Built detergent composition containing calcium-insensitive detergent and a carbonate-silicate builder
United States Patent 3892680
Biodegradable, phosphate-free detergent compositions are provided comprising a calcium insensitive detergent and a precipitating builder consisting essentially of a mixture of an alkali metal carbonate and an alkali metal silicate, the weight ratio of carbonate to silicate being from 3:1 to 1:3 and the weight ratio of the detergent to builder being in the range of 1:10 to 3:1.
US Patent References:
Detergent composition
Inamorato - August 1966 - 3265624
/3600318.html
Mast - August 1971 - 3600318
/3658727.html
Mast - April 1972 - 3658727
/3801511.html
Lemoff - April 1974 - 3801511
Detergent composition
Inamorato - August 1966 - 3265624
/3600318.html
Mast - August 1971 - 3600318
/3658727.html
Mast - April 1972 - 3658727
/3801511.html
Lemoff - April 1974 - 3801511
Inventors:
Benjamin, Lawrence (Springfield Twp., Hamilton County, OH)
Saylor, Jay Harold (Cincinnati, OH)
Saylor, Jay Harold (Cincinnati, OH)
Application Number:
05/341182
Publication Date:
07/01/1975
Filing Date:
03/14/1973
View Patent Images:
Export Citation:
Assignee:
The Procter & Gamble Company (Cincinnati, OH)
Primary Class:
Other Classes:
510/495, 510/276, 510/359, 510/352, 510/490, 510/494
International Classes:
C11D3/00; C11D3/02; C11D3/08; C11D3/10
Field of Search:
252/135,526,551,DIG.14,532,98,113
Other References:
McCutcheon, Synthetic Detergents, MacNair-Dorland Company, New York, 1950, pp. 250 and 282..
Primary Examiner:
Sebastian, Leland A.
Attorney, Agent or Firm:
Witte, Richard Filcik Julius Allen George C. P. W.
Parent Case Data:
CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in part of the application of Lawrence Benjamin and Jay Harold Saylor having Ser. No. 98,113, filed Dec. 14, 1970 now abandoned.
Claims:
Having thus described the invention, what is claimed is
1. A laundry composition consisting essentially of
2. a synthetic organic detergent having a formula
3. as a detergency builder, a mixture of an alkali metal carbonate and an alkali metal silicate wherein the weight ratio of carbonate to silicate is from 3:1 to 1:3 and the SiO2 /M2 O weight ratio of the silicate when M is an alkali metal is from 1.0 to 3.5:1; and the weight ratio of the detergent to builder is from 1:10 to 3:1.
4. The composition of claim 1 wherein the organic detergent is a compound of the formula
5. The composition of claim 2 in which the synthetic organic detergent is sodium triethoxy sulfate.
1. A laundry composition consisting essentially of
2. a synthetic organic detergent having a formula
3. as a detergency builder, a mixture of an alkali metal carbonate and an alkali metal silicate wherein the weight ratio of carbonate to silicate is from 3:1 to 1:3 and the SiO2 /M2 O weight ratio of the silicate when M is an alkali metal is from 1.0 to 3.5:1; and the weight ratio of the detergent to builder is from 1:10 to 3:1.
4. The composition of claim 1 wherein the organic detergent is a compound of the formula
5. The composition of claim 2 in which the synthetic organic detergent is sodium triethoxy sulfate.
Description:
BACKGROUND OF THE INVENTION
It has been known that when detergency builders are combined with synthetic detergents, an improvement in cleaning or whiteness maintenance or both is obtained.
Water-soluble polyphosphates, and in particular, the water-soluble pyrophosphates and tripolyphosphates, are well known builders for heavy duty detergent compositions. Sodium tripolyphosphate has been widely used in granular detergent compositions.
Public attention has been drawn to the role of phosphates generally in the natural life cycle of lakes, and specifically to the contribution by detergent phosphates to this process. An imbalance of nutrients, e.g. carbon, nitrogen, phosphates and the like in lakes appears to adversely affect the ecological balance between algae and fish. The consequence is that an ordinary and natural lake-aging process can be accelerated.
It is a basic object of this invention to provide detergent compositions which are free of nitrates and phosphates.
It is a further object of this invention to provide detergent compositions which are biodegradable, and phosphate- and nitrate-free and which are effective heavy-duty compositions over a wide range of concentrations.
It is an object of the invention to provide an effective phosphate-free heavy-duty laundry detergent composition.
SUMMARY OF THE INVENTION
This invention is based on the discovery that an effective phosphate-free detergent composition comprises a calcium insensitive detergent and a precipitating builder consisting essentially of an alkali metal carbonate and an alkali metal silicate. The invention thus involves the preparation of laundry detergent compositions consisting essentially of the following components:
A. from 5% to 85% of a calcium insensitive organic synthetic detergent characterized by:
1. having solubility in water in a concentration of at least about 0.05% at a temperature of about 70°F. to about 200°F;
2. efficient soil-removing and soil-dispersing properties in a concentration of about 0.05% in water; and
3. resistance to precipitation by hard water mineral ions; and
B. from 10% to 95% of a builder consisting essentially of an alkali metal carbonate and an alkali metal silicate, the weight ratio of carbonate to silicate being from 3:1 to 1:3 and the weight ratio of detergent to builder being from 1:10 to 3:1; said composition having a pH of from 6 to 12 in aqueous solution at a concentration of 0.12%.
DETAILED DESCRIPTION OF THE INVENTION
The calcium insensitive organic synthetic detergents useful herein include certain anionic, nonionic, zwitterionic and ampholytic detergents and mixtures thereof. In the context of this invention, the term "calcium insensitive" is used to designate those detergents which possess superior detergency and dispersancy and relative resistance to precipitation or insoluble complex formation under the conditions of pH and water hardness contemplated. The terms detergency and dispersancy where employed herein refer, respectively, to the capacity to remove particulate and lipid soils from a substrate and the capacity to keep such soils in suspension in a washing solution. Detergent and dispersant compounds to be useful herein must, in addition, perform satisfactorily in washing solutions containing hardness mineral ions normally present in tap water. In other words, the detergents must be "insensitive" to such hardness ions, especially calcium and magnesium. A detergent and dispersant material which forms a precipitate or insoluble-complex with hard water ions, the detergent not available to function for its intended purpose. A detergent useful herein is one whose detergency properties are not compromised by hardness mineral ions, i.e. calcium and the like.
The synthetic organic detergent compounds utilizable herein and having the hereinbefore described calcium insensitive properties include certain anionic, semi-polar nonionic, ampholytic and zwitterionic materials. These materials include water-soluble salts of certain materials such as sulfonated fatty acid esters of β-acyloxyalkane-1-sulfonic acids; β-alkyloxy alkane sulfonates; alkyl polyoxyethylene sulfates, water-soluble olefin sulfonates; and certain ampholytic and zwitterionic detergents. Of the organic detergents investigated, only detergents more specifically described hereinafter have been found in the compositions of the present invention to provide the levels of cleaning which equal or surpass those normally attained in the course of washing with a conventional detergent composition. Only the hereinafter described highly efficient detergent compounds have been found to permit the attainment of levels of cleaning comparable to those obtainable heretofore with phosphate builder compositions. Mixtures of these detergent materials can be employed to advantage.
