Aqueous, hard water-resistant wetting agent and detergent composition, and the preparation and use thereof in textile pretreatment

Aqueous, hard water-resistant wetting agent and detergent compositions comprising (a) a mixture of monomeric and oligomeric phosphoric acid esters, (b) a water-soluble or water-dispersible copolymer, (c) a nonionic surfactant, (d) an alkali metal hydroxide and optionally (e) an antifoam. These compositions can be used as wetting agents and detergents in textile pretreatment.

The present invention relates to a novel aqueous, hard water-resistant 
wetting agent and detergent composition and to the preparation and use 
thereof in textile pretreatment. 
The hard water-resistant wetting agent and detergent composition of this 
invention comprises 
(a) a mixture of monomers and oligomers of formula 
##STR1## 
wherein Y.sub.1 is hydrogen or --CO--T.sub.1, R.sub.1, X.sub.1 and T.sub.1 
are each C.sub.1 -C.sub.4 alkyl, and m.sub.1 is an integer from 1 to 17, 
(b) a water-soluble or water-dispersible copolymer which contains not less 
than 20% by weight, based on said copolymer, of a hydrophilic component 
which is attached to a carbon atom and at least one hydrophobic radical 
which is attached through a polyglycol ether chain to the hydrophilic 
component, which polyglycol ether chain contains 2 to 200 
##STR2## 
groups, 
(c) a nonionic surfactant, 
(d) an alkali metal hydroxide, and optionally 
(e) an antifoam. 
Component (a) of this invention is mixture of water-soluble monomers and 
oligomers of formula (1) which are preferably in the form of alkali metal 
salts, more particularly sodium salts and, most preferably, potassium 
salts. 
Preferred mixtures of monomers and oligomers which are used as component 
(a) of the composition of this invention are in particular those of 
formula 
##STR3## 
wherein R.sub.2 is methyl or ethyl and m.sub.2 is 1 to 13. 
The monomer unit of the mixture of monomers and oligomers of formula (1) 
has the general formula 
##STR4## 
wherein Y.sub.1 is hydrogen or --CO--T.sub.1 and R.sub.1 and T.sub.1 are 
each independently of the other C.sub.1 -C.sub.4 alkyl. 
A particularly preferred monomer is that of formula 
##STR5## 
The compounds suitable for use as component (b) are water-soluble graft 
polymers which, on the one hand, contain a main chain consisting of an 
anionic, cationic, amphoteric or, preferably, nonionic alkylene oxide 
polyadduct which carries a hydrophobic radical and, on the other, side 
chains of structural units grafted on to individual carbon atoms of said 
main chain, which structural units are derived from ethylenically 
unsaturated polymerisable monomers which contain hydrophilic groups, for 
example monomeric sulfonic acids or, preferably, carboxylic acids or the 
anhydrides thereof. 
The monomers required for introducing the side chains may be used singly or 
in admixture with one another. 
Preferred graft polymers of this invention have a main chain consisting of 
at least one nonionic alkylene oxide polyadduct which carries a 
hydrophobic radical and whose second terminal hydroxyl group is 
unsubstituted. These nonionic surfactants are preferably polyadducts of 2 
to 200 mol of alkylene oxide, for example ethylene oxide and/or propylene 
oxide, with 1 mol of an aliphatic monoalcohol containing not less than 8 
carbon atoms, of a trihydric to hexahydric aliphatic alcohol or of a 
C.sub.8 -C.sub.22 fatty acid. The trihydric to hexahydric alkanols contain 
3 to 6 carbon atoms and are, in particular, glycerol, trimethylolpropane, 
erythritol, mannitol, pentaerythritol and sorbitol. 
