US 3282852 A
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United States Patent 7 Claims. (a. 252-152 The present invention relates to a detergent composition comprising in combination a higher alkyl aryl sulfonate detergent, a multi-branched higher alkyl polyoxyethylene ethanol, an alkanolamine and a sulfonated solubilizing or hydrotropic agent in an aqueous medium, as hereinafter described and claimed.
More particularly, it has been found that -a liquid detergent composition of superior qualities can be formulated which comprises essentially about 10 to 40% by weight of a mixture of a water-soluble higher alkyl mononuclear aryl sulfonate salt material having about 8 to 15 carbon atoms in the alkyl group and a multibranched alkyl polyoxyethylene ethanol material having about 8 to 18 carbon atoms in said alkyl group and an average of about to 30 ethylene oxide groups, the ratio of said sulfonate to polyethoxamer being from about :1 to about 1:4 by weight with at least about 3% of each material present in the composition, about 5 to 20% by Weight of a water-soluble alkanolamine having 2 to 3 carbons in the alkanol group, about 1 to by Weight of a Water-soluble sulfonated hydrotropic salt material and the balance being primarily water, said composition having an alkaline pH and being in the form of a substantially homogeneous, pourable liquid at room temperature. A feature of the invention relates to said composition having heavy-duty properties Without an inorganic builder content characterized by alkali metal higher alkyl benzene sulfonate, multi-branched tridecyl polyoxyethylene ethanol, alkali metal sulfonated hydrotropic salt and triethanolamine proportioned as herein described in combination with a minor amount of a soil-suspending material to form a substantially homogeneous and stable, pourable liquid exhibiting a high level of foaming and detergency properties in use. Various other distinctive aspects of the present invention will be apparent from the following description.
Such product exhibits many desirable characteristics with regard to both physical properties and performance in use. As to its physical properties, the composition is homogeneous, pourable, and free-flowing from the container as manufactured and after aging. It exhibits a high degree of stability upon storage at normal room temperature of about 70 F. over a period of many months without any appreciable precipitation or formation of immiscible layers. It has appreciable stability under adverse temperature conditions. It can be subjected to elevated temperatures of the order 110 F., or cooled to 40 F. or below, and the liquid is in a substantially homogeneous form when returned to room temperature. As a result, the consumer can utilize it conveniently by the addition to a laundering bath or the like of small portions which will have practically the same composition. The composition having the main ingredients will normally be a clear solution. The soil-suspending material or other added ingredients may render the final product translucent to opaque but are maintained in colloidal solution or fine suspension without precipitation so as to insure the practical use of a stable and homogeneous liquid. The product may be employed in any suitable container or packaging material.
In performance, the product exhibits a particularly high level of washing power suitable for the laundering of soiled natural and synthetic materials in washing machines and in other cleansing operations. It exhibits effective detergency in both soft and hard water, particularly with the compositions containing soil-suspending material. The detersive power is comparable to heavy-duty liquids containing substantial amounts of water-soluble inorganic builder salts such as phosphates. A high level of foaming power can be obtained in suitable washing concentrations in soft and hard Water also.
In the formulation of the products of the present invention, there are a number of factors which are of consid eration. The properties are aifected by these factors which are properly selected and correlated to provide the product hereafter claimed. Among such considerations are the chemical constitution of the materials and their effects in combination which are to be integrated with the suitable ratios and/or proportions thereof so as to produce compositions having the desired properties.
With regard to the higher alkyl mononuclear aryl sulfonate detergent, it is preferred to use the higher alkyl benzene sulfonates, though other similar detergents having a mononuclear aryl group derived from toluene or xylene may be also used. The aryl nucleus has at least one alkyl substituent having an average number of about 8 to 15 carbons and preferably about 12 to 15 carbons. The alkyl group may be branched such as nonyl, dodecyl and pentadecyl groups including mixtures thereof which are derived from polymers of lower mono-olefins, e.'g., polypropylene. A commercial tridecyl benzene sulfonate contains a mixture of propylene polymers averaging about 13 carbons. The alkyl group may be straight-chained also such as the n-decyl, keryl, dodecyl and tridecyl groups.