Anionic organic detergents utilizable herein include alkali metal, ammonium and substituted-ammonium salts of esters of an α-sulfonated fatty acid in which the esters contain about 15 to about 25 carbon atoms. These detergent compounds have the following structure: ##SPC1##
wherein R 1 is alkyl or alkenyl of about 10 to about 20 carbon atoms (forming with the two carbon atoms a fatty acid group); R 2 is alkyl of 1 to about 10 carbon atoms; and M is a salt-forming cation.
The salt-forming radical M in the hereinbefore described structural formula is a water-solubilizing cation and can be, for example, an alkali metal cation (e.g., sodium, potassium, lithium), ammonium or substituted-ammonium cation. Specific examples of substituted ammonium cations include methyl-, dimethyl-, and trimethyl- ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
Specific examples of this class of compounds include the sodium and potassium salts of esters where R 2 is selected from methyl, ethyl, propyl, butyl, hexyl and octyl groups and the fatty acid group (R 1 plus the two carbon atoms in the structure above) is selected from lauric, myristic, palmitic, stearic, palmitoleic, oleic, linoleic acids and mixtures thereof. A preferred ester material herein is the sodium salt of the methyl ester of α-sulfonated tallow fatty acid, the term tallow indicating a carbon chain distribution approximately as follows: C 14 -- 2.5%, C 16 -- 28%, C 18 -- 23%, palmitoleic -- 2%, oleic -- 41.5%, and linoleic -- 3% (the first three fatty acids listed are saturated).
Other examples of suitable salts of α-sulfonated fatty esters utilizable herein include the ammonium and tetramethyl-ammonium salts of the hexyl, octyl, ethyl, and butyl esters of α-sulfonated tridecanoic acid; the potassium and sodium salts of the ethyl, butyl, hexyl, octyl, and decyl esters of α-sulfonated pentadecanoic acid; and the sodium and potassium salts of butyl, hexyl, octyl, and decyl esters of α-sulfonated heptadecanoic acid; and the lithium and ammonium salts of butyl, hexyl, octyl, and decyl esters of α-sulfonated nonadecanoic acid.
The salts of α-sulfonated fatty acid esters of the present invention are known compounds and are described in U.S. Pat. No. 3,223,645, issued Dec. 14, 1965 to Kalberg, this patent being hereby incorporated by reference.
Another class of suitable anionic organic detergents includes salts of 2-acyloxy-alkane-1-sulfonic acids. These salts have the formula ##SPC2##
where R 1 is alkyl of about 9 to about 23 carbon atoms (forming with the two carbon atoms an alkane group); R 2 is alkyl of 1 to about 8 carbon atoms; and M is a salt-forming radical hereinbefore described.
Specific examples of β-acyloxy-alkane-1-sulfonates, or alternatively 2-acyloxy-alkane-1-sulfonates, utilizable herein to provide excellent cleaning levels under household washing conditions include the sodium salt of 2-acetoxy-tridecane-1-sulfonic acid; the potassium salt of 2-propionyloxy-tetradecane-1-sulfonic acid; the lithium salt of 2-butanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of 2-pentanoyloxy-pentadecane-1-sulfonic acid; the ammonium salt of 2-hexanoyloxy-hexadecane-1-sulfonic acid; the sodium salt of 2-acetoxy-hexadecane-1-sulfonic acid; the dimethylammonium salt of 2-heptanoyloxy-tridecane-1-sulfonic acid; the potassium salt of 2-octanoyloxy-tetradecane-1-sulfonic acid; the dimethylpiperdinium salt of 2-nonanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of 2-acetoxy-heptadecane-1-sulfonic acid; the lithium salt of 2-acetoxy-octadecane-1-sulfonic acid; the dimethylamine salt of 2-acetoxyoctadecane-1-sulfonic acid; the potassium salt of 2-acetoxy-nonadecane-1-sulfonic acid; the sodium salt of 2-acetoxy-uncosane-1-sulfonic acid; the sodium salt of 2-propionyloxy-docosane-1-sulfonic acid; and isomers thereof.
Preferred β-acyloxy-alkane-1-sulfonate salts herein are the alkali metal salts of β-acetoxy-alkane-1-sulfonic acids corresponding to the above formula wherein R 1 is an alkyl of about 14 to about 18 carbon atoms, these salts being preferred from the standpoints of their excellent cleaning properties and ready availability.
Typical examples of the above described β-acetoxy alkanesulfonates are described in the literature: Belgian Pat. No. 650,323 issued July 9, 1963, discloses the preparation of certain 2-acyloxy alkanesulfonic acids. Similarly, U.S. Pat. No. 2,094,451 issued Sept. 28, 1937, to Guenther et al. and No. 2,086,215 issued July 6, 1937 to DeGroote disclose certain salts of β-acetoxy alkanesulfonic acids. These references are hereby incorporated by reference.
Other synthetic anionic detergents useful herein are alkyl ether sulfates. These materials have the formula RO(C 2 H 4 O) x SO 3 M wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, x is 1 to 30, and M is a salt-forming cation defined hereinbefore.
The alkyl ether sulfates of the present invention are condensation products of ethylene oxide and monohydric alcohols having about 10 to about 20 carbon atoms. Preferably, R has 14 to 18 carbon atoms. The alcohols can be derived from fats, e.g., coconut oil or tallow, or can be synthetic. Lauryl alcohol and straight chain alcohols derived from tallow are preferred herein. Such alcohols are reacted with 1 to 30, and especially 3 to 6, molar proportions of ethylene oxide and the resulting mixture of molecular species, having, for example, an average of 3 to 6 moles of ethylene oxide per mole of alcohols, is sulfated and neutralized.
Specific examples of alkyl ether sulfates of the present invention are sodium coconut alkyl ethylene glycol ether sulfate; sodium tallow alkyl triethylene glycol ether sulfate; lithium tallow alkyl triethylene glycol ether sulfate; sodium tallow alkyl hexaoxyethylene sulfate; and ammonium tetradecyl octaoxyethylene sulfate.
Preferred herein for reasons of excellent cleaning properties and ready availability are the alkali metal coconut- and tallow-alkyl oxyethylene ether sulfates having an average of about 1 to about 10 oxyethylene moieties. The alkyl ether sulfates of the present invention are known compounds and are described in U.S. Pat. No. 3,332,876 to Walker (July 25, 1967) incorporated herein by reference.
A preferred class of anionic organic detergents are the β-alkyloxy alkane sulfonates. These compouhds have the following formula: ##SPC3##
where R 1 is a straight chain alkyl group having from 10 to 20 carbon atoms, R 2 is a lower alkyl group having from 1 to 3 carbon atoms, and M is a salt-forming radical hereinbefore described.
