US 3775052 A
A carpet shampoo containing as essential ingredient a mixture of A. 10-70 % BY WEIGHT OF A DETERGENT OF THE FORMULA [RO-(C2H4O)n-(CH2)xCOO]mM wherein R is hydrophobic hydrocarbon residue of 8 to 20 carbon atoms which may contain one or more hydrophobic oxyalkylene units, n has an average value of 0-10, x is 1 or 2, m is 1 or 2, and M is a monovalent or divalent cation; and B. 90-30 % BY WEIGHT OF A FINELY DIVIDED ADSORBENT SOLID, IS PROVIDED. This shampoo can be prepared in the form of an aqueous concentrate of a solids content of e.g. 20-50 % and this concentrate can be diluted to the use concentration of 1-30 %. The shampoo can also be prepared conveniently in the form of an aerosol.
Description (OCR text may contain errors)
nited States Patent [191 Van Paassen DETERGENT COMPOSITIONS FOR CARPETS AND THE LIKE Inventor: Nicolaas A. 1. Van Paassen, Rijswijk,
Netherlands Chem-y, Fabriek Van Chemische Produkten N.V., Bodegraven, Netherlands Filed: Nov. 5, 1971 Appl. No.: 196,215
Foreign Application Priority Data Nov. 6, 1970 Great Britain 52,959/70 U.S. Cl 8/137, 252/88, 252/89, 260/78.5
Int. Cl D061 Field of Search 8/137; 252/88, 89; 260/857, 78.5
References Cited UNITED STATES PATENTS 6/1962 de Jong et a1. 252/551 8/1957 Hofer et al 8/139 12/1971 Sheaffer et al 8/137 6/1968 Muskat 260/78.5
OTHER PUBLICATIONS Rug Shampoo Clean" Chemical Week, July 12, 1969 pages 26 & 27
Primary Examiner -Mayer Weinblatt Attorney-Alvin Browdy et a1.
[ 5 7 ABSTRACT A carpet shampoo containing as essential ingredient a mixture of a. 10-70 by weight of a detergent of the formula l 2 4 )1| 2)1 ]m wherein R is hydrophobic hydrocarbon residue of 8 to 20 carbon atoms which may contain one or more hydrophobic oxyalkylene units, n has an average value of 010, x is l or 2, m is 1 or 2, and M is a monovalent or divalent cation; and
b. 90-30 by weight of a finely divided adsorbent solid, is provided. This shampoo can be prepared in the form of an aqueous concentrate of a solids content of e.g. 20-50 and this concentrate can be diluted to the use concentration of l-30 The shampoo can also be prepared conveniently in the form of an aerosol.
10 Claims, No Drawings DETERGENT COMPOSITIONS FOR CARPETS AND THE LIKE This invention relates to improved detergent compositions which are especially suitable for the'cleaning of carpets, rugs, furniture upholstery, car upholstery and the like.
Solutions of anionic detergents like alkyl benzene sulfonates and alkyl-(polyoxyethylene)-sulfates in the form of the usual sodium or potassium salts or salts of various amines, e.g. mono-, dior triethanolamine, have been used for this purpose. Although such detergents do have a cleaning action on the carpet, rug or the like, they suffer from the disadvantage that they leave a tacky residue thereon. Accordingly, one could not walk on the carpet or rug, or not sit on an upholstered chair until this residue has completely dried so that the time necessary for the entire cleaning operation became impractically long.
The general aim is of course to arrive at cleaning operations which require so little time that it is possible for example to have a carpet in an office cleaned early in the morning, whereafter it can be used again at the start of the normal office hours. An improvement towards this aim has been the combined use of a detergent solution with a solid capable of taking up the residue of detergent and dirt. On drying, such a combined detergent forms a solid residue on the carpet or the like, which residue can be removed by brushing, vacuum-cleaning or the like. Various kinds of solids have been proposed in this respect. Thus, the examples of Dutch patent application 6409345 (which will be discussed more fully hereinafter) describe the use of solids having sorbent properties, such as bentonite, and kieselguhr. More recently brittle resins have also been used for this purpose, vide Chemical Week, July 12, 1969, page 26.