Aliphatic monoalcohols for the preparation of the nonionic surfactants are, 
for example, water-insoluble monoalcohols containing not less than 8 
carbon atoms, preferably from 12 to 22 carbon atoms. These alcohols may be 
saturated or unsaturated and branched or straight chain, and may be used 
singly or in admixture. Alcohols which may be reacted with the alkylene 
oxide are, for example, natural alcohols such as myristyl alcohol, cetyl 
alcohol, stearyl alcohol or oleyl alcohol, or synthetic alcohols, for 
example oxoalcohols such as preferably 2-ethylhexanol, and also trimethyl 
hexanol, trimethylnonyl alcohol, hexadecyl alcohol or linear primary 
alcohols containing on average (8 to 10), (10 to 14), (12), (16), (18), or 
(20 to 22) carbon atoms. 
The fatty acids preferably contain from 8 to 12 carbon atoms and may be 
saturated or unsaturated, and are, for example, capric acid, lauric acid, 
myristic acid, palmitic acid or stearic acid, or decenoic acid, dodecenoic 
acid, tetradecenoic acid, hexadecenoic acid, oleic acid, linoleic acid, 
linolenic acid or, preferably, ricinolic acid. 
Ethylenically unsaturated polymerisable carboxylic acids or sufonic acids 
which may be suitably used for introducing the grafted monomers (side 
chains) into the alkylene oxide polyadducts which constitute the main 
chain may be monocarboxylic acids as well as dicarboxylic acids and the 
anhydrides thereof and also sulfonic acids, each containing an 
ethylenically unsaturated aliphatic radical and preferably not more than 7 
carbon atoms. The monocarboxylic acids are for example acrylic acid, 
methacrylic acid, .beta.-haloacrylic acid, 2-hydroxyethylacrylic acid, 
.beta.-cyanoacrylic acid, crotonic acid and vinylacetic acid. Preferred 
ethylenically unsaturated dicarboxylic acids are fumaric acid, maleic acid 
or itaconic acid, and also mesaconic acid, citraconic acid, glutaconic 
acid and methylenemalonic acid. The preferred anhydride of these acids is 
maleic anhydride. 
Examples of suitable sulfonic acids are vinylsulfonic acid or 
2-acrylamido-2-methylpropanesulfonic acid. It is preferred to use 
monocarboxylic acids of 3 to 5 carbon atoms, more particularly methacrylic 
acid, and, most preferably, acrylic acid. 
Particularly interesting graft polymers contain, as main chain, radicals of 
a polyadduct of 2 to 40 mol of ethylene oxide with 1 mol of a C.sub.12 
-C.sub.22 -fatty alcohol and, as side chains, not less than 30% by weight, 
preferably not less than 50% by weight, based on said graft polymer, of 
grafted acrylic acid. 
The preparation of the graft polymers is carried out by methods which are 
known per se, for example those described in European patent application 0 
098 803. 
Exemplary of nonionic alkylene oxide polyadducts which are used as main 
chain of component (a) are the following products: 
A.sub.1 the polyadduct of 6 mol of ethylene oxide with 1 mol of 
2-ethylhexanol, 
A.sub.2 the polyadduct of 5 mol of ethylene oxide with 1 mol of 
2-ethylhexanol, 
A.sub.3 the polyadduct of 15 mol of ethylene oxide with 1 mol of stearyl 
alcohol, 
A.sub.4 the polyadduct of 3 mol of ethylene oxide with 1 mol of alfol 
(8-10), 
A.sub.5 the polyadduct of 5 mol of ethylene oxide with 1 mol of hexadecyl 
alcohol, 
A.sub.6 the polyadduct of 18 mol of ethylene oxide with 1 mol of oleyl 
alcohol, 
A.sub.7 the polyadduct of 12 mol of ethylene oxide with 1 mol of oleic 
acid, 
A.sub.8 the polyadduct of 5 mol of ethylene oxide with 5 mol of propylene 
oxide and 1 mol of alfol (12-14), 
A.sub.9 the polyadduct of 7 mol of ethylene oxide with 1 mol of C.sub.9 
-C.sub.13 oxoalcohol. 
