Quaternized condensation products of trialkanolamines

The present invention relates to quaternized condensation products of 
(A) a precondensate of one or more trialkanolamines of the general formula 
I 
##STR6## 
where R.sup.1, R.sup.2 and R.sup.3 are each 1,2-alkylene of from 2 to 4 
carbon atoms, and 
(B) from 1 to 30 mol % per mole of I of one of the following compounds II: 
(a) a carboxylic acid or carboxylic acid derivative of the general formula 
IIa 
##STR7## 
where n is 0 or 1 
R.sup.4 and R.sup.5 are each hydroxyl except if n is 0, or C.sub.1 -C.sub.8 
-alkoxy which if n is 0 may be bonded together to form a five- or 
six-membered ring, or chlorine or bromine, and 
R.sup.6 is alkylene of from 1 to 50 carbon atoms which may be interrupted 
by one or more nonadjacent oxygen atoms, 
(b) a carboxamide of the general formula IIb 
##STR8## 
where m, n, and r are each 0 or 1, 
R.sup.7 is hydrogen or C.sub.1 -C.sub.4 -alkyl and 
R.sup.8 is hydrogen, C.sub.1 -C.sub.25 -alkyl, C.sub.2 -C.sub.25 -alkenyl, 
or phenyl which may be substituted by C.sub.1 -C.sub.4 -alkyl, C.sub.1 
-C.sub.4 -alkoxy, fluorine, chlorine or bromine, 
(c) an epihalohydirin of the general formula IIc 
##STR9## 
where X is chlorine or bromine, (d) a monofunctional compound of the 
general formula IId 
EQU R.sup.9 --Y IId 
where 
R.sup.9 is C.sub.1 -C.sub.25 -alkyl, C.sub.2 -C.sub.25 -alkenyl, or phenyl 
which may be substituted by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 
-alkoxy, fluorine, chlorine or bromine, and 
Y is isocyanate or one of the groups 
##STR10## 
and/or (e) a bifunctional compound of the general formula IIe 
EQU Z.sup.1 --R.sup.10 --Z.sup.2 IIe 
where 
R.sup.10 is alkylene of from 1 to 50 carbon atoms which may be interrupted 
by one or more nonadjacent oxygen atoms and/or contain one or more 
mutually nonvicinal hydroxyl groups, and 
Z.sup.1 and Z.sup.2 are each chlorine, bromine, isocyanate or one of the 
groups 
##STR11## 
and 
(C) from 25 to 100 mol % per mole of I of a benzyl halide of the general 
formula III 
##STR12## 
where p is from 0 to 2 and 
R.sup.11 is C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, fluorine, 
chlorine or bromine. 
The present invention also relates to a process for preparing the 
quaternized condensation products and to the use thereof as aftertreating 
agents for fixing dyeings and prints on textile materials which contain 
cellulose fibers and have been dyed or printed with reactive or direct 
dyes, and to a process for this aftertreatment. 
Textile materials which contain cellulose fibers and have been dyed or 
printed with reactive or direct dyes are usually subjected to an alkali 
wash in the presence of surfactants in order to remove the unfixed dye 
portions. This procedure gives dyed or printed cellulose materials which, 
it is true, have adequate wash fastness properties but are in need of 
improvement in respect of the waterfastness, the hot-press fastness and 
the perspiration fastness. 
The aftertreating process described in DE-A-3,526,101 using cationic 
condensation products obtainable by reaction of piperazine derivatives 
with bifunctional halogen or epoxy compounds and subsequent quaternization 
with benzyl chloride leads to substantial elimination of the defects 
described, but in some cases impairs the crock fastness and in particular 
the lightfastness. 
EP-B-087,147 relates to reaction products of triethanolamine condensates 
and xylylene dichlorides. However, these products are not used in the 
textile industry, but are used as emulsion breakers, lubricants and paper 
assistants. 
EP-A-223,064 deals with benzyl chloride-quaternized condensation products 
of triethanolamine and/or triisopropanolamine as aftertreating agents for 
the fixation of reactive dyeings. These compounds bring about an 
improvement not only in the wet but also in the crock and lightfastness 
properties. To obtain the desired application properties, however, 
trialkanolamine condensates of a high degree of condensation which 
corresponds to a viscosity of not less than 40,000 mPa.s in the undiluted 
state in the case of triethanolamine and of not less than 600,000 mPa.s in 
the undiluted state in the case of triisopropanolamine are required. The 
preparation of such high-viscosity polyaminoethers is, as explained in 
EP-B-087,147 highly problematical at just below the gel point because of 
the difficult-to-control condensation reaction, since the reaction mixture 
tends to form a solid, insoluble mass here which is no longer handlable 
for any further reaction. 
It is an object of the present invention to provide conveniently preparable 
aftertreating agents for the purpose mentioned which ensure high 
wetfastness properties without impairing the crock and lightfastness 
properties. 
We have found that this object is achieved by the quaternized condensation 
products defined at the beginning. 