Specific examples of β-alkyloxy alkane sulfonates or alternatively 2-alkyloxy-alkane-1-sulfonates, utilizable herein to provide superior cleaning and whitening levels under household washing conditions include
potassium β-methoxydecanesulfonate,
sodium β-methoxy-tridecanesulfonate,
potassium β-ethoxytetradecylsulfonate,
sodium β-isopropoxyhexadecylsulfonate,
lithium βt-butoxytetradecylsulfonate,
sodium β-methoxyoctadecylsulfonate, and
ammonium βn-propoxydodecylsulfonate.
Other suitable anionic detergents utilizable herein are olefin sulfonates having about 12 to about 24 carbon atoms. The term "olefin sulfonates" is used herein to mean compounds which are produced by the sulfonation of α-olefin by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that sultones formed in the reaction are hydrolyzed to give corresponding hydroxy-alkanesulfonates. The sulfur trioxide may be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid SO 2 , chlorinated hydrogen, etc., when used in the liquid form, or by air, nitrogen, gaseous SO 2 , etc., when used in the gaseous form.
The α-olefins from which the olefin sulfonates are derived are mono-olefins having 12 to 24 carbon atoms, preferably 14 to 16 carbon atoms. Preferably, they are straight chain olefins. Examples of suitable 1-olefins include 1-dodecene; 1-tetradecene; 1-hexadecene; 1-octadecene; 1-eicosene and 1-tetracosene.
In addition to the true alkene sulfonates and a proportion of hydroxy-alkanesulfonates, the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportions of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process.
Ampholytic synthetic detergents useful herein are broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical is straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, or sulfate. These detergents have the formula ##SPC4##
wherein R 1 is alkyl of about 8 to about 18 carbon atoms, R 2 is alkyl of 1 to about 3 carbon atoms or is hydrogen, R 3 is alkylene of 1 to about 4 carbon atoms, Z is carboxy, sulfonate, or sulfate, and M is a salt-forming cation. Examples of compounds falling within this definition are sodium 3-dodecylaminopropionate; sodium 3- dodecylaminopropane sulfonate; N-alkyltaurines such as the ones prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Pat. No. 3,658,072; sodium salts of N-higher alkyl aspartic acids such as those produced according to the teaching of U.S. Pat. No. 2,438,091; and the products sold under the trade name "Miranol" and described in U.S. Pat. No. 2,528,378.
Useful Zwitterionic synthetic detergents are broadly described as derivatives of aliphatic quaternary ammonium, and sulfonium compounds, in which the aliphatic radicals are straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate or sulfate. A general formula for these compounds is: ##SPC5##
wherein R 1 contains an alkyl, alkenyl, or hydroxyalkyl radical of from about 8 to about 18 carbon atoms having from 0 to about 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety; Y is selected from the group consisting of nitrogen and sulfur atoms; R 2 is an alkyl or monohydroxy alkyl group containing 1 to about 3 carbon atoms; x is 1 when Y is a sulfur atom and 2 when Y is a nitrogen atom, R 3 is an alkylene or hydroxy alkylene of from 1 to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate and phosphate groups.
Examples include: 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carbo xylate; 5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1 -sulfate; 3-[P,P-diethyl-P-3,6,9-trioxatetracosanephosphonio]-2-hydrox ypropane-1-pho sphate; 3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropylammonio]-propane -1-phosphonate ; 3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate, 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfo nate, 4-[N,N-di(2-hydroxyethyl)-N-(2-hydroxydodecyl)ammonio]-butan e-1-carboxylat e, 3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-1 -phosphate, 3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate, and 3-[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxypent ane-1-sulfonat e. Examples of compounds falling within this definition are 3-(N,N-dimethylN-N-hexadecylammonio)propane-1-sulfonate and 3-(N,N-dimethyl-N-tridecylammonio)-2-hydroxypropane-1-sulfon ate which are especially preferred for their excellent cool water detergency characteristics.
The alkyl groups contained in said detergent surfactants can be straight or branched, preferably straight, and saturated or unsaturated as desired.
The calcium insensitive detergent compounds of the present invention can be employed in varying amounts in the compositions of the present invention. As there will be considerable variation in the strengths of washing solutions employed by different users, i.e., some users may tend to use more or less than others, the requisite amount of detergent compound in the detergent formulation is an amount sufficient to provide effective cleaning and whitening levels under diverse conditions of soiling and usage. The enzyme-containing detergent compositions of the present invention can contain from 5 to 85% by weight of the synthetic organic detergent depending upon the detergent employed. A preferred amount of detergent (sole detergent or mixtures) is from 15 to 50%.
The builder is a mixture of two inorganic salts selected from alkali metal silicates and carbonates. The preferred salts are the potassium and sodium salts such as sodium carbonate and sodium silicate, and potassium carbonate and potassium silicate.
In detergent formulations, the SiO 2 /M 2 O weight ratio of the silicate, where M is an alkili metal is critical. The effective range of this weight ratio as SiO 2 /M 2 O is from 1:1 to 3.5:1; the preferred range is from 1.6:1 to 3.2:1.
The heavy duty compositions of this invention can be made into any of the several commercially desirable composition forms, for example, granular, flake, liquid and tablet forms.
In general, the essential ingredients are (a) the calcium insensitive detergent and (b) the builder mixture, as described herein.
The specific action of the built detergent compositions of this invention will vary to some extent depending upon the ratio of active detergent to building mixture in any given detergent composition. There is considerable variation in the strengths of the washing solutions employed by different housewives, i.e., some housewives tend to use less or more of the detergent compositions than others. Moreover, there are variations in temperature and soil loads as between washing operations. Further, the degree of hardness of the water used to make up the washing solutions can also cause differences in the cleaning and whiteness maintenance results. Different fabrics respond in different ways to different detergent compositions. The most useful detergent composition for household use is a composition which provides effective cleaning and whiteness maintenance under diverse cleaning conditions. The built detergent compositions of this invention are especially valuable in this respect.
Useful degrees of building activity are attained in the practice of this invention with ratios of detergent to builder of from about 1:10 to about 3:1, preferably 1:5 to 1:1.
The compositions of this invention can contain various ingredients for special purposes. Thus, they can contain such ordinary additives as suds builders, suds depressants, anti-corrosion agents, antiredeposition agents, germicidal agents, anti-bacterial agents, dyes, fluorescers, perfumes, enzymes and the like. In the manufacture of liquid detergents, liquid vehicles, for example water and alcohol, together with solubilizing agents and the like can be used. These form no limitation on the invention, but are intended to come within the contemplation of the present invention.
Superior cleaning is obtained with the detergent compositions of this invention in aqueous washing solution having a pH range in the range of about 7 to about 12. Washing temperatures can range from about 80°F. to about 200°F. Fabrics are preferably rinsed and dried after washing.
The invention is further demonstrated by the following examples.
EXAMPLE I
An effective granular detergent product was made with the following composition; the percentages given are by weight:
25% Sodium salt of sulfuric acid ester of one mole tallow 25% Sodium carbonate 25% Sodium silicate (SiO 2 /Na 2 O weight ratio of 3.2:1) 15% Sodium sulfate 10% Moisture
This formulation provides excellent results in home laundry-type applications.
