Process for reinforcing nonwovens

A process for reinforcing nonwovens by the foaming process accompanied by the use of binding agents and foaming assistants is provided. The nonwovens are treated with preparations which contain at least one binding agent and as foaming agents and a reactive surfactant which is converted into the irreversibly insoluble state at elevated temperature and thereby loses its surface activity. The treated nonwovens are then subjected to a heat treatment, time-consuming washing and rinsing procedures of the treated materials are not necessary.

In the production of nonwovens a base of fibre (fleece) is manufactured 
initially. This fleece, however, does not have as yet any strength. It is 
consolidated by the application of binders, which may be done either in 
the spraypadding-pressure or foaming process. The advantage of the foaming 
process is that, on the one hand, about 50% air instead of water is 
applied, which leads to a rapid drying; and on the other hand, the 
punctiform deposit of the binder on the points of intersection of the 
fibres is promoted. 
Besides the binder, large amounts of wetting agents are used according to 
known processes for reinforcing the fleece, but the disadvantage here is 
that the latter still has to be washed out after the drying. For this 
reason, the very interesting foaming process has hitherto been relatively 
little used. 
In the known foaming process, the binder is initially diluted or emulsified 
with the requisite amount of water in a preparing vessel. The wetting 
agent is then added and the batch is very vigorously stirred in order that 
as much air as possible is brought in. As a rule, this step is not 
sufficient to bring in enough air and for this reason it is possible to 
bubble in additional air through fine jets or to add an aerating agent, 
e.g. sodium bicarbonate and acetic acid or azodicarbonamide, or so-called 
kickers, promoters or activators. 
It has now been found that by using reactive surfactants instead of the 
conventional wetting agents it is possible to dispense with the expensive 
and time-consuming washing and rinsing procedures of the treated material 
which are necessary with the known processes. 
The invention therefore provides a process for reinforcing nonwovens by 
means of the foaming process accompanied by the use of binders and foaming 
assistants, wherein these nonwovens are treated with preparations which 
contain at least one binder and, as foaming assistant, a reactive 
surfactant which is converted at elevated temperature into the 
irreversibly insoluble state and in the process loses its surface 
activity, and the thus treated nonwoven is then subjected to a heat 
treatment. 
By surfactants are meant substances which are generally soluble in water or 
also in organic solvents and reduce the surface tension of the solvent; 
they are therefore active in the form of emulsifying or dispersing agents. 
Surfactant molecules contain both hydrophobic and hydrophilic groups and 
have the property of concentrating at phase interfaces (e.g. oil-water). 
If they are shaken with the solvent, they form voluminous and stable 
foams. In dilute solution these compounds are able to markedly reduce the 
surface tension of the solvent. Under certain circumstances, preferably in 
acid reaction or at elevated temperature, reactive surfactants also have a 
wetting capacity and this gives rise to the formation of insoluble, 
resin-like condensates which no longer possess surfactant properties. 
Surfactants of this kind with a particularly high rate of reactivity are 
derived from aminoplasts, preferably urea/formaldehyde or 
melamine/formaldehyde compounds, which are substituted with both 
hydrophobic and hydrophilic groups. Such reactive surfactants which are 
used according to the invention are known, e.g. from French Pat. Nos. 
1,065,686; 1,470,103 and 1,581,989. 
The reactive surfactants which are used according to the invention are 
preferably highly surface active aminoplast precondensates. 
Particularly suitable reactive surfactants are aminoplast precondensates 
which contain methylol groups and 
a. radicals of monohydroxy compounds containing at least 4 carbon atoms and 
b.sub.1. radical of an amine containing hydroxyl groups or 
b.sub.2. radicals of a polyethylene glycol or 
b.sub.3. radicals of an alcohol which contains at least 2 hydroxyl groups 
and radicals of Me--O.sub.3 S groups which are bonded to carbon atoms, 
wherein Me represents an alkali metal atom or 
b.sub.4. radicals of aliphatic hydroxycarboxylic acids which are bonded 
with the hydroxyl group to the aminoplast precondensate and, optionally, 
with an amine which contains hydroxyl groups. 
By aminoplast precondensates, from which these reactive surfactants are 
derived, are meant addition products of formaldehyde with metholylatable 
nitrogen compounds. The following may be cited here as aminoplast formers: 
1,3,5-aminotriazines, such as N-substituted melamines, e.g. 
N-butylmelamine, N-trihalogenomethylmelamines, also ammeline, guanamines, 
e.g. benzoguanamine, acetoguanamine or also diguanamines. Also suitable 
are alkyl or aryl ureas and thioureas, alkylene ureas or diureas, e.g. 
ethylene urea, propylene urea, acetylene diurea or 
4,5-dihydroxyimidazolid-2-one and derivatives thereof, e.g. 
4,5-dihydroxyimidazolid-2-one which is substituted in 4-position at the 
hydroxyl group by the radical --CH.sub.2 CH.sub.2 CO--NH--CH.sub.2 --OH. 
Preferably the methylol compounds of urea and melamine are used. In 
general, products which are as highly methylolated as possible yield 
particularly valuable products. Suitable starting products are both the 
preponderantly monomolecular and higher precondensed compounds. The 
aminoplast precondensates which are used as starting products for the 
manufacture of the reactive surfactants may also be ethers of alkanols 
containing from 1 to 3 carbon atoms, particularly methyl ethers. 
Accordingly, the use of highly surface active, etherified methylalmelamines 
or methylol ureas as reactive surfactants is preferred. 
The great number of reactive surfactants which are suitable for the process 
according to the invention include non-ionic, anionic and cationic 
surfactants. 
Particularly suitable non-ionic reactive surfactants are e.g. hardenable 
aminoplast precondensates which contain etherified methylol groups and 
whose methylol groups are etherified partly with hydroxy compounds of the 
formula 
EQU HO -- (CH.sub.2 -- CH.sub.2 -- O --).sub.n --H, (12) 
wherein n represents an integer from 2 to 115 partly with a monoalcohol 
containing from 4 to 18 carbon atoms. 
Compounds of the formula (a) are preferably polyethylene glycols. The 
monoalcohols are, e.g. amyl alcohols, hexanol-(1), 2-ethylbutanol-(1), 
dodecanol, benzyl alcohol, stearyl alcohol or, primarily, n-butanol. 
As reactive surfactants, particular interest attaches to cutable ethers of 
methylol ureas or methylol melamines, whose methylol groups are etherified 
partly with a polyethylene glycol with an average molecular weight of 1000 
to 5000 and partly with an alkanol containing from 4 to 7 carbon atoms. 
Reaction surfactants of this kind are described in French Pat. No. 
1,381,811. 
Non-ionic reactive surfactants, which are likewise suitable, are low 
molecular, preferably monomer reactive surfactants from carbamides. They 
are obtained by etherifying the monomethylol compound of a carbamide with 
a hydrophobic or hydrophilic hydroxy compound, then introducing a second 
methylol group by reaction with formaldehyde or a formaldehyde donor, and 
subsequently etherifying this second methylol group with a hydrophobic or 
hydrophilic hydroxyl compound in such a way that, at the conclusion, the 
molecule of the reactive surfactant contains at least one hydrophobic and 
one hydrophilic group. 
Suitable low molecular reactive surfactants are derived from the 
monomethylol compounds of acyclic ureas, in particular from monomethylol 
ureas. 
These reactive surfactants are obtained, for example, by reacting a 
compound of the formula 
EQU H.sub.2 N -- CO -- NH -- CH.sub.2 -- O -- R, (16) 
wherein R represents alkyl or alkenyl containing from 6 to 22 carbon atoms, 
alkylcyclohexyl or alkylphenyl containing from 2 to 12, preferably 6 to 10 
carbon atoms in the alkyl radical, or cycloalkyl containing from 8 to 12 
ring carbon atoms, with formaldehyde or a formaldehyde donor, and 
subsequently etherifying the reaction product with a polyalkylene glycol 
having an average molecular weight of at most 2000, preferably between 106 
and about 1200. 
Preferably, R is alkyl or alkenyl containing from 6 to 22, in particular 
from 10 to 18 carbon atoms. 
