Foam inhibitors and their use for defoaming aqueous systems

Foam inhibitors for aqueous systems which contain a fatty acid salt of a polyvalent metal, especially an alkaline earth metal or aluminium, an anionic surfactant or a non-ionic reaction product of an alcohol or an alkyl phenol with an alkylene oxide, an aliphatic alcohol of 5 to 18 carbon atoms or a mixture of such alcohols, and a hydrophobic organic solvent or solvent mixture; these foam inhibitors are stable, they are miscible to any extent with water or organic solvents and can be used e.g. for defoaming aqueous dyebaths, treatment baths, printing pastes, pulp suspensions, paints, detergent solutions or also wastewaters.

The present invention relates to foam inhibitors for aqueous systems which 
contain a fatty acid salt of a polyvalent metal, a surfactant, an 
aliphatic alcohol and a hydrophobic organic solvent, e.g. paraffin oil, 
and which are in the form of stable solutions. 
It is already known to use metal salts of a fatty acid, e.g. aluminium 
stearate, in defoaming compositions. Such compositions which contain a 
water-insoluble metal salt, a dispersant, e.g. Turkey red oil, and an 
organic solvent, e.g. paraffin oil, are described in U.S. Pat. No. 
1,957,513. These defoaming compositions are, on the one hand, not stable, 
i.e. they demix, and, on the other, they spread only slowly and 
incompletely onto the systems which it is desired to defoam, so that 
overall only an insignificant foam inhibition is obtained. 
U.S. Pat. No. 3,492,242 describes a defoaming composition which contains 
aluminium stearate, a long chain alcohol and a fluid organic solvent, e.g. 
a fluid hydrocarbon. Upon addition of water, this composition forms an 
opaque emulsion which readily demixes, so that its foam inhibiting action 
is impaired. 
The present invention has for its object the provision of foam inhibitors 
which are stable when stored, which do not demix even after addition of 
water, and which furthermore are miscible with water in any ratio. 
It has now been found that mixtures of fatty acid salts of polyvalent 
metals, an anionic or non-ionic surfactant, an aliphatic alcohol and a 
hydrophobic organic solvent are very effective foam inhibitors for aqueous 
systems. 
Accordingly, the present invention provides foam inhibitors for aqueous 
systems, said foam inhibitors containing 
(1) 1 to 10% by weight of a fatty acid salt of a polyvalent metal, 
(2) 1 to 6% by weight of an anionic surfactant or of a non-ionic reaction 
product of an alcohol or alkylphenol with an alkylene oxide, 
(3) 0.5 to 10% by weight of an aliphatic alcohol containing 5 to 18 carbon 
atoms or of a mixture of such alcohols, and 
(4) 74 to 97.5% of a hydrophobic organic solvent or solvent mixture which 
is different from component (3). 
The foam inhibitors of this invention differ in the composition of their 
components from the foam inhibitors of the prior art, they have a very 
good shelf life, and they are miscible with water, with the alcohols 
suitable for use as component (3) or with the hydrophobic organic solvents 
suitable for use as component (4) in any desired ratio, without 
subsequently demixing. 
Further objects of the invention are concerned with the use of the novel 
foam inhibitors for defoaming aqueous systems, in particular baths and 
treatment liquors employed in the dyeing and finishing of textiles, with 
foam control in the manufacture and processing of paper and in wastewater 
purification, and also with their use as foam regulators, e.g. in 
detergents. 
As component (1) in the foam inhibitors of the invention it is possible to 
use fatty acid salts of polyvalent metals, e.g. of magnesium, calcium, 
strontium, barium, zinc or aluminium. Fatty acid salts of alkaline earth 
metals, and especially of aluminium, are preferred. These salts can be 
salts of mono-, di- or tri-fatty acids and can be employed singly or in 
admixture. They should be in solid aggregate state at room temperature. 
Suitable fatty acids, which can be saturated or unsaturated, are those 
containing 8 to 22 carbon atoms, e.g. caprylic, pelargonic, capric, 
lauric, myristic, palmitic, stearic, arachinic, behenic, coconut fatty, 
tallow fatty, decenoic, linolic, linolenic, oleic, ricinolic, eicosenoic, 
docosenoic or clupadonic acid. 
Preferred fatty acids are those containing 16 to 22 carbon atoms. The 
aluminium salts of these fatty acids, in particular aluminium stearate, 
are especially suitable. By aluminium stearate within the scope of the 
present invention is meant aluminium mono-, di- or tristearate or a 
mixture thereof. 
If the surfactants of component (2) are anionic surfactants, they are 
preferably esterified alkylene oxide adducts, e.g. adducts containing acid 
ester groups of inorganic or organic acids of alkylene oxides, in 
particular ethylene oxide and/or propylene oxide, with organic hydroxyl, 
carboxyl, amino or amido compounds containing aliphatic hydrocarbon 
radicals having a total of at least 4, and preferably at least 8, carbon 
atoms, or mixtures thereof. These acid esters can be in the form of free 
acids or salts, e.g. alkali metal, alkaline earth metal, ammonium or amine 
salts. 
These anionic surfactants are obtained by known methods by addition of at 
least 1 mole, preferably of more than 1 mole, e.g. 2 to 60 moles, of 
ethylene oxide or propylene oxide, or alternately, in any order, ethylene 
oxide and propylene oxide, to the above organic compounds, and 
subsequently etherifying or esterifying the adducts and, if desired, 
converting the ethers or esters into their salts. Suitable starting 
materials are e.g. higher fatty alcohols, i.e. alkanols or alkenols, each 
containing 8 to 22 carbon atoms, alicyclic alcohols, phenylphenols, 
benzylphenols, alkylphenols containing one or more alkyl substituents 
which together contain at least 4, and preferably at least 8, carbon 
atoms, or fatty acids which contain 8 to 22 carbon atoms. 