EXAMPLE II
A granular detergent product was made with the following composition; the percentages given are be weight:
25% Sodium salt of β-methoxydodecane sulfonic acid 25% Sodium carbonate 25% Sodium silicate (SiO 2 /Na 2 O weight ratio of 3.2:1) 15% Sodium sulfate 10% Moisture
This formulation provides excellent cleaning results in home laundry-type applications.
Substantially similar results can be obtained when the sodium β-methoxydodecane sulfonate is replaced by sodium, potassium, and lithium salts of β-methoxydecane sulfonate, β-ethoxytetradecyl sulfonate, β-isopropoxyhexadecyl sulfonate, βt-butoxytetradecyl sulfonate, β-methoxyoctadecyl sulfonate, βn-propoxydodecyl sulfonate, β-ethoxyoctadecyl sulfonate, and β-methoxyhexadecyl sulfonate.
EXAMPLE III
A granular detergent product was made with the following composition; the percentages are given by weight:
25% Sodium salt of β-acetoxytridecane-1- sulfonic acid 25% Sodium carbonate 25% Sodium silicate (SiO 2 /Na 2 O weight ratio of 2.0:1) 15% Sodium sulfate 10% Moisture
This formulation gives excellent results in home laundry-type applications.
Substantially similar results can be obtained when the sodium β-acetoxytridecane-1-sulfonic acid salt is replaced with the potassium salt of 2-propionyloxy-tetradecane-1-sulfonic acid; the lithium salt of 2-butanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of 2-pentanoyloxy-pentadecane-1-sulfonic acid; the ammonium salt of 2-hexanoyloxy-hexadecane-1-sulfonic acid; the sodium salt of 2-acetoxy-hexadecane-1-sulfonic acid; the dimethylammonium salt of 2-heptanoyloxy-tridecane-1-sulfonic acid; the potassium salt of 2-octanoyloxy-tetradecane-1-sulfonic acid; the dimethylpiperdinium salt of 2-nonanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of 2-acetoxy-heptadecane-1-sulfonic acid; the lithium salt of 2-acetoxy-octadecane-1-sulfonic acid; the dimethylamine salt of 2-acetoxyoctadecane-1-sulfonic acid; the potassium salt of 2-acetoxy-nonadecane-1-sulfonic acid; the sodium salt of 2-acetoxy-uncosane-1-sulfonic acid; the sodium salt of 2-propionyloxy-docosane-1-sulfonic acid; and isomers thereof.
EXAMPLE IV
An effective granular detergent product has the following composition; the percentages are given by weight:
25% Sodium salt of the methyl ester of α-sulfonated tallow fatty acid 25% Sodium carbonate 25% Sodium silicate (SiO 2 /Na 2 O weight ratio of 1.6:1) 15% Sodium sulfate 10% Moisture
Substantially similar results can be obtained when the sodium and potassium salts of esters where the methyl is replaced by ethyl, propyl, butyl, hexyl and octyl groups and the tallow fatty acid group is replaced by lauric, myristic, palmitic, stearic, palmitoleic, oleic, linoleic acids and mixtures thereof.
EXAMPLE V
An effective granular detergent product has the following composition; the precentages are given by weight:
25% Sodium 1-hexadecene sulfonate 30% Sodium carbonate 20% Sodium silicate (SiO 2 /Na 2 O weight ratio of 3.2:1) 15% Sodium sulfate 10% Moisture
This formulation gives excellent results in home laundry-type applications. Substantially similar results can be obtained when the sodium 1-hexadecene sulfonate is replaced by sodium 1-tetradecene sulfonate; sodium 1-octadecene sulfonate; sodium 1-eicosene sulfonate; sodium 1-tetracosene sulfonate, and sodium 1-dodecene sulfonate.
EXAMPLE VI
A granular detergent product of this invention has the following composition; the percentages are given by weight:
25% Sodium 3-dodecyl-amino-propionate 25% Sodium carbonate 25% Sodium silicate (SiO 2 /Na 2 O weight ratio of 3.0:1) 15% Sodium sulfate 10% Moisture
This formulation provides excellent results in home laundry-type applications. Substantially similar results can be obtained when the sodium 3-dodecyl-amino-propionate is replaced with sodium 3-dodecyl-amino-propane sulfonate.
EXAMPLE VII
A granular detergent product of this invention has the following composition; the percentages are given by weight:
25% 3-(N,N-dimethyl-N-hexadecylammonio)- propane-1-sulfonate 20% Sodium carbonate 30% Sodium silicate (SiO 2 /Na 2 O weight ratio of 1.6:1) 15% Sodium sulfate 10% Moisture
Substantially similar results can be obtained when the 3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate is replaced by 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carbo xylate; 5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1 -sulfate; 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfo nate, 4-[N,N-di(2-hydroxyethyl)-N-(2-hydroxydodecyl)ammonio]-butan e-1-carboxylat e; 3-[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxypent ane-1-sulfonat e; and 3-(N,N-dimethyl-N-tridecylammonio)-2-hydroxypropane-1-sulfon ate. The 3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sullfonate and 3-(N,N-dimethyl-N-tridecylammonio)-2-hydroxy-propane-1-sulfo nate, when used in the above formulation, give exceptional results in cool water.
A facial swatch test was conducted comparing representative compositions of this invention with two other household laundry compositions. One of the household laundry compositions had a linear alkyl benzene sulfonate-tallow alkyl sulfate active and a nitrilotriacetic-phosphate builder, while the other composition has a tallow undecyl ethoxylate surface active agent and the carbonate-silicate builder system common to the examples representative of the invention.
TABLE I ______________________________________ Test Composition Component by Weight Percent 1 2 3 4 5 6 ______________________________________ Sodium carbonate 25 25 25 25 25 Sodium silicate (SiO 2 /Na 2 O wt. ratio of 3.2:1) 25 25 25 25 25 Trisodium nitrilotriacetate 12.4 Sodium tripolyphosphate 37.1 Sodium tallow triethoxy sulfate 25 12.5 Sodium dodecyl benzene sulfonate 12.5 25 Sodium β-methoxy hexadecyl sulfonate 7.6 25 Tallow undecyl ethoxylate 25 Sodium tallow sulfate 9.4 Sodium silicate (SiO 2 /Na 2 O wt. ratio of 1.6:1) 6.0 Sodium sulfate 17.5 15 15 15 15 15 Moisture 10 10 10 10 10 10 ______________________________________
The facial switch test requires fourteen panelists and is completely replicated, using a second set of fourteen panelists with the two results being averaged to obtain one complete test. The 4×4 inch cotton swatches used in this test are fastened to the concave cup of an electrical massaging device. The cup is then rubbed over designated areas of a panelist's face for a period of 30 seconds while the machine is vibrating. The swatches thus become soiled. The soiled swatches are washed in a Tergotometer for 10 minutes in 1 liter of the product solution. The solution, containing 7 grains calcium ion hardness, is kept at 110°F. The detergent product is used at a 0.12% level by weight. The swatches are then rinsed for 1 minute at a temperature of 100°F. using water containing 7 grains of calcium ion hardness. They are then dried and graded.
