|Publication number||US3835071 A|
|Publication date||Sep 10, 1974|
|Filing date||Mar 24, 1972|
|Priority date||Nov 17, 1969|
|Also published as||CA946704A, CA946704A1, DE2056556A1, DE2056556B2|
|Publication number||US 3835071 A, US 3835071A, US-A-3835071, US3835071 A, US3835071A|
|Inventors||Allen W, Gower B|
|Original Assignee||Atlantic Richfield Co|
|Export Citation||BiBTeX, EndNote, RefMan|
|Referenced by (38), Classifications (11), Legal Events (2)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent 3,835,071 RUG SHAMPOO COMPOSITIONS William E. Allen, Laurel Springs, N.J., and Bob G.
Gower, Park Forest, 111., assignors to Atlantic Richfield Company, Philadelphia, Pa.
No Drawing. Continuation of abandoned application Ser. No. 877,414, Nov. 17, 1969. This application Mar. 24, 1972, Ser. No. 237,979
Int. Cl. C11d 1/10, 1/14 U.S. or. 252-545 11 Claims ABSTRACT OF THE DISCLOSURE This is a continuation of application Ser. No. 877,414, filed Nov. 17, 1969, and now abandoned.
This invention relates to cleaning compositions for rugs, carpets, and upholstery. More particularly, this invention relates to improved rug shampoo compositions for cleaning natural and synthetic carpets, rugs, upholstery, and area coverings.
With the rapid expansion of the carpet industry and the use of tougher synthetic fibers in area carpeting, there is an increasing demand for improved carpet cleaning compositions. A serious problem in the cleaning of carpets is that freshly shampooed carpets tend to soil faster than new carpets. This resoilin appears to be largely due to a tacky or sticky residue left behind after the rug has been cleaned. The sticky rug fibers attract and hold dirt thereby contributing to rapid resoiling. This tacky residue is caused by detergents used in the shampoo formulation in order to eifect proper cleaning action. Consequently, there is urgent need for rug shampoo formulations that will provide the necessary cleaning properties and also dry to a non-tacky powdery or brittle residue which can be more readily removed as by vacuuming.
Commercial carpet cleaning compositions, such as conventional rug shampoos, are typically composed of a primary detergent which assists the cleaning solvent, such as water, in loosening soil and a foam stabilizer or detergent extender which builds and maintains thick foam desired in cleaning heavy pile materials. The thick foam carries loosened soil to the top of the carpet fibers where it may be removed, and in addition prevents wetting of the carpet backing. The primary detergent may be a liquid or a solid, but formulations that dry to a removable powder are preferred. The trend in rug and upholstery shampoos is toward cleaning compositions that dry to a powder which can be removed easily by vacuuming. A shampoo residue which cannot be completely removed from carpet materials contributes to dulling of the carpet fibers, retention of loosened soil, and resoiling of cleaned carpets. Optimum removal of such residues is not readily accomplished due to the tacky or waxy nature of detergents, surfactants and additives, such as foam stabilizers, contained in the carpet cleaning compositions.
This invention provides improved carpet cleaning or rug and upholstery shampoo compositions which upon drying on the carpet leave very brittle, non-tacky residues which are easily removed when dry and make little, if any, con- 3,835,071 Patented Sept. 10, 1974 tribution to resoiling. In accordance with this invention, the improved carpet and upholstery cleaning or rug shampoo composition comprises a water-soluble metal, ammonium or amine salt of a styrene-maleic anhydride copolyrner or its half-ester with a rug shampoo detergent or with a rug shampoo foam builder or foam stabilizer. Usually, both a Water-soluble rug shampoo detergent and Watersoluble rug shampoo foam builder are employed.
The Water-soluble metal, ammonium or amine salt of the styrene-maleic anhydride copolyrner or its half-ester can be used in amounts of about 5 to by weight of the total active material in the rug shampoo composition and in ratio or parts by weight to the rug shampoo detergent of about 1:20 to 20: 1, preferably of about 1:1 to 1:7. Thus, the water-soluble salt of the styrene-maleic anhydride polymer or of its half-ester can be used as an additive to existing or other rug shampoo compositions in amounts of from about 5 to 95%, preferably about 25 to 50%, by weight of total solids material in the composition.
By incorporating the water-soluble salt of styrene-maleic anhydride or of its half-ester as a primary organic active component or additive into rug shampoo compositions, there results the improved shampoo composition of this invention which cleans the carpet by shampooing and leaves, upon drying, an easily removable, non-tacky residue which does not contribute significantly to resoiling. Thus, the present additive also makes possible the use in rug shampoo compositions of inexpensive detergents which otherwise give unsatisfactory results through their tendency to leave oily residues.
While from about 5 to 95% of the water-soluble salt of the styrene-maleic anhydride polymer by weight of the total solids in the rug shampoo composition can be used, it is preferred to employ from about one part by weight of water-soluble salt of the styrene-maleic anhydride copolymer or its ester to about 1 to 7 parts by weight of the detergent in the shampoo rug formulation.
The water-soluble foam builder or stabilizer, if used, can be employed in sufficient amount to produce a foam which is usually about 5- to 50% by Weight of the total solids and preferably about 10 to 35% by weight of the total solids in the rug shampoo composition. Thus, the rug shampoo composition of this invention may be a dry solid mixture which is dissolved in water prior to use. By Weight of total solids of the rug shampoo composition is meant the components other than water and alcohol, hydrocarbon or other solvent, if any is present.
The rug shampoo composition of this invention is usually prepared in concentrated aqueous solution wherein the water-soluble, metal, ammonium or amine salt of the styrene maleic anhydride copolyrner or its half-ester and the detergent and foam builder or stabilizer, if any, comprise at least about 5 weight percent, preferably about 12% and often up to about 50 to 70 weight percent of the total aqeuous composition, the ratio by weight of the watersoluble salt and the detergent and the weight percent of the foam stabilizer, if any, being as heretofore stated. The remainder of the rug shampoo composition is usually Water.