The precondensates used for preparing the cationic resins according to the 
invention can be obtained by heating the trialkanolamines I, in particular 
triethanolamine or triisopropanolamine N[CH.sub.2 
--CH(CH.sub.3)--OH].sub.3, in the presence of acid catalysts, preferably 
phosphorous or hypophosphorous acid, at from 120.degree. to 280.degree. C. 
as described in EP-A-223,064. In a departure from the process of this 
EP-A, however, the reaction of the process according to the invention is 
advantageously discontinued by cooling at distinctly below the gel point 
once a viscosity range from 5,000 to 35,000 mPa.s, preferably from 10,000 
to 25,000 mPa.s, for triethanolamine or from 100,000 to 600,000 mPa.s, 
preferably from 200,000 to 500,000 mPa.s, for triisopropanolamine or from 
100,000 to 250,000 mPa.s for a cocondensate of preferably equimolar 
amounts of triethanolamine and triisopropanolamine has been reached (in 
each case the viscosity is measured in the undiluted state at 20.degree. 
C.). To effect further crosslinking and/or to incorporate groups of 
different polarities at the chains which carry the alcohol functions 
and/or to quaternize the central nitrogen atoms, the precondensates 
obtained are reacted with one or more compounds IIa-IIe. The amount of 
these compounds is within the range from 1 to 30 mol %, preferably from 1 
to 15 mol %, per mole of I. 
Suitable compounds IIa-IIe are: 
(a) the carboxylic acids or carboxylic acid derivatives . IIa of the type 
defined, where R.sup.4 and R.sup.5 are each hydroxyl, C.sub.1 -C.sub.8 
-alkoxy,, preferably C.sub.1 -C.sub.4 -alkoxy, chlorine or bromine and the 
linkage member R.sup.6 is in particular the group 
##STR13## 
where q is from 1 to 50, preferably from 2 to 10, k is from 0 to 24, 
preferably from 0 to 12, and R.sup.12 is hydrogen, methyl or ethyl; 
preference is further given to unbranched linkage members R.sup.6. 
Examples of compounds IIa are: 
(.alpha.) carbonic acid derivatives (n =0), eg. dimethyl carbonate, diethyl 
carbonate, dipropyl carbonate, dibutyl carbonate, ethylene carbonate, 
1,2-propylene carbonate, 1,3-propylene carbonate, 1,2-butylene carbonate, 
1,3-butylene carbonate, 2,3-butylene carbonate, phosgene, monomethyl 
chlorocarbonate or bromocarbonate, monoethyl chlorocarbonate or 
bromocarbonate. Preference is given to cyclic carbonates, in particular 
ethylene carbonate and 1,3-propylene carbonate; 
(.beta.) dicarboxylic acids (n=1, R.sup.4 =R.sup.5 =OH), eg. malonic acid, 
succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, 
azelaic acid and sebacic acid; 
(.gamma.) dicarboxylic acid derivatives (n=1; R.sup.4,R.sup.5 =alkoxy, Cl, 
Br), eg. the dimethyl, diethyl, dipropyl and dibutyl esters and the 
chlorides and bromides of the dicarboxylic acids mentioned under (.beta.); 
(b) the carboxamides IIb of the type defined, examples of which are: 
(.alpha.) monocarboxamides (n=r=0), eg. formamide, acetamide, propionamide, 
butyramide, benzamide and the N-methyl, N-ethyl, N-propyl and N-butyl 
derivatives thereof; 
(.beta.) dicarboxamides (m=0, n=r=1), eg. malonamide, succinamide, 
glutaramide, adipamide, pimelamide, suberamide, azelaamide, sebacamide and 
N,N'-dimethyl, N,N'-diethyl, N,N'-dipropyl and N,N'-dibutyl derivatives 
thereof; 
(.gamma.) ureas (n=0, r=1), eg. urea, N-methylurea, N-ethylurea, 
N-propylurea, N-butylurea, N,N'-dimethylurea, N,N'-diethylurea, 
N,N'-dipropylurea, N,N'-dibutylurea, N-(2-ethylhexyl)urea, N-isononylurea, 
N-isotridecylurea, N-laurylurea, N-myristylurea, N-palmitylurea, 
N-stearylurea, N-oleylurea, N-linolylurea, N-linolenylurea and 
N-phenylurea. Preference is given to monosubstituted ureas and in 
particular to unsubstituted urea; 
(.delta.) bisureas (m=n=r=1), eg. methylenediurea, ethylene-1,2-diurea, 
propylene-1,3-diurea, butylene-1,4-diurea, pentamethylene-1,5-diurea, 
hexamethylene-1,6-diurea, di(2-ureidoethyl) ether, di(3-ureidopropyl) 
ether, ethylene glycol bis(2-ureidoethyl) ether, ethylene glycol 
bis(3-ureidopropyl) ether, diethylene glycol bis(2-ureidoethyl) ether, 
triethylene glycol bis(2-ureidoethyl) ether and tetraethylene glycol 
bis(2-ureidoethyl) ether. Preference is given to bisureas having an 
alkylene linkage R.sup.6 of from 4 to 10 carbon atoms, particular 