Particularly suitable anionic surfactants have the formula 
##STR1## 
wherein R is an aliphatic hydrocarbon radical containing 8 to 22 carbon 
atoms or a cycloaliphatic, aromatic or aliphatic-aromatic hydrocarbon 
radical containing 10 to 22 carbon atoms, R.sub.1 is hydrogen or methyl, A 
is 
##STR2## 
X is the acid radical of an inorganic oxygen-containing acid, the acid 
radical of a polybasic carboxylic acid or a carboxyalkyl radical, and m is 
an integer from 1 to 50. 
The radical R-A in the compounds of the formula (1) is derived e.g. from 
higher alcohols, such as 2-ethyl-hexanol, decyl, lauryl, tridecyl, 
myristyl, cetyl, stearyl, oleyl, arachidyl or behenyl alcohol; from 
alicyclic alcohols, such as hydroabiethyl alcohol; from fatty acids, such 
as caprylic, capric, lauric, myristic, palmitic, stearic, arachinic, 
behenic, C.sub.1 -C.sub.18 coconut fatty, decenoic, dodecenoic, 
tetradecenoic, hexadecenoic, oleic, linolic, linolenic, eicosenic, 
docosenoic or clupanodonic acid; from alkylphenols, such as butylphenol, 
hexylphenol, n-octylphenol, n-nonylphenol, p-tert-octylphenol, 
p-tert-nonylphenol, decylphenol, dodecylphenol, tetradecylphenol or 
hexadecylphenol, or from arylphenols, such as the o- or p-phenylphenols. 
Preferred radicals are those containing 10 to 18 carbon atoms, especially 
those which are derived from the alkylphenols. 
The acid radical X is ordinarily the acid radical of a polybasic, in 
particular low molecular, mono- or dicarboxylic acid, e.g. of maleic acid, 
malonic acid, succinic acid or sulfosuccinic acid, or it is a carboxyalkyl 
radical, in particular a carboxymethyl radical (derived in particular from 
chloroacetic acid), and is bonded to the radical R--A--(CH.sub.2 CHR.sub.1 
O).sub.m --through an ether or ester bridge. In particular, however, X is 
derived from an inorganic polybasic acid, such as orthophosphoric acid and 
sulfuric acid. The acid radical X exists preferably in salt form, i.e. for 
example in the form of an alkali metal salt, alkaline earth metal salt, 
ammonium or amine salt. Examples of such salts are sodium, calcium, 
ammonium, trimethylamine, ethanolamine, diethanolamine or triethanolamine 
salts. The alkylene oxide units --CH.sub.2 CHR.sub.1 O-- in formula (1) 
are normally ethylene oxide and 1,2-propylene oxide units. The latter are 
preferably in admixture with ethylene oxide units in the compounds of the 
formula (1). 
Particularly interesting anionic compounds are those of the formula 
EQU R.sub.2 O--CH.sub.2 CH.sub.2 O).sub.m X (2) 
wherein R.sub.2 is a saturated or unsaturated aliphatic hydrocarbon radical 
containing 8 to 22 carbon atoms, o-phenylphenyl or alkylphenyl containing 
4 to 12 carbon atoms in the alkyl moiety, and X and m have the given 
meanings. 
Especially preferred compounds which are derived from alkylphenol/ethylene 
oxide adducts are also those of the formulae 
##STR3## 
wherein p is an integer from 4 to 12, n is an integer from 1 to 20, 
n.sub.1 is an integer from 1 to 10, X.sub.1 is a phosphoric acid radical 
which can exist in salt form, and X has the given meaning. 
Further anionic surfactants which can be used as component (2) are 
the adducts of 1 to 60 moles of ethylene oxide and/or propylene oxide with 
trihydric to hexahydric alkanols containing 3 to 6 carbon atoms, which 
adducts have been converted into an acid ester with a dicarboxylic acid, 
e.g. maleic acid, malonic acid or sulfosuccinic acid, but preferably with 
an inorganic polybasic acid, such as orthophosphoric acid or, in 
particular, sulfuric acid; 
sulfated aliphatic alcohols containing 8 to 18 carbon atoms in the alkyl 
chain, e.g. sulfated lauryl alcohol; 
sulfated unsaturated fatty acids or lower alkyl esters of fatty acids which 
contain 8 to 20 carbon atoms in the fatty acid radical, e.g. ricinolic 
acid and oils containing such fatty acids, e.g. castor oil; 
sulfonates of polycarboxylic acid esters, e.g. dioctylsulfosuccinate; 
alkylsulfonates which contain 8 to 20 carbon atoms in the alkyl chain, e.g. 
dodecylsulfonate; and in particular 
alkylarylsulfonates with straight or branched alkyl chain containing at 
least 6 carbo atoms, e.g. dodecylbenzenesulfonate or 
3,7-diisobutylnaphthalenesulfonate. 
If component (2) is a non-ionic reaction product of an alcohol or 
alkylphenol with an alkylene oxide, it is e.g. a reaction product of an 
aliphatic alcohol containing 4 to 22 carbon atoms with up to 80 moles of 
ethylene oxide and/or 1,2-propylene oxide. 
The alcohols can preferably contain 4 to 18 carbon atoms, they can be 
branched or straight chain and they can be employed singly or in 
admixture. 