The concentrated rug shampoo composition is diluted with water to give a total concentration of the water-soluble metal, ammonium or amine salt of the styrene-maleic anhydride copolyrner or its esters and detergent and foam builder, if any, in from about 0.5 to 2 or 3 weight percent of the total aqueous solution, preferably about 1 weight percent, which is the final form of the rug shampoo composition for applying to the carpet for cleaning or shampooing. In addition to water, the solvent may include minor amounts of water-soluble alcohols, and silicates or other alkaline builders, e.g. phosphates, while function as water softeners and also aid in the removal of dirt. Also, additional components, such as grease or oil solvents, sequestrants, viscosity builders and optical brighteners, may be added when the cleaning composition is utilized for a specified purpose.
The use of these water-soluble salts of styrenemaleic anhydride copolymers in carpet shampoo preparations results in less dust attraction to the carpet fibers, and results in less wear, i.e. abrasive cutting of the carpet fibers. The use of these salts embrittles the residue of the dried shampoo left on the rug and also tends to stiffen and shine the carpet fibers, restoring them to a like-new appearance and results in less ma-ttings of the carpet pile. Also, the rugs dry faster. The improved rug shampoo compositions of this invention containing the water-soluble salt of styrene-maleic anhydride copolymer is effective for cleaning all highly soiled pile materials, exhibits improved stain removal on carpet materials and inhibits resoiling.
The water-soluble, metal, ammonium, and amine salts of styrene-maleic anhydride polymers and their half-esters are well known as shown by US. Pat. 3,388,106, issued June 11, 1968. The preferred water-soluble, metal salts are those of Group II and the alkali metals, particularly magnesium and sodium. The preferred amine salts are the morpholine, lower amine and lower alkanolamine salts, such as ethanolamine and Z-hydroxypropyla-mine salts. However, various primary or secondary water-soluble amine salts can be used, such as those of alkylamines, alkanolamines of l to about 18 carbon atoms, preferably 1 to about 6 carbon atoms, e.g. ethylamine, propylamine or octadecylamine. The preferred half-esters are the cycloalkanol and alkanol half esters particularly of alcohols of up to about 18 carbon atoms and preferably of up to about 8 carbon atoms, such as the cyclohexanol and n-propyl alcohol half-esters. The ammonium salts are most preferred.
The styrene-maleic anhydride ammonium salt solutions often have a pH range of about 7.5 to 10. The pH measurements were taken on styrene-maleic anhydride ammonium salt solutions with and without foam builders. Commercial carpet cleaning compositions have a pH range of about 7.2 to 7.9.
Various water-soluble rug shampoo detergents can be used with the water-soluble salt of the styrene-maleic anhydride polymer, but it is preferable to use a watersoluble sulfate of the formula where 'R is alkyl of about 8 to 20 carbon atoms, preferably 10 to 14 or even up to about 18 carbon atoms, at is to about or more, preferably 2 or 3, and M is the ammonium, amino or metal cation which forms a watersoluble salt, such as a Group II metal or an alkali metal, preferably magnesium or sodium. The preferred amine salts are the morpholine, lower amine and lower alkanolamine salts, such as ethanolamine and Z-hydroxypropylamine. However, various primary or secondary amine salts such as those of alkylamines, alkanolamines or heterocyclic amines usually alkylmonoamines or alkanolmonoamines of 1 to about 18 carbon atoms, preferably 1 to 6 carbon atoms, e.g. ethylamine, propylamine or oct-adecylamine, can be used.
These rug shampoo detergents are the water-soluble ammonium, amine and metal salts of fatty alkyl sulfates (i.e. sulfated fatty alcohols) and fatty alkyl ethoxylated sulfates (i.e. sulfated oxyethylated fatty alcohols). EX- amples of the fatty alkyl sulfates and fatty alkyl ethoxylated sulfates include the sodium, potassium, calcium, zinc, ammonium, magnesium and the monoand diethanolamine salts of lauryl sulfate and of lauryl ethoxylated sulfates. Sodium and magnesium lauryl sulfates are preferred.
The water-soluble sarcosines or sarcosinates are condensates of fatty acid and sarconsine (N-acylsarcosines 4 or N-acylsarcosinates) and can be represented by the formula:
R |3N-CHz-C O O A O CH:
where R is alkyl of about 12 to 18 carbon atoms and A is hydrogen, ammonium, amino or metal which forms a water-soluble sarcosinate salt, such as a Group II metal or an alkali metal, e.g. sodium or magnesium. The amino radical can be the same as in the sulfates. The preferred sarcosinate is sodium lauryl sarcosinate. These sarcosinates posses detergent properties and have bactericidal and bacteriostatic characteristics and have been used in rug shampoo formulations as shown by British Pat. 882,- 635, published Nov. 15, 1961. They can be used in the rug shampoo compositions of this invention and also in combination with the other detergents.
A water-soluble foam builder stabilizer can be used with the water-soluble salt of styrene-maleic anhydride polymer and detergent compositions of this invention but is not necessary, although many rug shampoo formulations include a foam builder. These foam builders are well known to the art and include sulfosuccinates, alkanol and alkyl amides, and cycloimidines. However, as the water-soluble, metal, ammonium or amine salts of the styrene-maleic anhydride copolymer and its halfesters do have rug cleaning properties, they can be used as the sole detergent with a foam builder or stabilizer, some of which, such as the sulfosuccinates, also have detergent properties. In such rug shampoo compositions the water-soluble salt of the styrene-maleic anhydride c0- polymer or its half-ester and the detergent, if any, would generally be about 25 to 95%, preferably about 50 to 90% by weight of total solids and the foam builder or stabilizer about 75 to 5%, preferably 50 to 10% by weight of total solids.
Alkanolamides and alkylamides are foam and viscosity builders. They are condensation products of alkanolamines or alkylamines and fatty acids. These fatty acid alkanolamides and alkylamides can be represented by the formula:
0 RJLN where R is alkyl of about 8 to 20 carbon atoms, preferably of about 10 to 14 carbon atoms. R is hydrogen alkyl of 1 to about 6 carbon atoms or hydroxyalkyl of 1 to about 6 carbon atoms. A typical alkanol amide is lauric diethanolamide. Particularly suitable alkylamides for use in this invention are lauryl amides, e.g., lauryl isopropyl amide and lauryl diisopropyl amide.