The compositions of the products used in this test are found in Table I. Each component was added separately to the wash solution while minor ingredients normally found in household laundry products such as carboxymethylcellulose, optical brightening agents and enzymes were omitted in all cases.
The washed and dried facial swatches were graded visually to assess the relative cleaning differences of the products used.
A control product for the test was provided by Composition I, Table I. Composition I was used at two concentration levels, 0.15% product and 0.06% product. Each of the product grades and usage levels are presented in Table II.
TABLE II ______________________________________ Composition Solution Strength Tested (% by weight) Grade ______________________________________ 1 0.15 7.6 1 0.06 4.1 2 0.12 6.2 3 0.12 5.6 4 0.12 3.8 5 0.12 5.2 6 0.12 3.8 ______________________________________
In Table II, grades below 4.5 indicate poor performance, grades between 4.5 to 6.0 represent fair to average performance, while a grade above 6.0 represents good performance. It can be seen from Table II that the compositions of this invention, Nos. 2, 3, and 5, all provide performance that is average or better than average and compare favorably with the control product used in the test, even noting that the control product was used at a slightly higher solution concentration.
A complete discussion of this type of testing for detergency is found in Comite International de la Detergence Chemistry, Physics and Application of Surface Active Substances Proceedings of the IVth International Congress on Surface Active Substances, Brussels, 7-12 Sept., 1964, Vol. 3, 221-229, New York, Gordon & Breach, 1967.
It has been known that when detergency builders are combined with synthetic detergents, an improvement in cleaning or whiteness maintenance or both is obtained.
Water-soluble polyphosphates, and in particular, the water-soluble pyrophosphates and tripolyphosphates, are well known builders for heavy duty detergent compositions. Sodium tripolyphosphate has been widely used in granular detergent compositions.
Public attention has been drawn to the role of phosphates generally in the natural life cycle of lakes, and specifically to the contribution by detergent phosphates to this process. An imbalance of nutrients, e.g. carbon, nitrogen, phosphates and the like in lakes appears to adversely affect the ecological balance between algae and fish. The consequence is that an ordinary and natural lake-aging process can be accelerated.
It is a basic object of this invention to provide detergent compositions which are free of nitrates and phosphates.
It is a further object of this invention to provide detergent compositions which are biodegradable, and phosphate- and nitrate-free and which are effective heavy-duty compositions over a wide range of concentrations.
It is an object of the invention to provide an effective phosphate-free heavy-duty laundry detergent composition.
SUMMARY OF THE INVENTION
This invention is based on the discovery that an effective phosphate-free detergent composition comprises a calcium insensitive detergent and a precipitating builder consisting essentially of an alkali metal carbonate and an alkali metal silicate. The invention thus involves the preparation of laundry detergent compositions consisting essentially of the following components:
A. from 5% to 85% of a calcium insensitive organic synthetic detergent characterized by:
1. having solubility in water in a concentration of at least about 0.05% at a temperature of about 70°F. to about 200°F;
2. efficient soil-removing and soil-dispersing properties in a concentration of about 0.05% in water; and
3. resistance to precipitation by hard water mineral ions; and
B. from 10% to 95% of a builder consisting essentially of an alkali metal carbonate and an alkali metal silicate, the weight ratio of carbonate to silicate being from 3:1 to 1:3 and the weight ratio of detergent to builder being from 1:10 to 3:1; said composition having a pH of from 6 to 12 in aqueous solution at a concentration of 0.12%.
DETAILED DESCRIPTION OF THE INVENTION
The calcium insensitive organic synthetic detergents useful herein include certain anionic, nonionic, zwitterionic and ampholytic detergents and mixtures thereof. In the context of this invention, the term "calcium insensitive" is used to designate those detergents which possess superior detergency and dispersancy and relative resistance to precipitation or insoluble complex formation under the conditions of pH and water hardness contemplated. The terms detergency and dispersancy where employed herein refer, respectively, to the capacity to remove particulate and lipid soils from a substrate and the capacity to keep such soils in suspension in a washing solution. Detergent and dispersant compounds to be useful herein must, in addition, perform satisfactorily in washing solutions containing hardness mineral ions normally present in tap water. In other words, the detergents must be "insensitive" to such hardness ions, especially calcium and magnesium. A detergent and dispersant material which forms a precipitate or insoluble-complex with hard water ions, the detergent not available to function for its intended purpose. A detergent useful herein is one whose detergency properties are not compromised by hardness mineral ions, i.e. calcium and the like.
The synthetic organic detergent compounds utilizable herein and having the hereinbefore described calcium insensitive properties include certain anionic, semi-polar nonionic, ampholytic and zwitterionic materials. These materials include water-soluble salts of certain materials such as sulfonated fatty acid esters of β-acyloxyalkane-1-sulfonic acids; β-alkyloxy alkane sulfonates; alkyl polyoxyethylene sulfates, water-soluble olefin sulfonates; and certain ampholytic and zwitterionic detergents. Of the organic detergents investigated, only detergents more specifically described hereinafter have been found in the compositions of the present invention to provide the levels of cleaning which equal or surpass those normally attained in the course of washing with a conventional detergent composition. Only the hereinafter described highly efficient detergent compounds have been found to permit the attainment of levels of cleaning comparable to those obtainable heretofore with phosphate builder compositions. Mixtures of these detergent materials can be employed to advantage.
Anionic organic detergents utilizable herein include alkali metal, ammonium and substituted-ammonium salts of esters of an α-sulfonated fatty acid in which the esters contain about 15 to about 25 carbon atoms. These detergent compounds have the following structure: ##SPC1##
wherein R 1 is alkyl or alkenyl of about 10 to about 20 carbon atoms (forming with the two carbon atoms a fatty acid group); R 2 is alkyl of 1 to about 10 carbon atoms; and M is a salt-forming cation.
The salt-forming radical M in the hereinbefore described structural formula is a water-solubilizing cation and can be, for example, an alkali metal cation (e.g., sodium, potassium, lithium), ammonium or substituted-ammonium cation. Specific examples of substituted ammonium cations include methyl-, dimethyl-, and trimethyl- ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
Specific examples of this class of compounds include the sodium and potassium salts of esters where R 2 is selected from methyl, ethyl, propyl, butyl, hexyl and octyl groups and the fatty acid group (R 1 plus the two carbon atoms in the structure above) is selected from lauric, myristic, palmitic, stearic, palmitoleic, oleic, linoleic acids and mixtures thereof. A preferred ester material herein is the sodium salt of the methyl ester of α-sulfonated tallow fatty acid, the term tallow indicating a carbon chain distribution approximately as follows: C 14 -- 2.5%, C 16 -- 28%, C 18 -- 23%, palmitoleic -- 2%, oleic -- 41.5%, and linoleic -- 3% (the first three fatty acids listed are saturated).