It is possible to use natural alcohols, e.g. myristyl alcohol, cetyl 
alcohol, stearyl alcohol, oleyl alcohol, arachidyl alcohol or behenyl 
alcohol, or synthetic alcohols, in particular 2-butanol, n-butanol, 
isobutanol, 2-ethyl-hexanol, amyl alcohol, n-hexanol, trimethylhexanol, 
triethylhexanol, trimethylnonyl alcohol, or the ALFOL.RTM. (registered 
trademark). The ALFOLS.RTM. are linear primary alcohols. The number after 
the name indicates the average number of carbon atoms which the alcohol 
contains. Thus, for example, ALFOL.RTM. (12-18) is a mixture of decyl, 
dodecyl, tetradecyl, hexadecyl and octadecyl alcohol. Further 
representatives are ALFOL.RTM. (6-10), (8-10), (10-14), (12) (16), (18), 
and (20-22). 
Preferred ethylene oxide/alcohol reaction products can be illustrated by 
the formula 
EQU R.sub.3 O(CH.sub.2 CH.sub.2 O).sub.s H (5) 
wherein R.sub.3 is a saturated or unsaturated aliphatic hydrocarbon 
radical, preferably an alkyl or alkenyl radical containing 8 to 18 carbon 
atoms, and s is an integer from 1 to 80, preferably from 1 to 30. 
Also suitable for use as non-ionic component (2) are reaction products of 
ethylene oxide and/or 1,2-propylene oxide and alkylphenols containing 4 to 
12 carbon atoms in the alkyl moiety, while the phenol can contain one or 
more alkyl substituents. Preferably these compounds have the formula 
##STR4## 
wherein R.sub.1 is hydrogen or at most one of the two symbols R.sub.1 is 
methyl, p is an integer from 4 to 12, preferably 8 or 9, and t is an 
integer from 1 to 60, in particular from 1 to 20 and preferably from 1 to 
10. 
At least one compound of component (2), or optionally a mixture of the 
above compounds, is used. 
If desired, these adducts of an alcohol or alkylphenol with ethylene oxide 
and/or 1,2-propylene oxide can additionally contain smaller amounts of 
block polymers of the cited alkylene oxides. 
Component (3) of the foam inhibitors of the present invention is an 
aliphatic alcohol containing 5 to 18 carbon atoms or a mixture of such 
alcohols. The alcohols can be straight chain or branched, saturated or 
unsaturated, and should normally be liquid at room temperature. Examples 
of such alcohols are: n-amyl alcohol, n-hexanol, trimethylhexanol, 
2-ethyl-n-hexanol, octyl alcohol (octanol, mixture of isomers), nonyl 
alcohol, decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl 
alcohol, cetyl alcohol, stearyl or oleyl alcohol, and the ALFOLS.RTM., 
e.g. ALFOL.RTM. (6-10), (8-10), (10-14), (12), (16), (18). Preferred 
alcohols are those containing 5 to 10 carbon atoms; 2-ethyl-n-hexanol is 
especially preferred. 
Hydrophobic organic solvents which are employed as component (4), and which 
are different from component (3), are e.g. aliphatic or cycloaliphatic 
hydrocarbons, pine oil, dibutyl phthalate, dioctyl phthalate, butyl 
stearate, cyclohexyl acetate, benzyl acetate or phenyl acetate. These 
solvents should also be fluid at room temperature. Aliphatic hydrocarbons 
advantageously have an average molecular weight of 140 to 250 or are 
preferably paraffin oils with as low a pour point as possible (e.g. below 
-20.degree. C.), a high boiling point (e.g. above 300.degree. C.), and a 
low viscosity (e.g. 5 to 60 cS at 50.degree. C.). Cycloaliphatic solvents 
are in particular cyclopentane, cyclohexane and decalin. 
The pine oil which is also suitable as component (4) is a colourless to 
pale yellow liquid which is insoluble in water, but is soluble in organic 
solvents. Pine oil is obtained e.g. by distillation of the waste of 
different American pinewoods and contains at least 65% of terpene alcohols 
[Rompp, Chemie Lexikon, 2703, (1974)]. 
Preferred foam inhibitors contain 
(1) 1 to 10% by weight of an alkaline earth metal salt or aluminium salt of 
a fatty acid, wherein the fatty acid radical contains 8 to 22 carbon 
atoms, 
(2) 1 to 6% by weight of 
(a) an anionic surfactant of the formula (1) or 
(b) a non-ionic reaction product of an aliphatic alcohol containing 4 to 22 
carbon atoms or of an alkylphenol containing 4 to 12 carbon atoms in the 
alkyl moiety with ethylene oxide and/or 1,2-propylene oxide, 
(3) 0.5 to 10% by weight of a straight-chain or branched, saturated or 
unsaturated aliphatic alcohol containing 5 to 18 carbon atoms or of a 
mixture of such alcohols, and 
(4) 74 to 97.5% by weight of an aliphatic or cycloaliphatic hydrocarbon or 
pine oil or of a mixture thereof. 
Especially preferred foam inhibitors contain 
(1) 2 to 5% by weight of aluminium stearate or of a mixture of aluminium 
stearate and magnesium stearate, 
(2) 2 to 4% by weight of an acid phosphoric acid ester of the reaction 
product of nonylphenol and 10 moles of ethylene oxide, 
(3) 3 to 7% by weight of 2-ethyl-n-hexanol and 
(4) 84 to 93% by weight of paraffin oil. 
The ratio of aluminium stearate to magnesium stearate can be e.g. 1:5 to 
5:1. Foam inhibitors which contain these two salts are distinguished by 
the neutral reaction of their aqueous solutions. 
The foam inhibitors of the present invention can be obtained by stirring 
components (1) to (4) at room temperature, heating the mixture, with 
further stirring, to a temperature ranging from 50.degree. to 150.degree. 
C., preferably from 80.degree. to 110.degree. C., for about 10 to 60 
minutes, and then cooling to room temperature, affording a homogeneous, 
clear mixture which is stable at room temperaature. The foam inhibitors 
can be employed in acid or alkaline preparations (pH range from about 1 to 
12) and in a wide temperature range, e.g. from 20.degree. to 150.degree. 
