SE453399B - LIQUID DETERGENT COMPOSITION AND SET FOR ITS PREPARATION - Google Patents

Description

453,399 U.S. Patent 4,148,762 disclosing a detergent composition containing a betaine and 5-30% anionic surfactants such as alkyl sulfate, alkyl ether sulfate and alkyl aryl ether sulfate; and U.S. Patent No. 4,166,845 which discloses a high foaming anti-dandruff shampoo. containing a betaine and an additional surfactant which may be an alkyl sulphate. The foaming of the mentioned compositions is a result of the use of the conventional foaming agents or of the special combination of surfactants.

However, none of the above patents discloses a liquid detergent composition containing the three component mixture of a betaine, an alkyl sulfate and an acylene ethoxy ether sulfate.

U.S. Pat. No. 4,075,131 discloses a conditioning shampoo which contains an amphoteric surfactant, such as a betaine, and a hybrid ion polymer, and which may also contain foaming agents, such as alkanolamide (Example 1). The three component mixture of alkyl sulfate, alkyl ether sulfate and betaine is described herein (column 7) as a control concentrate for testing the effectiveness of the conditioning shampoo containing the hybrid ion polymer conditioning agent.

Prior art also includes the use of hydroxyalkyl ethers of guar gum (a galactomannan gum) as a thickener in printing pastes, paint dispersions and explosive slurries, as disclosed in U.S. Pat. Nos. 3,748,201 and 3,700,612. The compositions described include however, non-liquid detergent compositions.

The Jaguar Catalog from Stein-Hall & Company, Inc. discloses hydroxypropylated guar gum derivatives useful as thickeners. Guar gum is chemically classified as a galactomannan and is a high molecular weight carbohydrate polymer or polysaccharide made up of several linked mannose and galactose units (page 5 in the catalog).

Japanese Patents 76 20,202 and 20,203 (1976) to Unitaka describe the preparation of hydroxypropyl sugar or glucose and its use as a detergent builder; and the preparation of hydroxyethyl starch or hydroxypropyl amylose and its use in detergents as an agent which prevents loosened dirt from sticking again, the detergent composition containing a sodium salt of coconut alcohol sulphate ester, sodium carbonate and sodium sulphate. The example specifically cited in these patents shows that when the surfactant is lauryl alcohol sulfate, the commonly used detergent salt, tripolyphosphate, can be exchanged for hydroxypropyl glucose while still maintaining the cleaning ability of the composition. The special detergent substitutes mentioned herein are hydroxyalkyl (ethyl, propyl and butyl) ethers of mono- and disaccharides. However, this is not about guar gum or guar gum derivatives, nor about foam stabilization.

It has now been found that the addition of small amounts of a nonionic hydroxypropyl guar gum derivative (0.01-1%) to a mild liquid detergent containing a three component mixture of an alkylene ethoxy ether sulphate, an alkyl sulphate and a betaine, significantly improves the foam stability. the cleaning ability and consistency of the liquid detergent.

Thus, an object of the present invention is to provide novel mild detergent compositions containing small quantities of a nonionic hydroxypropyl guar gum derivative as foam stabilizers and thickeners.

Another object of the invention is to provide a new liquid detergent composition containing a reduced amount of detergent active components and having improved foaming and cleaning properties. Yet another object of the present invention is to provide a novel liquid detergent composition having improved foaming properties and having a viscosity of at least 100 cP, containing the three component mixture of an alkyl ether sulfate, an alkyl sulfate and a betaine.

Other objects as well as advantages and novel features of the invention will be apparent from the following description, and will be apparent to those skilled in the art upon examination of the same, or to be ascertained upon practical application of the invention. The objects and advantages of the invention may be realized and attained in the manner and with the combinations particularly pointed out in the appended claims.

To achieve said and other objects of the invention in accordance with the present design and description, the novel mild liquid detergent composition of the invention contains a three component mixture of the surfactants alkylene ethoxy ether sulfate, alkyl sulfate and betaine and about 0.01-1%, preferably 0.1-0.6%, of a nonionic hydroxypropyl guar gum derivative.

The present invention thus relates to a mild liquid detergent composition with good foam stability and mainly consisting of 0.01-1% by weight, preferably 0.025-0.6% by weight and in particular 0.1-0.6% by weight, of a nonionic hydroxypropyl guar gum derivative in an aqueous vehicle containing at most 40% by weight, preferably at most G5% by weight, of an active detergent system consisting of a water-soluble three-component mixture of a C8-C18-alkyl-ethyleneoxy ether sulfate, a C8-C18-alkyl sulfate and a betaine.

Compositions containing as little as 22% of active ingredients are capable of maintaining foaming and cleaning ability in the presence of small quantities of hydroxypropyl guar gum derivatives.