By the addition of these kinds of solids a great improvement is indeed achieved, in that the entire cleaning operation now requires much less time. However, the results of the cleaning still were not satisfactory. Apparently, the usual detergents suitable for various purposes are not ideally suited for cleaning carpets and the like. A proposal to use special detergents for these purposes is found in the already mentioned Dutch patent application 6409345. According to this patent application one should not use the anionic detergents in the form of the usual sodium or potassium salts, but in the form of the lithium salts. It is stated in the application that the use of the lithium salts would lead to two effects: the forming of a less tacky residue, and a longer lasting cleaning effect. The first mentioned statement is probably due to an error, because in most of the examples an adsorbing solid is added according to the above-discussed technique, and of course the effect on the tackiness of such a solid is considerable. Moreover, in experiments carried out by the present inventor the lithium salts of most anionic detergents still yielded a more or less tacky residue, both in the presence and in the absence of added solids. Also the comparisons made in the various examples of the Dutch patent application only relate to the longer lasting cleaning effect of the lithium salts.
The Dutch patent application 6409345 states explicitly that any of the various classes of anionic detergents can be used in the form of their lithium salts in shampoos for carpets, rugs and the like. As examples are mentioned fatty alcohol sulfates, fatty alcohol ether sulfates, alkyl benzene sulfonates, alkyl succinic ester sulfonates, alkane sulfonates and also higher carboxylates. No preference is stated for any of these classes of compounds; only a preference is stated for compounds containing l2-l 8 carbon atoms. This preference in this form is rather incomprehensible, but is probably meant to relate to the hydrophobic part of the molecule. However, even when reading this statement in the above sense, it is not quite logical, because the action of a detergent for a certain purpose will depend on its HLB- value (HLB hydrophilic-lyophilic balance), and of course this value can strongly differ for various compounds, even though they have the same number of carbon atoms in the hydrophobic portion of their molecules. Experiments carried out by the present inventor has shown that all other factors being equal, the lithium salt does not always work better in a shampoo for carpets, rugs and the like than the corresponding sodium or potassium salt, and that there are much more important differences between the various classes of compounds mentioned in the Dutch patent application, so that the lithium salts of compounds of some of the classes mentioned therein are even inferior to sodium salts of some other classes of compounds.
It has now been found that a special class of anionic surfactants which have not even been mentioned in the Dutch patent application discussed hereinabove has outstanding properties, when used in shampoos for carpets and rugs and the like, and that within this class both the lithium salts and the corresponding salts of sodium, potassium or amines etc. have an excellent action, so that all these salts are detergents which are far better suited for use in shampoos for carpets, rugs and the like than any other anionic surfactant used for this purpose up till now. The surfactants are compounds of the formula [RO(C H.,O),,-(CH COO],,,M wherein R is a hydrophobic hydrocarbon residue of eight to 20 carbon atoms, which may contain one or more hydrophobic oxyalkylene units, n has an average value of 0-10, I is one of the numbers 1 and 2, m is one of the numbers 1 and 2 and M is a monovalent or divalent cation.
The hydrocarbon residue R can be saturated or unsaturated, and it may contain an aromatic nucleus. Of course, the number of carbons of this residue has some influence on the HLB-value of the product, and therefore it is preferred that the average value of n is in the lower end of the defined range in case the number of carbon atoms in R is smaller than 12, whereas values of n near the upper limit are more desirable, when R contains 16 carbon atoms or more. Preferably, the residue R contains 12-14 carbon atoms in which case average values of n in the range of 3-4 yield a highly satisfactory product.
As is well known, the present compounds, wherein at is 1, can be prepared by either reacting a polyether alcoholate of the formula RO--(C H O),,Me, wherein Me is an alkali metal, with a haloacetic acid or salt thereof, or oxidizing a compound of the formule RO(C2H4O),, H, whilst compounds, wherein x is 2, can be prepared by reacting a compound RO(C H4O),,H with e.g. acrylonitrile, followed by hydrolysis. The above-mentioned ethoxylated intermediates are in turn prepared by ethoxylating a compound of the formula ROH. A particularly suitable starting product of the formula ROH is commercial lauryl alcohol derived from oils and fats which contains about 70-75% of n-lauryl alcohol and about 25-30% of other alcohols having even numbers of carbon atoms. mainly tetradecyl alcohol. From this commercial alcohol a very satisfactory detergent product can be prepared. Of course, synthetic alcohol products, also the branched products (such as the oxo alcohols) and the like can be used likewise.
As is well known, a mixture of products having various values of n is formed during the ethoxylation reaction, and accordingly, the final product will also be a mixture having various values of n. According to a further aspect of the invention it is sometimes preferred to use a product which is a mixture which shows a rather narrow distribution of n values. As disclosed in British patent specification 1,027,481, salts of the formula RO(C:H ),,CH C0OM (wherein M is a cation) having a narrow distribution of n values can be prepared by starting from an ethoxylation product RO-(C2H4O),,H having already such a narrow distribution. The ethoxylation product having the desired narrow distribution of n values can be obtained in turn by separating a desired fraction from a broader range of ethoxylation products, but it is also possible to carry out the ethoxylation with acidic catalysts, such as described for example in US. Pat. No. 2,870,220.