C., without losing their effectiveness. For use in actual practice they 
can be added to the aqueous systems undiluted or after dilution with 
organic solvents or water in amounts of about 0.001 to 50 g/l (kg), 
preferably 0.001 to 20 g/l (kg). Treatment baths for textiles can contain 
about 0.1 to 10 g/l, preferably 0.5 to 5 g/l. In wastewater purification, 
amounts of 0.001 to 1 g/l, preferably 0.001 to 0.1 g/l, will ordinarily be 
used. The amount depends also on the surfactants present in the wastewater 
or in the other aqueous systems. 
If the foam inhibitors of the invention are used as foam regulators for 
detergents by incorporating them in aqueous pastes of the detergents or of 
individual constituents of the detergents, then up to 20 g of foam 
inhibitor per liter or kilogram of the aqueous paste can be used before 
drying this latter. 
If desired, the foam inhibitors can also be employed in the form of dilute 
aqueous or organic preparations (solutions), e.g. in the form of 1 to 99% 
aqueous solutions or solutions in an organic solvent, e.g. 
2-ethyl-n-hexanol or toluene or a solvent mixture. These dilute foam 
inhibitor preparations make it easier to control the rate of addition to 
e.g. printing pastes, dyebaths or wastewaters. 
The foam inhibitors can be employed in the most diverse processes in which 
aqueous preparations which readily tend to foam are used, e.g. 
(a) dyeing wool with 1:1 or 1:2 metal complex dyes, acid or reactive dyes; 
exhaust or continuous dyeing processes for dyeing synthetic polyamide 
fibres with acid or disperse dyes; dyeing cellulose fibres with reactive 
and direct dyes; dyeing polyacrylonitrile fibres with cationic dyes; 
(b) finishing processes for textiles; shrinkproofing of wool and 
wool-containing blends, providing cellulosic fibre material with a 
flame-retardant and crease-resistant finish, providing different fibre 
substrates with an oil-, water- and dirt repellent finish, providing 
different fibre substrates with an antistatic finish and a soft handle, 
whitening different fibre substrates; 
(c) pulp and paper manufacture (pulp suspensions) or paper finishing, 
especially sizing paper with aqueous resin preparations or surface-coating 
paper; 
(d) defoaming wastewaters, especially those occurring in the manufacture of 
textiles, leather, paper and pulp, or in the manufacture of dyes and 
fluorescent whitening agents, such as dyehouse, bleaching plant or 
gelatin-containing wastewaters. In addition to the entrained or dissolved 
impurities they contain, communal or industrial wastewaters of the above 
kind usually also have the drawback that they foam strongly. This foaming 
can hinder processing in purification plants and the introduction of air 
in biological water treatment plants. It is therefore advantageous to add 
foam inhibitors to such wastewaters. In order to manage with very small 
amounts of such foam inhibitors on the one hand, and on the other not to 
diminish the efficiency of the water treatment plant, such a foam 
inhibitor must be very stable and as inert as possible. The foam 
inhibitors described herein fulfill these conditions in exceptional manner 
and are therefore particularly suitable for this use; 
(e) as foam regulators for detergents or their components (manufacture of 
foam regulated detergents); 
(f) as foam regulators in wash liquors for washing in domestic washing 
machines; 
(g) for the production of non-foaming paint preparations. 
When the foam inhibitors of this invention are used in textile dyeing and 
finishing processes, a good foam inhibition is obtained, even if other 
readily foaming assistants (surfactants) are concurrently used.

In the following Examples parts and percentages are by weight. The 
following reaction products are examples of component (2): 
COMPONENT (2): (anionic surfactants) 
A.sub.1 the ammonium salt of the acid sulfuric acid ester of the adduct of 
1 mole of ethylene oxide and 1 mole of ALFOL.RTM. (10-14); 
A.sub.2 the ammonium salt of the acid sulfuric acid ester of the adduct of 
1 mole of ethylene oxide and 1 mole of stearyl alcohol; 
A.sub.3 the ammonium salt of the acid sulfuric acid ester of the adduct of 
1 mole of ethylene oxide and 1 mole of 2-ethyl-hexanol; 
A.sub.4 the ammonium salt of the acid sulfuric acid ester of the adduct of 
35 moles of ethylene oxide and 1 mole of stearyl alcohol; 
A.sub.5 the ammonium salt of the acid sulfuric acid ester of the adduct of 
3 moles of ethylene oxide and 1 mole of tridecyl alcohol; 
A.sub.6 the ammonium salt of the acid sulfuric acid ester of the adduct of 
4 moles of ethylene oxide and 1 mole of hydroabietyl alcohol; 
A.sub.7 the ammonium salt of the acid sulfuric acid ester of the adduct of 
3 moles of ethylene oxide and 1 mole of ALFOL.RTM. (20-22); 
A.sub.8 the ammonium salt of the acid sulfuric acid ester of the adduct of 
3 moles of ethylene oxide and 1 mole of lauryl alcohol; 
A.sub.9 the ammonium salt of the acid sulfuric acid ester of the adduct of 
3 moles of ethylene oxide and 1 mole of butylphenol; 