The foam promoting agent used in the present invention, which also serves as a thickener, is a nonionic hydroxypropyl guar gum derivative. The derivative is prepared by hydroxypropylation of the guar molecule, which is a straight chain with mannan branches at relatively regular intervals and with single galactose units on alternating mannose units, as described in the mentioned Jaguar catalog from Stein-Hall Company. The hydroxypropylated guar gum derivatives used in the present invention are water-soluble, dry, finely divided hydrocarbon materials with such a particle size that at least 90% passes through a 140 mesh screen according to US standard, and with an MS (molar substitution) value in the range 0.2-0.8, preferably between 0.3 and 0.65. Generally, 1% aqueous solutions thereof have a pH in the range of 5-11 and a viscosity of about 3000-4000 cP, measured in a Brookfield RVF viscometer using a No. 3 spindle rotating at 20 rpm and at a temperature of 25 ° C, and the resulting solutions are thixotropic because the viscosity changes with the shear rate. Suitable hydroxypropyl guar gum derivatives can be obtained from Steiïš-Hall Company under the trademarks Jagua HP 60, Jagua HP 8 and Jagua HP 11, which usually contain -13%, preferably 8-10%, water on delivery. 453 399 The hydroxypropyl guar gum derivatives are known to have thickening properties in aqueous solutions. In general, however, it is not known that a thickener improves the foaming properties of aqueous solutions containing surfactants, whereas the hydroxypropyl guar gum derivative defined above both increases the viscosity of a detergent composition and improves its foaming properties. Since foam volume and foam stability are often used as a measure of the cleaning effect, it is desirable; to provide a detergent composition with improved foaming properties. Another advantage of the novel detergent compositions containing hydroxypropyl guar gum derivatives is that this foaming agent has a thickening effect, which makes it possible to reduce the content of the active ingredient in a composition and still maintain the foaming ability, thereby reducing costs. can be achieved in the preparation of this mild liquid detergent product. Another advantage is also that smaller amounts of this defoamer (0.01-1% as opposed to 3-6%) are required compared to conventional defoamers which further reduces the cost of the detergent product.

In addition, it has been found that the nonionic hydroxypropyl guar gum derivative acts as a foam stabilizer in certain detergent systems, but has no effect on the foam properties of other systems, such as linear alkyl benzene sulfonate / alkyl ether sulfate or linear alkyl benzene sulfonate / alkyl ether sulfate / lauric acid mist - syramonoethanolamide. Accordingly, it has been found that the particular detergent system in which the foaming properties are markedly improved in the presence of the nonionic guar gum derivative is a three-component mixture consisting of an alkylene ethoxy ether sulfate, an alkyl sulfate and a betaine. Thus, it is apparent that the particular detergent system used in conjunction with the nonionic hydroxypropylated guar gum derivative is critical to the preparation of a mildly liquid detergent having markedly improved foam properties.

The main components of this mild liquid detergent are a water-soluble C8-C18-alkylene ethoxyether sulfate and an ammonium or alkali metal salt of a C8-C18-alkyl sulfate, both of which are anionic substances; and a betaine, preferably an amido betaine, which is a hybrid ionic surfactant, dissolved in an aqueous vehicle. The betaine component constitutes about 2-3% by weight and more than 5% by weight of the liquid detergent composition, and the anionic substances preferably constitute about 20-30% by weight of the liquid composition, the ratio of alkyleneoxy ether sulfate to alkyl sulfate not being critical. Ratios of 1/29 to 29/1 between alkyl sulfate and alkylene ethoxy ether sulfate and preferably 17/13 and 12/8, respectively, can be used according to the invention.

The anionic surfactants which can be used in the detergent composition of the invention include at least one surfactant selected from the group consisting of water-soluble salts, for example sodium, potassium, ammonium and alkanolammonium salts of a C8-C18-alkyl sulphate, and preferably C12-C16- and C12-C15-alkyl sulphates such as lauryl sulphates, myristyl sulphates and the like; and at least one surfactant selected from the group consisting of the water-soluble alkylene ethoxy ether sulfates of the general formula R (CH 2 CH 2 O) nOSO 3 M, in which R represents an alkyl radical having 8-18 carbon atoms, n is an integer having the value 1-12 and preferably 1- 5, and M represents an alkali metal, ammonium or alkylolammonium, such as lauryltrietheneoxyetherulfate, tridecyl alcohol triethyleneoxyetherulfate and the like. Other anionic agents, such as 453 399 In sodium lauryl sarcosinates, alkyl sulfonates, alkyl benzene sulfonates and lauryl alcohol sulfate or the like can not be substituted for either of the above two groups of anionic surfactants as a component of the three component system of the present invention to provide a liquid product. foam properties.

The betaine component of the liquid detergent composition has the general formula: 1 wherein R 1 represents an alkyl group having 10 to about 20 carbon atoms, preferably 12-16 carbon atoms, or the amide radical: OH II I RCN- (CH 2) a - wherein R represents an alkyl group having about 9-19 carbon atoms and a is an integer between 1 and 4; R 2 and R 3 each represent alkyl groups having 1 to 3 carbon atoms and preferably 1 carbon atom; R 4 represents an alkylene or hydroxyalkylene group having 1-4 carbon atoms and, optionally, a hydroxyl group. Typical alkyl dimethyl betaines are decyl dimethyl betaine or 2- (N-decyl-N, N-dimethylammonium) acetate, coconut dimethyl betaine or 2- (N-coconut-N, N-dimethylammonium) acetate, myristyldimethyl betaine, palmityldimethylene tyl betaine, Zlauyldimethyl betaine, cetyldimethyl betaine, stearyldimethyl betaine, etc. The amido betaines also include coconut amidoethyl betaine, coconut amidopropyl betaine and the like. , ;; _ f ... f.J.-..... Ü.,. v, ~ fl¶¿., ..., _ .., ___, __, _ __ _ 453 399 '' M _; ¿»» _, V -, - w '' 'w ""' f "" "* 'fi i fl wws = znwrx ~ syfr-r.v flfl fírífra«: um wwwvnwwwcnïff ..