preference being given to hexamethylene-1,6-diurea; 
(c) an epihalohydrin IIc where X is chlorine or bromine. Preference is 
given to epichlorohydrin; 
(d) the monofunctional compounds IId of the type defined, examples of which 
are: 
(.alpha.) isocyanates, eg. methyl isocyanate, ethyl isocyanate, propyl 
isocyanate, butyl isocyanate, 2-ethylhexyl isocyanate, isononyl 
isocyanate, isotridecyl isocyanate, lauryl isocyanate, myristyl 
isocyanate, palmityl isocyanate, stearyl isocyanate, oleyl isocyanate, 
linolyl isocyanate, linolenyl isocyanate, phenyl isocyanate, o-, m- or 
p-chlorophenyl isocyanate and o-, m- or p-tolyl isocyanate; 
(.beta.) urethanes, eg. methyl carbamate, ethyl carbamate, propyl 
carbamate, butyl carbamate and the N-methyl, N-ethyl, N-propyl and N-butyl 
derivatives thereof; 
(.gamma.) glycidyl ethers, eg. methyl glycidyl ether, ethyl glycidyl ether, 
propyl glycidyl ether, butyl glycidyl ether, (2-ethylhexyl) glycidyl 
ether, isononyl glycidyl ether, isodecyl glycidyl ether, isotridecyl 
glycidyl ether, lauryl glycidyl ether, myristyl glycidyl ether, palmityl 
glycidyl ether, stearyl glycidyl ether, oleyl glycidyl ether, linolyl 
glycidyl ether, linolenyl glycidyl ether, cyclohexyl glycidyl ether, 
glycidyl ethers of C.sub.13 -C.sub.15 oxoalcohol, C.sub.12 -C.sub.14 fatty 
alcohol and C.sub.16 -C.sub.18 fatty alcohol, and phenyl glycidyl ether; 
(e) the bifunctional compounds IIe of the type defined where R.sup.10 is 
alkylene of from 1 to 50 carbon atoms, preferably of from 2 to 26 carbon 
atoms, which may be interrupted by one or more nonadjacent oxygen atoms 
and/or contain one or more mutually nonvicinal hydroxyl groups. The 
linkage member R.sup.10 is in particular the group 
##STR14## 
where q is from 1 to 50, preferably from 2 to 10, k is from 0 to 24, 
preferably from 0 to 12, and R.sup.12 is hydrogen, methyl or ethyl; 
preference is further given to unbranched linkage members R.sup.10. 
Examples of compounds IIe are: 
(.alpha.) dichlorides or dibromides, eg. methylene chloride, 
1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, 
1,5-dichloropentane, 1,6-dichlorohexane, di[2-chloroethyl] ether, 
di[3-chloropropyl] ether, ethylene glycol bis[2-chloroethyl] ether, 
ethylene glycol bis[3-chloropropyl] ether, diethylene glycol 
bis[2-chloroethyl] ether, triethylene glycol bis[2-chloroethyl] ether, 
1,3-dichloro-2-propanol, di[3-chloro-2-hydroxypropyl] ether, ethylene 
glycol bis[3-chloro-2-hydroxypropyl] ether, diethylene glycol 
bis[3-chloro-2-hydroxypropyl] ether, triethylene glycol 
bis[3-chloro-2-hydroxypropyl] ether, neopentylene 
bis[3-chloro-2-hydroxypropyl] ether or the corresponding bromine 
compounds; 
(.beta.) diisocyanates, eg. ethylene 1,2-diisocyanate, propylene 
1,3-diisocyanate, butylene 1,4-diisocyanate, pentamethylene 
1,5-diisocyanate, hexamethylene 1,6diisocyanate, di(2-isocyanatoethyl) 
ether, di(3-isocyanatopropyl) ether, ethylene glycol 
bis(2-isocyanatoethyl) ether, ethylene glycol bis(3-isocyanatopropyl) 
triethylene glycol bis(2-isocyanatoethyl) ether and tetraethylene glycol 
bis(2-isocyanatoethyl) ether; 
(.gamma.) bisurethanes, eg. the dimethyl, diethyl, dipropyl and dibutyl 
esters of ethylene 1,2-dicarbamic acid, propylene-1,3-dicarbamic acid, 
butylene-1,4-dicarbamic acid, pentamethylene-1,5-dicarbamic acid, 
hexamethylene-1,6-dicarbamic acid, di[2-(carboxyamino)ethyl] ether, 
di[3-(carboxyamino)propyl] ether, ethylene glycol 
bis[2-(carboxyamino)ethyl] ether, ethylene glycol 
bis[3-(carboxyamino)propyl] ether, diethylene glycol 
bis[2-(carboxyamino)ethyl] ether, triethylene glycol 
bis[2-(carboxyamino)ethyl] ether and tetraethylene glycol 
bis[2-(carboxyamino)ethyl] ether; 
(.delta.) bisglycidyl ethers, eg. ethylene glycol bisglycidyl ether, 
1,3-propanediol bisglycidyl ether, 1,4-butanediol bisglycidyl ether, 
1,5-pentanediol bisglycidyl ether, 1,6-hexanediol bisglycidyl ether, 
diethylene glycol bisglycidyl ether, di[3-(glycidyloxy)propyl] ether, 
triethylene glycol bisglycidyl ether, ethylene glycol 
bis[3-(glycidyloxy)propyl] ether, tetraethylene glycol bisglycidyl ether, 
pentaethylene glycol bisglycidyl ether, hexaethylene glycol bisglycidyl 
ether and neopentylene glycol bisglycidyl ether; 
(.epsilon.) .gamma.-alkoxy- or .gamma.-aryloxy-propylene halohydrides, eg. 