The higher alkyl aryl sulfonate detergent material (including mixtures) is employed preferablyin the form of its alkali metal salt, particularly the sodium salt. Other water-soluble salts may be used also such as the potassium salt, ammonium salt, lower alkylolamine salts including the mono-, diand tri-ethanolarnine salts, alkaline earth metal salts including the magnesium and similar salts, and the like including suitable mixtures thereof. While the composition is a liquid containing ionized or dissociated salts in solution, reference to a particular salt above includes the addition of such salt to the mixture or its formation by neutralization or ion interchange during or after manufacture on the basis of its solubility in the liquid. It is understood that there may be small amounts of water-soluble inorganic salts such as sodium or potassium sulfate in the sulfonated detergent (and hydrotropic salt) resulting from the method of manufacture. In general, these inorganic sulfate salts and the like should be maintained at as low a concentration as practicable. Examples of desired sulfonate materials have a purity of at least about by weight, preferably over by weight.
The alkyl polyethoxamer is prepared usually by the reaction of the higher aliphatic alcohol having 8 to 18 carbons with a predetermined proportion within the range of 5 to 30 moles of ethylene oxide in order to obtain a Patented Nov. 1, i966 product having the desired physical properties and performance characteristics. Optimum effects are obtained with polyethoxamers, preferably with 10 to 20 moles ethylene oxide, of multi-branched higher alcohols, preferably containing 11 to 15 carbons, such as produced by the Oxo process known in the art. This process involves the reaction of a multi-branched olefin of 7-17 carbons (e.g. tri-, tetra-, and penta-propylene, di-isobutylene) with carbon monoxide and hydrogen to form the corresponding aldehyde, followed by reduction to the corresponding primary alcohol. Similar alcohols may be obtained by other processes however. Examples of suitable primary multi-branched alcohols are 2,4,5,5,7 pentamethyl 1- octanol; 2,3,5,7 tetramethyl 1 nonanol; 3,5-di-ethyl-1- octanol; 2,4,6,8 tetramethyl 1 nonanol, and the like. It is preferred to use the polyethoxamer of tridecyl alcohol (corresponding to alcohol produced from tetrapropylene and/or tri-isobutylene by the Oxo process) which has been found to give particularly outstanding results. The optimum proportion of condensed ethylene oxide varies with the type of alcohol so as to produce a suitable water-soluble derivative having the desired solubilizing, detersive and foaming effects. As indicated, the preferred proportion of ethylene oxide to alcohol corresponds to the reaction product of an average of 10 to 20 moles ethylene oxide with tridecyl alcohol.
The water-soluble sulfonated hydrotropic salts are usually the alkali metal organic sulfonated (including sulfated) salts having a lower alkyl group up to about 6 carbons. It is preferred to employ an alkyl aryl sulfonate having up to 3 carbons in a lower alkyl group such as the sodium and potassium xylene, toluene, ethylbenzene and isopropyl benzene sulfonates. Sulfonates made from' xylene include orthoxylene sulfonate, metaxylene sulfonate, paraxylene sulfonate and ethylbenzene sulfonate. Commercial xylene sulfonates usually contain metaxylene sulfonate as the main ingredient. Analyses of typical commercial products show about 4050% metaxylene sulfonate, 10-35% orthoxylene sulfonate and 15-30% paraxylene sulfonate with 0.20% ethylbenzene sulfonate. Any suitable isomeric mixture may be employed, however. Suitable lower alkyl sulfate salts having about 5 to 6 carbons in the alkyl group may be employed also such as the alkali metal n-arnyl and n-hexyl sulfates. The use of an amount of hydrotrope in excess of the amount desired to improve the physical properties is not helpful since it tends to add additional salt to an already concentrated system.