The sulfosuccinates are the salts of fatty acid alkylolamide sulfosuccinic acid half-esters and the salts of sulfosuccinic acid half-esters of fatty alcohols. These sulfoscuccinates have been used in rug shampoo formulations as shown by US. Pat. 3,401,007, issued Sept. 10, 1968, and are represented by the general formula:
wherein R is a fatty acid residue or fatty alcohol residue usually acyl or alkyl of about 10-18 carbon atoms, X is oxygen or an alkylene grouping joined respectively to R and to the su'lfosuccinic residue via amide type or ester type linkages, one of Y and Z is hydrogen and the other is the group M, and M is any salt-forming metal cation of Groups I, II and III of the Periodic Table. Examples of such sulfosuccinates are the sodium salt of the sulfosuccinic acid half-ester of cocoanut oil fatty alcohols, the sodium salt of the sulfosuccinic half-ester of lauric acid monoethanolamide, the sodium salt of the su'lfosuccinic acid half-ester of myristic acid monoisopropanolamide and the sodium salt of the sulfosuccinic acid half-ester of lauryl alcohol. Preferred sulfosuccinates are the sulfosuccinic acid half-esters of fatty acid alkylo'lamides or fatty alcohols. These sulfosuccinates may be used singly or in combination of two or more in the rug shampoo compositions with the water-soluble salt of the styrene-maleic anhydride polymer or of its half-ester of this invention. These sulfosuccinates not only give added detergent strength to the rug shampoo compositions, but also act as a foam stabilizer that aids the detergent to form a dry residue which can be vacuumed out with the carpet soil and also tends to reduce electrostatic charge build-up on the cleaned carpets.
The amphoteric cycloimidines or imidazolines are foam builders useful in shampoo formulations as disclosed in US. Pat. 3,231,580, issued Jan. 25, 1966. The foam builders are used in an amount sufiicient to build a foam such as about 5 to 75%, preferably to 50% of total solids.
As typical of the commercial rug shampoo concentrated formulations to which the water-soluble, metal, ammonium or amine salt of styrene-maleic anhydride polymer or its half-ester can be added to obtain the improved rug shampoo compositions of this invention is the following formulation TABLE A Weight percent Sodium or magnesium lauryl sulfate (30%) 12 Laurie diethanolamine foam stabilizer 3 Water 85 The commercial rug shampoo formulation may also contain a small amount, such as 1.5% by weight of a sequestrant, such as ethylene diamine-tetraacetic acid and its water-soluble salts, such as alkali metal salts, particularly sodium salts. A typical dilution ratio of the above formulation for use to shampoo the carpet is 1 part of this concentrate to about 8 parts of water.
Generally, about 30 to 50% of the lauryl sulfate salt can be replaced by the water-soluble salt of the styrenemaleic anhydride polymer or its half-ester to give best results. This can readily be done by mixing into the commercial shampoo concentrate the water soluble salt of the polymer in amount of about 40% to 100% by weight of the detergent or even of the total solids in the commercial shampoo formulations. However, often about 10% to 100% by weight of the water-soluble salt to detergent is used as shown by the following typical rug shampoo composition of this invention in diluted form ready for use on the carpet.
TABLE B Parts by weight Ammonium salt of styrene-maleic anhydride polymer (dry) 0.1-0.5 Sodium or magnesium lauryl sulfate (dry) 0.5-0.9 Sodium lauryl sarcosine (dry) 0.15 Water, balance to make 100%.
It is to be understood that other rug shampoo detergents and foam builders can be used. The amount of water-soluble salt of styrene-maleic anhydride polymer to be incorporated in the rug shampoo formulation need only be sufficient to embrittle the residue left on the carpet after shampooing so it can easily be removed. This prevents rapid resoiling of the carpet since early resoiling is related to a waxy residue adhering to the carpet after sbampooing.
A typical rug shampoo concentrate of this invention is as follows:
TABLE C Rug Shampoo Concentrate at 10% Active Solids Parts by weight Amonium salt of styrene-maleic anhydride copolymer at 15% concentration in aqueous solution 27 Sodium lauryl sulfate (detergent) 5 Foam stabilizer 1 Water 67 6 This rug shampoo concentrate can be diluted 1 part shampoo concentrate to 9 parts of water before application to the carpet.
The foam stabilizer can be the various foam builders used in rug shampoos, such as lauric diethanolamide, lauryl isopropyl amide, the sodium salt of sulfosuccinic half-ester of lauric acid monoethanolamide or an amphoteric cycloimidine, such as of the formula:
The styrene-maleic anhydride resins used in the rug shampoo compositions of the present invention are watersoluble, metal, ammonium and amine salts of styrenemaleic anhydride resins and their partial or half-esters, having about 1 to 4 moles, preferably about 1 to 3 moles of styrene per mole of maleic anhydride. If desired, maleic esters can be used instead of maleic anhydride in formation of the resins with styrene.
These resinous polymers contain repeating units of polymerized styrene and maleic anhydride and have an average molecular weight of about 600 to 50,000. The preferred average molecular Weight of these resins is about 700 to 5,000. The melting points of these lower molecular weight polymers will often range from about to 200 C. as determined by the Fisher-Johns melting point apparatus.
These polymers of styrene and maleic anhydride can be prepared by known methods. A preferred method is by solution polymerization where the monomers are polymerized in a suitable solvent employing as a polymerization catalyst a free-radical peroxide catalyst, preferably benzoyl peroxide or dicumyl peroxide at a temperature of about 75 to 300 C. or more. Suitable solvents include the aromatic hydrocarbon solvents, such as cumene, pcymene, xylene, toluene and the like. The aromatic solvents may serve as chain terminating solvents and give lower molecular weight products. Other suitable solvents are the ketones, such as methylethyl ketone, which may also be chain-terminating solvents.
The preferred manner of carrying out the polymerization is by what is known in the art as incremental feed addition. By this method the monomer and catalyst are first dissolved in a portion of the solvent in which the polymerization is to be conducted and the resulting solution fed in increments into a reactor containing solvent heated to reaction temperature, usually the reflux temperature of the mixture. When an aromatic solvent is employed as the solvent for the polymerization, the formulation of the polymers causes a heterogeneous system, the polymer layer being the heavier layer and recoverable by merely decanting the upper aromatic solvent layer and drying. On the other hand, when a ketone is the solvent, the formed polymer is usually soluble in the solvent media so that recovery of the products necessitates a solvent stripping operation.