A.sub.10 the ammonium salt of the acid sulfuric acid ester of the adduct of 
5 moles of ethylene oxide and 1 mole of tributylphenol; 
A.sub.11 the ammonium salt of the acid sulfuric acid ester of the adduct of 
2 moles of ethylene oxide and 1 mole of nonylphenol; 
A.sub.12 the ammonium salt of the acid sulfuric acid ester of the adduct of 
10 moles of propylene oxide and 10 moles of ethylene oxide and 1 mole of 
nonylphenol; 
A.sub.13 the ammonium salt of the acid sulfuric acid ester of the adduct of 
35 moles of ethylene oxide and 1 mole of nonylphenol; 
A.sub.14 the ammonium salt of the acid sulfuric acid ester of the adduct of 
50 moles of ethylene oxide and 1 mole of nonylphenol; 
A.sub.15 the ammonium salt of the acid sulfuric acid ester of the adduct of 
15 moles of propylene oxide and 1 mole of nonylphenol; 
A.sub.16 the ammonium salt of the acid sulfuric acid ester of the adduct of 
6 moles of ethylene oxide and 1 mole of dodecylphenol; 
A.sub.17 the ammonium salt of the acid sulfuric acid ester of the adduct of 
6 moles of ethylene oxide and 1 mole of pentadecylphenol; 
A.sub.18 the ammonium salt of the acid sulfuric acid ester of the adduct of 
8 moles of ethylene oxide and 1 mole of o-phenylphenol; 
A.sub.19 the ammonium salt of the acid sulfuric acid ester of the adduct of 
2 moles of ethylene oxide and 1 mole of coconut fatty acid; 
A.sub.20 the ammonium salt of the acid sulfuric acid ester of the adduct of 
2 moles of propylene oxide and 1 mole of coconut fatty acid; 
A.sub.21 the sodium salt of the acid maleic acid ester of the adduct of 2 
moles of ethylene oxide and 1 mole of p-nonylphenol; 
A.sub.22 the sodium salt of the acid monosulfosuccinic acid ester of the 
adduct of 2 moles of ethylene oxide and 1 mole of p-nonylphenol; 
A.sub.23 the ammonium salt of the acid phosphoric acid ester of the adduct 
of 2 moles of ethylene oxide and 1 mole of nonylphenol; 
A.sub.24 the acid phosphoric acid ester of the adduct of 10 moles of 
ethylene oxide and 1 mole of p-nonylphenol; 
A.sub.25 the sodium salt of the carboxymethyl ether of the adduct of 4 
moles of ethylene oxide and 1 mole of octylphenol; 
A.sub.26 the di-(.beta.-hydroxyethyl)amine salt of the acid sulfuric acid 
ester of the adduct of 3 moles of ethylene oxide and 1 mole of lauryl 
alcohol; 
A.sub.27 the sodium salt of the acid sulfuric acid ester of the adduct of 2 
moles of ethylene oxide and 1 mole of lauryl alcohol; 
A.sub.28 the sodium salt of the acid sulfuric acid ester of the adduct of 3 
moles of ethylene oxide and 1 mole of lauryl alcohol; 
A.sub.29 the acid phosphoric acid ester of the adduct of 5 moles of 
ethylene oxide and 1 mole of 2-ethyl-n-hexanol. 
COMPONENT (2): (NON-IONIC SURFACTANTS) 
B.sub.1 the reaction product of 3 moles of ethylene oxide and 1 mole of 
2-ethyl-hexanol; 
B.sub.2 the reaction product of 5 moles of ethylene oxide and 1 mole of 
2-ethyl-hexanol; 
B.sub.3 the reaction product of 3 moles of ethylene oxide and 1 mole of 
stearyl alcohol; 
B.sub.4 the reaction product of 9 moles of ethylene oxide and 1 mole of 
ALFOL.RTM. (10-14); 
B.sub.5 the reaction product of 3 moles of ethylene oxide and 1 mole of 
hexadecyl alcohol; 
B.sub.6 the reaction product of 6 moles of ethylene oxide and 1 mole of 
oleyl alcohol; 
B.sub.7 the reaction product of 5 moles of ethylene oxide and 1 mole of 
tributylphenol; 
B.sub.8 the reaction product of 8 moles of ethylene oxide and 1 mole of 
octylphenol; 
B.sub.9 the reaction product of 9 moles of ethylene oxide and 1 mole of 
nonylphenol; 
B.sub.10 the reaction product of 4 moles of ethylene oxide and 1 mole of 
nonylphenol; 
B.sub.11 the reaction product of 6 moles of ethylene oxide and 1 mole of 
nonylphenol; 
B.sub.12 the reaction product of 9.5 moles of 1,2-propylene oxide and 9.5 
moles of ethylene oxide and 1 mole of nonylphenol; 
B.sub.13 the reaction product of 9 moles of ethylene oxide and 7 moles of 
1,2-propylene oxide and 1 mole of lauryl alcohol; 
B.sub.14 the reaction product of 12 moles of ethylene oxide and 12 moles of 
propylene oxide and 1 mole of C.sub.4 -C.sub.18 fatty alcohol; 
B.sub.15 the reaction product of 80 moles of ethylene oxide and 1 mole of 
oleyl alcohol; 
B.sub.16 mixture of a reaction product of 12 moles of ethylene oxide and 12 
moles of propylene oxide and 1 mole of a C.sub.4 -C.sub.18 fatty alcohol 
and a poly)oxyethylene).sub.12 -poly(oxypropylene).sub.12 block polymer; 
B.sub.17 the reaction product of 2 moles of ethylene oxide and 1 mole of 
p-octylphenol; 
B.sub.18 the reaction product of 5 moles of ethylene oxide and 5 moles of 
propylene oxide and 1 mole of ALFOL.RTM. (12-14). 
EXAMPLE 1 
In a stirred vessel equipped with anchor agitator and heatable by means of 
a double casing, 6 kg of 2-n-ethyl-hexanol, 3 kg of surfactant A.sub.24 
and 4 kg of aluminium distearate are heated to 110.degree. C. with 
continual stirring. Then 87 g of paraffin oil are added and the mixture is 
stirred for a further hour at 110.degree. C., then allowed to cool to 
room temperature in the course of 1 hour, affording 100 kg of stable foam 
inhibitor. 