3-chloro-2-hydroxypropyl methyl ether, 3-chloro-2-hydroxypropyl ethyl 
ether, 3-chloro-2-hydroxypropyl propyl ether, 3-chloro-2-hydroxy-propyl 
butyl ether, 3-chloro-2-hydroxypropyl-2-ethylhexyl ether, 
3-chloro-2-hydroxypropyl isononyl ether, 3-chloro-2-hydroxypropyl 
isotridecyl ether, 3-chloro-2-hydroxypropyl lauryl ether, 
3-chloro-2-hydroxypro-pyl myristyl ether, 3-chloro-2-hydroxypropyl 
palmityl ether, 3-chloro-2-hydroxypropyl stearyl ether, 
3-chloro-2-hydroxypropyl oleyl ether, 3-chloro-2-hydroxypropyl linolyl 
ether, 3-chloro-2-hydroxypropyl linolenyl ether and 
3-chloro-2-hydroxypropyl phenyl ether or the corresponding bromine 
compounds. 
The precondensate formed from triethanolamine is preferably reacted with a 
urea IIb (n=0, r=1), a bisurea IIb ( m=n=r=1) or a cyclic carbonate IIa 
(R.sup.4 -R.sup.5 =O-alkylene-O, n=0) at from 100.degree. to 210.degree. 
C., preferably from 140.degree. to 200.degree. C., without solvent to a 
viscosity of from 20,000 to 300,000 mPa.s, preferably from 28,000 to 
150,000 mPa.s, and with an epihalohydrin IIc without a solvent at from 
40.degree. to 150.degree. C., preferably from 60.degree. to 130.degree. 
C., or in an aqueous or even aqueous-alcoholic solution not less than 40% 
strength by volume at from 40.degree. to 100.degree. C. to a viscosity at 
20.degree. C. of an 80% strength by weight aqueous solution of from 12,000 
to 40,000 mPa.s, preferably from 15,000 to 36,000 mPa.s 
The precondensate formed from triisopropanolamine is preferably reacted 
with a urea IIb (n=0, r=1), a bisurea IIb (m=n-r-1) or a cyclic carbonate 
IIa (R.sup.4 -R.sup.5 =O-alkylene-O, n=0) at from 100.degree. to 
210.degree. C., preferably from 140.degree. to 200.degree. C., without 
solvent to a viscosity of more than 500,000 mPa.s and with an 
epihalohydrin IIc without solvent at from 40.degree. to 150.degree. C., 
preferably from 60.degree. to 130.degree. C., or in an aqueous or even 
aqueous-alcoholic solution not less than 40% strength by volume at from 
40.degree. to 100.degree. C. 
The precondensate formed from a mixture of triethanolamine and 
triisopropanolamine, preferably in a molar ratio of 1:1, is reacted for 
example with a urea IIb (n=0, r=1), a bisurea IIb ( m=n=r=1) or a cyclic 
carbonate IIa (R.sup.4 -R.sup.5 =O-alkylene-O, n=0) at from 100.degree. to 
210.degree. C., preferably from 140.degree. to 200.degree. C., without 
solvent to a viscosity of more than 300,000 mPa.s. 
The reaction products of the polyaminoether precondensates and compounds 
IIa-IIe are then reacted with from 25 to 100 mol %, preferably from 60 to 
95 mol %, of one or more of the benzyl halides III of the type defined. 
Preference is given to benzyl chlorides which are monosubstituted in the 
para position (X=Cl, p=1), but particular preference is given to 
unsubstituted benzyl chloride (X=Cl, p=0). 
The benzyl halide reacts chiefly with the central nitrogen atom of the 
polyaminoether/compound IIa-IIe condensation product, thereby quaternizing 
said condensation product. 
The reaction with the benzyl halide is preferably carried out in aqueous or 
even aqueous-alcoholic medium at from 60.degree. to 100.degree. C., but 
can also be carried out at higher temperatures using shorter reaction 
times, although in this case it will have been necessary to employ 
superatmospheric pressure. The aqueous or aqueous-alcoholic solution of 
the quaternized product can be used directly, with or without an addition 
of diethylene glycol, in the textile sector as provided for by the 
invention. 
The condensation product according to the invention can be used as an 
aftertreating agent for fixing dyeings and prints on textile materials 
which contain cellulose fibers and have been dyed or printed with direct 
or preferably reactive dyes. 
The textile materials which contain cellulose fibers can be present in the 
form of fibers, yarns, fabrics or other piece goods. The cellulose fibers 
are preferably cotton, linen or staple viscose. The textile materials 
which can be aftertreated according to the invention can consist of 
cellulose fibers alone or contain cellulose fibers blended with synthetic 
fibers such as polyamide, polyacrylonitrile or polyester fibers. 