Other examples of suitable salts of α-sulfonated fatty esters utilizable herein include the ammonium and tetramethyl-ammonium salts of the hexyl, octyl, ethyl, and butyl esters of α-sulfonated tridecanoic acid; the potassium and sodium salts of the ethyl, butyl, hexyl, octyl, and decyl esters of α-sulfonated pentadecanoic acid; and the sodium and potassium salts of butyl, hexyl, octyl, and decyl esters of α-sulfonated heptadecanoic acid; and the lithium and ammonium salts of butyl, hexyl, octyl, and decyl esters of α-sulfonated nonadecanoic acid.
The salts of α-sulfonated fatty acid esters of the present invention are known compounds and are described in U.S. Pat. No. 3,223,645, issued Dec. 14, 1965 to Kalberg, this patent being hereby incorporated by reference.
Another class of suitable anionic organic detergents includes salts of 2-acyloxy-alkane-1-sulfonic acids. These salts have the formula ##SPC2##
where R 1 is alkyl of about 9 to about 23 carbon atoms (forming with the two carbon atoms an alkane group); R 2 is alkyl of 1 to about 8 carbon atoms; and M is a salt-forming radical hereinbefore described.
Specific examples of β-acyloxy-alkane-1-sulfonates, or alternatively 2-acyloxy-alkane-1-sulfonates, utilizable herein to provide excellent cleaning levels under household washing conditions include the sodium salt of 2-acetoxy-tridecane-1-sulfonic acid; the potassium salt of 2-propionyloxy-tetradecane-1-sulfonic acid; the lithium salt of 2-butanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of 2-pentanoyloxy-pentadecane-1-sulfonic acid; the ammonium salt of 2-hexanoyloxy-hexadecane-1-sulfonic acid; the sodium salt of 2-acetoxy-hexadecane-1-sulfonic acid; the dimethylammonium salt of 2-heptanoyloxy-tridecane-1-sulfonic acid; the potassium salt of 2-octanoyloxy-tetradecane-1-sulfonic acid; the dimethylpiperdinium salt of 2-nonanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of 2-acetoxy-heptadecane-1-sulfonic acid; the lithium salt of 2-acetoxy-octadecane-1-sulfonic acid; the dimethylamine salt of 2-acetoxyoctadecane-1-sulfonic acid; the potassium salt of 2-acetoxy-nonadecane-1-sulfonic acid; the sodium salt of 2-acetoxy-uncosane-1-sulfonic acid; the sodium salt of 2-propionyloxy-docosane-1-sulfonic acid; and isomers thereof.
Preferred β-acyloxy-alkane-1-sulfonate salts herein are the alkali metal salts of β-acetoxy-alkane-1-sulfonic acids corresponding to the above formula wherein R 1 is an alkyl of about 14 to about 18 carbon atoms, these salts being preferred from the standpoints of their excellent cleaning properties and ready availability.
Typical examples of the above described β-acetoxy alkanesulfonates are described in the literature: Belgian Pat. No. 650,323 issued July 9, 1963, discloses the preparation of certain 2-acyloxy alkanesulfonic acids. Similarly, U.S. Pat. No. 2,094,451 issued Sept. 28, 1937, to Guenther et al. and No. 2,086,215 issued July 6, 1937 to DeGroote disclose certain salts of β-acetoxy alkanesulfonic acids. These references are hereby incorporated by reference.
Other synthetic anionic detergents useful herein are alkyl ether sulfates. These materials have the formula RO(C 2 H 4 O) x SO 3 M wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, x is 1 to 30, and M is a salt-forming cation defined hereinbefore.
The alkyl ether sulfates of the present invention are condensation products of ethylene oxide and monohydric alcohols having about 10 to about 20 carbon atoms. Preferably, R has 14 to 18 carbon atoms. The alcohols can be derived from fats, e.g., coconut oil or tallow, or can be synthetic. Lauryl alcohol and straight chain alcohols derived from tallow are preferred herein. Such alcohols are reacted with 1 to 30, and especially 3 to 6, molar proportions of ethylene oxide and the resulting mixture of molecular species, having, for example, an average of 3 to 6 moles of ethylene oxide per mole of alcohols, is sulfated and neutralized.
Specific examples of alkyl ether sulfates of the present invention are sodium coconut alkyl ethylene glycol ether sulfate; sodium tallow alkyl triethylene glycol ether sulfate; lithium tallow alkyl triethylene glycol ether sulfate; sodium tallow alkyl hexaoxyethylene sulfate; and ammonium tetradecyl octaoxyethylene sulfate.
Preferred herein for reasons of excellent cleaning properties and ready availability are the alkali metal coconut- and tallow-alkyl oxyethylene ether sulfates having an average of about 1 to about 10 oxyethylene moieties. The alkyl ether sulfates of the present invention are known compounds and are described in U.S. Pat. No. 3,332,876 to Walker (July 25, 1967) incorporated herein by reference.
A preferred class of anionic organic detergents are the β-alkyloxy alkane sulfonates. These compouhds have the following formula: ##SPC3##
where R 1 is a straight chain alkyl group having from 10 to 20 carbon atoms, R 2 is a lower alkyl group having from 1 to 3 carbon atoms, and M is a salt-forming radical hereinbefore described.
Specific examples of β-alkyloxy alkane sulfonates or alternatively 2-alkyloxy-alkane-1-sulfonates, utilizable herein to provide superior cleaning and whitening levels under household washing conditions include
potassium β-methoxydecanesulfonate,
sodium β-methoxy-tridecanesulfonate,
potassium β-ethoxytetradecylsulfonate,
sodium β-isopropoxyhexadecylsulfonate,
lithium βt-butoxytetradecylsulfonate,
sodium β-methoxyoctadecylsulfonate, and
ammonium βn-propoxydodecylsulfonate.
Other suitable anionic detergents utilizable herein are olefin sulfonates having about 12 to about 24 carbon atoms. The term "olefin sulfonates" is used herein to mean compounds which are produced by the sulfonation of α-olefin by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that sultones formed in the reaction are hydrolyzed to give corresponding hydroxy-alkanesulfonates. The sulfur trioxide may be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid SO 2 , chlorinated hydrogen, etc., when used in the liquid form, or by air, nitrogen, gaseous SO 2 , etc., when used in the gaseous form.
The α-olefins from which the olefin sulfonates are derived are mono-olefins having 12 to 24 carbon atoms, preferably 14 to 16 carbon atoms. Preferably, they are straight chain olefins. Examples of suitable 1-olefins include 1-dodecene; 1-tetradecene; 1-hexadecene; 1-octadecene; 1-eicosene and 1-tetracosene.
In addition to the true alkene sulfonates and a proportion of hydroxy-alkanesulfonates, the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportions of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process.