The alkanolamines have one or more hydroxyalkyl groups of 2 to 3 carbons, such as mono-, dior tri-ethanolamine, isopropanolamine or the like. It is preferred to employ the triethanolamine which in commercial form may contain small amounts of monoand di-ethanolamine. The alkanolamine used is considered to be essentially in free form so as to be available for its necessary contribution to the physical properties and performance. Where alkylolamine detersive salts are employed, an excess of alkanolamine should be used or the pH adjusted with caustic soda or the like so as to release or otherwise render the alkanolamine effective in the composition. In general, the pH of the final concentrated liquid is at least about 9, usually within the range of 9.5 to 12, and preferably from 10 to 11.5.
It has been found that a suitable soil-suspending material may be incorporated and stabilized in these formulations. The addition of a soil-suspending material converts the system to a more complex one which has improved detersive efficiency in washing operations and will usually render the final product translucent to opaque in appearance. In general, the soil-suspending agent is a hydrophilic colloid which is classified as water-soluble (including water-dispersible) and is maintained in colloidal solution or fine suspension in the liquid product. It is preferred to use the alkali metal salt of a carboxy lower alkyl cellulose having up to 3 carbons in the alkyl group, such as the sodium and potassium salt of carboxymethylcellulose. The commercial grade of sodium carboxymethylcellulose and the like may be employed. Other known water-soluble cellulosic material are the lower alkyl and hydroxy alkyl ethers having up to 3 carbons in the alkyl group such as methylcellulose, ethylcellulose and hydroxyethylcellulose. Suitable cellulose sulfate materials may be employed also. The soil-suspending material is a minor amount, usually within the range of 0.1 to 5% preferably 0.1-2% of the product.
Other types of soil-suspending agents may be employed such as the water-soluble vinyl polymers. Examples are water-soluble polyvinyl alcohol which may contain minor amounts of polyvinyl acetate as commercially made. Water-soluble polyvinyl polymeric amides such as polyvinylpyrrolidone of suitable molecular weight may be employed also. Various materials or mixtures may be employed which assist in maintaining the soil-suspending materials in suspension or dispersion in the liquid. Suitable mixtures of cellulosic compounds, or a mixture of a cellulosic compound with a vinyl polymer, or a mixture of a cellulosic compound with castor wax, or any combination thereof, may be employed as known in the art.
The desirable qualities of the product are a result of the mutual effects or inter-action of the ingredients in proper proportions in the combination. The alkyl benzene sulfonate detergent, the polyethoxamer, the alkylolamine and'the hydrotrope all contribute to the desired properties of the system supplemented by the soil-suspending agent when employed. As indicated, the total amount of sulfonate detergent and polyethoxamer is within the range of 10 to 40%, preferably 20 to 30% of the liquid. The ratio of sulfonate to polyethoxamer is selected from the range of about 10:1 to 1:4, preferably 5:1 to 1:1 with at least about 3% of each in the liquid. The alkylolamine is about 5 to 20%, preferably 7-12% and the hydrotrope is about 1-15%, preferably 1-7%. In general, the combination of the sulfonate detergent and polyethoxamer yields improved detergency as compared with similar products having only one of these two materials in the same total concentration. In addition, the sulfonate detergent and polyethoxamer exert solubilizing effects. As an illustration, the omission of the sulfonate detergent from the formulation of Example I described herein results in separation into two layers, particularly upon storage at elevated temperatures. The polyethoxamer has a solubilizing effect also, particularly when higher concentrations of sulfonate detergent are employed. The triethanolamine or the like exerts an added solubilizing effect and has been found to act as a suds builder in the composition even though it has no foaming properties by itself. It is a desirable source of sustained alkalinity for heavy-duty cleaning also. trope varies with the balance of the formula and may serve a multiplicity of functions. It can act as a coupling agent to prevent phase separation and desirably reduces the viscosity, particularly in the presence of carboxymethylcellulose, and improve aging characteristics.