The textile material is dyed or printed with commercial reactive or direct 
dyes in a conventional manner. For instance, reactive dyes are applied at 
from 20.degree. to 100.degree. C. by the exhaust method or at room 
temperature by the cold pad-batch method; after dyeing, the textile 
material is thoroughly rinsed with water, advantageously first at least 
once with cold water and then at least once with water at from 70.degree. 
to 100.degree. C. 
The aftertreatment of the dyed or printed cellulose fiber materials wherein 
the cellulose fibers may be present blended with other types of fibers is 
preferably effected batchwise or continuously with an aqueous liquor of 
the quaternized condensation product using a customary technique for 
applying aftertreating agents. The batchwise aftertreatment of the dyed or 
printed materials with the aqueous liquor takes in general from 5 to 30 
minutes. The concentration of the water-soluble quaternized resin in the 
aftertreating liquor is preferably from 0.1 to 5.0 g/l, particularly 
preferably from 0.25 to 2.0 g/l. The liquor ratio (ratio of aqueous liquor 
in 1 to dry textile material in kg) is within the range from 5:1 to 50:1, 
preferably from 10:1 to 20:1. The aftertreating liquor preferably has a pH 
within the range from 4 to 11, particularly preferably from 5 to 8. 
However, the quaternized resin can also be applied to the textile material 
which is to be aftertreated by padding. Padding is generally effected with 
an aqueous solution of quaternized resin in a concentration of from 1.0 to 
50 g/l, preferably from 2.5 to 15 g/l. 
The aftertreatment according to the invention is customarily carried out 
within the temperature range from 5.degree. to 100.degree. C., preferably 
at from 40 to 70.degree. C., by a method similar to the exhaust method. 
Alternatively, the dyed or printed textile material is first rinsed with 
cold and hot water, then treated with the aqueous solution of the 
quaternized resin, almost to boiling point within the range from 
70.degree. to 100.degree. C., and subsequently rinsed with water. After 
the aftertreatment according to the invention the textile material which 
contains cellulose fibers can be rinsed. It is then dried. 
The aftertreating process with the quaternized condensation product 
prepared according to the invention leads to the dyeings and prints 
obtained having high wetfastness properties. Excellent results are 
obtained in particular in the severe waterfastness test, for the 
perspiration fastness and for the hot/moist test. The light fastness 
properties are not impaired compared with a dyeing which has not been 
aftertreated according to the invention, in contradistinction from 
conventional aftertreating agents which frequently cause the lightfastness 
properties to deteriorate. Nor are the crock fastness properties impaired 
by the aftertreating process according to the invention; in some cases 
they are even somewhat improved. 
Further advantages of the aftertreating process according to the invention 
are the nonappearance of precipitates which frequently result when 
assistants come together with hydrolyzed reactive dye portions washed out 
of the textile material, and the nonbrightening of dyeings or prints, so 
that there are no shade changes even in the case of combination shade 
dyeings.

EXAMPLES 
The percentages used in the Synthesis and Use Examples are by weight, 
unless otherwise stated. The viscosities were measured at 20.degree. C. in 
a rotary viscometer (Haake, Rotavisco). 
SYNTHESIS EXAMPLES 
Synthesis Example 1 
1788 g of triethanolamine and 12 g of hypophosphorous acid (50% strength 
aqueous solution) were heated with stirring to 225.degree.-230.degree. C. 
while a slow stream of nitrogen was passed through the mixture. The water 
formed in the course of the reaction was distilled off. After 7-8 hours, 
the condensation was discontinued at a viscosity of 21,000 mPa.s by 
cooling to room temperature, affording 1492 g of triethanolamine 
condensate (amine number: 7.69 mmol/g). 
130 g of this triethanolamine polyether were heated together with 3.0 g of 
urea (corresponding to 5 mol %) with stirring to 170.degree.-180.degree. 
C. under nitrogen, and the mixture was maintained at that temperature for 
6 hours until the evolution of ammonia had ceased. The urethane thus 
obtained (viscosity 41,000-45,000 mPa.s) was diluted with 100 g of water 
and heated to 70.degree. C. 101 g of benzyl chloride (corresponding to 80 
mol %) were then added dropwise in the course of 2 hours. The mixture was 
then stirred at 80.degree. C. for 3 hours and adjusted with 133 g of water 
to a 50% level in respect of cationic compound. 
The method of Synthesis Example 1 was also used to prepare the quaternized 
compounds listed in Table 1. 
TABLE 1 
______________________________________ 
Quaternized condensation products with urea 
Triethanol- Reaction with 
amine pre- urea 
Synthesis 
condensate visco- Quaternizing 
Example 
viscosity sity agent 
No. [mPa.s] mol % [mPa.s] (mol %) 
______________________________________ 
2 25,000 5 65,400 Benzyl 
chloride (80) 
3 10,000 10 35,000 Benzyl 
chloride (80) 
4 10,000 15 65,000 Benzyl 
chloride (80) 
5 20,000 5 39,000 Benzyl 
chloride (90) 
6 21,000 5 42,000 4-Chlorobenzyl 
chloride (80) 
7 21,000 5 42,000 4-Methylbenzyl 
chloride (80) 
______________________________________ 
Synthesis Example 8 
260 g of a triethanolamine precondensate (amine number: 7.69 mmol/g) of 
viscosity 19,900, prepared as in Synthesis Example 1, and 10.1 g of 
hexamethylene-1,6-diurea (corresponding to 2.5 mol %) were stirred under 
nitrogen at 160.degree. C. for 2 hours and then at 180.degree. C. for 
hours until the evolution of ammonia had ceased. The viscosity of the 
resulting mixture was 63,000 mPa.s. After dilution with 200 g of water, 
203 g of benzyl chloride (corresponding to 80 mol %) were added dropwise 
at 60.degree.-70.degree. C. in the course of 2 hours. The mixture was then 
stirred at 80.degree. C. for 3 hours and diluted with 268 g of water. 