The partial esters of the styrene-maleic anhydride polymers can be prepared by known methods. Thus, partial esters of from about 20 to half-ester can be prepared by known methods. Thus, partial esters of from about 20 to 120% half-ester can be prepared by esterifying the styrene-maleic anhydride polymer with the required equivalent amount of an alcohol, such as an alkanol or cycloalkanol, generally up to about 18 carbon atoms, preferably of up to about 8 carbon atoms, such as methanol, ethanol, propanol, hexanol, cyclohexanol, octanol, octadecanol and the like. The usual known methods of partial esterification can be employed, such as by heating in a solvent, the alcohol and the styrenemaleic anhydride polymer.
Physical properties of typical styrene-maleic anhydride resins which can be used in the form of their water-soluble, metal, ammonium, or amine salts in this invention are set forth in the following table.
Norm-Gardner Color was in 15% aqueous ammonia solution.
Resin D is a cyclohexyl half-ester of a 1 to 1 mole ratio styrene-maleic anhydride resin esterified to about 65% half-ester with cyclohexyl alcohol.
Resin E is an n-propyl half-ester of a 2 to 1 mole ratio styrene-maleic anhydride resin esterified to about 65% half-ester with n-propyl alcohol. All of the styrenemaleic anhydride resins A to C and their half-esters D and E are in powder form.
The ammonium salt and Water-soluble metal salts of the copolymers of styrene and maleic anhydride and their partial esters can be prepared by simple hydrolysis of the copolymer or partial ester with water in the presence respectively of ammonium hydroxide or water-soluble metal hydroxide, such as alkali metal hydroxides. The hydrolysis can be conveniently carried out by making a slurry in distilled water of the ammonium hydroxide or water-soluble metal hydroxide and heating over a water bath until the hydrolysis is complete. It is desirable to use excess ammonium hydroxide or metal hydroxide, say up to about weight percent or more, over that stoichiometrically required to form the ammonium or water-soluble metal salt of the copolymer of styrene and maleic anhydride. Thus, it is usually preferable to use at least two moles or more of ammonium hydroxide or metal hydroxide per mole equivalent of the repeating copolymer unit. Various water-soluble metal hydroxides can be used, such as the alkali metal hydroxides, such as sodium, potassium and lithium, but sodium hydroxide is preferred.
Water-soluble amine salts of the styrene-maleic anhydride polymers and their partial esters can be prepared by known methods. Thus the styrene-maleic anhydride polymers and their partial esters can be reacted with primary amines, such as alkylamines, alkanolamines or heterocyclic amines, usually alkyl monoamines or alkanol monoamines of 1 to about 18 carbon atoms, preferably 1 to about 6 carbons, e.g. ethylamine, propylarnine, octadecylamine, ethanolamine, 2-hydroxypropylamide and morpholine. An excess of the amine over that stoichiometrically required to react with the styrene-maleic anhydried polymer is used such as 2 moles or more of amine per anhydride unit of the polymer.
The presence of ammonia salt solubilized styrene and maleic anhydride resin increases the rate of hydrolysis of added resin. Therefore, it is preferable that styrene and maleic anhydride resins be hydrolyzed with ammonium hydroxide at high solids and subsequently reduced to the lower concentration. Styrenemaleic anhydride resin C and the partial esters D and E can be hy drolyzed at 20% solids with subsequent dilution for end use purposes. The 20% solution of styrene-maleic anhydride resin C can be reduced to solution while still at hydrolysis temperature to circumvent the high viscosity of the solution at room temperature. Styrenemaleic anhydride resins A and B can be hydrolyzed up to 50% and respectively. However, the ammonia should be added very slowly or the exotherm will cause the resin solution to boil over the hydrolysis kettle. The following examples are typical preparation of aqueous ammonia salt solutions of these styrene-maleic anhydride resins. Styrene-maleic anhydride resin C. is preferred for use in household shampoo formulations. However, to obtain more concentrated shampoo formulations, resins A and B are desirable in that they give lower solution viscosities at high solids concentrations.
EXAMPLE A An aqueous solution of styrene and maleic anhydride resin A was prepared by the addition of 500 parts by weight of said styrene and maleic anhydride resin to 165 parts by weight of Water under agitation. The water-resin slurry was then heated to 150 F. and 335 parts by weight of 26 B. ammonium hydroxide (28% ammonia) slowly added under continued agitation solution had a pH in the range of about 8.0 to 8.5 and contained about 50 weight percent of solids of the styrene-maleic anhydride resin A.
EXAMPLE B An aqueous solution of styrene and maleic anhydride resin B was prepared by the addition of 250 parts by Weight of said styrene and maleic anhydride resin to 630 parts by weight of water under agitation. The water-resin slurry was then heated to 150 F. and parts by weight of 26 B. ammonium hydroxide (28% ammonia) slowly added under continued agitation at 165 F. for 30 minutes. The resulting aqueous solution had a pH in the range of about 8.0 to 8.5 and contained about 25 weight percent solids of the styrene and maleic anhydride resin.
EXAMPLE C .An aqueous solution of styrene and maleic anhydride resin C was prepared by the addition of 150 parts by Weight of said styrene and maleic anhydride resin to 540 parts by weight of water under agitation. The waterresin slurry was then heated to 150 F. and 60 parts by weight of 26 B. ammonium hydroxide (28% ammonia) added under continued agitation at 165 F. for 30 minutes. The heat was discontinued and 250 parts by weight of water was then added to this 20 percent resin solids solution. The resulting aqueous solution had a pH in the range of 9.0 to 9.5 and contained about 15 percent solids of the styrene and maleic anhydride resin.
EXAMPLE D An aqueous solution of the styrene and maleic anhydride-cyclohexyl partical ester resin D was prepared by the addition of 150 parts by weight of said styrene and maleic anhydride-cyclohexyl partial ester resin to 553 parts by weight of water under agitation. The water-resin slurry was then heated to 120 F. and 47 parts by weight of 26 B ammonium hydroxide (28% ammonia) added under continued agitation at F. for 30 minutes. The heat was discontinued and 250 parts by weight of water was then added to this 20 percent resin solids solution. The resulting aqueous solutions had a pH in the range of 8.8 to 9.3 and contained about 15 percent solids of the styrene and maleic anhydride-cyclohexyl partial ester resin.