Examples of individual detergent compounds are the following, wherein E0 means an oxyethylene unit: The salts of octyloxy-CH CO0H, octyloxy- E0CH CO0H, octyloxy-EO-CH CH COOH, octyloxy-(E0) CH CH C0OH, octyloxy- (E0) C1-l C00l-l, nonylQXy-CH COOH, nonyloxy- (E0) CH CH COOH, decyloxy-CH C00H, decyloxy-EO--CH CO0H, decyloxy-E0CH CH CO0H, decyloxy-( EO) -CH COOH, decyloxy- (EO) CH CH C00H, dodecyloxy- (E0) --CH CO0H, dodecyloxy-(EO) CH COOH,
dodecyloxy-(EO) --CH CH C00H, dodecyloxy- E0 CH CH C0OH, tert.dodecyloxy- (E0 -CH C00H, branched tridecyloxy- E0 CH C1-l- COOH tetradecyloxy- E0--CH CO0H, tetradecyloxy- (E0 -CH Cl-l C0OH, tetradecyloxy- (EO) CH CH COOH, tetradecyloxy- (E0 CH CO0H, hexadecyloxy- (EO) -CH CH C001-l, hexadecyloxy- (EO CH C0OH, hexadecyloxy- (E0) CH COOH, hexadecyloxy- (EO) CH CH C00H, octadecyloxy- (E0) CH C00H, octadecyloxy- EO) CH CH CO0H, eicosyloxyoleyloxy-(EO CH CH C0OH, butylphenoxy- EO-Cl-hCOOl-l, butylphenoxy- (E0 CH CH C0OH, octylphenoxy- 2 octylphenoxy- (E0 -,CH CH COOH, nonylphenoxy- (E0 ),CH C00H, nonylphenoxy- (E0) CH CH,C00H, dodecylphenoxy- (EO) --CH C00H, dodecylphenoxy- (EO) CH CH,CO0H, tert.dodecylphenoxy- (E0) CH C0OH, tert.dodecylphenoxy- (E0) C1-l CH C00l-l, dodecenylphenoxy- (EO) C1-1 C00H, and dodecenylphenoxy- (EO) -CH CH COOH with lithium, sodium, potassium, magnesium, calcium, strontium, barium, cadmium, zinc, copper, nickel, manganese, beryllium, methylamine, dimethylamine, ethylamine, diethylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, di-isopropylamine, butanolamine, trihexylamine, cyclohexylamine, piperidine, morpholine, piperazine, di-octylamine, dodecylamine, tripentadecylamine, eicosylamine, butyl ethanolamine, hexyl propanolamine, butylene diamine, 1,6-diaminohexane, 1,8-diaminooctane, 1,1 l-diaminoundecane, ethyl hexylamine, butylcyclohexylamine etc.
Within the series of preferred products wherein R is the residue of an aliphatic alcohol, the properties vary slightly with the nature of the alcohol, even though the value of n is varied at the same time, in order to keep the HLB-value substantially constant. Products, wherein R is in the upper part of the indicated range (1620 carbon atoms) dry somewhat quicker, but give a somewhat less good detergent action than the corresponding compounds containing lower aliphatic groups, and also for this reason, products derived from alcohols of 12-14 carbon atoms are preferred, since they yield an optimal combination of these two properties.
Of course, the detergents used according to this invention, are formulated to rug shampoos or the like in the usual manner, i.e. preferably with solids with which they give a quick-drying residue which takes up the dirt. To this end, one can use any solid having the required action, such as the absorbing materials mentioned in Dutch patent application 6409345, or artificial resins as mentioned in the above-cited article in Chemical Week. In actual practice, brittle artificial resins, i.e. resins which are filmforming at temperatures above 50C are preferred. Such resins may be derived entirely or partially from methyl methacrylate, styrene monomers and similar hard monomers.
According to a particular embodiment of the invention the resins to be used in the shampoo of the invention are prepared by emulsion polymerization, using as emulsifier or dispersing agent a salt of an acid R0(C- H4O),,(CH COOH. After the polymerization some more of the same or a different salt according to the above general formula can be added, if necessary. In this way a composition is obtained, containing both the desired detergetn salts and the artificial resin component.