Ampholytic synthetic detergents useful herein are broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical is straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, or sulfate. These detergents have the formula ##SPC4##
wherein R 1 is alkyl of about 8 to about 18 carbon atoms, R 2 is alkyl of 1 to about 3 carbon atoms or is hydrogen, R 3 is alkylene of 1 to about 4 carbon atoms, Z is carboxy, sulfonate, or sulfate, and M is a salt-forming cation. Examples of compounds falling within this definition are sodium 3-dodecylaminopropionate; sodium 3- dodecylaminopropane sulfonate; N-alkyltaurines such as the ones prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Pat. No. 3,658,072; sodium salts of N-higher alkyl aspartic acids such as those produced according to the teaching of U.S. Pat. No. 2,438,091; and the products sold under the trade name "Miranol" and described in U.S. Pat. No. 2,528,378.
Useful Zwitterionic synthetic detergents are broadly described as derivatives of aliphatic quaternary ammonium, and sulfonium compounds, in which the aliphatic radicals are straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate or sulfate. A general formula for these compounds is: ##SPC5##
wherein R 1 contains an alkyl, alkenyl, or hydroxyalkyl radical of from about 8 to about 18 carbon atoms having from 0 to about 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety; Y is selected from the group consisting of nitrogen and sulfur atoms; R 2 is an alkyl or monohydroxy alkyl group containing 1 to about 3 carbon atoms; x is 1 when Y is a sulfur atom and 2 when Y is a nitrogen atom, R 3 is an alkylene or hydroxy alkylene of from 1 to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate and phosphate groups.
Examples include: 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carbo xylate; 5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1 -sulfate; 3-[P,P-diethyl-P-3,6,9-trioxatetracosanephosphonio]-2-hydrox ypropane-1-pho sphate; 3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropylammonio]-propane -1-phosphonate ; 3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate, 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfo nate, 4-[N,N-di(2-hydroxyethyl)-N-(2-hydroxydodecyl)ammonio]-butan e-1-carboxylat e, 3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-1 -phosphate, 3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate, and 3-[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxypent ane-1-sulfonat e. Examples of compounds falling within this definition are 3-(N,N-dimethylN-N-hexadecylammonio)propane-1-sulfonate and 3-(N,N-dimethyl-N-tridecylammonio)-2-hydroxypropane-1-sulfon ate which are especially preferred for their excellent cool water detergency characteristics.
The alkyl groups contained in said detergent surfactants can be straight or branched, preferably straight, and saturated or unsaturated as desired.
The calcium insensitive detergent compounds of the present invention can be employed in varying amounts in the compositions of the present invention. As there will be considerable variation in the strengths of washing solutions employed by different users, i.e., some users may tend to use more or less than others, the requisite amount of detergent compound in the detergent formulation is an amount sufficient to provide effective cleaning and whitening levels under diverse conditions of soiling and usage. The enzyme-containing detergent compositions of the present invention can contain from 5 to 85% by weight of the synthetic organic detergent depending upon the detergent employed. A preferred amount of detergent (sole detergent or mixtures) is from 15 to 50%.
The builder is a mixture of two inorganic salts selected from alkali metal silicates and carbonates. The preferred salts are the potassium and sodium salts such as sodium carbonate and sodium silicate, and potassium carbonate and potassium silicate.
In detergent formulations, the SiO 2 /M 2 O weight ratio of the silicate, where M is an alkili metal is critical. The effective range of this weight ratio as SiO 2 /M 2 O is from 1:1 to 3.5:1; the preferred range is from 1.6:1 to 3.2:1.
The heavy duty compositions of this invention can be made into any of the several commercially desirable composition forms, for example, granular, flake, liquid and tablet forms.
In general, the essential ingredients are (a) the calcium insensitive detergent and (b) the builder mixture, as described herein.
The specific action of the built detergent compositions of this invention will vary to some extent depending upon the ratio of active detergent to building mixture in any given detergent composition. There is considerable variation in the strengths of the washing solutions employed by different housewives, i.e., some housewives tend to use less or more of the detergent compositions than others. Moreover, there are variations in temperature and soil loads as between washing operations. Further, the degree of hardness of the water used to make up the washing solutions can also cause differences in the cleaning and whiteness maintenance results. Different fabrics respond in different ways to different detergent compositions. The most useful detergent composition for household use is a composition which provides effective cleaning and whiteness maintenance under diverse cleaning conditions. The built detergent compositions of this invention are especially valuable in this respect.
Useful degrees of building activity are attained in the practice of this invention with ratios of detergent to builder of from about 1:10 to about 3:1, preferably 1:5 to 1:1.
The compositions of this invention can contain various ingredients for special purposes. Thus, they can contain such ordinary additives as suds builders, suds depressants, anti-corrosion agents, antiredeposition agents, germicidal agents, anti-bacterial agents, dyes, fluorescers, perfumes, enzymes and the like. In the manufacture of liquid detergents, liquid vehicles, for example water and alcohol, together with solubilizing agents and the like can be used. These form no limitation on the invention, but are intended to come within the contemplation of the present invention.
Superior cleaning is obtained with the detergent compositions of this invention in aqueous washing solution having a pH range in the range of about 7 to about 12. Washing temperatures can range from about 80°F. to about 200°F. Fabrics are preferably rinsed and dried after washing.
The invention is further demonstrated by the following examples.
EXAMPLE I
An effective granular detergent product was made with the following composition; the percentages given are by weight:
25% Sodium salt of sulfuric acid ester of one mole tallow 25% Sodium carbonate 25% Sodium silicate (SiO 2 /Na 2 O weight ratio of 3.2:1) 15% Sodium sulfate 10% Moisture
This formulation provides excellent results in home laundry-type applications.
EXAMPLE II
A granular detergent product was made with the following composition; the percentages given are be weight:
25% Sodium salt of β-methoxydodecane sulfonic acid 25% Sodium carbonate 25% Sodium silicate (SiO 2 /Na 2 O weight ratio of 3.2:1) 15% Sodium sulfate 10% Moisture
This formulation provides excellent cleaning results in home laundry-type applications.
Substantially similar results can be obtained when the sodium β-methoxydodecane sulfonate is replaced by sodium, potassium, and lithium salts of β-methoxydecane sulfonate, β-ethoxytetradecyl sulfonate, β-isopropoxyhexadecyl sulfonate, βt-butoxytetradecyl sulfonate, β-methoxyoctadecyl sulfonate, βn-propoxydodecyl sulfonate, β-ethoxyoctadecyl sulfonate, and β-methoxyhexadecyl sulfonate.
EXAMPLE III
A granular detergent product was made with the following composition; the percentages are given by weight:
25% Sodium salt of β-acetoxytridecane-1- sulfonic acid 25% Sodium carbonate 25% Sodium silicate (SiO 2 /Na 2 O weight ratio of 2.0:1) 15% Sodium sulfate 10% Moisture
This formulation gives excellent results in home laundry-type applications.