EXAMPLE E An aqueous solution of the styrene and maleic anhydride-propyl partial ester resin E was prepared by the addition of parts by weight of said resin at 558 parts by weight of water under agitation. The water-resin slurry was then heated to 120 F. and 42 parts by weight of 26 B. ammonium hydroxide (28% ammonia) added under continued agitation at 130 F. for 30 minutes. The heat was discontinued and 250 parts by Weight of water was then added to this 20 percent resin solids solution. The resulting aqueous solution had a pH in the range of 9 to 9.5 and contained about 15 percent solids of the styrene and maleic anhydride-propyl partial ester resin.
The following examples are illustrative of various embodiments of the rug shampoo compositions of this invention and their use in carpet cleaning, and illustrate preferred embodiments thereof.
EXAMPLE I Three aqueous rug shampoo solutions were prepared designated solution numbers I, II and III. Solution No. I contained one percent by weight of the ammonium salt of the styrene-maleic anhydride resin C of Table I, .05 percent by weight of magnesium lauryl sulfate and .15 percent by weight of sodium lauroyl sarcosinate (referred to herein as Na lauroyl sarcosine). This rug shampoo composition is one embodiment of this invention.
Solution No. II contained one percent by weight of sodium lauryl sulfate and .20 percent by weight of sodium lauroyl sarcosinate. Solution No. III contained one percent by weight of magnesium lauryl sulfate and .20 percent by weight of sodium lauroyl sarcosinate. All three of these rug shampoo solutions contained 9880 percent by weight of water. The compositions of these three rug shampoo solutions is tabulated below in Table 1.
TABLE 1 Solution number. I
Ammonium salt of styrenemaleie anhydride Resin Sufiicient soiling material to result in heavy soiling (10 gms.) was spread evenly on a 6" X 6" carpet sample. The soil was thoroughly worked into the fibers and the sample allowed to stand for 60 minutes, then vacuumed to remove as much loose soil as possible. At this time a 1" strip of soiled material is covered to prevent cleaning.
Test rug shampoo formulations were prepared in aqueous solution at concentrations of 0.5%, 1.0% and 1.5% by weight respectively of sodium lauryl sulfate, magnesium lauryl sulfate and ammonium salt of styrenemaleic anhydride resin C. In addition, 0.5% by weight of lauryl isopropyl amide was added to each solution for,
foam production and stabilization.
Each of these test rug shampoo formulations was used to shampoo one of the soiled carpet samples at an approximate coverage of 0.75 ml./sq. in. The test rug shampoo formulation was drained onto the surface of the carpet sample and worked to a foam by brushing with a soft nylon brush. The samples were allowed to dry at room temperature. After drying, the samples were vacuumed thoroughly to remove loosened soil and the shampoo residue. Sample appearances were evaluated by comparison of soiled sections, shampooed cleaned sections and unsoiled samples. Relative ratings were assigned to each shampoo prepartion based on three tests as follows:
X indicates original brightness restored. Test 2:
X indicates soiled strip was invisible. Z indicates soiled strip was not invisible. Test 3:
Relative effectiveness in the series in which tested.
The following table summarizes the results obtained on initial cleaning of the soiled samples by these test rug shampoo formulations.
TABLE 3 Evaluation of foam built ammonium salt of styrenemaleie anhydride resin 0 against foam built Na laury Sulfate and Mg lauryl sulfate Ammonium salt of styrene- S 1 t maleic anhydride resin 0 Na lauryl sulfate Mg lauryl sulfate 0 11 ion concentration Test 1 Test 2 Test 3 Test 1 Test 2 Test 3 Test 1 Test 2 Test 3 X 1 Z X 1 Z Z 3 X 1 Z X 2 Z X 3 X 1 Z X 2 Z X 3 Norm-All solutions contain 0.5% lauryl isopropyl amide. Test description: Test l=X inieates original brightness restored; Z not restored; Test 2=X indicates soiled strip was invisible; Z not invisible; Test 3=relative efieetiveness in the series.
cally to evaluate resoiling. The carpet was rotated endfor-end after 3 days exposure. Table 2 indicates the results.
TABLE 2.RESOILING CHARACTERISTICS Solution number I II III 1 day Light soiling Medium soiling. Medium soil- 1 week Light-medium Very-heavy soiling. Heavy soiling.
In addition to the above, a trend in dirt pick-up or attraction was noticed. After the first day the test sections of the carpet sample treated with solutions No. II and No. HI became heavily solied. This was also determined by collecting the soil upon vacuuming. Samples treated with solutions No. II and No. III continually resulted in a much greater collection of soil than the sample treated with solution No. I.
EXAMPLE II As a soiling material for use in this and following examples, household vacuum cleaner dirt was collected and sieved to obtain more uniformity. The final sieve was #20 mesh. This procedure does not remove the oily soils and retains most of the solid soils. This soil material was then thoroughly mixed.
EXAMPLE III Companisons were carried out with prepared and commercial rug shampoo formulations on an acrylic/ 20% mod-acrylic, sculptured, looped pile sample at a coverage of 0.75 ml./ sq. in. On initial cleaning, a reasonable amount of cleaning was not obtained with any of these preparations. However, second cleaning gave much improved results, although original appearance was not restored. The rug shampoo formulations tested were as follows:
.5% lauryl isopropyl amide.
TABLE 4rContinued 1 part formulation to 8 parts water.
No further dilution.
1 part formulation to 8 parts water.
The following Table shows the comparative results obtained with the formulations of Table 4.
TABLE 5.EVALUATION OF FOAM BUILT AMMONIUM SALT OF STYRENE-MALEIO ANHYDRIDE RESIN O AGAINST LABORATORY AND COMMERCIAL BUG SHAMPOO PREPARATIONS (SOIL REMOVAL) Cleaner formulation designation Test 1 Test 2 Test 3 Z X 1 Z X 1 Z X 2 Z X 2 Z X 2 Z X 2 Z X 3 Z X 3 Z X 3 Z X 3 EXAMPLE IV Tests similar to Example III were carried out using a coarse, thick, stright pile carpet of mixed synthetic fibers. The cleaner coverage was reduced to 0.4 mL/sq. in. to lower residue build-up. Again, satisfactory cleaning was not obtained initially with any formulation. However, cleaning was apparent on the second cleaning. The rating assigned in Test 3 in one series is not relative to that in another series, i.e. a 1 rating in the first cleaning is not equivalent to a 1 rating in the second cleaning; a lower rating in the second cleaning than was originally assigned means that this formulation did not improve in appearance to the extent of the other members of the series. The ammonium salt of styrene-maleic anhydride resin with sodium lauroyl sarcosine (formulation b) exhibited low foam and foam stability on this thick pile carpet. However, the ammonium salt of styrenemaleic anhydride resin with lauryl sulfate salts (formulations c and g) cleaned Well. Results are shown in the following Table 6.