As reactive anionic surfactants there are used, for example, aminoplast 
precondensates which contain etherified methylol groups and whose methylol 
groups are reacted partly with monohydroxy compounds containing at least 4 
carbon atoms, and partly with alcohols containing at least two hydroxyl 
groups, and which contain Me--O.sub.3 S groups, wherein Me represents an 
alkali metal atom. Me may also thus be a sodium, potassium or lithium 
atom. Particularly suitable surfactants of this kind are chiefly 
etherified methylol ureas or methylol melamines whose methylol groups are 
etherified partly with alkanols which contain from 4 to 18 carbon atoms, 
and partly with alcohols of the formula H--(O--CH.sub.2 --CH.sub.2).sub.m 
-OH, wherein m represents an integer of at most 25, and which contain 
Me--O.sub.3 S groups which are bonded to carbon atoms, wherein Me 
represents an alkali metal atom. Such anionic reactive surfactants are 
known from French Pat. No. 1,470,103. 
Other interesting anionic reactive surfactants are, for example, aminoplast 
precondensates which contain etherified methylol groups and whose methylol 
groups are etherified partly with monohydroxy compounds which contain from 
4 to 22 carbon atoms, partly with aliphatic hydroxycarboxylic acids which 
contain from 2 to 4 carbon atoms, and, optionally, partly with an 
alkanolamine which contains from 2 to 6 carbon atoms. Particularly 
preferred among these reactive surfactants are etherified methylol ureas 
or methylol melamine whose methylol groups are etherified partly with 
alkanols which contain from 4 l to 22 carbon atoms, partly with saturated 
hydroxylcarboxylic acids which contain from 2 to 5 carbon atoms, and, 
optionally, partly with ethanol-, diethanol- or triethanolamine. Anionic 
reactive surfactants of this kind are described in French Pat. No. 
1,065,686. 
The anionic and cationic reactive surfactants are preferred to the 
non-ionic surfactants. 
The process according to the invention is carried out preferably in aqueous 
medium; but it is also possible to carry it out in organic solvents, 
preferably solvents which are miscible with water, such as alcohols, 
glycols etc., or in mixtures of water and solvent. 
In the process according to the invention, it is possible to initiate and 
carry through the conversion of the reactive surfactants into the 
irreversibly insoluble state by various means, among which particular 
mention may be made of raising the temperature, adjusting certain pH 
values, adding substances which react with the surfactants or aminoplast 
precondensates accompanied by the formation of high molecular products, 
and, above all, adding curing catalysts which display acid reaction. 
If the reinforcing is carried out in aqueous medium, the pH of the 
preparation is advantageously 2 l to 4.5, preferably 2.8 to 3.5. 
Principally, aliphatic low molecular carboxylic acids, such as formic, 
acetic or citric acid, or inorganic acids such as hydrochloric or 
phosphoric acid, also acid or hydrolysable salt such as aluminium 
sulphate, titanium oxychloride, megnesium chloride, ammonium salts of 
strong acids, such as ammonium chloride, nitrate, sulphate or dihydrogen 
phosphate, are suitable for adjusting the pH. Also suitable are oxidants 
which can oxidise formaldehyde to formic acid, such as hydrogen peroxide. 
However, the use of volatile acids has proved most appropriate of all. 
As examples of suitable binders there may be mentioned: acrylic resins, 
butadiene/styrene, butadiene/acrylonitrile/styrene, 
butadiene/acrylonitrile, melamine resins, epoxide resins, polyester 
resins, polyurethane, phenol resins, polyvinyl acetate, polyvinyl alcohol, 
polyvinyl chloride, natural latex, and, in particular, epoxide reaction 
products. 
As binding agents, particular interest attaches to reaction products of 
epoxides and fatty amines with basic polyamides or dicarboxylic acids. 
Suitable reaction products of epoxides, fatty amines and basic polyamines 
are obtained by reacting, in the presence of an organic solvent at 
temperatures of up to 95.degree. C, a reaction product of at least 
a. an epoxide which contains at least 2 epoxide groups per molecule, and 
b. at least one higher molecular fatty amine, 
wherein the equivalent ratio of epoxide groups to amino groups is 1:0.1 to 
1:0.85, with a basic polyamide which is obtained by condensing 
c. polymeric, unsaturated fatty acids and 
c'. polyalkylene polyamines, 
wherein the equivalent ratio of epoxide groups of the reaction product of 
components (a) and (b) to amino groups of the basic polyamide of the 
components (c) and (c') is 1:1 to 1:6, preferably 1:1 to 1:5, and, by 
addition of acid at the latest upon completion of the reaction, ensuring 
that a sample of the reaction mixture present in the organic medium has a 
pH of 2 to 8 after addition of water. 
The amine equivalent is to be understood as indicating the amount of 
polyamide in grams which is equivalent to one mole of monoamine. 
Also suitable are reaction products of epoxides, fatty amines and 
dicarboxylic acids, wherein at least 
a. an epoxide which contains at least 2 l epoxide groups per molecule, 
b. a higher molecular fatty amine and 
c.sub.1. an aliphatic, saturated dicarboxylic acid containing at least 7 
carbon atoms and, optionally, 
c.sub.2. an anhydride of an aromatic dicarboxylic acid containing at least 
8 carbon atoms or of an aliphatic di- or monocarboxylic acid containing at 
least 4 carbon atoms, 
and optionally one or more of the following components: 
d. an aminoplast precondensate which contains an alkyl ether group, 
e. an aliphatic diol containing from 2 to 22 carbon atoms, and 
f. a polyfunctional preferably difunctional, organic compound which 
possesses as functional groups or atoms, mobile halogen, vinyl or ester 
groups, or at most one acid, nitrile, hydroxyl or epoxide group together 
with at least one other functional group or an atom of the indicated kind, 
are reactesd with one another to give a reaction product which contains 
free carboxyl groups, and then, optionally at elevated temperature, 
treating said reaction product optionally with 
g. ammonia or a water soluble, organic base, in particular aliphatic 
tertiary monoamines or polyamines, 
and, optionally by addition of further ammonia or further water soluble 
organic bases, ensuring that a sample of the reaction mixture present in 
the organic medium has a pH of 7.5 to 12 after dilution with water. 
The epoxides of the component (a) are derived preferably from polyvalent 
phenols or polyphenols, such as resorcinol, phenol/formaldehyde 
condensation products of the type of the resols or novolaks. Preferred 
starting compounds for the manufacture of the epoxides are in particular 
bisphenols, such as bis-(4-hydroxyphenyl)-methane, and, above all, 
2,2-bis-(4'-hydroxyphenyl)-propane. 
Particular mention may be made here of epoxides of 
2,2-bis(4'-hydroxyphenyl)-propane which have an epoxide content of 1.8 to 
5.8 epoxy group equivalents/kg, but preferably have at least 5 epoxy group 
equivalents/kg and correspond to the formula 
##STR1## 
wherein z represents a mean number having a value from 0 to 0.65. Such 
epoxides are obtained by reacting epichlorohydrin with 
2,2-bis-(4'-hydroxyphenyl)-propane. 
Mono-fatty amines containing from 12 to 22 carbon atoms have above all 
proved to be very suitable components (b). As a rule, these are amines of 
the formula 
EQU H.sub.3 C -- (CH.sub.2).sub.x -- NH.sub.2 , (3) 
wherein x represents an integer having a value from 11 to 21, preferably 
from 17 to 21. The amines are therefore, for example, laurylamine, 
palmitylamine, stearylamine, arachidylamine or behenylamine. Mixtures of 
such amines obtainable in the form of commercial products are also 
possible. 
The ratio of epoxides (a) to amines (b) is so chosen that an excess of 
epoxides is used, so that more than one epoxide group is provided for 
every amino group. 
According to the invention, the amount of the components (a) and (b) is to 
be so determined that there is an equivalent ratio of 1 epoxide group to 
0.1 to 0.5 amino groups, i.e. the amount of epoxide which corresponds to 
one epoxide group equivalent is reacted with the amount of amine which 
corresponds to an amino group equivalent of 0.1 to 0.5. The equivalent 
ratio of epoxide groups to amino groups is preferably 1:0 to 1:0.5, or 
especially 1:0.25 to 1:0.5. 