In addition to the nonionic surfactants mentioned above, compounds suitable 
for use as component (c) are nonionic polyadducts of 2 to 200 mol of 
alkylene oxide, for example, ethylene oxide and/or propylene oxide, with 1 
mol of a phenol or of an alkyl- or phenyl-substituted phenol or of a 
C.sub.8 -C.sub.22 fatty acid. Monoalcohols of 8 to 22 carbon atoms are 
preferred. 
Examples of unsubstituted or substituted phenols are phenol, o-phenylphenol 
or alkylphenols which contain 1 to 16, preferably 4 to 12, carbon atoms in 
the alkyl moiety. Examples of these alkylphenols are: p-cresol, 
butylphenol, tributylphenol, octylphenol and, most preferably, 
nonylphenol. 
Typical examples of nonionic surfactants are: 
polyadducts of preferably 1 to 30 mol of alkylene oxide, preferably 
ethylene oxide, in which individual ethylene oxide units may be replaced 
by substituted epoxides such as styrene oxide and/or propylene oxide, with 
higher unsaturated or saturated fatty alcohols, fatty acids, fatty amines 
or fatty amides of 8 to 22 carbon atoms, or with phenylphenol or 
alkylphenols whose alkyl moieties contain not less than 4 carbon atoms; 
condensates of alkylene oxide, preferably of ethylene oxide and/or 
propylene oxide; 
reaction products of a C.sub.8 -C.sub.22 fatty acid and a primary or 
secondary amine containing at least one hydroxy-lower alkyl group or lower 
alkoxy-lower alkyl group, or adducts of alkylene oxide with said 
hydroxyalkylated reaction products, the reaction being carried out such 
that the ratio of hydroxyalkylamine to fatty acid may be 1:1 or greater 
than 1, for example 1:1 to 2:1; and 
polyadducts of propylene oxide with a trihydric to hexahydric aliphatic 
alcohol of 3 to 6 carbon atoms, for example glycerol or pentaerythritol, 
which polypropylene oxide adducts have an average molecular weight of 250 
to 1800, preferably 400 to 900; and 
esters of polyalcohols, especially mono- or diglycerides of C.sub.12 
-C.sub.18 -fatty acids, for example monoglycerides of lauric, stearic or 
oleic acid. 
Very suitable nonionic surfactants are polyadducts of 2 to 15 mol of 
ethylene oxide with 1 mol of C.sub.8 -C.sub.22 fatty alcohol or C.sub.8 
-C.sub.22 fatty acid or with 1 mol of C.sub.4 -C.sub.12 alkylphenol or 
fatty acid dialkanolamides containing 8 to 22 carbon atoms in the fatty 
acid moiety. 
Alkali metal hydroxides suitable for use as component (d) are sodium 
hydroxide and, preferably, potassium hydroxide. 
Optional component (e) of the detergent composition of this invention is an 
antifoam based on tributylphosphate or a higher alcohol, for example 
2-ethylhexanol or isooctyl alcohol. It is, however, also possible to use 
antifoams based on silicone oil or alkylenediamines containing amide 
groups of formula RCONH--, wherein R is an aliphatic or cycloaliphatic 
radical, for example C.sub.9 -C.sub.23 alkyl or cyclohexyl, as well as 
silicone oils themselves. Further antifoams are disclosed in GB patent 
specification 1 197 776 or in U.S. Pat. No. 4,767,568. 
The wetting agent and detergent composition of this invention comprises 
with advantage, based on the entire composition, 
4-8% by weight of component (a), 
5-10% by weight of component (b), 
8-15% by weight of component (c), 
4-8% by weight of component (d), 
0-5% by weight of component (e), and 
water to make up 100% by weight. 
The novel formulations are especially suitable for use as effective wetting 
agents and detergent compositions in textile pretreatment. 
Accordingly, the present invention also relates to a process for washing 
and wetting untreated textiles. The process comprises treating these 
materials, in aqueous medium, in the presence of a novel wetting agent. 
The amounts in which the wetting agent and detergent composition is added 
to the treatment liquors range from 0.1 to 20 g, preferably from 0.5 to 10 
g, per liter or treatment liquor. This liquor may contain further 
ingredients, for example desizing agents, dyes, fluorescent whitening 
agents, synthetic resins and alkalies such as sodium hydroxide. 