Of course, usual other constituents of shampoos for rugs, carpets or upholstery can be incorporated into the compositions of this invention. Thus, one can add inorganic salts, perfumes, biocidal agents, etc.
The shampoos of the invention can be prepared in the form of concentrates which can be diluted in the final use concentration. In the use concentration the concentration of the detergent is usually about 0.5 to 3 by weight. The content of the solid sorbents, such as brittle resins or bentonite or the like in the rug shampoos in the use concentration is usually also about 0.5 to 3 by weight. However, in aerosol compositions higher use concentrations are usually applied, such as 5-15 by weight of the aqueous composition (with the exclusion of the propelling gas). Preferably roughly equal amounts of detergent and solid are used, but of course this is not essential, and a broad range of weight ratios between these two substances can be used. For
special purposes, it is also possible to prepare a shampoo without the sorbent solid, but of course, the drying time willthen be longer. I
Of course, other solids than mentioned hereinabove can also be used, such as suitable grades of alumina or silica. i
The following examples illustrate the invention, without, however, limiting the invention in any sense.
EXAMPLE 1 The following products and pure compounds of the formula [R-(C H O),,OCH COO],,,M were used.
1. Product mixtures:
n m M (average value) a C C 3 I Na (commercial lauryl) b C 3 1 Na c C 4 1 Na d C 4 l Na 8 C 5 1 Na f C 5 l Li 2. Pure compounds:
' R n m M g C 3 2 Zn h c,, 3 2 Mg l C 3 2 Ca In order to test the above products and compounds under somewhat more severe conditions than in actual practice, an aqueous solution of each of them was prepared and with these solutions nylon carpets were cleaned. Thereafter the treated carpets were left to dry at ambient temperature (about C).
In all these experiments a dry residue was obtained which could be removed by vacuum-cleaning. The drying times varied between 5 and 6 hours. As was to be expected, the drying time was somewhat dependent on the hydrophility of the detergent. Thus, product b showed a somewhat shorterdrying time than product a and than product 0.
Of course, these drying times are still relatively long, but'not entirely unacceptable for practical purposes, However, as mentioned already, much higher concentrations were used than are usual in normal practice.
A further series of cleaning tests was carried out in the above described way, but this time the solutions contained also varying amounts (3 to 14 by weight) of sorbent materials. Several of these solid materials were tested, such as styrene-acrylate resins which are marketed as Ubatol 3101, bentonite, alumina (the product Dispal" sold by Condea), kieselguhr, etc., whilst also mixtures of such materials were used. All these experiments again yielded a dry residue, but now the drying time was always much shorter, in the order of 1-2 hours. Again some effect was noticed of the degree of hydrophility of the detergent, just as in the first series of tests, but the nature of the added solid had also some effect, and the shortest drying times were obtained with the resin products.
EXAMPLE 2 A nylon carpet of 2 metres X 2 metres was used. The carpet was divided into four equal parts by cellophane strips which were stuck into the pole of the carpet. Each of the so obtained carpet quarts was treated with a 15 aqueous solution of a detergent, and the follow ing four different detergents were used for the four quarts:
a. Lithium dodecylbenzenesulfonate.
b. Myristyl-(C H O),,OCH,COOLi, wherein n has an average value of 3.5. This lithium salt had been prepared from the corresponding carboxylic acid which was of technical grade, i.e. that it also contained about 6 of water and about 10 of non-ionic ethoxylated myristyl alcohol.
0. A lithium salt of the same general formula, but wherein n has an average value of 4.
d. N0nylphenol-(C H O),,OCH COOLi, wherein n has an average value of 4.
The carpet parts treated with the products b) and c) were dry and non-tacky after about six hours; the products b) and c) can be considered equivalent in this respect. However, the parts treated with the products a) and d) still had a stiff and tacky feel after one or two nights. Accordingly, in this respect the products b) and c) are clearly superior over the products a) and d), and
.it appears therefrom that the nature of the anionic part of the detergent is of much greater importance than would appear from the above-discussed Dutch patent application 6409345.
It should be noted here that in combination with a suitable sorbent solid product (1) yields a shampoo which has a quite acceptable drying time and which, as will appear from Example 12 hereinbelow, shows excellent resoiling properties.