Synthesis Example 9 
131.2 g of a triethanolamine precondensate (amine number: 7.62 mmol/g) of 
viscosity 20,400 mPa.s, prepared as in Synthesis Example 1, and 36.3 g of 
isotridecylurea (corresponding to 15 mol %) were stirred under nitrogen at 
165.degree. C. for 1.5 hours and then at 180.degree. C. for 5 hours until 
the evolution of ammonia had ceased. The viscosity of the reaction product 
was 34,800 mPa.s. After dilution with 100 g of water, 101 g of benzyl 
chloride (corresponding to 80 mol %) were added dropwise at 70.degree. C. 
in the course of 1.5 hours. After three hours' stirring at 85.degree. C., 
158 g of diethylene glycol were added to prepare a clear solution. 
Synthesis Example 10 
670.5 g of triethanolamine and 860.7 g of triisopropanolamine (in each case 
4.5 mol) were stirred together with 9.0 g of hypophosphorous acid (50% 
strength aqueous solution) at 220.degree. C. while a slow stream of 
nitrogen was passed through the mixture. The water formed in the course of 
the reaction was distilled off. After 7-8 hours the condensation was 
discontinued at a viscosity of 174,600 mPa.s by cooling to room 
temperature, affording 1332 g of cocondensate (amine number: 6.46 mmol/g). 
309.6 g of this cocondensate were heated together with 6.0 g of urea 
(corresponding to 5 mol %) with stirring to 170.degree.-180.degree. C. 
under nitrogen and maintained at that temperature for 5 hours until the 
evolution of ammonia had ceased. The reaction product (viscosity 383,000 
mPa.s) was diluted with 200 g of water and heated to 70.degree. C. 203 g 
of benzyl chloride (corresponding to 80 mol %) were then added dropwise in 
the course of 2 hours. The mixture was then stirred at 100.degree. C. for 
5 hours and 318 g of diethylene glycol were added to prepare a clear 
solution. 
Synthesis Example 11 
1530 g of triisopropanolamine and 8.0 g of hypophosphorous acid (50% 
strength aqueous solution) were heated with stirring to 
200.degree.-225.degree. C. as described in Synthesis Examples 1 and 10 
while a slow stream of nitrogen was passed through the mixture. The water 
formed in the course of the reaction was distilled off. The condensation 
was discontinued at a viscosity of 390,000 mPa.s by cooling to room 
temperature. 
359.6 g of this triisopropanolamine precondensate (amine number: 5.56 
mmol/g) were heated with 6.0 g of urea (corresponding to 5 mol %) with 
stirring to 170.degree.-180.degree. C. under nitrogen and maintained at 
that temperature for 5 hours until the evolution of ammonia had ceased. On 
cooling to room temperature, the reaction product became solid. It was 
dissolved in a mixture of 210 g of water and 85 g of isobutanol at 
70.degree. C. and admixed at that temperature with 208 g of benzyl 
chloride (corresponding to 82 mol %) in the course of 2 hours. It was then 
refluxed for 13 hours. The isobutanol was then distilled off, and a 
sufficient amount of water was added by weight to replace the distillate. 
270 g of diethylene glycol were added to prepare a clear solution. 
Synthesis Example 12 
A mixture of 128.4 g of a triethanolamine precondensate (amine number: 7.79 
mmol/g) of viscosity 15,000 mPa.s, prepared as in Synthesis Example 1, and 
32 g of water (viscosity of the resulting mixture 2800 mPa.s) was admixed 
with 5.6 g of epichlorohydrin (corresponding to 6 mol %) added dropwise. 
The solution was heated to 70.degree. C. The pH was maintained at 9 by the 
addition of a total of 5.0 g of concentrated hydrochloric acid. The 
viscosity of the solution rose from 15,000 to 16,000 mPa.s in the course 
of 8 hours. After addition of 76.8 g of water, 76 g of benzyl chloride 
(corresponding to 60 mol %) were added dropwise at 70.degree. C. The 
mixture was stirred at 80.degree. C. for 3 hours and diluted with 100 g of 
water. 
The method of Synthesis Example 12 was also used to prepare the quaternized 
compounds listed in Table 2. 