Suitable fibre materials are: cellulose, especially non-pretreated natural 
cellulose such as raw cotton, hemp, linen, jute, and regenerated cellulose 
such as viscose rayon, viscose staple fibre, acetate rayon, wool, 
polyamide, polyacrylonitrile or polyester fibre materials and fibre 
blends, for example polyacrylonitrile/cotton or polyester/cotton blends. 
The fibre material to be treated may be in any form of presentation, for 
example the cellulosic material in the form of open fabric, yarn, woven or 
knitted fabrics. The material will usually be in the form of textile fibre 
materials which are made from pure textile cellulosic fibres or from 
blends of textile cellulosic fibres with synthetic textile fibres or from 
blends of textile cellulosic fibres and synthetic textile fibres. The 
fibre material can be treated continuously or batchwise in an aqueous 
liquor. 
The aqueous treatment liquors can be applied in known manner to the fibre 
materials, conveniently by impregnating on a pad to a pick-up of ca. 50 to 
120% by weight. The pad process used will preferably be the pad-steam 
method as well as the pad-batch method. 
Impregnation can be effected in the temperature range from 20.degree. to 
60.degree. C., preferably at room temperature. After impregnation, the 
cellulosic material is subjected to a heat treatment direct, i.e. without 
first being dried, by steaming in the temperature range from 95.degree. to 
120.degree. C., preferably from 98.degree. to 106.degree. C., which 
treatment may take from 30 seconds to 40 minutes, in accordance with the 
nature of the heat development and the temperature range. In the pad-batch 
method, the impregnated goods are rolled up without being dried and 
subsequently packed in a plastic sheet and stored for 1 to 24 hours at 
room temperature. 
The treatment of the fibre materials may also, however, be carried out in 
long liquors at a liquor to goods ratio of, for example, 1:3 to 1:100, 
preferably 1:8 to 1:25, and in the temperature range from 20.degree. to 
100.degree. C., preferably from 80.degree. to 98.degree. C., for ca. 1/4 
hour to 3 hours under normal conditions, i.e. under atmospheric pressure 
in conventional apparatus, for example a jigger, a winch beck or a jet. If 
desired, however, the treatment may also be carried out in the temperature 
range up to 150.degree. C., preferably from 105.degree. to 140.degree. C., 
under pressure in high-temperature (HT) apparatus. 
If the process requires it, the fibre materials are subsequently thoroughly 
rinsed with hot water of ca. 90.degree. to 98.degree. C. and then with 
warm and finally with cold water, neutralised, and then hydroextracted 
preferably at elevated temperature and dried. 
Material advantages of the textile assistants of this invention are, in 
addition to their excellent wetting action, their good hard water 
resistance and low foaming tendency in use.

In the following Examples, percentages are by weight throughout. 
Preparation of the formulations 
113 g of a 50% aqueous solution of potassium hydroxide in 239 g of 
deionised water are charged at a stirring rate of 60 rpm to a ground glass 
flask of 1500 ml capacity fitted with an anchor agitator. In this 
solution, 157 g of the mixture of oligomers of formula (2), wherein 
R.sub.2 is methyl, are partially neutralised, whereupon the temperature 
rises to ca. 55.degree. C. Then 315 g of a 25% aqueous formulation of the 
polymerisation product of the polyadduct of 1 mol of a C.sub.13 oxoalcohol 
with 9 mol of ethylene oxide and 1 mol of acrylic acid, 126 g of the 
polyadduct of 4 mol of ethylene oxide with 1 mol of a C.sub.9 -C.sub.11 
fatty alcohol, and 50 g of an antifoam based on 2-ethylhexanol and 
silicone oil are slowly stirred in, in succession. A pourable, milky 
formulation with a pH of 4.5 is obtained. 