TABLE 6.FURTHER EVALUATION OF FOAM BUILT AM- MONIUM SALT OF STYRENEIVIALEIO .ANHYDRIDE RESIN C AGAINST LABORATORY AND COMMERCIAL RUG SHAMPOO PREPARATIONS (SOIL REMOVAL) Initial cleaning Second cleaning Cleaner formu- Various types of carpet materials which differed in design and fiber type, i.c. W001, 100% acrylic, 100% nylon and 80/20 acrylic-modacrylic, were soiled with common stain producers. Stains were produced by rubbing a known amount of the staining material, i.c. oil, coffee, and Coca- Cola, into the test area (6" X 6" carpet sample) and al- 12 lowed to dry thoroughly. Ten ml. of shampoo preparation were drained on the stained area and worked to a foam. The sample was allowed to dry and residual materials removed by vacuuming.
The rug shampoo formulations tested were three of the commercial formulations designated a, f and in i Table 4 of Example III, 1.5% aqueous sodium lauryl sulfate (1.5% NaLS) and 0.5 and 1.0% aqueous solutions of the ammonium salt of styrene-maleic anhydride resin C designated respectively, 0.5% NH salt and 1.0% NH salt. The styrene-maleic anhydride ammonium salt formulations were found to respond as well as the commercial products to coifee and soft drink stains and improved stain removal on acrylic and modacrylic materials. Most of the rug cleaner solutions were not effective on the oil stain. An additional sample composed of looped polyolefinic pile was found to be very stain resistant and cleaned effectively regardless of the formulation. The following Table 7 shows results of stain removal with ratings of l-stain removed and 2-stain present; includes some removal.
TABLE 7.-EVALUATION OF FOAM BUILT STYRENE- MALEIC ANHYDRIDE AMMONIUM SALT AGAINST LAB- AND COMMERCIAL PREPARATIONS (STAIN Cleaner identification 1.5% N114 N H4 Stain l NaLS a 1 salt salt Coca-Cola 1 2 2 2 2 2 /20 aerylic-modaerylic:
Coffee 2 2 1 1 Coca-Cola 2 2 2 2 2 EXAMPLE VI Rust stains were produced by placing 5 gm. of cast iron powder on the rug sample and wetting with 10 ml. of water. The rug samples were dried, and brushed to remove loose material. The rug shampoo preparations tested for rust removal and prevention were 1% aqueous ammonium salt styrene-maleic anhydride resin C, designated 1% NH, salt, 1% aqueous solution of 1% NH; salt with 0.5% sodium lauroyl sarcosine, designated 1% NH /sarcosine and 1% aqueous solution of 1% sodium lauryl sulfate and 0.5% sodium lauroyl sarcosine, designated 1% NaLS/sarcosine.
Ten ml. of the rug shampoo formulation were drained onto the surface of the rug samples and worked to a foam. The samples were then dried and vacuumed to remove loose material.
Ratings were as follows:
Good-A11 stain removed or only slight brownish tinge remaining.
Fair-Some stain removed.
Poor-No removal noticeable.
For testing rust prevention, the shampoo is drained onto the sample, worked to a foam and then covered with 5 gm. of the powdered iron. The carpet is vacuumed after drying. Diiferences were seen as good corresponding to all rust prevented or slight brownish tinge, fair corresponding to some prevention and poor corresponding to no prevention. The results are shown in Table 8. The trends shown in Table 8 are to more effective rust removal with the 1% aqueous solution of the ammonium salt of styrene-maleic anhydride resin C and more effective rust prevention with the 1% aqueous solution of the 1% NH, salt with 0.5 sodium lauroyl sarcosine.
TABLE 8.EVALUATION OF AMMONIUM SALT OF S'IYRENE-MALEIC ANHYD RIDE RESIN C IN RUST REMOVAL AND RUST PREVENTION 1% N H4 salt 1% N114 salt/sarcosine 1% NaLS/sarcosine Carpet description Removal Prevention Removal Prevention Removal Prevention 100% acrylic Good Poor Fair Good Poor Fair. 100% nylon, looped Poor do. Poor do do Do. 100% polyolefin, looped Fair Fair Fair Fain". Fair Poor 100% nylon do .-do Poor Goo oor o 80/20 aerylie-modaorylic do Poor "do.--" air ..do Do EXAMPLE VII 4. A rug shampoo composition of claim 1 wherein said Shampoo residue characteristics of the ammonium adfhuve IS the antmomum salt styrene'malelc anhysalt of styrene-maleic anhydride resin C, designated NH 3 Polymer i i g g t to salt, were compared against laboratory and commercial w ii s g gg 2 3 an y n e an a mo ecu ar preparations. The commercial preparations were a and i g a i 0 l f l 1 h of Table 4 and other other commercial preparations of rug S ampoo composltlon o c am} w erem unknown formulation designated x and The effects detergent is selected from the group consisting of sodium of incorporating varying amounts of the a Onium salt lauryl sulfate, magnesium lauryl sulfate, sodium lauroyl of styrene-maleic anhydride resin C into prepared and Sarcosmate and mixtures 9 commercial carpet shampoo formulations were deter- 2 i shampoo composmon of claim} wherem sald mined by evaporating constant volumes of the admixtures addlilve 15 Selected from the group cons lstmg of the and examining the residues. The following Table 9 demomuni Salt of Styrene-mama aphydnde P the scribes the physical appearance of these residues. ammomum salt of styrene'malelc Zanhydnde