EXAMPLE 3 Aqueous compositions were prepared which contained 2 by weight of detergent and 2 by weight (as dry resin) of the commercial product Ubatol 3101 (styrene-acrylate resin). Three different compositions were prepared which contained the following detergents: v
a. The lithium salt of a technical grade (C -C )(OC H.,)3.3QCH COOH. The acid had been prepared by ethoxylating a technical grade lauryl alcohol with an acidic catalyst to obtain a product RO(C H O) H having a narrow distribution of n-values, whereafter this product had been reacted with chloroacetic acid. This preparation had been carried out on commercial scale and the so obtained carboxylic acid still contained about 10 of the non-ionic (C C 4)( 2 4):;.a
b. The sodium salt of the same commercial detergent carboxylic acid.
0. Lithium dodecylbenzenesulfonate.
Nylon carpets were treated with the three above compositions. Thereafter they were left to dry at ambient temperature (about 20C).
The carpets treated with the composition containing detergent a. were well-cleaned and dry after about 2 hours so that they could be vacuum-cleaned to remove the dry residue.
The composition containing detergent b) yielded about the same good results, but the composition containing detergent a) was somewhat superior to this composition.
The carpets treated with the composition containing detergent 0) still had a tacky feel after one or two nights. It is clear that the composition containing detergent c) has no commercial usefulness.
Again it appears from the above that the nature of the anionic part of the detergent is particularly important.
EXAMPLE 4 A composition was prepared containing 6 parts of the same lithium salt as used in part a) of Example 3, 6 parts by weight of alumina (a product marketed under the name Dispal" by Condea), and for the rest water. A nylon carpet was treated with this composition and then dried at ambient temperature. A dry powdery residue was obtained within 2 hours.
EXAMPLE A number of aqueous compositions were prepared, all of which contained 4 by weight of a mixture of detergent and adsorbing solid. In all these cases the weight ratio between pure detergent and adsorbing solid was 38:62. For simplicitys sake, the mixtures have been summarized in the table below. The detergents used in this Example were all salts with monovalent cations, and accordingly they can be indicated with the formula RO(C H O),,CH,COOM. Those products, wherein R is lauryl or oleyl, were derived from technical grade lauryl alcohol, and technical grade oleyl alcohol, respectively. Furthermore, all detergents contained about of non-ionic ethoxylated starting alcohol. The table states the nature of R, the value of n and the nature of the cation M. The adsorbing solids have been indicated in the table with the following codes:
Ne: a methyl methacrylate polymer, available from P0]- yvinyl Chemie Holland N.V.
U 3101: an acrylic-styrene resin, available as emulsion from Stapol S.A., Lausanne D: Dispal, alumina sold by Condea B: Bentonite K: Kaolin Styr: a pure polystyrene.
The values of n are of course average values. In those cases, where the ethoxylation has been carried out with an acidic catalyst, and the product has a narrow distribution of n-values, this has been indicated with N after the value for n. In the column of the cations DEA means diethanolamine, and Morph means morpholine.
Composition R n M Adsorbent a decyl 2N Li Ne b myristyl 3.5N DEA Ne c myristyl 3.5N K Ne d decyl 2N Li U 3101 e myristyl 3.5N Li Ne f myristyl 3,5N K B 3 myristyl 3.5N Morph Ne h cetyl 8 NH. U 3101 i cetyl 8 NH Ne j myristyl 3.5N Li Styr k myristyl 3.5N Li U 3101 I myristyl 3.5N K U 3101 m decyl (C,H,0), 3 Na Ne n myristyl 3.5N DEA U 3101 o oleyl 7 Na Ne p myristyl 3.5N Morph U 3101 q myristyl 3.5N Li B r lauryl 8 NH, B .r lauryl 8 NH, U 3101 I myristl 3.5N K K u oleyl 7 Na U 3l0l v myristyl 3.5N Li K w cetyl 8 NH. K x lauryl 8 NH, Ne y decyl (C,H,O), 3 Na U 3101 z decyl c,H.o), 3 Li U 3101 The above compositions were tested as shampoos on nylon carpets. The treated carpets were left to dry at ambient temperature.
All of the above compositions cleaned the carpets well and had dried within about 2 to 3 hours.
EXAMPLE 6 A number of mixtures showing varying ratios between detergent and polymer were prepared as follows: Mixture I.
160 g of a 22.5 aqueous solution of stearyl- (QC- H ),,OCH COONa, wherein n had an average value of 2 38.6 g of a 40 emulsion of poly(methyl methacrylate) This amounts to a weight ratio between detergent and polymer of 3600:1542, i.e. about 7:3. Mixture II.