EXAMPLE 2 
113 g of a 50% solution of potassium hydroxide in 284 g of deionised water 
are charged to an apparatus as described in Example 1. In this solution, 
157 g of the mixture of oligomers of formula (2), wherein R.sub.2 is 
methyl, are partially neutralised, whereupon the temperature rises to 
55.degree. C. Then 315 g of a 25% aqueous formulation of a polymerisation 
product of the polyadduct of 1 mol of a C.sub.13 oxoalcohol with 9 mol of 
ethylene oxide and 1 mol of acrylic acid, 125 g of the polyadduct of 4 mol 
of ethylene oxide with 1 mol of a C.sub.9 -C.sub.11 fatty alcohol, and 5 g 
of a silicone oil formulation are slowly stirred in, in succession. A 
pourable, milky formulation with a pH of 4.5 is obtained. 
EXAMPLE 3 
113 g of a 50% aqueous solution of potassium hydroxide in 284 g of 
deionised water are charged to an apparatus as described in Example 1. In 
this solution, 157 g of the mixture of oligomers of formula (2), wherein 
R.sub.2 is methyl, are partially neutralised, whereupon the temperature 
rises to ca. 55.degree. C. Then 315 g of a 25% aqueous formulation of a 
polymerisation product of the polyadduct of 1 mol of a C.sub.13 oxoalcohol 
with 9 mol of ethylene oxide and 1 mol of acrylic acid, 126 g of the 
polyadduct of 5 mol of ethylene oxide with 1 mol of isotridecyl alcohol, 
and 5 g of a silicone oil formulation are slowly stirred in, in 
succession. A pourable, milky formulation with a pH of 4.5 is obtained. 
EXAMPLE 4 
113 g of a 50% solution of potassium hydroxide in 239 g of deionised water 
are charged to an apparatus as described in Example 1. In this solution, 
157 g of a mixture of oligomers of formula (2), wherein R.sub.2 is methyl, 
and for 30% of the mixture 2.ltoreq.m.sub.2 .ltoreq.13 and for 70% of the 
mixture m.sub.2 =1, are partially neutralised, whereupon the temperature 
rises to ca. 60.degree. C. Then 315 g of a 25% aqueous formulation of a 
polymerisation product of the polyadduct of 1 mol C.sub.13 oxoalcohol with 
9 mol of ethylene oxide and 1 mol of acrylic acid, 126 g of the polyadduct 
of 4 mol of ethylene oxide with 1 mol of a C.sub.9 -C.sub.11 fatty 
alcohol, and 50 g of an antifoam based on 2-ethylhexanol and silicone oil 
are slowly stirred in, in succession. A pourable, milky formulation with a 
pH of 4.5 is obtained. 
EXAMPLE 5 
The procedure of Example 1 is repeated, charging a solution of potassium 
hydroxide in 189 g of water to the apparatus and using, as antifoam, 100 g 
of a defoamer consisting of 1.65 g of N,N'-ethylene bis(stearamide), 2 g 
of magnesium stearate, 37 g of bis(2-ethylhexyl)maleate, 37.35 g of 
paraffin oil (Shelloil L 6189), 11 g of a nonionic emulsifier, for example 
Tween 65.RTM. and 11 g of an anionic emusifier, for example Phospholan 
PNP9.RTM.. 
EXAMPLE 6 
The procedure of Example 5 is repeated, using as antifoam 100 g of a foam 
inhibitor consisting of 47 g of the copolymer of butyl acrylate and 
bis(2-ethylhexyl)maleate 50:50, 39 g of isopalmityl alcohol, 7 g of an 
ethoxylated polydimethyl siloxane, 3.5 g of the polyadduct of 9 mol of 
ethylene oxide with 1 mol of styrene oxide and 1 mol of C.sub.13 
oxoalcohol, and 3.5 g of oleic acid. 
EXAMPLE 7 
113 g of a 50% solution of potassium hydroxide in 289 g of deionised water 
are charged to an apparatus as described in Example this solution, 157 g 
of a mixture of oligomers of formula (2), wherein R.sub.2 is methyl, are 
partially neutralised, whereupon the temperature rises to ca. 50.degree. 