The reaction of component (a) with component (b) takes place advantageously 
at 80.degree. to 120.degree. C, preferably 100.degree. C. 
The polymer unsaturated fatty acids which are used as component (c) for the 
manufacture of the basic polyamides are preferably aliphatic, 
ethylenically unsaturated dimeric to trimeric fatty acids. The reaction 
products are manufactured preferably from the polyalkylene polyamines (c') 
and aliphatic unsaturated dimeric to trimeric fatty acids (c), which are 
derived from monocarboxylic acids containing from 16 to 22 carbon atoms. 
These monocarboxylic acids are fatty acids with at least one, preferably 2 
to 5, ethylenically unsaturated bonds. Representatives of this class of 
acids are e.g. oleic acid, hiragonic acid, eleostearic acid, licanic acid, 
arachidonic acid, clupanodonic acid and especially linoleic and lonoleic 
acid. These fatty acids may be obtained from natural oils, in which they 
occur as glycerides. 
The dimeric to trimeric fatty acids (c) are obtained in known manner by 
dimerisation of monocarboxylic acids of the indicated kind. The so-called 
dimeric fatty acids always contain some trimeric acids and a small amount 
of monomeric acids. 
Particularly suitable for use as component (c) are the dimerised to 
trimerised linoleic or linolenic acids. The commercial products of these 
acids contain as a rule 75 to 95 percent by weight of dimeric acid, 4 to 
25 percent by weight of trimeric acid and a trace to 3% of monomeric acid. 
The molar ratio of dimeric to trimeric acid is accordingly about 5:1 to 
36:1. 
Suitable components (c') are chiefly polyamines, such as 
diethylenetriamine, triethylenetetramine or tetraethylenepentamine, i.e. 
amines of the formula 
EQU H.sub.2 N -- (CH.sub.2 -CH.sub.2 -NH).sub.n -- CH.sub.2 -- CH.sub.2 -- 
NH.sub.2 , (4) 
wherein n is 1, 2 or 3. 
In the case of amine mixtures, it is also possible to adopt a non-integral 
mean number, e.g. between 1 and 2. 
As a component of particular interest there is used a basic polyamide of 
dimerised to trimerised linoleic or linolenic acid and a polyamine of the 
formula (4). 
Suitable organic solvents in the presence of which the reaction of the 
individual components takes place are primarily water soluble organic 
solvents, and advantageously those which are miscible with water. As 
examples there may be cited: dioxan, isopropanol, ethanol and methanol, 
ethylene glycol-n-butyl-ether (=n-butylglycol), diethylene glycol 
monobutyl ether. 
It is also possible, moreover, to carry out the reaction in the presence of 
water insoluble organic solvents, e.g. in petroleum hydrocarbons, such as 
petroleum or petroleum ether, benzene, halogenated benzenes or benzenes 
which are substituted by lower alkyl groups, such as toluene, xylene, 
chlorobenzene; alicyclic compounds, such as tetralin or cyclohexane; 
halogenated hydrocarbons, such as methylene chloride, methylene bromide, 
chloroform, carbon tetrachloride, ethylene chloride, ethylene bromide, 
s-tetrachloroethane, and above all, trichloroethylene or 
perchloroethylene. 
The reaction products of epoxide-fatty amine and polyamide may optionally 
also be obtained with the conjoint use of a third component (w), namely a 
further mono- or bifunctional compound which is different from the first. 
These mono- or bifunctional compounds contain as functional groups or 
atoms mobile halogen atoms, vinyl, acid, ester, acid anhydride, isocyanate 
or epoxide groups. Of the monofunctional compound (w), advantageously 
about 0.25 mole is used for one amino group equivalent of the polyamide; 
but this content can also be raised to e.g. 0.5 mole per amino group 
equivalent. Of bifunctional compounds, preferably 0.05 to 0.5 mole is used 
for one amino group equivalent of the polyamide. 
These components (w) are preferably aralkyl or alkyl halides, nitriles, 
amides or methylolamides of acids of the acrylic acid series, aliphatic or 
aromatic carboxylic acids, their esters or anhydrides, and aliphatic or 
aromatic isocyanates, epoxides or epihalogenohydrins. 
As monofunctional components (w) there are advantageously used alkyl 
halides such as ethyl bromide or butyl chloride, aralkyl halides such as 
benzyl chloride; nitriles, amides or methylolamides of acrylic or 
methacrylic acid, e.g. acrylonitrile, acrylic amide or N-methylolacrylic 
amide. Instead of methylolacrylic amide, it is also possible to use a 
mixture consisting of acrylic amide and formaldehyde or a formaldehyde 
donor, with the N-methylolacrylic amide being formed in situ. 
Alkanecarboxylic acids of up to 18 carbon atoms, such as coconut fatty 
acid or stearic acid, or esters thereof with alkanols, which contain at 
most 5 carbon atoms, e.g. methanol, ethanol or n-butanol, or their 
anhydrides such as acetic anhydride, aromatic isocyanates, such as 
phenylisocyanate, or aliphatic or aromatic epoxides, such as propylene 
oxide, butylene oxide, dodecene oxide or styrene oxide, may also be used. 
Particularly suitable compounds (w) are alkylene oxides of at most 12 
carbon atoms, alkanecarboxylic acids of at most 18 carbon atoms, 
monocyclic aralkyl halides or acrylonitrile. 
The sequence in which the reaction of the polyamides with the 
monofunctional compounds and epoxide-fatty amide reaction products takes 
place is of secondary importance. The polyamides can first be reacted with 
a monofunctional compound and then with the epoxide-fatty amine reaction 
product, or vice versa. If there are no great differences in the 
reactivity, it is also possible in many cases to carry out the reaction 
simultaneously. 
The reaction to give the reaction product of components (a) and (b) with 
(c) and (c') is carried out in such a way that polyaddition products which 
are soluble or dispersible in water are formed by adjusting the pH--at the 
latest upon completion of the reaction--to 2 to 8, preferably 2 to 7, but 
especially 5 to 6. This pH value is adjusted by using, for example, 
inorganic or organic acids, advantageously readily volatile organic acids, 
such as formic or acetic acid. Immediately, or shortly after, the basic 
polyamide has begun to combine with the epoxide, it is advisable to add a 
certain amount of acid, and also to add more acid during the further 
course of the reaction continuously or in small amounts. Furthermore, the 
process is carried out preferably at temperatures of up to 80.degree. C, 
consequently, for example, from 25.degree. to 80.degree. C, especially 
40.degree. to 70.degree. C. The resulting solutions or dispersions--in 
most instances faintly opalescent to turbid solutions--which have been 
adjusted with acid to the indicated pH value and appropriately adjusted 
with an organic solvent or preferably with water to a content of 10 to 
40%, especially 10 to 30% of reaction product, are distinguished by high 
stability. 
Products with advantageous properties are also obtained if, after the 
addition of the acid and the water, the preparations is then stored at 
room temperature, e.g. for 4 hours at 70.degree. C, or a longer period of 
time at lower temperature. 
Alkylenedicarboxylic acids containing from 7 to 14 carbon atoms have all 
proved advantageous components (c.sub.1). As a rule, these are 
dicarboxylic acids of the formula 
EQU HOOC -- (CH.sub.2).sub.y -- COOH (5) 
wherein y represents an integer having a value of 5 to 12, preferably 6 to 
10. 
Accordingly, possible components (c.sub.1) are, for example, dicarboxylic 
acids, such as pimelic, suberic, azelaic or sebacic acid, 
nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic 
acid or dodecanedicarboxylic acid. 
The components (c.sub.1) can be employed alone or together with the 
component (c.sub.2). As the components (c.sub.2), an anhydride of a 
monocyclic or bicyclic aromatic dicarboxylic acid with 8 to 12 carbon 
atoms or of an aliphatic dicarboxylic acid with 4 to 10 carbon atoms is 
preferably used. Anhydrides of a monocyclic aromatic dicarboxylic acid 
containing from 8 to 10 carbon atoms have proved particularly 
advantageous. Optionally methyl-substituted phthalic anhydride is of 
particular interest. 