Instead of using 2-ethyl-hexanol, it is also possible to use an equal 
amount of n-amyl alcohol, n-hexanol, trimethylhexanol, n-octanol, 
n-decanol or a mixture thereof. Pine oil can also be used instead of 
paraffin oil. Instead of using A.sub.24, it is also possible to use equal 
amounts of the other reaction products designated by A or B. 
EXAMPLE 2 
A strongly foaming industrial wastewater having a surface tension of 40.5 
dyn/cm is sprayed in an activated sludge tank with a 0.01% dilution of the 
foam inhibitor of Example 1. The amount added is such that 5 ppm is used 
for the entire amount of wastewater. The foam inhibitor makes it possible 
to keep the height of the foam on the wastewater constant at about 10 to 
20 cm. Without the addition of the foam inhibitor, the foam formation is 
so great that the tank foams over after about 30 to 60 minutes. 
It is to be noted in addition that the strong foam formation is greatly 
promoted by the entrainment of air caused by a large agitator. This 
entrainment of air is necessary, however, to make possible the degradation 
of ballast materials. 
EXAMPLE 3 
In a glass beaker, 15 ppm of sodium dodecylbenzenesulfonate are added to 
1000 ccm of water of 20.degree.-25.degree. C. and then the mixture is made 
to foam with the aid of a mixer and by blowing in air (32 liters of air 
per hour). A foam height of 10 cm is obtained after 5 minutes. Then 3 ppm 
of the foam inhibitor of Example 1 are added after it has been diluted 
with water to 1:100. After 2 seconds the foam is completely eliminated. No 
fresh foam formation is observed even after further mixing and blowing in 
air for 30 minutes. If the test is carried out in the same manner, but 
without the addition of a foam inhibitor, then the foam rises to a height 
of over 15 cm. The use of a conventional foam inhibitor, e.g. one based on 
silicone oil, on the one hand requires 10 to 20 times the amount to 
eliminate the foam, and on the other hand, fresh foam formation occurs 
after a few minutes. 
EXAMPLE 4 
100 kg of cotton jersey are wetted in a concentrated bath jet dyeing 
machine in 600 liters of permutite water. To the bath are then added 36 g 
of sodium chloride, 5 kg of the dye of the formula 
##STR5## 
and 0.3 kg of the foam inhibitor of Example 1, diluted with water to 
1:100. Dyeing is carried out in the jet for 45 minutes at 40.degree. C. 
Then 0.6 kg of calcined sodium carbonate is added, followed by the 
addition of 1.2 kg of aqueous sodium hydroxide solution (36%) after 5 
minutes. A fast, level red dyeing is obtained. No hindrance to the passage 
of the goods occurs during the dyeing procedure. Dyeing in the same bath 
without foam inhibitor results in hindrance to the passage of the goods 
because of foam formation. 
EXAMPLE 5 
100 kg of cotton jersey are dyed as described in Example 4, the following 
components being added to the bath: 3 kg of the dye of the formula 
##STR6## 
12 kg of sodium chloride and 0.5 kg of the foam inhibitor of Example 1. 
The dye is added to the bath at 50.degree. C., the temperature is raised 
to 80.degree. C. in the course of 30 minutes and dyeing is carried out at 
this temperature. One half of the indicated amount of salt (NaCl) is added 
after 5 minutes and the other half after 15 minutes. Dyeing is complete 
after a further 30 minutes at 80.degree. C. and the fabric is rinsed. A 
level green dyeing is obtained. The passage of the goods is not hindered. 
EXAMPLE 6 
100 kg of cotton jersey are dyed as described in Example 4, the following 
components being added to the bath: 4 kg of the dye of the formula 
##STR7## 
0.3 kg of calcined sodium carbonate, 12 kg of sodium chloride, 1.2 kg of 
copper sulfate and 1 kg of acetic acid (80%). After wetting the fabric at 
50.degree. C., the dye and the sodium carbonate are added to the bath, 
which is then heated in the course of 30 minutes to 80.degree. C. One half 
of the sodium chloride is added after 5 minutes and the other half after 
15 minutes. Dyeing is subsequently carried out for 30 minutes at 
80.degree. C. The goods are then rinsed and a fresh bath is prepared at 
40.degree. C. with copper sulfate and acetic acid. The fabric is 
aftertreated in this bath, which is heated to 70.degree. C., for 30 
minutes. At the conclusion of the treatment the goods are rinsed cold, 
wrung out, and dried. A level, fast dyeing is obtained. The passage of the 
goods is not hindered by foam formation. 
EXAMPLE 7 
In a beam dyeing machine, 100 kg of polyester jersey are wetted in 1000 
liters of water of 70.degree. C. Then 2 kg of ammonium sulfate and 4 kg of 
the dye of the formula 
##STR8## 
are added and the pH of the bath is adjusted with formic acid to 5.5. Then 
0.8 kg of the foam inhibitor of Example 1 is added. The bath is heated to 
130.degree. C. and dyeing is carried out at this temperature for 60 
minutes. The bath is then cooled and the goods are given a reductive 
after-clear in an alkaline bath in the conventional manner, then rinsed, 
wrung out, and dried. A level, speck-free dyeing is obtained. Dyeing 
without addition of the foam inhibitor results in the entrainment of air, 
which leads to the formation of specks on the fabric. 