Substantially similar results can be obtained when the sodium β-acetoxytridecane-1-sulfonic acid salt is replaced with the potassium salt of 2-propionyloxy-tetradecane-1-sulfonic acid; the lithium salt of 2-butanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of 2-pentanoyloxy-pentadecane-1-sulfonic acid; the ammonium salt of 2-hexanoyloxy-hexadecane-1-sulfonic acid; the sodium salt of 2-acetoxy-hexadecane-1-sulfonic acid; the dimethylammonium salt of 2-heptanoyloxy-tridecane-1-sulfonic acid; the potassium salt of 2-octanoyloxy-tetradecane-1-sulfonic acid; the dimethylpiperdinium salt of 2-nonanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of 2-acetoxy-heptadecane-1-sulfonic acid; the lithium salt of 2-acetoxy-octadecane-1-sulfonic acid; the dimethylamine salt of 2-acetoxyoctadecane-1-sulfonic acid; the potassium salt of 2-acetoxy-nonadecane-1-sulfonic acid; the sodium salt of 2-acetoxy-uncosane-1-sulfonic acid; the sodium salt of 2-propionyloxy-docosane-1-sulfonic acid; and isomers thereof.
EXAMPLE IV
An effective granular detergent product has the following composition; the percentages are given by weight:
25% Sodium salt of the methyl ester of α-sulfonated tallow fatty acid 25% Sodium carbonate 25% Sodium silicate (SiO 2 /Na 2 O weight ratio of 1.6:1) 15% Sodium sulfate 10% Moisture
Substantially similar results can be obtained when the sodium and potassium salts of esters where the methyl is replaced by ethyl, propyl, butyl, hexyl and octyl groups and the tallow fatty acid group is replaced by lauric, myristic, palmitic, stearic, palmitoleic, oleic, linoleic acids and mixtures thereof.
EXAMPLE V
An effective granular detergent product has the following composition; the precentages are given by weight:
25% Sodium 1-hexadecene sulfonate 30% Sodium carbonate 20% Sodium silicate (SiO 2 /Na 2 O weight ratio of 3.2:1) 15% Sodium sulfate 10% Moisture
This formulation gives excellent results in home laundry-type applications. Substantially similar results can be obtained when the sodium 1-hexadecene sulfonate is replaced by sodium 1-tetradecene sulfonate; sodium 1-octadecene sulfonate; sodium 1-eicosene sulfonate; sodium 1-tetracosene sulfonate, and sodium 1-dodecene sulfonate.
EXAMPLE VI
A granular detergent product of this invention has the following composition; the percentages are given by weight:
25% Sodium 3-dodecyl-amino-propionate 25% Sodium carbonate 25% Sodium silicate (SiO 2 /Na 2 O weight ratio of 3.0:1) 15% Sodium sulfate 10% Moisture
This formulation provides excellent results in home laundry-type applications. Substantially similar results can be obtained when the sodium 3-dodecyl-amino-propionate is replaced with sodium 3-dodecyl-amino-propane sulfonate.
EXAMPLE VII
A granular detergent product of this invention has the following composition; the percentages are given by weight:
25% 3-(N,N-dimethyl-N-hexadecylammonio)- propane-1-sulfonate 20% Sodium carbonate 30% Sodium silicate (SiO 2 /Na 2 O weight ratio of 1.6:1) 15% Sodium sulfate 10% Moisture
Substantially similar results can be obtained when the 3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate is replaced by 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carbo xylate; 5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1 -sulfate; 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfo nate, 4-[N,N-di(2-hydroxyethyl)-N-(2-hydroxydodecyl)ammonio]-butan e-1-carboxylat e; 3-[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxypent ane-1-sulfonat e; and 3-(N,N-dimethyl-N-tridecylammonio)-2-hydroxypropane-1-sulfon ate. The 3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sullfonate and 3-(N,N-dimethyl-N-tridecylammonio)-2-hydroxy-propane-1-sulfo nate, when used in the above formulation, give exceptional results in cool water.
A facial swatch test was conducted comparing representative compositions of this invention with two other household laundry compositions. One of the household laundry compositions had a linear alkyl benzene sulfonate-tallow alkyl sulfate active and a nitrilotriacetic-phosphate builder, while the other composition has a tallow undecyl ethoxylate surface active agent and the carbonate-silicate builder system common to the examples representative of the invention.
TABLE I ______________________________________ Test Composition Component by Weight Percent 1 2 3 4 5 6 ______________________________________ Sodium carbonate 25 25 25 25 25 Sodium silicate (SiO 2 /Na 2 O wt. ratio of 3.2:1) 25 25 25 25 25 Trisodium nitrilotriacetate 12.4 Sodium tripolyphosphate 37.1 Sodium tallow triethoxy sulfate 25 12.5 Sodium dodecyl benzene sulfonate 12.5 25 Sodium β-methoxy hexadecyl sulfonate 7.6 25 Tallow undecyl ethoxylate 25 Sodium tallow sulfate 9.4 Sodium silicate (SiO 2 /Na 2 O wt. ratio of 1.6:1) 6.0 Sodium sulfate 17.5 15 15 15 15 15 Moisture 10 10 10 10 10 10 ______________________________________
The facial switch test requires fourteen panelists and is completely replicated, using a second set of fourteen panelists with the two results being averaged to obtain one complete test. The 4×4 inch cotton swatches used in this test are fastened to the concave cup of an electrical massaging device. The cup is then rubbed over designated areas of a panelist's face for a period of 30 seconds while the machine is vibrating. The swatches thus become soiled. The soiled swatches are washed in a Tergotometer for 10 minutes in 1 liter of the product solution. The solution, containing 7 grains calcium ion hardness, is kept at 110°F. The detergent product is used at a 0.12% level by weight. The swatches are then rinsed for 1 minute at a temperature of 100°F. using water containing 7 grains of calcium ion hardness. They are then dried and graded.
The compositions of the products used in this test are found in Table I. Each component was added separately to the wash solution while minor ingredients normally found in household laundry products such as carboxymethylcellulose, optical brightening agents and enzymes were omitted in all cases.
The washed and dried facial swatches were graded visually to assess the relative cleaning differences of the products used.
A control product for the test was provided by Composition I, Table I. Composition I was used at two concentration levels, 0.15% product and 0.06% product. Each of the product grades and usage levels are presented in Table II.
TABLE II ______________________________________ Composition Solution Strength Tested (% by weight) Grade ______________________________________ 1 0.15 7.6 1 0.06 4.1 2 0.12 6.2 3 0.12 5.6 4 0.12 3.8 5 0.12 5.2 6 0.12 3.8 ______________________________________
In Table II, grades below 4.5 indicate poor performance, grades between 4.5 to 6.0 represent fair to average performance, while a grade above 6.0 represents good performance. It can be seen from Table II that the compositions of this invention, Nos. 2, 3, and 5, all provide performance that is average or better than average and compare favorably with the control product used in the test, even noting that the control product was used at a slightly higher solution concentration.
A complete discussion of this type of testing for detergency is found in Comite International de la Detergence Chemistry, Physics and Application of Surface Active Substances Proceedings of the IVth International Congress on Surface Active Substances, Brussels, 7-12 Sept., 1964, Vol. 3, 221-229, New York, Gordon & Breach, 1967.