120 g of a 22.5 solution of cetyl- (OC I-L),,OCH COONa, wherein n had an average value of 8 (narrow distribution) 67.5 g of the same 40 poly(methyl methacrylate) emulsion This amounts to a weight ratio between detergent and polymer of 2700:2700, i.e. l:l.
44.5 g of a 22.5 solution of lauryl- (OC,I-I ),,OCH COONa, wherein n had an average value of 2.2 (narrow distribution) g of the same 40 poly(methyl methacrylate) emulsion This amounts to a weight ratio between detergent and polymer of about 1000:3000 or 1:3.
40 g of a 22.5 solution of decyl- (OC I-I ),,OCH COONa, wherein n had an average value of 2 202 g of the same 40 poly(methyl methacrylate) emulsion This amounts to a weight ratio between detergent and polymer of 90028080, i.e. about 1:9.
40 g of a 22.5 solution of decyl- (OC I-L, ,,0c1-r,cooNa, wherein n had an average value of 2 (narrow distribution) 202 g of the same 40 poly(methyl methacrylate) emulsion As in Mixture IV this amounts to a weight ratio of detergent and polymer of about 1:9.
With the above five mixtures soiled strips of carpet were cleaned. All these mixtures cleaned the soiled strips well; so that this entire range of ratios proved to be suitable. The results with mixtures III, IV, and V were slightly better than with mixtures I and II, and accordingly mixtures wherein the resin component is present in an excess over the detergent component are somewhat preferred.
EXAMPLE 7 Compounds [RO-(C H O),,CH COO],,,M
Deter- R n m M gent avg) a decyl 2 1 diethylamine b lauryl 4.5 l tri-ethanolamine c myristyl 6 1 pyridine d cetyl 8 1 cyclohexylamine e stearyl 7 1 isopropylamine f lauryl 4.5 2 ethylenediamine g myristyl 6 l piperidine. "h decyl 2 2 calcium 1' lauryl 4.5 2 magnesium j myristyl 6 2 Zn-ammonium complex k cetyl 8 2 barium I stearyl 7 2 cadmium m Mixture of dodecyl 3.2 l lithium and tridecyl (about 25% branch-chained) All mixtures cleaned the carpets well, the best results being obtained with the mixtures containing detergents c, e, and a.
All the mixtures yielded a dry residue, the residue obtained with the mixture containing detergent a was somewhat less easy to remove than that of the other mixtures. The mixtures containing detergents b, c, f, g, i, j, k, and m yielded residues which could be removed very easily.
EXAMPLE 8 Electrical resistivity measurements were carried out with 4 nylon carpets, two of which had a short needlelike pile, whilst the other two had a long pile with loops. One of each kind of carpets was untreated, and the other had been shampooed with a composition of this invention. The detergent of this composition was a product of the formula R(OC I-I ),.OCl-I- -COOLi, wherein R was derived from commercial lauryl alcohol (about 70 of n-dodecyl and about 30 of n-tetradecyl alcohol), and n had an average value of 3.3 (narrow distribution). The detergent as a 22.5 solution was mixed with a 40% poly( methyl methacrylate) emulsion in the weight ratio 485:515 and the so obtained mixture was diluted with water to the 14-fold volume. This diluted composition was used as the shampoo.
The surface resistivity in ohms was measured for each of the carpets in accordance with the method DIN 53482-852. Then each of the carpets was laid in a room, where people used to come frequently, and the measurements were repeated after 1,000, 2,000, 3,000, and 5,000 persons had walked thereon. In all cases it took about a wek until 1,000 persons had walked on the carpet.
The results are as follows:
Carpet- A: Short pile; untreated; surface resistivity 10 Ohms. After 1,000, 2,000, 3,000, and 5,000 persons had walked on the carpet, the value found remained always 10 Ohms.
Carpet B: Short pile, shampooed with the above composition: Initial value 7.5.10 Ohms.
After 1,000 persons had walked thereon: 4.5.10 Ohms.
After 2,000 persons had walked thereon: 1.7.10 Ohms.
After 3,000 persons had walked thereon: 1.5.10 Ohms.
After 5,000 persons had walked thereon: 5.7.10 Ohms.
Carpet C: Long pile; untreated; surface resistance 10 Ohms. Values of 10 Ohms were also found after 1,000, 2,000, 3,000, and 5,000 persons had walked on this carpet.
Carpet D: Long pile; shampooed with the above composition: Initial value: 6.6. 10' Ohms.
After 1,000 persons had walked thereon: 1.6.10 Ohms.
After 2,000 persons had walked thereon: 7.2.10 Ohms.
After 3,000 persons Ohms.