EXAMPLE 8 
In a single-tier hank dyeing machine, 100 kg of polyacrylonitrile high-bulk 
yarn are first shrunk in 2000 liters of water at 90.degree. C., then 
cooled to 60.degree. C. The following components are then added to the 
bath: 1.5 g of the dye of the formula 
##STR9## 
0.13 g of the dye of the formula 
##STR10## 
0.5 kg of the dye of the formula 
##STR11## 
2 kg of 80% acetic acid, 10 kg of calcined sodium sulfate and 0.3 kg of 
the foam inhibitor of Example 1. After all the components have been 
homogenised, the bath is heated to boiling temperature in the course of 45 
minutes and dyeing is carried out for 60 minutes at this temperature. The 
bath is subsequently cooled and the goods are rinsed, wrung out and dried. 
The yarn is dyed in a level and fast shade. Dyeing without addition of the 
foam inhibitor results in flecked dyeings caused by channel formation and 
entrained air. 
EXAMPLE 9 
It is unavoidable in textile printing that, when stirring printing pastes, 
air in the form of microfoam is entrained. This affects the print quality 
and, in particular, also the reproducibility of the prints. The 
entrainment of air can be completely avoided by preparing a printing paste 
as follows: 
With continuous stirring, the following components are mixed together in a 
stirred vessel which is initially charged with 406 g of boiling water: 20 
g of the dye of the formula 
##STR12## 
and then, after the dye has dissolved 
______________________________________ 
100 g of urea 
10 g of the sodium salt of m-nitrobenzenesulfonic acid 
4 g of the foam inhibitor of Example 1 
400 g of alginate thickening 
60 g of sodium carbonate 
1000 g of printing paste. 
______________________________________ 
The printing paste contains no entrained air. This can be verified e.g. as 
follows: 
1. by microscopic examination 
2. by comparing the volume directly after stirring and after leaving the 
printing paste to stand for 24 hours in a closed container 
3. by the weighing method described below. 
WEIGHING METHOD 
Exactly 25 ccm of each of the printing pastes obtained after stirring and 
after storage for 24 hours respectively are put into a balanced weighing 
pan, dried to constant weight and weighed. The amount of previously 
entrained air can be calculated from the difference in weight. 
Percentage of entrained air 
##EQU1## 
A.sub.II =weight of the sample stored for 24 hours 
A.sub.I =weight of the sample directly after stirring 
V.sub.I =entrained air in % 
In this Example, the volume of the sample obtained directly after stirring 
corresponds exactly to the volume of the sample stored for 24 hours. The 
weighing method also gave the same weight. 
If the test is carried out without the foam inhibitor, then the volume of 
the sample obtained directly after stirring is 25% greater than that of 
the sample stored for 24 hours and the weighed sample also contains 25% of 
entrained air. 
The printing paste of this Example is used in the conventional manner for 
printing cotton fabric. The colour yield is about 25% greater than that 
obtained with the same printing paste which does not contain foam 
inhibitor. In addition, the print is smoother and more level. 
Similar results are obtained by using a semi-emulsion thickening instead of 
alginate thickening. The thickenings have the following compositions: 
ALGINATE THICKENING 
______________________________________ 
70 g of sodium alginate 
5 g of sodium tetrametaphosphate and sodium hexameta- 
phosphate 
925 g of water 
1000 g of sodium alginate thickening 
______________________________________ 
SEMI-EMULSION THICKENING 
______________________________________ 
50 g of the reaction product of oleyl alcohol and 80 moles 
of ethylene oxide (12.5%, aqueous) 
150 g of water 
400 g of white spirit 
400 g of 5% aqueous sodium alginate thickening (as indicated) 
1000 g 
of semi-emulsion thickening 
______________________________________ 
EXAMPLE 10 
A printing paste for printing polyester woven fabric by the thermofix 
process is prepared as follows: 
With continuous stirring, 920 g of stock thickening and 80 g of the dye of 
the formula 
##STR13## 
are mixed together. The composition of the stock thickening is as follows: 
______________________________________ 
500 g of alginate thickening (5%) 
470 g of water 
5 g of 50% aqueous tartaric acid solution 
5 g of foam inhibitor of Example 1 
20 g of the reaction product of octadecyl alcohol and 35 moles 
of ethylene oxide (25%, aqueous) 
1000 g 
of stock thickening 
______________________________________ 
This printing paste also contains no entrained air. Without foam inhibitor, 
it contains 15% of entrained air and the colour yield is correspondingly 
15% lower when printing textile material. Furthermore, the resulting print 
is unlevel. 
EXAMPLE 11 
280 g of water are mixed with 16 g of the foam inhibitor of Example 1 to 
form an emulsion. With continuous stirring, 704 g of sodium bicarbonate 
are added and a homogeneous paste is obtained. The water is removed by 
vacuum distillation, affording 720 g of a colourless powder which can be 
used as a foam inhibiting neutraliser e.g. for acid baths or wastewaters. 
EXAMPLE 12 
(a) In a heatable stirred vessel, 370 g of water and 20 g of the foam 
inhibitor of Example 1 are homogenised. Then 610 g of potassium dihydrogen 
pyrophosphate are added and the mixture is stirred to a homogeneous 
slurry. The mixture is subsequently heated and the water is removed by 
vacuum distillation with continuous stirring. A dry, odourless powder is 
obtained in quantitative yield. 
(b) The above powder is used to prepare a foam regulating detergent which 
has the following composition: 
______________________________________ 
10% of dodecylbenzenesulfonate 
5% of tallow alcohol ethoxylate [R(OCH.sub.2 CH.sub.2).sub.25 OH] 
30% of potassium dihydrogen pyrophosphate 
10% of the preparation of (a) 
35% of sodium perborate 
0.1% of the fluorescent whitening agent of the formula 
##STR14## (110) 
1.5% of carboxymethylcellulose 
2.4% of sodium silicate 
0.2% of magnesium silicate 
0.8% of ethylenediaminetetracetic acid 
5% of sodium sulfate 
100% of detergent 
______________________________________ 
The constituents are homogenised in an appropriate mixing device. 
