight. 
The data in the "Exp." column relate to the explanations of Table 1. All 
the chemicals listed in Table 1 are commercially obtainable. 
Table 1: EXPLANATIONS 
1 Tall oil distillate with 25-30% of resin (acid number 155-190) 
2 a) isononanoic acid 
b) 2,2-dimethyl-octanoic acid 
3 Spindle oil, viscosity: 22 mm.sup.2 /s at 40.degree. C. 
4 a) Reaction product of 1 mol of chloroacetic acid with a condensation 
product of 1 mol of a technical-grade oleyl alcohol with 10 mol of 
ethylene oxide (ether-carboxylic acid) 
b) Reaction product of 1 mol of chloroacetic acid with a condensation 
product of 1 mol of C.sub.9 - to C.sub.13 oxo alcohols with 3 mol of 
ethylene oxide and 2 mol of propylene oxide (ether-carboxylic acid) 
5 a) Technical-grade oleyl alcohol (about 90% strength, iodine number about 
95) 
b) 2-hexyldecanol 
6 a) Condensation product of 1 mol of a technical-grade mixture of oleyl 
and cetyl alcohol with 5 mol of ethylene oxide 
b) Fatty alcohol polyglycol ether (Emulsogen.sup.R LP) 
7 a) Condensation product of 40 parts by weight of diethanolamine with 60 
parts by weight of olein 
b) as a) with addition of 20% of ethanolamine, based on the total amount of 
condensation product and ethanolamine 
8 a) diethylene glycol 
b) butyldiglycol 
c) butylglycol 
9 a) Sodium petroleumsulphonate having a molecular weight of about 460 
b) Sodium alkylbenzenesulphonate having a molecular weight of about 350 
10 50% strength potassium hydroxide solution 
11 Fungicidal mixture of 
10% of the sodium salt of pyrithione 
10% of N-(cyclohexyl-diazenium dioxide) potassium hydrate in the form of a 
30% strength aqueous solution 
10% of propylene glycol 
70% of demineralized water 
12 Condensation product of 1 mol of boric acid with 3 mol of ethanolamine 
13 Arylsulphonamidocarboxylic acid having a molecular weight of about 350 
(Hostacor.sup.R H liquid; acid content about 90%, remainder solubilizing 
agent). 
______________________________________ 
Exp. 
______________________________________ 
Comparison Example 1 
7% of fatty acids 1 
2% of sulphonates 9b) 
5% of fatty acid alkanolamides 
7b) 
2% of auxiliaries 8a) 
1% of auxiliaries 10 
83% of spindle oil 3 
Comparison Example 2 
8% of fatty acids 1 
17% of sulphonates 9a) 
4% of fatty acid alkanolamides 
7a) 
3% of auxiliaries 8c) 
2% of auxiliaries 10 
36% of spindle oil 3 
30% of water 
Comparison Example 3 
20% of boric acid product 12 
10% of fatty acids 1 
10% of fatty acid alkanolamides 
7a) 
10% of auxiliaries 8b) 
20% of spindle oil 3 
30% of water 
Example 13 
25% of Example 1 
31% of spindle oil 3 
10% of fatty acids 1 
5% of fatty acids 2b) 
4% of ether-carboxylic acids 
4b) 
6% of fatty alcohols 5a) 
14% of water 
5% of non-ionic emulsifiers 
6a) 
Example 14 
25% of Example 2 
31% of spindle oil 3 
10% of fatty acids 1 
5% of fatty acids 2b) 
4% of ether-carboxylic acids 
4b) 
6% of fatty alcohols 5a) 
5% of non-ionic emulsifiers 
6a) 
14% of water 
Example 15 
22% of Example 3 
11% of fatty acids 2a) 
17% of fatty acids 1 
6% of ether-carboxylic acids 
4a) 
9% of fatty acid alkanolamides 
7a) 
4% of fatty alcohols 5a) 
22% of spindle oil 3 
8% of water 
1% of fungicides 11 
Example 16 
21% of Example 5 
21% of fatty acids 1 
11% of fatty acids 2a) 
7% of ether-carboxylic acids 
4a) 
5% of fatty alcohols 5b) 
20% of spindle oil 3 
13% of water 
2% of fungicides 11 
Example 17 
25% of Example 7 
31% of spindle oil 3 
10% of fatty acids 1 
3% of fatty acids 2a) 
8% of fatty alcohols 5a) 
5% of non-ionic emulsifiers 
6a) 
4% of ether-carboxylic acids 
4b) 
1% of fungicides 11 
13% of water 
Example 18 
25% of Example 8 
31% of spindle oil 3 
10% of fatty acids 1 
5% of fatty acids 2b) 
4% of ether-carboxylic acids 
4b) 
6% of fatty alcohols 5a) 
5% of non-ionic emulsifiers 
6a) 
1% of fungicides 11 
13% of water 
Example 19 
19% of Example 10 
29% of fatty acids 1 
29% of spindle oil 3 
5% of auxiliaries 8b) 
3% of non-ionic emulsifiers 
6b) 
1% of fungicides 11 
14% of water 
Example 20 
23% of Example 11 
28% of fatty acids 1 
25% of spindle oil 3 
5% of non-ionic emulsifiers 
6b) 
2% of fatty alcohols 5b) 
2% of auxiliaries 8b) 
1% of fungicides 11 
14% of water 
Example 21 
23% of Example 12 
28% of fatty acids 1 
1% of fatty alcohols 5a) 
4% of non-ionic emulsifiers 
6a) 
4% of auxiliaries 8b) 
1% of fungicides 11 
27% of spindle oil 3 
12% of water 
______________________________________ 
Microbiological Test Method 
An inoculation cycle test developed in-house was carried out. For this, the 
following dilutions of the formulations of Comparison Examples 1 to 3 and 
of Examples 26 to 42 were prepared with Hamburg town water: 1.25%, 2.5% 
and 5.0% (corresponds to 1:80, 1:40 and 1:20). 