Certain guiding principles should be used in formulating products with optimum properties. The solids content should not be excessive as it tends to gel the system. In general, the solubilizing effects of each of the main ingredients can be varied by varying its concentration up to a maximum effect beyond which additional amounts would not be helpful and may even be harmful to the system. With higher amounts of sulfonate detergent, it may be advisable to add increased amounts of hydrotropic salt which can be tolerated by the system. Excessive amounts of hydrotrope or the polyethoxamer tend to produce phase separation, an excessive amount of sulfonate detergent tends to gel the system and an excessive amount of the alkanolamine will adversely affect the product also. Thus, a homogeneous The effect of the hydro-- product can be formulated by suitable proportioning of the ingredients so as to complement one another.
It is preferred that the liquid contain a higher fatty acid alkylolamide material in a sufiicient amount to act as a suds builder. It has been found also that the combination of the above ingredients with a suitable amount of the alkylolamide results in a product which exhibits highly improved foaming power in use, particularly in the stability of the foam generated during laundering operations. In certain formulations, the alkylolamide may provide an additional solubilizing effect. The acyl radical of the alkylolamide is selected from the class of fatty acids having 8 to 18 carbons and each alkylol group has up to 3 carbon atoms usually. It is preferred to use the diethanolamides, isopropanolamides and monoethanolamides of fatty acids having about 10 to 14 carbons in the acyl radical. Suitable examples are the lauric, capric, myristic and coconut diethanolamides, monoethanolamides and isopropanolamides, and mixtures thereof. There may be employed also the alkylolamides which are substituted by additional alkylol groups, suitable examples being the above monoethanolamides, diethanolamides and isopropanolamides condensed with one or two moles of ethylene oxide. In general, the alkylolamides are employed in amounts of about 1 to 10% by weight, and preferably from about 1.5 to 5% in the product. It should not be employed in an amount sufficient to destroy the desired physical properties since it is considered as part of the total solids content.
The solids content (which is essentially organic and includes the alkanolamine) of the concentrated liquid product is variable and is within the range from about 16 to 60%, preferably 28 to 50% by weight of the concentrated liquid, with the balance being primarily water. The ingredients are proportioned in the aqueous solubilizing medium so as to form a substantially homogeneous product of desired physical properties.
The liquid detergent is prepared in any suitable manner by admixture at room or reasonably elevated temperatures depending upon the specific ingredients. A preferred method utilizes room temperature for admixing the main ingredients to a homogeneous solution. This procedure involves preparing an aqueous slurry of the alkyl benzene sulfonate essentially free from inorganic salts. A suitable base is an aqueous slurry of 56% solids having sodium alkyl benzene sulfonate in at least about 95% by weight of solids. It is convenient to add additional water at this stage to thin the mixture and facilitate mixing. The hydrotropic salt may be added as a powder, aqueous solution or slurry with stirring. A convenient form is a 44.5% solids slurry of sodium xylene sulfonate of at least about 90% purity. The liquid triethanolamine or the like and the polyethoxamer are added in any desired order with stirring. Any additional ingredients such as alkylolamide or soilsuspending agents are added in powdered or solution form as desired with moderate heating if necessary to facilitate formation of a homogeneous solution or dispersion. In general, waxy materials such as castor wax should be in molten or liquid form and added to the aqueous mixture previously warmed, e.g. 160 F., to insure ready dispersion.
Various other ingredients may be added as desired in suitable amounts. The liquid should be substantially free from inorganic salts. It is an effective heavy-duty liquid in the absence of alkaline inorganic builder salts such as phosphates and silicates. Such salts, particularly the hydrated salts, tend to adversely affect certain physical properties such as low temperature aging characteristics, e.g. small amounts of hydrated sodium phosphate may cause gelling at moderately reduced temperatures of 4050 F., but the composition is a homogeneous and effective heavy-duty liquid upon return to room temperature. If desired for a particular purpose suitably small amounts of inorganic salts may be added or permitted to remain in the product such as up to about 7.5% in certain cases depending upon the specific formulation. Other ingredients employed in suitable amounts include compatible perfumes, coloring materials, corrosion or tarnish inhibitors, sequestering agents, germicides, softening, bleaching or other textile-treating agents, fluorescent dyes or optical bleaches; additional viscosity or foam modifiers or solvents including fatty alcohol, ethanol, urea, other amides or detergents, or the like provided that they do not substantially adversely affect the product.