Polymer A tacky residue contributes to dulling of the carpet cycllqhexyl l ester and the ammomum salt of Styrene fibers and decreased soil removal and also hastens the ma elc anhydfilde Polymer 'PF halffesterresoiling process. The brittleness obtained with the A S arrfpoo composltlon of clalm 1 wllereln sald ammonium salt of styrene-maleic anhydride resin even detergent 1S f l r sulfate or magnoslum lauryl when incorporated into other rug shampoo formulations sulfale and salfl addltlve 15 the ammonium Salt of y facilitates residue removal and slows resoiling. After final 30 maleic anhydride P y have a le ratio of about 3 vacuum, presence of the residue, if any, is indicated by moles of Styrene P mole of maleic anhydride and a wetting the cleaned surface and brushing to raise a foam. molecular Weight of about 700 to TABLE 9.EFFECT ON RESIDUE CHARACTERISTICS OF INCORPORATION OF AMMONIUM SALT OF STYRENE-MALEIO ANHYDRIDE RESIN (NH4 SALT) INTO LABORATORY AND COMMERCIAL RUG SHAMPOO PREPARATIONS Plus ammonium salt of styrene-maleic anhydride resin Cleaner formulation 1.0%
NH4 salt Brittle, glassy flakes Na lamyl sulfate Hard, waxy powder M lanryl sulfate Soft, waxy. a
1.0% N114 salt/5% lauryl isopropyl amide Brittle, glassy flakes 1.5% N aLS/.5 laurylisopropyl amide Hard, waxy powder... Bri tle, waxy powder. Brittle, waxy powder. Brittle, glassy fl k 1.5% MgLS/.5 laurylisopropyl amide Soft, waxy Brittle flakes Brittle, glassy flakes... Commercialu don-.. Hard,wexy Hard, waxy Do. Commercial SoilbWaXY d0 Hard, waxy flakes. Commerciali Hard, waxy Hard, waxy powder Brittle, glassy flakes Commercial 1! Hard, waxy powder. Brittle powder--. .do
I i l i d; 8. A concentrated aqueous rug shampoo composition 1. A rug shampoo composition which dries to an easily consisting essentially of from about 5 to 70 weight perremovable brittle residue on the rug after shampooing and 50 cent of the rug shampoo composition of claim 7 and consists essentially of a water-soluble rug shampoo deabout 95 to weight percent of water. tergent and an additive present in an amount of about 25 9. An aqueous rug shampoo composition of claim 7 in to percent based on the total weight of solids in the dilute aqueous solution for applying as a shampoo to a composition, said amount being sufiicient to embrittle the g Which consists essentially of m about .5 t0 3 shampoo residue left on the rug after shampooing, said weight percent of the rug shampoo composition of claim additive being selected from the group consisting of water- 7 and from about 99.5 to 97 Weight Percent of Water. soluble, metal, ammonium and amine salts of styrene- The comp sition of claim 1 in ludin a watensohl. maleic anhydride polymers and half-esters there f f ble rug shampoo foam builder in an amount sufiicient to alkanols and cycloalkanols containing up to about 18 build a foamcarbon atoms, said styrene-maleic anhydride polymers A method of inhibiting Tug soiling comprising the having a mole ratio of about 1 to 4 moles of styrene per Steps of: mole of maleic anhydride and a molecular weight of shampooing the rug With a Shampoo composition about 00 to 0 000 Said detergent being Selected f which dries to an easily removable brittle residue on the group consisting of water-soluble alkyl sulfates, alkyl the rug after shampooing and Consists essentially of ethoxylated sulfates, N-acylsarcosines, N-acylsarcosinates, P Tug ShamPoo rgent and an addiand mixtures thereof tlve in amount sufiicient to embrittle the shampoo 2. A concentrated aqueous rug shampoo composition rFS1due leftn the rug after Shampooilig, d addiconsisting essentially of from about 5 to weight perfive bemg selected from the gr up consisting of cent f the rug shampoo composition of claim 1 and 70 water-soluble, metal, ammonium and amine salts of about 95 to 30 weight percent f Waten styrene-maleic anhydride polymers and half-esters 3 An aqueous rug shampoo composition f claim 1 in thereof of alkanols and cycloalkanols containing up dilute aqueous solution for applying as a shampoo to a to about 18 Carbon atoms, Said y -maleic anhy rug, which consists essentially of from about 0.5 to 3 dride polymers having a mole ratio of about 1 to 4 weight percent of the rug shampoo composition of claim moles of styrene per mole of maleic anhydride and 1 and from about 99.5 to 97 weight percent of water. a molecular weight of about 600 to 50,000, said de- 1 5 tergent being selected from the group consisting of Water-soluble alkyl sulfates, alkyl ethoxylatecl sulfates, N-acylsarcosines, N-acylsarcosinates, and mixtures thereof, the ratio of detergent to additive being within the range of 1:20 to 20:1 by weight;
(2) allowing said shampoo to dry on the rug; and (3) removing all visible residue from the rug.
References Cited UNITED STATES PATENTS 2,874,124 2/1959 Vitalis 252-410 3,206,408 9/1965 Vitalis et a1. 252557 16 3,485,762 12/ 1969 Gower et a1. 252-541 3,639,290 2/1972 Fearnley et al. 252545 FOREIGN PATENTS 1,416,813 9/ 1965 France.
LEON D. ROSDOL, Primary Examiner P. E. WILLIS, Assistant Examiner U.S. Cl. X.-R.