The samples were inoculated several times with a concentrated mixed germ 
flora. The germ flora contained bacteria, yeasts and fungi from running 
emulsion systems of varying origin. Their total germ count was about 
10.sup.7 germs/ml. 
The amount of mixed germ flora for inoculation of the samples corresponded 
to six times the amount proposed according to DAB 9 (German 
Pharmacopoeia). 6 ml of germ flora were used per 100 ml of sample. 
The samples were inoculated repeatedly (a maximum of 6 inoculations) by 
this method (in accordance with K. H. Wallhausser; Praxis der 
Sterilisation-Desinfektion-Konservierung-Keimidentifizierung (Practice of 
Sterilization-Disinfection-Preservation-Germ Identification), 4th edition, 
Georg Thieme Verlag, Stuttgart 1988), until an antimicrobial action was no 
longer detectable. From experience, 1 inoculation corresponded to 3 
inoculation cycles according to the DAB 9/Wallhauser method. 
This method has the following advantages: 
1. A mixed germ flora such as occurs in practice is employed. 
2. The samples are exposed to a massive germ loading several times. 
3. The method is quick and therefore appropriate for industry. In 
comparison with the conventional method, which often takes several months, 
the results are available in a maximum of 8 weeks, if they do not have to 
be repeated. 
4. Conclusions as to the service lives of the emulsions in use in the 
central systems can be drawn from the results. 
The action time of the microorganisms on the samples was about 1 week. 
After this time, the samples were spread out onto in each case two special 
nutrient media and incubated. The colony count was then determined under 
the microscope, and the germ count per ml of sample was determined 
therefrom. The number of inoculation cycles after which a first germ 
attack is to be observed is shown in Table 2. This is a measure of the 
activity of the biocides in the particular samples. The formulations of 
Examples 13, 14, 15 and 18 based on the compounds of Examples 1, 2, 3 and 
8 proved to be particularly active. Example 14 shows a fungicidal action 
even without addition of pyrithione or derivatives thereof. 
TABLE 2 
__________________________________________________________________________ 
Microbiological Results 
Dilution % 
1.25 2.5 5 
Example 
B Y F IC 
B Y F IC 
B Y F IC 
__________________________________________________________________________ 
Comp. Ex. 1 +++ ++ 0 3 
Comp. Ex. 2 +++ ++ 0 3 
Comp. Ex. 3 0 0 +++ 18 
13 +++ +++ 0 3 +++ 0 ++ 12 
0 0 0 18 
14 +++ ++ 0 9 ++ ++ 0 12 
+ 0 0 18 
15 ++ ++ 0 3 ++ ++ 0 12 
0 0 0 18 
16 +++ 0 0 3 +++ 0 +++ 9 
0 0 0 18 
17 ++ ++ 0 3 + 0 0 6 
++ + 0 9 
18 +++ ++ 0 6 0 0 0 18 
0 0 0 18 
19 +++ ++ 0 3 ++ ++ 0 3 
+ + 0 15 
__________________________________________________________________________ 
+++ = severe attack germ count/ml &gt; 
++ = moderate attack germ count/ml 10.sup.3 
+ = mild attack germ count/ml &lt; 
0 = no attack 
B = bacteria 
Y = yeasts 
F = fungi 
IC = first germ attack after x inoculation cycles