(c) Comparison foam test in accordance with DIN 53 902. Amount of detergent 
employed: 10 g/l. 
______________________________________ 
Test results: 
Foam formation (ml of foam) 
Detergent 1 minute 5 minutes 
______________________________________ 
detergent of (b) 10 10 
detergent of (b) without the 
addition of preparation (a) 
650 390 
detergent of (b) but with only 
5% of preparation (a) 
60 10 
______________________________________ 
Instead of potassium dihydrogen pyrophosphate, it is also possible to treat 
the sodium perborate or sodium sulfate or also the whole detergent as 
described in (a), in which case comparable results are obtained. However, 
treatment of the entire detergent is generally less economic than 
treatment of the constituents of the detergent. 
EXAMPLE 13 
A stirred vessel equipped with anchor agitator is charged with the 
individual components in the following order to produce a white disperse 
paint for interior and exterior painting. 
______________________________________ 
72.5 g of 1,2-propylene glycol 
560 g of aqueous polyacrylate solution (50%) 
6 g of foam inhibitor of Example 1 
240 g of titanium dioxide 
2 g of 25% ammonia (aqueous) 
20 g of benzyl acetate 
99.5 g of water 
1000 g of paint 
______________________________________ 
The deaeration action can be demonstrated by applying comparison coatings 
with a polyurethane paint roller to a previously painted and dried 
non-absorbent substrate. With the paint prepared in accordance with this 
Example there is markedly less foam formation than when using a paint 
prepared without foam inhibitor. This has a positive effective on the 
evenness of the coating (no pitting). 
EXAMPLE 14 
A heatable stirred vessel is charged with 1.3 kg of water and heated to 
96.degree. C. Simultaneously 0.2 kg of starch, 1 kg of kaolin, 10 g of 
foam inhibitor of Example 1 and 50 g of a methylolmelamine methyl ether 
(75% aqueous solution) are added. The mixture is stirred for 30 minutes at 
96.degree. C. and then cooled to room temperature with continuous 
stirring, affording 2555 g of a coating paste for paper coating. 
Verification by methods described in Example 9 shows that the paste 
contains only 2.5% of entrained air. A coating paste prepared without foam 
inhibitor contains 7.5% of entrained air. 
EXAMPLE 15 
(a) A foam inhibitor of the following composition is prepared in accordance 
with Example 1: 1% of magnesium stearate, 4% of aluminium stearate, 86% of 
paraffin oil, 3% of the surfactant A.sub.23, 6% of 2-ethyl-n-hexanol. 
Aqueous solutions of this foam inhibitor are neutral, e.g. 1 to 99% 
solutions (pH 6.9), and accordingly do not have a corrosive action. In 
addition, they have a very good shelf life. A solution of 80 parts of this 
foam inhibitor and 20 parts of water can be used e.g. with the same good 
results as those described in Examples 2 to 14. 
(b) By diluting the foam inhibitor of Example 1 with an organic solvent, 
e.g. 2-ethyl-n-hexanol or toluene, foam inhibitor compositions are 
obtained the addition of which can be more easily controlled for certain 
uses, e.g. in printing pastes. Such a composition contains e.g. 80 parts 
of 2-ethyl-n-hexanol and 20 parts of the foam inhibitor of Example 1. 
In Examples 2 to 15, the same amount of each of the following foam 
inhibitors can be used instead of the foam inhibitor of Example 1 with 
equally good results: 
(1) foam inhibitor consisting of 
5% of aluminium distearate 
3% of component A.sub.24 
6% of ALFOL.RTM. (6-10) 
20% of an aliphatic hydrocarbon having an average molecular weight of 170 
66% of aliphatic paraffin oil; 
(2) foam inhibitor consisting of 
4% of aluminium tristearate 
3% of sodium dodecylbenzenesulfonate 
10% of octanol (mixture of isomers) 
10% of pine oil 
73% of aliphatic paraffin oil; 
(3) foam inhibitor consisting of 
6% of aluminium tristearate 
3% of component B.sub.18 
3% of amyl alcohol 
88% of paraffin oil; 
(4) foam inhibitor consisting of 
4% of aluminium monostearate 
3% of component B.sub.11 
5% of trimethylhexanol 
5% of 2-butanol 
10% of an aliphatic hydrocarbon (molecular weight 170) 
73% of aliphatic paraffin oil; 
(5) foam inhibitor consisting of 
5% of aluminium distearate 
4% of component B.sub.10 
3% of component A.sub.24 
88% of aliphatic paraffin oil; 
(6) foam inhibitor consisting of 
3% of aluminium distearate 
3% of sodium dodecylbenzenesulfonate 
4% of ALFOL.RTM. (6-10) 
4% of stearyl alcohol 
10% of decalin 
76% of aliphatic paraffin oil; 
(7) foam inhibitor consisting of 
4% of aluminium distearate 
6% of sodium dodecylbenzenesulfonate 
10% of amyl alcohol 
80% of aliphatic paraffin oil; 
(8) foam inhibitor consisting of 
10% of aluminium tristearate 
3% of component A.sub.24 
6% of ALFOL.RTM. (6-10) 
81% of aliphatic paraffin oil; 
(9) foam inhibitor consisting of 
1% of aluminium distearate 
1% of component A.sub.24 
1% of component B.sub.9 
10% of 2-butanol 
87% of aliphatic paraffin oil; 
(10) foam inhibitor consisting of 
3% of aluminium distearate 
6% of component B.sub.8 
0.5% of ALFOL.RTM. (6-10) 
10% of dibutylphosphate 
80.5% of aliphatic paraffin oil; 
(11) foam inhibitor consisting of 
18% of foam inhibitor of Example 1 
82% of an aliphatic hydrocarbon (molecular weight 170).