TABLE 2 
______________________________________ 
Quaternized condensation products with epichlorohydrin 
Triethanol- Reaction with 
amine pre- epichloro- 
condensate hydrin 
Synthesis 
viscosity viscosity 
Quaternizing 
Example 
undiluted diluted agent 
No. [mPa.s] mol % [mPa.s ] 
(mol %) 
______________________________________ 
13 10,000 10 17,900 Benzyl 
chloride (75) 
14 20,000 5 35,700 Benzyl 
chloride (75) 
15 33,000 1.9 16,000 Benzyl 
chloride (75) 
16 20,400 3.4 15,400 4-Methoxybenzyl 
chloride (70) 
______________________________________ 
Synthesis Example 17 
129.5 g of a triethanolamine precondensate (amine number: 7.72 mmol/g) of 
viscosity 23,500 mPa.s, prepared as in Synthesis Example 1, and 4.6 g of 
epichlorohydrin (corresponding to 5 mol %) were heated to 
100.degree.-105.degree. C. and stirred at that temperature for 5 hours. 
The viscosity of the melt after it had cooled down to 20.degree. C. was 
65,400 mPa.s. After 80 g of water had been added, the mixture was reacted 
at from 70.degree. to 80.degree. C. with 85.3 g of benzyl chloride 
(corresponding to 67 mol %). 
Synthesis Example 18 
129.5 g of a triethanolamine precondensate (amine number: 7.72 mmol/g) of 
viscosity 23,600 mPa.s, prepared as in Synthesis Example 1, and 5.1 g of 
1,3-propylene carbonate (corresponding to 5 mol %) were stirred at 
150.degree. C. for 2.5 hours and then at 180.degree. C. for 2.5 hours 
while a slow stream of nitrogen was passed through the mixture. The 
viscosity was then 28,300-29,500 mPa.s. After the addition of 80 g of 
water, 91 g of benzyl chloride (corresponding to 72 mol %) were slowly 
added dropwise at 70.degree. C. The mixture was then stirred at 80.degree. 
C. for 3 hours. 
The preparation of a quaternized condensation product with ethylene 
carbonate can take place in the same way as the reaction with 
1,3-propylene carbonate. 
USE EXAMPLES 
The suitability of the quaternized condensation products according to the 
invention as aftertreating agents was tested on bleached, mercerized and 
reactive-dyed cotton cloth. 
General dyeing method I (for reactive dyes of medium reactivity): the 
cotton material was introduced at 25.degree. C. and a liquor ratio of 10:1 
into a dyebath containing the dyes mentioned in the Use Examples in 
commercial form, 60 g/l of sodium sulfate, 2.0 ml/l of 38.degree. Be 
sodium hydroxide solution and 5.0 g/l of sodium carbonate and 1.0 g/l of 
sodium m-nitrobenzenesulfonate to prevent undesirable reduction of the 
dye. Following a dwell period of 15 minutes at 25.degree. C., the bath was 
heated to 80.degree. C. in the course of 30 minutes and kept at that 
temperature for 60 minutes. After dyeing, the material was rinsed with 
cold water in a liquor ratio of 20:1 for 10 minutes, the rinse liquor was 
dropped, and the material was then treated with water at 98.degree. C. for 
10 minutes. 
General dyeing method II (for reactive dyes of high reactivity): the cotton 
material was introduced at 15.degree.-17.degree. C. and a liquor ratio of 
10:1 into a dyebath containing the dyes mentioned in the Use Examples in 
commercial form, 60 g/l of sodium sulfate and 15 g/l of sodium carbonate. 
Following a dwell period of 10 minutes, the bath was heated to 30.degree. 
C. in the course of 15 minutes and kept at that temperature for 60 
minutes. After dyeing, the cloth was rinsed cold and hot as in general 
dyeing method I. 
The following tests were used to assess the fastness properties of the 
dyeings: 
lightfastness following Xenotest irradiation (DIN 54 004) 
alkaline and acid perspiration fastness (DIN 54 020) 
dry and wet crock fastness (DIN 54 021) 
severe waterfastness test (DIN 54 006) 
hot/moist test (storage in saturated steam at 80.degree. C. for 72 hours). 
In the hot/moist or hot-press test, the dyed material, after it has been 
stored in saturated steam, is placed between two white cotton fabrics; 
this sandwich is thoroughly wetted with water and then hot-pressed twice 
at 180.degree. C. in a hot-press machine for 30 seconds each time and 
dried in the machine. As a result of this treatment, the unfixed dyes or 
the dyes which have been hydrolyzed by the thermal treatment migrate from 
the dyed to the white material. The hot/moist test simulates six months, 
storage of the reactive dyeings at room temperature. This test method is 
very sensitive and tougher than the severe waterfastness test of DIN 54 
006. The assessment ranges from 0 to 10, a rating of 10 being best. 
Use Example 1 
Bleached and mercerized cotton cloth was dyed with 0.8% of the dye C.I. 
Reactive Blue 41 by method I. It was then treated for 15 minutes at 
50.degree. C. with an aqueous solution containing, based on the dry 
textile material, 1.0% of the quaternized resin of Synthesis Example 2. 
The pH of the liquor was 7.6. The result obtained was a dyeing whose 
lightfastness was not impaired compared with a dyeing which had been 
soaped off in a conventional manner, ie. without aftertreating agent. The 
hot/moist test rating was 10. 
Use Example 2 
A dyeing was prepared with 10% of the dye C.I. Reactive Blue 41 and then 
aftertreated, both steps being carried out as described in Use Example 1. 