Accordingly, suitable components (c.sub.2) are anhydrides, for example, 
maleic anhydride or phthalic anhydride. 
Where the component (d) is used conjointly for the manufacture of the 
reaction products, its proportion, relative to the total of the components 
(a), (b), (c.sub.1) and (d), is 10 to 90, especially 4 to 70, percent by 
weight. 
The aminoplast condensates used as component (d) are completely etherified, 
or especially partially etherified, methylol compounds of 
nitrogen-containing aminoplast formers, such as urea, urea derivatives, 
for example ethyleneurea, propyleneurea or glyoxalmonourein. 
Preferably, however, etherified methylolaminotriazines are employed, for 
example, alkyl ethers of highly methylolated melamine, whose alkyl 
radicals contain from 1 to 4 carbon atoms. Possible alkyl radicals 
include, methyl, ethyl, n-propyl, isopropyl, n-butyl and n-hexyl radicals. 
In addition to such alkyl radicals, yet further radicals, for example 
polyglycol radicals, may also be present in the molecule. Furthermore, 
n-butyl ethers of a highly methylolated melamine, which contain 2 to 3 
n-butyl groups in the molecule, are preferred. By highly methylolated 
melamines are meant here those with an average of at least 5, 
appropriately about 5.5, methylol groups. 
If component (e) is conjointly used for the manufacture of the reaction 
products, these diols are preferably aliphatic diols containing from 2 to 
6 carbon atoms, and whose carbon chains are optionally interrupted by 
oxygen atoms. Alkylenediols with 2 to 6 carbon atoms or diethylene glycol 
or triethylene glycol are of particular interest. Of the alkylenediols 
containing from 2 to 6 carbon atoms which are particularly advantageously 
used, ethylene glycol, 1,4-butanediol or above all 1,6-hexanediol may, for 
example, be mentioned. 
The optional, polyfunctional, preferably difunctional, component (f) 
preferably contains, as functional groups or atoms, alkyl-bonded halogen 
atoms, vinyl or carboxylic acid ester groups, or at most one epoxide, 
carboxylic acid or hydroxyl group together with another functional group 
or another atom of the indicated type. In particular, these compounds are 
difunctional organic compounds which contain as functional groups or 
atoms, alkyl-bonded chlorine or bromine atoms, vinyl or carboxylic acid 
alkyl ester groups or at most one epoxide or carboxylic acid group 
together with another functional group or another atom of the indicated 
type. 
Particularly suitable difunctional organic compounds are aliphatic. These 
are, for example, epihalogenohydrins, such as epibromohydrin or above all 
epichlorohydrin. 
Other possible difunctional compounds are, for example, 
glycerine-dichlorohydrin, acrylic acid, methylolacrylamide and 
acrylonitrile. 
The component (g) is advantageously an aliphatic tertiary monoamine, 
ammonia or an amine containing at least two amino groups and exclusively 
basic nitrogen atoms, wherein the amino groups possess at least one 
nitrogen-bonded hydrogen atom. 
Preferred tertiary amines are trialkylamines containing from 3 to 12 carbon 
atoms, for example triethylamine, tri-n-propylamine or tri-n-butylamine. 
The diamines to be used as component (g) may be aliphatic or cycloaliphatic 
and preferably possess at least one primary amino group and a second amino 
group, wherein at least one hydrogen atom is bonded to nitrogen. 
Furthermore, just ammonia can also be used as component (g). However, 
diprimary aliphatic or cycloaliphatic amines are preferentially used as 
the component (g). 
Suitable aliphatic amines are here above all polyamines, such as 
diethylenetriamine, triethylenetetramine or tetraethylenepentamine, that 
is to say amines of the formula 
EQU H.sub.2 N--(CH.sub.2 --CH.sub.2 --NH).sub.n --CH.sub.2 --CH.sub.2 
--NH.sub.2 ( 6) 
wherein n is 1, 2 or 3. 
In the case of amine mixtures, a non-integral average value can also be 
assumed, for example between 1 and 2. 
Suitable cycloaliphtic amines are above all diprimary, cycloaliphatic 
diamines, which desides the two amine nitrogen atoms contain only carbon 
and hydrogen, and which possess a saturated 5-membered to 6-membered 
carbocyclic ring, a H.sub.2 N-- group bonded to a ring carbon atom and a 
H.sub.2 N--CH.sub.2 -- group bonded to another ring carbon atom. 
As examples of such amines, 3,5,5-trimethyl-1-amino-b 
3-aminomethyl-cyclohexane or 1-amino-2-amino-methyl-cyclopentane may be 
mentioned. 
The manufacture of the reaction products can be carried out according to 
methods which are known, in the art, wherein the components can be reacted 
with one another in varying sequence. Appropriately, components (a) and 
(b), or (a), (b) and (c.sub.1) are first reacted with one another. The 
reaction of the component (c.sub.1) with the already reacted components 
(a) and (b) can also take place simultaneously with component (e). The 
reaction with the components (d) and/or (f) is as a rule only carried out 
at the end, that is to say before the reaction with the component (g). 
On the one hand, it is thus possible initially to react the components (a), 
(b) and (c.sub.1) and optionally (c.sub.2), simultaneously with one 
another, and subsequently optionally to react the product with the 
components (d), (e) and (f). In this process variant the components (a), 
(b) and (c.sub.1) are appropriately reacted with one another at 
temperatures of 80.degree. to 120.degree. C, preferably 100.degree. C, 
with the proportions being advantageously so chosen that for an epoxide 
group equivalent of 1, the equivalent ratio of hydrogen bonded to amine 
nitrogen to carboxylic acid groups is 0.1:1 to 1:0.55. 
On the other hand, it is also possible first to react only the components 
(a) and (b) with one another and subsequently to react the products with 
the component (c.sub.1) and, optionally, in third stage with the 
components (d), (e) or (f). The manufacture of the reaction products from 
(a) and (b) is, according to this second variant, also appropriately 
carried out at temperatures of 80.degree. to 120.degree. C, preferably at 
about 100.degree. C. The reaction in the second stage, with the component 
(c.sub.1), appropriately takes place at 80.degree. to 110.degree. C, 
preferably at about 100.degree. C, with the proportions being 
advantageously so chosen that for an epoxide group equivalent of 1, the 
equivalent ratio of hydrogen bonded to amine nitrogen to carboxylic acid 
groups is 0.1:1 to 1:0.55. 
The ratio of epoxide (a) to fatty amine (b) and acid (c.sub.1) or anhydride 
(c.sub.2) is so chosen, according to the invention, that a less than 
equivalent amount of epoxide is used, so that there is fewer than one 
epoxide group per sum of the amino and acid groups. The raction products 
thus contain carboxyl end groups. 
The reaction product containing carboxylic acid groups as a rule has an 
acid number of 5 to 80, preferably 35 to 60. 
The reaction with the component (d) is as a rule carried out at 
temperatures of 60.degree. to 105.degree. C, preferably at about 
100.degree. C. In most cases, this reaction takes place in the presence of 
small amounts of organic solvent, for example, n-butanol. 
The reaction with the component (e) takes place, as already mentioned, 
simultaneously with that of component (c.sub.1). 
The reaction with the component (f) takes place before the treatment with 
component (g) at temperatures of about 60.degree. to 120.degree. C. 
The treatment with the component (g) can take place at room temperature of 
elevated temperature, so that either merely a neutralisation, with salt 
formation, occurs, or, provided tertiary amines are not used, a true 
reaction takes place. In both cases, however, polyaddition products which 
are soluble or dispersible in water are produced by ensuring that, upon 
completion of the reaction at the latest, if necessary by adding a base, a 
sample of the reaction mixture diluted with water has a pH of 7.5 to 12, 
preferably of 8 to 10. For this purpose inorganic or organic bases, 
advantageously readily volatile bases such as ammonia, are for example 
used. Furthermore it is advantageous to use temperatures of at most 
80.degree. C. For example 60.degree. to 70.degree. C, in a reaction with 
(g). When using ammonia or a tertiary amine as the component (g), the 
reaction is appropriately carried out at room temperature. The resulting 
solutions or dispersions which are optionally, treated with a base, and 
advantageously adjusted with an organic solvent or with water to a content 
of 10 to 40% of reaction product, are distinguished by high stability. 