After 5,000 persons Ohms.
As appears from the above experiments the present compositions have a very good and long-lasting antistatic effect. Accordingly they can also be used to treat carpets which have created problems by too high electrostatic charges which sometimes cause an electric shock to persons who standing on the carpet touch a metal doorknob or the like. The antistatic properties are also a cause of the excellent resoiling properties of the present compositions. Carpets treated with the present shampoo have acquired a better conductivity, and accordingly accumulate less electrostatic charges, and consequently attract less dust and soil particles.
EXAMPLE 9 This example shows that it is also possible to use mixtures of the present detergent salts.
Comparative experiments were carried out, wherein nylon carpets were cleaned with six different shampoos. The cleaning effect and the resoiling properties were examined.
The shampoos were prepared in the same way as in Example 8, but with various detergents and resins. ln shampoos A, B, and C the resin was a styrene-acrylate resin, the same commercial product as used in Example 3. In shampoos D, E, and F a poly(methyl methacrylate) resin was used. In shampoos A and D the detergent was the same as used in Example 8. In shampoos B and E a mixture of this same detergent with decyl- (OC I-I )',,OCH COOK wherein it had an average value of 0.5, was used in the weight ratio 9:1. In shampoos C and F a mixture of the same detergents was used in the weight ratio :25.
With all the six shampoos a good cleaning effect was obtained, and in this respect on significant differences could be observed for the various mixtures. As regards the resoiling properties, shampoos C, D, E, and F were somewhat superior to shampoos A and B.
EXAMPLE 10 A carpet shampoo was prepared by polymerizing methyl methacrylate in an aqueous emulsion which contained as emulsifier the detergent of Example 8. The methyl methacrylate was polymerized with the aid of a small amount of benzoyl persulfate catalyst. The concentrations in the emulsion were chosen in such a way that the final product had a solids content of about 31.5 by weight of which 10.9 was detergent and 20.6 polymer. The detergent was added to the polymerization mixture as a 22.5 aqueous solution.
In a second experiment the polymerization was carried out with the addition of only half the amount of detergent solution. After completion of the polymerization the remaining 50 of the detergent was added.
In a third experiment the process of the second experiment was followed with the exception that the second portion of surfactant was a 22.5 solution of the sodium salt instead of the lithium salt.
had walked thereon: 3.8.10
had walked thereon: 3.4.10
All three experiments yielded shampoo concentrates of this invention having the usual good properties.
EXAMPLE 1 l A rug shampoo was prepared in the form of an aerosol. A mixture of a 22.5 solution of the same detergent as in Example 8 with a 40 poly( methyl methacrylate) emulsion in the weight ratio 485:515 was prepared. 101.5 Grams of this mixture were diluted with l6l grams of water so that the solids content of the mixture was about 12 This mixture was filled in aerosol bottles, and an amount of 87.5 grams of propelling gas was used. As the propelling gas a butane-propane mixture was chosen. Of course, one can also use one of the well-known Freon products.
EXAMPLE 12 A number of shampoos was prepared in accordance with the process of Example 8, but using various detergents, and one shampoo was prepared according to Example ll. A carpet was divided into strips and each strip was treated with one of the shampoos, whereas two of the strips were just treated with water for comparative purposes. The resoiling properties were determined after l4 days by a panel of 4 persons.
The detergents used in the shampoos prepared according to Example 8 had the formula [RO(C H O)- ,,CH COO],,,M. They are further specified in the following table, wherein N.D. means narrow distribution.
Deter- R n m M gent (avg) a nonylphenyl 4 lithium b lauryl (technical grade, about 3.3 2 ethylenediamine 30% C ND. ditto do. 1 lithium d mixture of lauryl and tridecyl (about 25% branch-chained) 3.8 1 sodium ND. 2 isotridecyl 3 1 sodium The results of the resoiling test showed a clear difference between the strips treated with shampoo and those treated with plain water. The differences between the various strips treated with shampoo were only slight,. The results obtained with the shampoos containing detergents a, b, and 2 were very slightly superior to those obtained with the shampoos containing detergents c and d and with the shampoo prepared according to Example 11.
EXAMPLE 13 A number of rug shampoos was prepared according to the process described in Example 8, but using various detergents.
Shampoo 1 contained as detergent the lithium salt of lauroxy (4.5 E0) propionate, i.e. the compound RO-(CgH4O) CHg-CHzCOOLL wherein R was the residue of commercial lauryl alcohol (70% C12 d. 0 14 an! nhasiaitsvs ags t s of Shampoo 2 contained the ethylenediainine salt ofthe same propionate (i.e. a salt of a divalent nitrogen base).