C. Then 315 g of a 25% aqueous formulation of a polymerisation product of 
the polyadduct of 1 mol of a C.sub.13 oxoalcohol with 9 mol of ethylene 
oxide and 1 mol of acrylic acid, 126 g of the polyadduct of 4 mol of 
ethylene oxide with 1 mol of a C.sub.9 -C.sub.11 fatty alcohol are slowly 
stirred in, in succession. A pourable, milky formulation with a pH of 4.5 
is obtained. 
USE EXAMPLES 
EXAMPLE 1 
The detergent and wetting agent formulations prepared in accordance with 
Examples 1 to 3 are tested for their detergent properties in comparison 
with a detergent which does not contain components (a) and (e) of the 
formulations of this invention. 
The test is carried out by washing a polyester/cotton blend, which has been 
artificially soiled with soot and engine oil, in an AHIBA dyeing machine 
with twist for 30 minutes at 40.degree. C. and at a liquor to goods ratio 
of 1:25. The amount of each detergent composition used is 1 g/l. The pH is 
adjusted to 10 with sodium hydroxide solution. The water hardness is 
0.degree. and 10.degree. dH (German hardness). 
Upon termination of the washing, the fabrics are individually rinsed, 
hydroextracted and dried. 
The determination of the colour difference according to DIN 6174 between 
the washed and non-washed sample is then made. The non-washed sample is 
given the reflectance number 0. The higher the reflectance number, the 
better the detergent action. 
The results reported in the following Table show that a markedly better 
detergent action is achieved with the formulations of the invention using 
hard water (10.degree.) than with the comparison detergent. 
______________________________________ 
Reflectance number 0.degree. dH 
10.degree. dH 
______________________________________ 
formulation according 
24.1 20.8 
to Example 1 
formulation according 
23.1 25.1 
to Example 2 
formulation according 
23.0 21.6 
to Example 3 
comparison detergent 
24.1 4.5 
______________________________________ 
EXAMPLE 2 
The formulations prepared according to Examples 1-3 are tested for their 
foaming behaviour in comparison with a detergent that does not contain 
components (a) and (e) of the formulations of this invention. The test is 
carried out by diluting 1 g of active substance of each of the 
formulations prepared according to Examples 1-3 to 1 liter with deionised 
water and adjusting the pH to 10 with sodium hydroxide solution. The 
formulations are then tested for their foaming behaviour in relation to 
the comparison detergent composition in accordance with DIN 53 902 
(beating method). 
The results set forth in the Table below indicate that the formulations of 
this invention have a significantly better foaming behaviour than the 
comparison detergent composition. 
______________________________________ 
foam height (ml) 
immediately 
after 1 minute 
______________________________________ 
comparison detergent 
500 480 
formulation according 
70 60 
to Example 1 
formulation according 
70 60 
to Example 2 
formulation according 
30 20 
to Example 3 
______________________________________ 
EXAMPLE 3 
An untreated cotton fabric of 250 g/m.sup.2 is impregnated with the 
following formulation: 
10 g/l of the formulation according to Example 1 
60 g/l of solid sodium hydroxide. 
The pick-up is 90%. After this treatment, the goods are steamed for 10 
minutes with saturated steam at 101.degree. C., rinsed with hot and cold 
water, neutralised and dried. The detergent effect is determined by 
measuring the degree of whitness (CIBA-GEIGY Whiteness Scale). 
The untreated material has a degree of whiteness of -65, whereas the 
treated material has a degree of whiteness of 10. 
EXAMPLE 4 
A cotton/polyester blend (67/33) of 200 g/m.sup.2 is selectively soiled 
with loom lubricating oil and treated (aged) for 1 hour at 100.degree. C. 
The stained fabric is then washed for 30 minutes at 60.degree. C. in a 
washing liquor which contains 10 g/l of the formulation according to 
Example 1 and is adjusted to pH 10, and subsequently dried. The oil stain 
applied to the fabric and heat-aged is completely removed after the 
washing.