Suitable organic solvents in the presence of which the reaction products 
are manufactured are, above all, water-soluble organic solvents, and in 
particular advantageously those which are miscible with water to an 
unlimited extent. Dioxan, isopropanol, ethanol and methanol, ethylene 
glycol n-butyl ether (=n-butylglycol) and diethylene glycol monobutyl 
ether may be mentioned as examples. 
It is, moreover, also possible to carry out the reaction in the presence of 
water-insoluble organic solvents, for example in hydrocarbons, such as 
petroleum ether, benzene toluene and xylene, or in halogenated 
hydrocarbons, such as methylene chloride, methylene bromide, chloroform, 
carbon tetrachloride, ethylene chloride, ethylene bromide, 
s-tetrachloroethane and above all trichloroethylene. 
In adjusting the pH of the samples of a reaction product to 2 to 8 or 7.5 
to 12, the sample is diluted with water to the desired concentrations, 
e.g. from 10 to 40%. The desired pH is then adjusted within the indicated 
limits by addition of acid. 
So-called acrylic resins, e.g. copolymers of acrylic isobutyl ester, 
acrylonitrile and acrylic acid, are also very suitable binders. 
The binders are appropriately used in the form of aqueous solutions or 
dispersions which, in addition to the reactive surfactant, may contain yet 
further additives, such as an emulsifying agent or an organic solvent. 
The heat treatment which follows on the treatment of the nonwovens with the 
binder/foaming assistant preparation, consists preferably of a drying and 
subsequent heating to 60.degree. to 190.degree. C, especially 100.degree. 
to 150.degree. C. Drying is carried out preferably at room temperature. 
Since many binding agents have a relatively low viscosity, the foam which 
forms can very rapidly decompose again. It is therefore expedient to 
ensure a high viscosity, which is best done by adding thickeners. The 
thickeners used are preferably acid-resistant and should effect a 
considerable increase in the viscosity with as little substance as 
possible. Cellulose ethers, carubic acid derivatives, polyacrylic esters 
and, above all, ethyl cellulose, have proved to be very suitable products. 
The amounts used depend on the one hand on the viscosity of the binder 
emulsion, and on the other on the thickening action of the product; as a 
rule 2 to 30 g/l, preferably 3 to 20 g/l. suffice. 
The reactive surfactants are used appropriately in a concentration of 2 to 
100 g/l, preferably 5 to 50 g/l, of the treatment bath; whereas the 
binders are appropriately used in concentrations of 100 to 700 g/l, 
preferably 170 to 330 g/l, but particularly about 250 g/l. 
The preparations which are used according to the invention for setting 
nonwovens may contain yet further additives in order to attain at the same 
time other finishing effects, e.g. an antimicrobial effect. Aminoplast 
precondensates, for example, have proved suitable for this purpose, and it 
is possible to attain particularly good effects by mixing aminoplast 
precondensates which contain alkyl ether groups with the condensation 
products used as binding agents from the components a, b, c and c' and, 
above all, a, b, c.sub.1 and, optionally, c.sub.2, and in so doing the 
amount of these aminoplast precondensates may be about 40 percent by 
weight or more, relative to the whole mixture, and this mixture is used 
according to the invention together with the reactive surfactants. 
The nonwovens are impregnated with the binder preparations which contain 
the reactive surfactants by methods which are known in the art, preferably 
by the padding process. The increase in weight of the thus treated fibre 
fleece is as a rule 30 to 80%, preferably 40 to 70%. 
Practically all conventional textile fibres, and in addition glass fibres, 
are suitable for the manufacture of the basic fibre fleece. However, 
nonwovens which contain fibres of polyamide, viscose staple, polyester, 
polyacrylonitrile or polypropylene, are preferred. Any described blends of 
the cited fibres may be used as well.

EXAMPLES 
Manufacturing Instructions for Reactive Surfactants 
I. 126 Parts of melamine, with addition of 18 parts of 25% ammonia, are 
dissolved at 60.degree. C in 590 parts of 36.5% aqueous formaldehyde 
containing methanol. The solution is heated to 80.degree. C and 132 parts 
of a mixture of methanol and water are distilled off in vacuo over the 
course of about 20 minutes. The residue is then treated with 490 parts of 
n-butanol and distillation in vacuo is continued, in the course of which 
the water/n-butanol mixture which passes over is isolated. The n-butanol 
runs back again into the reaction vessel, while 118 parts of aqueous layer 
separate out. A solution of 3 parts of 85% formic acid in 5 parts of 
n-butanol is added and altogether 452 parts of n-butanol are distilled off 
and carry over the remainder of the water, to give 532 parts of a viscous, 
colourless resin, which is miscible with benzene in any desired ratio and 
is hereinafter designated as coating resin A. 
Coating resin A (445 parts) is treated with 50 parts of a polyethylene 
glycol having an average molecular weight of 4000. After heating to 
95.degree.-100.degree. C and adding 3 parts of glacial acetic acid heating 
is continued until a sample of the reaction product dissolves to a clear 
solution in water. The triethanolamine (70 parts) is added, the mixture 
stirred and heated for 2 hours to 120.degree. C. The reaction mixture is 
cooled and a colourless, wax-like substance is obtained which is readily 
miscible with water at 60.degree. C. A 50%, faintly turbid surfactant 
solution with a pH of 8.1 to 8.2 is obtained by adding the same amount of 
water and a small amount of acetic acid. In 5% aqueous solution, this 
reactive surfactant reduces the surface tension of the water from 72.75 
dyn/cm to 41.0 dyn/cm (= reactive surfactant I). 
II. 126 Parts of melamine and 600 parts of 30% formaldehyde are heated for 
about 1/2 hour at 90.degree. C and pH 8.2 until the initially clear 
solution starts to become turbid. Then 1000 parts of n-butanol and 8 parts 
of glacial acetic acid are added and the mixture is heated under reflux 
until the resin solution has again become clear. Using a descending 
cooler, butanol and water are distilled off in vacuo until the latter has 
completely passed over and the distillate runs clear when cold. Then 
polyethylene glycol (800 parts) having a molecular weight of 4000 is added 
and heating is continued in vacuo to 90.degree. C, in the course of which 
further amounts of butanol and water are distilled off. Heating is 
continued until a sample of the reaction product dissolves to give an 
almost clear solution in water. Then triethanolamine (18 parts) is added 
and the mixture is stirred and cooled. A colourless, wax-like substance 
which is readily soluble in water is obtained (= reactive surfactant II). 
III. 206 Parts of 36.5% aqueous formaldehyde, 170 parts of n-butanol and 60 
parts of urea are treated with 8 parts of 25% ammonia and the reaction 
mixture is heated in an agitator vessel fitted with a descending cooler 
for 2 hours to 96.degree. C, in the course of which 32 parts of an 
n-butanol/water mixture are distilled off. The residue is cooled to about 
50.degree. C and a solution of 1 part of 85% phosphoric acid in 20 parts 
of n-butanol is added. The reaction mixture is heated in vacuo to 
80.degree. C, in the course of which water and n-butanol are distilled 
off. The water is isolated from the distillate, while the n-butanol runs 
back again into the reaction vessel. After 4 hours the product is 
practically anhydrous and miscible with benzene in any desired ratio. It 
is then neutralised by adding 5 parts of triethanolamine and concentrated 
in vacuo to 212 parts, to give the product which is hereinafter designated 
as coating resin B. 
150 Parts of coating resin B are treated in an agitator flask with 100 
parts of glycolic butyl ester and 3 parts of glacial acetic acid and the 
mixture is heated in vacuo to 80.degree.-90.degree. C, in the course of 
which 63 parts of n-butanol are distilled off in 11/2 hours. Then a 
solution of 40 parts of solid potassium hydroxide in 200 parts of ethyl 
alcohol is added and the mixture is heated to the boil, in the process of 
which the initially clear mixture becomes turbid. It is evaporated to 
dryness in vacuo to give about 185 parts of a colourless, solid substance 
which dissolves in water to a clear vigorously foaming solution. The 
aqueous solution has a pH of 8.0 and a substantial emulsifying capacity. 