The following examples are further illustrative of the nature of the present invention, and it will be understood that the invention is not limited thereto. All amounts are by weight unless otherwise specified.
Example I Ingredients: Percent Sodium dodecyl benzene sulfonate 18 Tridecyl polyoxyethylene ethanol 8 Triethanolamine 10 Sodium xylene sulfonate 5 Laurie isopropanolamide 2 Sodium carboxymethylcellulose 0.8 Polyvinyl alcohol 0.25 Castor wax 0.3 Fluorescent brightener 0.28 Water Balance In the above formulation, the dodecyl benzene sulfonate is derived from a propylene tetramer. It is listed above on an active ingredient basis and is substantially free of inorganic salts. The tridecyl alcohol is derived by the Oxo process as described and condensed with an average of about 15 moles ethylene oxide. The sodium xylene sulfonate is on an active basis and is a commercial material of purity. It comprises a mixture of the meta-, para-, and ortho-xylene sulfonates with some toluene sulfonate. The carboxymethylcellulose is a known detergent grade having about 0.7 carboxy groups per glucose unit. It is listed on an active basis also though about 1.2% solid material of about 65% purity is used in the formula. The polyvinyl alcohol has a viscosity of about 1.8-3 cps. and about l030% ester content. The castor wax assists in suspending the soilsuspending materials and the fluorescent brighteners are known stilbene sulfonate materials suitable for detergent use. It is understood that suitable color and perfume may be added as desired. The product is essentially free of inorganic salts having a total of about 0.7% primarily as sodium sulfate. It is prepared by the preferred method previously described and has a specific gravity of about 1.1 and a pH adjusted with caustic soda to 10.5 to 11.
The final formulation is a homogenous, pourable heavyduty liquid at room temperature with superior qualities. It is stable upon storage under normal conditions and at F. and below 50 F. and even to about 25 F., without separation into a plurality of layers. When the product is frozen at sufficiently low temperatures, no apparent crystals are separated and the product returns to a substantially homogeneous condition upon return to room temperature conditions.
In use, the liquid exhibits a high degree of detergency which has been found to be superior to various commercial heavy-duty liquids and powders, both containing substantial amounts of water-soluble alkali metal polyphosphate builder salts. The product possesses high sudsing power, exhibiting a good volume of foam initially which has marked stability in the washing bath.
The soil-suspending materials, wax, amide, and dyes may be omitted from the above formulation which is otherwise transparent and can be employed as a foaming heavy-duty liquid exhibiting lower foaming and soil-suspending properties accordingly.
7 Examples II-VII Other suitable formulations having a pH of 10-11 and showing particular variations are listed below, the balance of the formulas being substantially the same as Example I:
Ingredients II III IV V VI VII Sodium dodeeyl benzene sulionate 25 Sodium tridecyl benzene sulionate nfiul 18 10 Trideo l 01 oxyet y ene etharl ol fl moles) 8 8. 8 8 12 6. 7 4. 4 Triethanolamine 10 ll 10 1O 8. 3 5. 6 Sodium xylene sulionate 2. 5 5 5 5 4. 2 2. 7 Carboxymethylcellulose 0. 3 0. 3 0. 8 0. 8 0. 66 0. 4 Trisodium phosphate 3 Example VIII The formulation of Example II is diluted with water to form two products having 15% and 10% alkyl benzene sulfonate respectively, and these formulations are satisfactory also.
- Example IX The formulation of Example I is repeated except that the following approximate proportions were used for the ingredients specified below.
Ingredients: Percent Sodium tridecyl benzene sulfonate 5 Tridecyl polyethoxamer (15 moles) 15 Triethanolamine 10 Sodium xylene sulfonate 2.5
A formulation similar to Example II is prepared substituting the tridecyl (Oxo) polyoxyethylene ethanol having an average of about 10 moles ethylene oxide as the non-ionic material. This formulation is satisfactory also.