The severe water fastness rating was 5, compared with the 3-4 of a dyeing 
without aftertreatment. The crock fastness properties were not impaired 
compared with a dyeing without aftertreatment. 
Use Example 3 
Two cotton dyeings by method I with 0.25% and 1.6% of the dye C.I. Reactive 
Brown 32 were aftertreated as described in Use Example 1. For comparison, 
two dyeings were also aftertreated with a commercial polycationic fixing 
agent. The lightfastness of the lighter dyeing was 4, that of the darker 
dyeing 5; the comparative dyeings were each lower by 1.5. The hot/moist 
test rating was 10 in each case; the ratings for the comparative dyeings 
were 10 for the lighter dyeing and 8 for the darker dyeing. 
Use Example 4 
The bleached and mercerized cotton material was dyed with 2.1% of the dye 
C.I. Reactive Red 204 by method I. It was then aftertreated for 15 minutes 
at 40.degree. C. with an aqueous solution which, based on the dry textile 
material, contained 1.0% of the resin of Synthesis Example 14. The pH of 
the aftertreating liquor was 7.7. The aftertreated dyeing gave a severe 
waterfastness test rating of 5 and a hot/moist test rating of 9-10. A 
comparative dyeing which had not been aftertreated had a severe 
waterfastness test rating of 3-4 and a hot/moist test rating of 4-5. 
Use Example 5 
The bleached and mercerized cotton material was dyed with 5.0% of the dye 
C.I. Reactive Red 120 by method I and was aftertreated by the method of 
Use Example 4 with the quaternized resin of Synthesis Example 18. The 
severe waterfastness test rating was 5 compared with the 3 of the same 
dyeing without aftertreatment. The hot/moist test rating was 9-10 compared 
with 4 without aftertreatment. 
Use Example 6 
A dyeing was prepared with 1.8% of the dye C.I. Reactive Red 120 which was 
then aftertreated with the quaternized resin of Synthesis Example 18, both 
steps being carried out as described in Use Example 5. The wet crock 
fastness test rating was 2-3, the rating for the untreated dyeing being 2. 
Use Example 7 
Bleached and mercerized cotton cloth was dyed with 5.0% of the dye C.I. 
Reactive Blue 168 by method II and then aftertreated for 15 minutes at 
60.degree. C. with an aqueous solution which, based on the dry textile 
material, contained 1.0% of the quaternized resin of Synthesis Example 13. 
The pH of the aftertreating liquor was 7.1. The dyeing thus aftertreated 
scored 9-10 in the hot/moist test, while the corresponding dyeing which 
had not been aftertreated scored 1-2. 
Use Example 9 
The bleached and mercerized cotton fabric was dyed with 1.8% of the dye 
Reactive Red 2 by method II and then aftertreated for 15 minutes at 
40.degree. C. with an aqueous solution which, based on the dry textile 
material, contained 1.0% of the quaternized resin of Synthesis Example 7. 
The result obtained was a dyeing which scored 5 on the severe 
waterfastness test; the same dyeing without aftertreatment scored 4. The 
hot/moist test rating was 9-10, compared with 7 for the dyeing without 
aftertreatment. The wet crock fastness test rating was 2-3 compared with 2 
for the dyeing which had not been aftertreated. 
Use Example 9 
Bleached and mercerized cotton cloth was dyed with 5.0% of the dye Reactive 
Blue 168 by method II and then aftertreated for 10 minutes at 50.degree. 
C. with an aqueous solution which, based on the dry textile material, 
contained 1.0% of the quaternized resin of Synthesis Example 15. The 
aftertreated dyeing scored 5 in both the severe waterfastness test and the 
perspiration fastness test. The hot/moist test rating was 9-10. The same 
dyeing without aftertreatment scored 3 in the hot/moist test and 3-4 each 
for the severe waterfastness and the perspiration fastness. 
Use Example 10 
Bleached and mercerized cotton cloth was dyed with 1.8% of the dye C.I. 
Reactive Red 120 by method I and was aftertreated by the method of Use 
Example 7 with the quaternized resin of Synthesis Example 8. A dyeing 
which had not been aftertreated served as a comparison. The alkaline 
perspiration fastness was 4-5 compared with 3-4 for the comparative 
dyeing. The wet crock fastness was 2-3, compared with 2 for the 
comparative dyeing. 
Use Example 11 
Bleached and mercerized cotton cloth was dyed with 0.7% and 4.0% of the dye 
C.I. Reactive Yellow 22 by method II and was then aftertreated for 10 
minutes at 50.degree. C. with an aqueous solution which, based on the dry 
textile material, contained 1.0% of the quaternized resin of Synthesis 
Example 8 (a). The fastness values were compared with those of 
corresponding dyeings which had not been aftertreated (b) and dyeings 
which had been aftertreated with a commercial polycationic fixing agent 
(c). The lightfastness test and hot/moist test ratings are shown in the 
following table: 
______________________________________ 
Ratings for Sample (a) Sample (b) 
Sample (c) 
______________________________________ 
0.7% of dye 5-6 6 4-5 
Lightfastness 
Hot/moist test 
10 7 9-10 
4.0% of dye 6-7 7 6 
Lightfastness 
Hot/moist test 
10 6 9 
______________________________________