If it is acidifed by the addition of acetic acid, a white resin 
precipitate immediately falls out which is no longer soluble in excess 
alkali. A similar product is obtained by using an equivalent amount of 
ethyl actate instead of glycolic butyl ester (= reactive surfactant III). 
IV. 206 Parts of 36.5% aqueous formaldehyde are added to 230 parts of 25% 
ammonia. Upon heating the mixture to 40.degree. C, 60 parts of urea are 
added and the whole mixture is heated to the boil and 37 parts of a 
mixture of methanol and water are distilled off. The batch is treated with 
a mixture of 1 part of 85% phosphoric acid in 20 parts of n-butanol, 
stirred for 15 minutes and a mixture of water and n-butanol is distilled 
off in vacuo, in the course of which the former is isolated and the latter 
is allowed to run back into the reaction vessel. After 134 parts of water 
with a butanol content have been removed, 87 parts of ethylene glycol and 
30 parts of lauryl alcohol are added and 218 parts of n-butanol are 
distilled off in vacuo, carrying the remainder of the water with them. 
Condensation is carried out for a further hour at 95.degree.-100.degree. 
C, then 15 parts of anhydrous sodium bisulphite are added. The reaction 
product has become slightly water soluble after 30 minutes at 100.degree. 
C. It is stirred with 8 parts of triethanolamine and the mixture cooled, 
to give 270 parts of a viscose, clear, resin-like product, which dissolves 
readily in water to give strongly foaming solutions (= reactive surfactant 
IV). 
V. 126 Parts of melamine with addition of 18 parts of 25% ammonia are 
dissolved at 60.degree. C in 590 parts of 36.5% aqueous formaldehyde which 
contains methanol. The solution is heated to 80.degree. C and 132 parts of 
a mixture of methanol and water are distilled off in vacuo over the course 
of about 20 minutes. The batch is then treated with 490 parts of n-butanol 
and distillation is continued in vacuo, in the course of which the 
water/n-butanol mixture which passes over is isolated. The n-butanol runs 
back again into the reaction vessel, while 118 parts of aqueous layer 
separate out. A solution of 3 parts of 85% formic acid in 5 parts of 
n-butanol is added and then altogether 452 parts of n-butanol are 
distilled off which carry the remainder of the water with them, giving 532 
parts of a viscose, colourless resin which is miscible with benzene in any 
desired ratio and is designated hereinafter as coating resin C. 
While stirring 532 parts of the melamine/n-butanol resin C (containing 1 
mole of melamine) are heated with 104 parts of triethanolamine for 11/2 
hours to 120.degree. C and then for 11/2 hours to 135.degree.-140.degree. 
C, in the course of which 76 parts of n-butanol are distilled off. The 
batch is cooled, to give 560 parts of a clear, viscose product is readily 
soluble in 10% acetic acid. Its acid solutions have an excellent 
emulsifying capacity. The formation of an insoluble resin occurs at pH 4 
and slightly elevated temperature. These properties define the product as 
a reactive surfactant; it has a solids content of 80 to 85%. In 5% aqueous 
solution this reactive surfactant effects a reduction of the surface 
tension of water from 72.75 dyn/cm to 37.6 dyn/cm (.reactive surfactant 
V). 
VI. 187 g (2 moles) of monomethylol urea which contains about 7 g of water 
(manufactured according to Houbon-Weyl, Methodon der organischen Chemie, 
4th. edition, Vol. XIV, part 2, page 348) are treated with 900 g of 
n-butanol and 4 g of glacial acetic acid and the reaction mixture is 
heated to 100.degree. C until a sample upon cooling, remains clear (this 
takes a few minutes). Then 334 g of dodecanol (=90% of 2 moles) are added 
and 880 to 890 g of n-butanol are distilled off in vacuo at 55-80.degree. 
C within 2 hours. The dodecyl ether which has formed is neutralised with 
10 g of triethanolamine and 200 g of ethanol and 200 g of 36.5% 
formaldehyde (2.4 moles) are added, the batch is stirred for 2 hours at 
85.degree. C and the insoluble resin which has formed is filtered off hot. 
The dimethylol urea monododecyl ether dissolves readily in hot dilute 
ethanol. Upon cooling, a portion crystallises out and the remainder may be 
obtained by evaporating the mother liquor. 
28.8 g of dimethylol urea monododecyl ether are condensed in vacuo at 20 mm 
Hg and 90-100.degree. C with 60 g of polyethylene glycol (average 
molecular weight = 600) in the presence of 1.0 g of glacial acetic acid, 
in the course of which 2.5 g of water and acetic acid escape. After 11/4 
hours the condensation mixture is treated with 2.1 g of triethanolamine 
and cooled, to give a liquid surfactant which dissolves readily in water 
to give a foaming solution of pH 7.9 (=reactive surfactant VI). 
VII. Monomethylol urea (cf. VI) is etherified with a mixture of higher 
alkanols containing from 12-15 carbon atoms and having an average 
molecular weight of 207. The etherification product is reacted with 
formaldehyde to give a derivative of dimethylol urea. 31 g (app. 1/10 
mole) of this dimethylol urea monoalkanol ether is condensed in vacuo at 
90.degree.-130.degree. C in the presence of 1 g of glacial acetic acid 
with 40 g of poylyethylene glycol having an average molecular weight of 
400. Altogether 1.6 g of distillate (water and some acetic acid are 
collected. After neutralisation by adding 2.6 g of triethanolamine and 
cooling, a liquid-viscose product is obtained which dissolves in water 
with slight trubidity to give a strongly foaming solution (= reactive 
surfactant VIIa). 
b. A similar product is obtained by condensing the dimethylol urea 
monoalkanol ether with 30 g of polyethylene glycol having an average 
molecular weight of 300 (= reactive surfactant VIIb). 
VIII. In alcoholic slightly alkaline solution 1 mole of formaldehyde is 
additively combined with 342 g (1 mole of monomethylol urea stearyl ether 
(manufactured from the n-butyl ether by transetherification with stearyl 
alcohol), After the resin which has formed has been filtered off, 340 g of 
dimethylol urea stearyl ether (M = 373) are obtained. 37.2 g (1/10 mole) 
of this product are condensed with 154 g of polyethylene glycol ether 
(having an average molecular weight of 1540) in the presence of 1.0 g of 
glacial acetic acid for 11/2 hours at 90.degree.-100.degree. C in vacuo. 
The condensation mixture is then treated with 2 g of triethanolamine, and 
the batch is stirred and cooled. A wax-like substance is obtained which is 
readily soluble in water to give a slightly turbid solution. Its clearly 
foaming solution displays a remarkable washing and wetting action. The 
product is found to be a typical reactive surfactant in that it is 
possible to totally destroy the surfactant properties (rapidly on heating, 
slowly at normal temperature) by acidifying. Insoluble resin falls out of 
the solution, which no longer foams. (Reactive surfactant VIII). 
IX. Instead of the stearyl ether mentioned in VIII, the corresponding 
monomethylol urea oleyl ether is chosen as starting material, converted by 
addition of 1 mole of formaldehyde into the dimethylol urea derivative and 
1 mole thereof is condensed with 1 mole of polyethylene glycol ether 
(average molecular weight = 1000) in the presence of acetic of formic 
acid. Nautralisation with morpholine or triethanolamine gives a soft, 
wax-like product which, like reactive surfactant VIII, is readily soluble 
in water and possesses the properties of a hardening primary condensate. 