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US3990977 *||Mar 27, 1975||Nov 9, 1976||Pearson Glenn A||Fire proofing shampoo composition and method|
|US3994744 *||Oct 1, 1974||Nov 30, 1976||S. C. Johnson & Son, Inc.||No-scrub cleaning method|
|US4002571 *||Oct 1, 1974||Jan 11, 1977||S. C. Johnson & Son, Inc.||Cleaning compositions|
|US4013595 *||May 23, 1975||Mar 22, 1977||S. C. Johnson & Son, Inc.||Non-flammable rug cleaning composition|
|US4087368 *||Jul 1, 1975||May 2, 1978||Colgate-Palmolive Company||Water-soluble enzyme granules|
|US4125370 *||Nov 30, 1977||Nov 14, 1978||The Procter & Gamble Company||Laundry method imparting soil release properties to laundered fabrics|
|US4132680 *||Apr 12, 1978||Jan 2, 1979||The Procter & Gamble Company||Detergent compositions having soil release properties|
|US4508635 *||Feb 15, 1984||Apr 2, 1985||Lever Brothers Company||General-purpose cleaning composition comprising nonionic surfactant and alcohol esterified resin copolymer|
|US4586962 *||May 10, 1984||May 6, 1986||Gaf Corporation||Surface cleaning process|
|US4725319 *||Sep 9, 1986||Feb 16, 1988||Henkel Kommanditgesellschaft Auf Aktien||Cleaning preparations for hard surfaces|
|US4925707 *||Dec 21, 1987||May 15, 1990||E. I. Du Pont De Nemours And Company||Treatment of carpets|
|US4948650 *||Oct 26, 1989||Aug 14, 1990||E. I. Du Pont De Nemours And Company||Stain-resistant textile substrates|
|US5001004 *||Apr 2, 1990||Mar 19, 1991||E. I. Du Pont De Nemours And Company||Stain-resistant aromatic/maleic anhydride polymers|
|US5057121 *||Aug 4, 1989||Oct 15, 1991||E. I. Du Pont De Nemours And Company||Process for imparting stain-resist agent|
|US5137759 *||May 11, 1990||Aug 11, 1992||E. I. Du Pont De Nemours And Company||Imparting stain resistance to installed nylon carpets treated with antimicrobial or deodorizing agents|
|US5338475 *||Aug 16, 1991||Aug 16, 1994||Sterling Drug, Inc.||Carpet cleaning composition with bleach|
|US5359010 *||Dec 10, 1992||Oct 25, 1994||Alliedsignal Inc.||Method to impart coffee stain resistant to polyamide textile substances|
|US5364541 *||Jun 5, 1992||Nov 15, 1994||Calcaterra Lidia T||Method to impart coffee stain resistance to polyamide textile substrates|
|US5395555 *||Nov 22, 1993||Mar 7, 1995||Eastman Kodak Company||Cleaning composition for animal urine removal|
|US5429684 *||Dec 2, 1991||Jul 4, 1995||Henkel Kommanditgesellschaft Auf Aktien||Water-based carpet cleaning composition and method|
|US5439610 *||Sep 16, 1994||Aug 8, 1995||Reckitt & Colman Inc.||Carpet cleaner containing fluorinated surfactant and styrene maleic anhydride polymer|
|US5738687 *||Jul 23, 1996||Apr 14, 1998||Minnesota Mining And Manufacturing Company||Method for treating carpets with polycarboxylate salts to enhance soil resistance and repellency|
|US5744201 *||Apr 15, 1997||Apr 28, 1998||Minnesota Mining And Manufacturing Company||Method for treating carpet using PH adjustment|
|US5756181 *||Jul 23, 1996||May 26, 1998||Minnesota Mining And Manufacturing Company||Repellent and soil resistant carpet treated with ammonium polycarboxylate salts|
|US5955414 *||Oct 5, 1995||Sep 21, 1999||S. C. Johnson & Son, Inc.||Cleaning foam having fluorinated stain repellent and low flammability|
|US6010539 *||Oct 6, 1997||Jan 4, 2000||E. I. Du Pont De Nemours And Company||Cleaning formulations for textile fabrics|
|US6074436 *||May 13, 1998||Jun 13, 2000||3M Innovative Properties Company||Carpet treatment composition comprising polycarboxylate salts|
|US6113654 *||Sep 12, 1996||Sep 5, 2000||Peterson; David||Carpet cleaning composition|
|US20130101782 *||Oct 4, 2012||Apr 25, 2013||E I Du Pont De Nemours And Company||Nonfluorinated soil and stain resist compositions|
|US20130101783 *||Oct 4, 2012||Apr 25, 2013||E I Du Pont De Nemours And Company||Nonfluorinated soil resist, repellency, and stain resist compositions|
|EP0328822A2 *||Dec 14, 1988||Aug 23, 1989||E.I. Du Pont De Nemours And Company||Stain-resistant agents for textiles|
|EP0328822A3 *||Dec 14, 1988||Oct 18, 1989||E.I. Du Pont De Nemours And Company||Stain-resistant agents for textiles|
|EP0329899A2 *||Dec 14, 1988||Aug 30, 1989||E.I. Du Pont De Nemours And Company||Stain-resistant aromatic/maleic anhydride polymers|
|EP0329899A3 *||Dec 14, 1988||Oct 18, 1989||E.I. Du Pont De Nemours And Company||Stain-resistant aromatic/maleic anhydride polymers|
|WO1985005294A1 *||Apr 17, 1985||Dec 5, 1985||Gaf Corporation||Surface cleaning process|
|WO1991002116A1 *||Jul 11, 1990||Feb 21, 1991||E.I. Du Pont De Nemours And Company||Process for imparting stain-resist agents|
|WO1996011249A1 *||Oct 5, 1995||Apr 18, 1996||S.C. Johnson & Son, Inc.||Cleaning composition|
|WO2016196020A1 *||May 19, 2016||Dec 8, 2016||3M Innovative Properties Company||Enzyme cleaner for textiles with styrene maleic anhydride copolymers|
|U.S. Classification||510/280, 510/476, 510/340|
|International Classification||C11D3/37, C11D3/00|
|Cooperative Classification||C11D3/37, C11D3/0031, C11D3/3765|
|European Classification||C11D3/37, C11D3/00B6, C11D3/37C6F|
|Jun 2, 1989||AS||Assignment|
Owner name: PONY INDUSTRIES, INC., A CORP. OF DE
Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:MANUFACTURERS HANOVER TRUST COMPANY;REEL/FRAME:005110/0013
Effective date: 19890310
|Jan 5, 1987||AS||Assignment|
Owner name: CHASE MANHATTAN BANK, N.A., THE, A NATIONAL BANKIN
Owner name: CIT GROUP/BUSINESS CREDIT, INC., THE, A NEW YORK C
Owner name: MANUFACTURES HANOVER TRUST COMPANY, A NEW YORK CO
Free format text: SECURITY INTEREST;ASSIGNOR:PONY INDUSTRIES, INC.;REEL/FRAME:004796/0001
Effective date: 19861206
Owner name: PONY INDUSTRIES, INC., A CORP. OF DE.
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:ATLANTIC RICHFIELD COMPANY, A DE. CORP.;REEL/FRAME:004659/0926
Effective date: 19861219