What is claimed is:
1. A detergent composition which consists essentially of about 10 to 40% by weight of a mixture of a watersoluble alkyl mononuclear aryl sulfonate detergent salt having about 8 to 15 carbon atoms in the alkyl group and a multi-branched alkyl polyoxyethylene ethanol having about 8 to 18 carbon atoms in the alkyl group which has a molecular configuration corresponding to that in the saturated aliphatic alcohol produced by the Oxo process from a polymerized olefin of 3 to 4 carbons and an average of about 5 to moles of ethylene oxide, the ratio of said alkyl aryl sulfonate to polyethoxamer being from about 10:1 to 1:4 by weight with at least 3% of each material being present in the composition, 5 to 20% by weight of a water-soluble alkanolamine having 2 to 3 carbons in the alkanol group, about 1 to 15 by weight of a Water-soluble alkali metal lower alkyl substituted benzene sulfonate hydrotropic salt having up to 3 carbons in each alkyl group, and the balance being primarily water, said composition having an alkaline pH and being in the form of a substantially homogeneous, pourable liquid.
2. A detergent composition in accordance with claim 1 which contains an alkali metal alkyl benezene sulfonate detergent salt and multi-branched alkyl polyoxyethylene ethanol having about 11 to 15 carbon atoms in the alkyl group which has a molecular configuration corresponding to that in the saturated aliphatic alcohol produced by the Oxo process from a polymerized olefin of 3 to 4 carbons and an average of about 5 to 30 moles of ethylene oxide, and about 5 to 20% by weight of an alkanolamine comprising essentially triethanolamine, about 1 to 15% by weight of alkali metal lower alkyl substituted benzene sulfonate hydrotropic salt having up to 3 carbons in said alkyl group, and the balance being primarily water, the composition having a pH from 9 to 12 and being in the form of a substantially homogeneous, pourable liquid.
3. A liquid detergent composition in accordance with claim 2 wherein said hydrotropic salt is selected from the group consisting of sodium and potassium toluene and xylene sulfonates.
4. A liquid detergent composition in accordance with claim 2 which contains about 1 to 10% by weight of alkylolamide selected from the group consisting of dieth anolamides, monoethanolamides and isopropanolamides of fatty acids having 10 to 14 carbons in the acyl radical.
5. A liquid detergent composition in accordance with claim 2 which has incorporated therein about 0.1 to 2% by weight of water-soluble soil-suspending material selected from the group consisting of alkali metal carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, polyvinyl alcohol and polyvinylpyrrolidone.
6. A detergent composition in accordance with claim 5 which contains sodium carboxymethylcellulose.
7. A detergent composition which consists essentially of about 20 to 30% by weight of a mixture of sodium alkyl benzene sulfonate having an average of 12 to 15 carbons in the alkyl groups and Oxo tridecyl polyoxyethylene ethanol having an average of about 10 to 20 moles ethylene oxide in a ratio from 5:1 to 1:1 by weight, 7 to 12% by weight of an alkali metal hydrotropic salt selected from the group consisting of xylene and toluene sulfonates, 0.1 to 2% by weight of sodium carboxymethylcellulose and 1.5 to 5% of a higher fatty acid alkylolamide having 10 to 14 carbons in the acyl radical and 2 to 3 carbons in the alkylol group, and the balance being primarily water, said composition having a pH of 10 to 11, a solids content of 28 to 50%, and in the form of a substantially homogeneous and stable, pourable liquid having heavy-duty properties in the absence of Watersoluble inorganic salts as builders.
References Cited by the Examiner UNITED STATES PATENTS 2,914,482 11/1959 Kopp 252-l52 2,932,617 4/1960 Lamberti et a1. 252-152 XR 2,934,568 4/1960 Barker 252- 152 XR 2,943,058 6/1960 Cook 252-152 XR 2,970,963 2/1961 Walker 252-152 XR LEON D. ROSDOL, Primary Examiner.
JULIUS GREENWALD, Examiner.
J. T. FEDIGAN, M. WEINBLATT,