Shampoo 3 contained as detergent decyl- (C H O ),,CH COOLi, wherein n had an average value of l.
Shampoo 4 contained as detergent stearyl- (C H.,O),,CH COOLi, I. wherein n had an average value of 10.
Shampoo 5 contained as detergent the compound lauryl-(C l-LO),,CH COOLi, wherein the lauryl residue was derived again from the commercial lauryl alcohol, and the value of n was 3.3 (narrow distribution). This is the same product as used in Example 8.
Shampoo 6 contained the sodium salt corresponding to the lithium salt of shampoo 5.
In the first place the cleaning action of these shampoos was compared. This was done with an untreated carpet which had been walked upon intensively during 8 days. The carpet was divided into strips and each strip was treated with 30 ml of one of the shampoos, whilst one strip was treated with 30 ml of plain water. After drying the carpet was vacuum cleaned. The cleaning effect was judged by a panel of three persons. In all cases a good cleaning effect was observed, also with water. However, the results obtained with shampoos 3, 5, and 6 were somewhat superior to those obtained with the other compositions.
Also resoiling experiments were carried out with these shampoos, and with water. To this end one started with a clean piece of carpet of 1 X 1 metre. This square piece was divided into trigonal sectors with the aid of adhesive tape along the diagonals and along lines through the centre parallel to the sides. Six of the eight sectors were each treated with 60 ml of one of the shampoos, and the two other sectors were treated with plain water. After drying, each of the sectors was vacuum-cleaned. Then the carpet was laid on a place where many people used to walk, and each day it was turned over 90.
After 2 weeks the resoiling result was judged by a panel of six persons. It appeared that the best results were obtained with shampoos 1, 6, and 3, whilst the results with shampoos 4 and 5 were still highly satisfactory. The result obtained with shampoo 2 was clearly less good and was about the same as that obtained with water.
Also other usual additives for rug shampoos can of course be used in the present compositions. Examples thereof are optical brighteners, dyes, perfumes, propelling gases for aerosols, solvents, bactericides, fungicides, corrosion inhibitors (which may be necessary for treating carpets attached to metal parts) etc. Antistatic agents are often added to rug shampoos, but since the detergents used according to the present invention have good antistatic properties themselves, it is in general not necessary to add additional antistatic agents to the present compositions.
It will be obvious to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is intended to include such as may be embraced within the following claims.
What I claim is:
1. In a carpet shampoo composition in concentrate form consisting essentially of a detergent and a solid sorbent capable of yielding with the detergent a quick drying residue which takes up dirt, the improvement wherein said detergent is present in a range of 10 by weight and has the formula:
2 4 )n 2): COOLIIM wherein R is a hydrophobic hydrocarbon residue of eight to 20 carbon atoms, which may contain one or more hydrophobic oxyalkylene units, n has an average value ofO- l0,xis l or 2, m is l or 2, and Misamonovalent or divalent cation.
2. A carpet shampoo consisting essentially of 0.5 3O by weight of the composition of claim 1 and 99 70 by weight of water.
3. A composition in accordance with claim 1 wherein R contains 12 14 carbon atoms and n has an average value of 3 to 4.
4. A composition in accordance with claim 1 wherein n is 2 to 3 when R has less than 12 carbon atoms, and n is 5 to 8 when R has more than 15 carbon atoms.
5. A composition in accordance with claim 1 wherein M is sodium, lithium, zinc, potassium, magnesium, calcium, cadmium, ammonium, monovalent amine and divalent amine.
6. A composition in accordance with claim 1 wherein x is 2.
7. A composition in accordance with claim 1 wherein said solid sorbent is selected from the group consisting of brittle artificial resins which are filmforming at temperatures above 50C, alumina, silica, bentonite and kieselguhr.
8. In a carpet shampoo in aerosol form consisting essentially of a carpet shampoo composition and a propelling gas, the improvement wherein said carpet shampoo composition is the composition of claim 1.
9. A method of shampooing rugs, carpets and upholstery fabrics, comprising applying the composition of claim 2 to the fabric to be cleaned, rubbing said composition into said fabric, drying the so wetted fabric, and removing the solid residue remaining after drying.
10. A method of shampooing rugs, carpets and upholstery fabrics, comprising applying the composition of claim 8 to the fabric to be cleaned, rubbing said composition into said fabric, drying the so wetted fabric, and removing the solid residue remaining after drying.