X. To a solution of 90 g (1/4 mole) of monomethylol urea hydroabiethyl 
ether (manufactured by transetherifying monomethylol urea butyl ether with 
hydrobiethyl alcohol) in 500 g of ethanol are added 30 g of 36.5 
formaldehyde and sufficient triethanolamine to cause the solution to show 
a clear alkaline reaction. The solution is stirred for 2 hours at 
70.degree. C and evaporated to dryness in vacuo to give 90 g (1/4mole) of 
dimethylol urea monohydroabiethyl ether. This ether is treated with 150 g 
of polyethylene glycol ether (average molecular weight = 600) and 4 g of 
glacial acetic acid and condensation is carried out for 11/2 hours at 
90.degree.-95.degree. C in vacuo, in the process of which 6 g of water and 
acetic acid collect in the condenser. The liquid-viscose reaction product 
is then made slightly alkaline again by addition of triethanolamine. It 
dissolves readily in water to give an opalescent, foaming solution. If 
this solution is treated with acid until a slightly acid reaction to Congo 
red is attained, an insoluble resin precipitates (slowly at normal 
temperature, rapidly on heating), in the process of which the aqueous 
liquid completely loses its foaming power. (Reactive surfactant X). 
Manufacturing Instructions for Binding Agents 
A. 196 g (1 epoxide equivalent) of an epoxide formed from 
2,2-bis-(4'-hydroxyphenyl)-propane and epichlorohydrin together with 155 g 
(0.5 amino group equivalent) of a mixture of 1-aminoeicosane and 
1-amino-docasane and 181 g of n-butylglycol are stirred for 1 hour at 
100.degree. C. The mixture is then cooled to room temperature. 
150.5 of the above solution are heated in an agitator flask to 60.degree. C 
internal temperature. Then 37.2 g of a polyamide from polymeised linoleic 
acid and diethylene-triamine (0.15 amino group equivalent), dissolved in 
16 g of n-butyl-glycol, are added dropwise within 30 minutes. The batch is 
then stirred for 5 hours at 60.degree. C internal temperature. 
Then 3.9 g of 1,3-dichloro-2-propanol (0.03 mole) are added and the mixture 
is stirred once more for 1 hour at 60.degree. internal temperature. Upon 
addition of 24 g of glacial acetic acid in 133 g of deionised water, the 
mixture is stirred until cold. 
A solution of medium viscosity, with a solids content of 40% and a pH of 
4.8 is obtained (=binding agent A). 
B. 98 g (0.5 epoxide equivalent) of an epoxide formed from 
2,2-bis(4'-hydroxy-phenyl)-propane and epichlorohydrin together with 77.5 
g (0.25 amino group equivalent) of the fatty amine used in Instruction A 
and 94.5 g of isopropanol are boiled under reflux for 11/2 hours. 
Then a solution of 247 g of the polyamide described hereinabove (1 amino 
group equivalent) in 328 g of isoporpanol is added dropwise within 1 hour. 
Then stirring is continued for 5 hours at reflux temperature. 
53.5 g of acrylic amide (0.75 mole) and 22.5 g of paraformaldehyde (0.75 
mole) are then added and stirring is continued again for 8 hours at reflux 
temperature. 
The batch is subsequently diluted with a solution of 60 g of glacial acetic 
acid in 1500 g of deonised water. A solution of low viscosity, which a 
solids content of 20% and a pH of 4.6, is obtained (=binding agent B). 
C. 98 g (0.5 epoxide equivalent) of an epoxide formed from 
2,2-bis-(4'-hydroxyphenyl)-propane and epichlorohydrin together with 31 g 
of a mixture of 1-aminoeicosane and 1-aminodocosane (0.1 amino equivalent) 
and 55.5 g of butylglycol are stirred for 3 hours at 100.degree. C 
internal temperature. Then 17.7 g of hexane-diol-1,6 and 25.5 g of sebacic 
acid are added and stirring is continued for 3 hours at 100.degree. C 
internal temperature. 10.2 g (0.1 mole) of methylolacrylic amide are then 
added and stirring is continued once more for 3 hours at 100.degree. C 
internal temperature. Upon addition of 146.9 g of butylglycol, stirring is 
continued until the mixture is cold. 
A clear solution of low viscosity with an acid number of 6 is obtained (= 
binding agent C). 
D 98 g (0.5 epoxide group equivalent) of an epoxide formed from 
2,2-bis-(4'-hydroxyphenyl)-propane and epichlorohydrin together with 31 g 
(0.1 amino group equivalent) of a mixture of 1-amino-eicosane and 1-amino 
docosane and 50 g of n-butylglycol are stirred for 3 hours at 100.degree. 
C internal temperature. Then 17.7 g of hexane-diol-1,6 (0.3 hydroxyl group 
equivalent) and 50.5 g of sebacic acid (0.5 acid group equivalent) are 
added and stirring is continued for 3 hours at 100.degree. C internal 
temperature. Upon addition of 4.6 g of epichlorohydrin (0.05 mole), 
stirring is continued for a further 3 hours at 100.degree. C internal 
temperature and the batch is subsequently diluted with 151.8 g of 
n-butylglycol. Stirring is continued until the mixture is cold. A clear 
product of low viscosity with an acid number of 43.6 is obtained (binding 
agent D). 
E. While stirring thoroughly, a solution of 49.4 g of a condensation 
product (amino equivalent weight = 247) of polymerised linoleic acid and 
diethylenetriamine and 49.4 g of methanol is added within 24 minutes to a 
solution heated to 51.degree. C of 38.4 g of an epoxide (epoxide 
equivalent weight =191) formed from 2,2-bis(4'-hydroxyphenyl)-propane and 
epichlorohydrin and 38.4 g of methanol, in the course of which the 
reaction temperature is 51.degree. to 53.degree. C. After 8 and 18 minutes 
3 g of glacial acetic acid are added on each occasion and after 24 minutes 
a further 2 g of glacial acetic acid are added. The reaction is continued 
for a further 2 hours and for 35 minutes at 55.degree. to 60.degree. C. 
The reaction product is then soluble in water to give an opalescent 
solution. While stirring, 4 g of glacial acetic acid and 273.4 g of water 
are added. A yellowish, viscous, turbid 20% solution with a pH of 5.2 is 
obtained. 
F. 68.5 g (0.1 epoxide group equivalent) of an epoxide (epoxide equivalent 
weight = 685) obtained from 196 g (1 epoxide group equivalent) of 
2,2-bis-(4'-hydroxyphenyl)-propane and epichlorohydrin as well as 155 g 
(0.5 amino group equivalent) of an amino mixture of 1-amino-eicosane and 
1-amino-docosane are dissolved in 37 g of isopropanol and the solution is 
heated to 88.degree. C internal temperature. Then a solution of 24.7 g 
(0.1 amino group equivalent) of a polyamide of polymerised linoleic acid 
and diethylene-triamine in 24.7 g of isopropanol and 15 g of isopropanol 
is added within 30 minutes. 
The mixture is stirred for 5 hours at 88.degree. C internal temperature 
under reflux and then 1.85 g of epichlorohydrin (0.02 mole) are added. 
After a further 10 minutes a solution of 16 g of glacial acetic acid and 
312 g of deionized water is added and stirring is continued until the 
mixture is cold. A product of low viscosity with a solids content of 20% 
and a pH of 4.6 is obtained. 
G. 98 g of an epoxide (0.5 epoxide group equivalent) from 
2,2-bis-(4'-hydroxyphenyl)-propane and epichlorohydrin together with 31 g 
(0.1 amino group equivalent) of a mixture of 1-amino eicosane and 1-amino 
docosane and 50 g of butylglycol are stirred for 3 hours at 100.degree. C. 
Then 15.6 g of neopentylglycol (0.3 hydroxyl group equivalent) and 50.5 g 
of sebacic acid (0.5 acid group equivalent) are added and stirring is 
continued for 3 hours at 100.degree. C. 13.9 g of epichlorohydrin (0.15 
mole) are then added and stirring is again continued for 3 hours at 
100.degree. C internal temperature. 
Subsequently the mixture is diluted with 159 g of perchloroethylene and 
stirred until cold. A clear solution of medium viscosity and with an acid 
number of 20 is obtained. 
100 g of this 50% resin solution are then mixed with 62.5 g of an 80% 
solution of hexamethylolmelamine-di- and tributyl ether in butanol. 
To this mixture are added 10 g of a 50% solution of an addition product of 
70 moles of ethylene oxide with a fatty amine mixture (C.sub.16 -C.sub.22) 
and the whole mixture is emulsified. A finely disperse emulsion with a 
resin content of 30% is obtained by slowly adding water. 
b. Instead of the mixture described under (a) it is also possible to react 
the epoxide resin with the hexamethylolmelamine di-and tributyl ether, the 
procedure being as follows: 
100 g of the 50% resin solution are mixed with 62.5 g of an 80% solution of 
hexamethylolmelamine di-and tributyl ether in butanol and the batch is 
reacted for 1 hour at 100.degree. internal temperature. The reaction 
mixture is then diluted with 37.5 g of perchloroethylene and a clear 
solution of medium viscosity and with a resin content of 50% is obtained. 
100 g of resin solution are emulsified with a 50% solution of an addition 
product of 70 moles of ethylene oxide with a fatty amine mixture 
(C.sub.16-C.sub.22). A finely disperse emulsion with a resin content of 
30% is obtained by slowly adding 56.5 g of deionized water. 
EXAMPLE 1 
30 liters of water are put into a vessel and then 2000 g of reactive 
surfactant I and 200 g of an aqueous 2% ethyl cellulose solution as 
thickener are added. This mixture is stirred until the thickener has 
become completely dispersed. Then 25000 g of binder A are added and 
thereupon the pH is adjusted to 3 with formic acid while stirring 
constantly. The liquor is then made up to 100 liters with water. The 
stirring apparatus is then so adjusted that a funnel is formed when the 
liquor is stirred. 
This special arrangement of the agitator enables as much air as possible to 
be brought into the system. Stirring is proceeded with until the volume of 
the liquor has risen to 200 liters. A polyester fleece is impregnated with 
this foam in a horizontal 2 roll padder. The increase in weight is 50 to 
60%. After the fleece has been removed from the padder it is dried at 
140.degree. C for 10 minutes and cured. In the course of this drying 
operation the reactive surfactant decomposes and loses its wetting action. 
A permanently reinforced nonwoven is obtained. 
EXAMPLE 2 
The same procedure is carried out as in Example 1, but binder B is 
substituted for binder A. A permanently reinforced nonwoven is likewise 
obtained. 
EXAMPLE 3 
The same procedure is carried out as in Example 1, but reactive surfactant 
I is substituted for reactive surfactant II and a permanently reinforced 
nonwoven is likewise obtained. 
EXAMPLE 4 
70 Liters of cold water are put into a preparing vessel (room temperature) 
and 20 g of binder C are added. Then 1000 g of a 2% aqueous ethyl 
cellulose solution are added. The mixture is then stirred with an impeller 
in order to uniformly disperse the thickener, and 5000 g of reactive 
surfactant III are added. 
The pH is adjusted with formic acid to 3 and the liquor is made up to 100 
liters with water. The agitator is so adjusted that as much air as 
possible is stirred in. In addition, air is also bubbled in through jets 
which are as fine as possible. The liquor is stirred until its volume has 
increased from 100 to 200 liters. A polyester fleece, which may be 
prereinforced by needles, is then impregnated with this foam liquor on a 
horizontal 2 roll padder or on a special screen-belt impregnating machine 
to an increase in weight of 50 to 70%. The fleece is subsequently dried 
and cured at 140.degree. C for 5 minutes. During this curing the reactive 
surfactant loses its wetting action. A permanently reinforced nonwoven is 
obtained. 
The wettability of fibre fleece: 
The wetting time indicated hereinbelow are determined as follows: 
A round sample with a diameter of 4 cm is punched out and dipped on a fish 
hook in water having a temperature of 20.degree. C. The time is measured 
between dipping and sinking of the sample: 
______________________________________ 
Drying 
Treatment temperature in .degree. C 
Wetting Times 
______________________________________ 
natural state 
140.degree. immediately 
binder only 140.degree. C over 10 mins. 
binder + reactive 
20.degree. immediately 
surfactant 
binder + reactive 
100.degree. C immediately 
surfactant 
binder + reactive 
120.degree. C immediately 
surfactant 
binder + reactives 
140.degree. C over 10 mins. 
surfactant 
______________________________________ 
EXAMPLE 5 
The procedure is carried out as in Example 4, but reactive surfactant IV is 
substituted for reactive surfactant III. Permanently reinforced nonwovens 
are likewise obtained. 
EXAMPLE 6 
The procedure is carried out as in Example 4, but 1000 g of magnesium 
chloride are substituted for the formic acid. Permanently reinforced 
nonwovens are likewise obtained. 
EXAMPLE 7 
The procedure is carried out as in Example 4, but binder D is substituted 
for binder C. Permanently reinforced nonwovens are likewise obtained. 
EXAMPLE 8 
A nonwoven consisting of viscose staple fibre is impregnated with the 
following foamed liquor: 
200 g of binder E 
170 g of water 
90 g of hydroxyethy cellulose (2.5%) 
6 g of reactive surfactant V 
50 g of acetic acid (40%). 
The batch is adjusted with formic acid to pH 3.6. This liquor is then 
foamed to twice its volume with an impeller and by bubbling in air. The 
impregnation is effected on a padder and the roller pressure is so 
adjusted that there is an increase in weight of the goods of 40-50%. The 
fabric is subsequently dried for 10 minutes at 110.degree. C. The reactive 
surfactant decomposes as a result of the drying and loses its wetting 
action which is important for the padding and its foaming capacity. 
An aftertreatment is thereby rendered superfluous. Similar results are also 
obtained with polyester and polypropylene fibre fleece. 
EXAMPLE 9 
The following foamed liquor is applied by padding to a viscose staple fibre 
fleece: 
200 g of a 50% aqueous emulsion of an acrylic resin binder, prepared by 
compolymerisation of the following monomers: 
85 parts of n-butylacrylate 
10 parts of acrylonitrile 
5 parts of acrylic acid 
4 g of reactive surfactant VII 
50 g of water 
40 g of carboxymethylcellulose (2.5%) 
10 ml of Mg Cl.sub.2 (20%). 
This liquor is adjusted with formic acid to pH 3, and subsequently foamed 
by stirring and bubbling in air. The fleece is padded to an increase in 
weight of 30-60%. It is then dried for 10 minutes at 140.degree. C. The 
hydrophilic action of the reactive surfactant is neutralised after the 
drying. 
Instead of reactive surfactant VII is is also possible to use reactive 
surfactant X. 
Instead of carboxymethylcellulose it is also possible to use methyl 
cellulose, methoxycellulose or polyacrylic ester. 
Instead of a nonwoven of viscose staple, it is also possible to use one of 
polyamide or polyester fibre material. 
EXAMPLE 10 
A polyester fleece which has been prereinforced by needling is padded with 
the following preparation: 
200 g of binder F 
4 g of reactive surfactant VI 
50 g of 5% aqueous carob bean meal thickening 
80 g of water. 
The batch is adjusted with formic acid to pH 3. The liquor is foamed by 
stirring and bubbling in air. The fabric is padded to an increase in 
weight of 40-60%. The material is padded to an increse of 40-60%. The 
reactive surfactant loses its hydrophilic action in the drying process. 
Instead of reactive surfactant VI it is also possible to use reactive 
surfactant VIII. 
Instead of polyester fleece it is also possible to use 
polyamide/polypropylene or viscose stable fibre fleece. 
It is also possible to use blends of these fibres. Besides blends of the 
cited fibres it is also possible to use further fibres, e.g. 
polyacrylonitrile fibres. 
EXAMPLE 11 
A polyamide needle fleece carpet is padded with the following foamed 
liquor: 
200 g of binder G a) 
3 g of reactive surfactant IX 
40 g of methyl cellulose (5%) 
150 g of water 
10 ml of MgCl.sub.2 (20%) 
50 g of butylglycol. 
The pH is adjusted with formic acid to 2.8. The liquor is foamed to twice 
its volume by stirring and bubbling in air. The material is padded to an 
increase in weight of 40-60%. It is then dried at 90.degree. C. During the 
drying the reactive surfactant loses its wetting action, so that an 
aftertreatment is superfluous. 
Instead of binder (G a) is is also possible to use a 50% 
butadiene/styrene/latex dispersion.