All the mentioned components of this mild detergent are water soluble and remain water soluble during storage.

This special combination of anionic sulphates and betaine provides a detergent system of three components which interacts with the nonionic hydroxypropyl guar gum derivative to give a liquid detergent composition with the desired foaming ability, foam stability, cleaning ability and also desired viscosity properties.

The resulting homogeneous liquid detergent exhibits superior foam properties over the same detergent composition without the nonionic guar gum derivative, as shown in the following Table I, using a Tergotometer foam tester, in which case dirty plates (1 "in diameter and 1/8" in height) were and one provided with 1 g of Criscosmuts, during a periodic increase (every two minutes) was added to a 0.1% aqueous sample solution. with a hardness of 150 ppm as CaCO3 (Ca / Mg = 2/1) and an alkalinity of 100 ppm as HCO3, at a temperature of SOOC, and stirred at 75 rpm for 1 minute. The foam level was noted when stirring was stopped after each addition of plates, and the total number of plates required to kill the foam was counted.

Table I. ; Detergent composition Number of washed plates 1. 17/13/3 AEOS / ALS / Betaine 19 2. 17/13/3 / 0.3 AEOS / ALS / Betaine / Jaguar HP-60 22 3. 12/8/2 AAEOS / ALS / Betaine 16 4. 12/8/2 / 0.5 AEOS / ALS / Betaine / Jaguar HP-60 19 453 399 '10 Asos ammonium-c12-c15-alkyl (c2H40) 3suipate Ars ~.

Betaine = coconut amidopropyl betaine ammonium lauryl sulphate Jaguar HP-60 = hydroxypropyl guar gum derivative (9% H 2 O) Furthermore, the addition of Jaguar HP-60 to the composition 3 increased its viscosity 18 times, from 22.5 to 407.5 cP according to a Brookfield fluorescent meter RVF , spindle No. 1, rpm and a temperature of the solution of 25 ° C. In addition, the removal of dirt, as an assessment of the cleaning ability, was not adversely affected by the presence of thickeners in the form of the guar gum derivative, as shown in Table II, in a static leaching test. A dirty plate (0.5 g of dirt), which in the foam test described above, aged for 1.5 minutes, was immersed for 30 seconds in a hot (5000) aqueous sample solution having a hardness of 150 ppm and an alkalinity of 100 ppm and containing 0 , 1% detergent, after which it was immediately transferred to a bath of ice water to stop the soil removal process. Non-removed dirt solidified on the plate, which was air-dried and% SR (removed dirt) was calculated as follows: amount of removed dirt X 100%% SR = initial amount of dirt Table II Effect of thickener on cleaning ability -ll ubLJN- fl Composition% SR) irl Talg Keen (abbreviation) Ä 94.4 77.2 50.6 96.0 78.0 '50 .6 94.8 80.4 52.6 96.6 78.4 51.6 Täsàlzeq. 11, In addition to the aforementioned main constituents of the mild liquid detergent, typical and conventional additives may also be added, provided that they do not adversely affect the properties of the detergent.

Thus one can add different dyes and perfumes; UV absorbers such as Uvinuls, which are products of GAF Corporation; preservatives such as formaldehyde or hydrogen peroxide; pearlescent and opalescent agents; pH modifiers; hydrotropes such as ammonium or sodium xylene sulfonate, ethyl alcohol; citric acid, etc. The amount of such additives cold generally does not exceed 15% of the detergent composition. The percentages of most of these individual components should not exceed 5% and preferably less than 5%.

The mild liquid detergent compositions in question, such as liquid detergent, can be readily prepared by simple mixing of the readily available components, which on storage have no adverse effect on the composition as a whole. However, it is important that the guar gum derivative is added slowly and while stirring to the pre-prepared aqueous solution of the three-component surfactant system. The three-component surfactant system is prepared by adding, with stirring, an aqueous solution of the alkyl sulfate and then the betaine to an aqueous solution of an alkyl ethyleneoxy ether sulfate, which may have been premixed with a hydrotropic agent such as ethyl alcohol and / or xylene sulfonate as adjuvants. during the solubilization of the surfactants, after which the remaining water is added with stirring to provide the aqueous solution of the surfactant three-component system. Careful heating (to 100 ° C) facilitates the dissolution of the surfactants. The viscosities can be adjusted by 4ss s99 12 "a change in the total percentage of active ingredients and by modifying the percentage of thickener-foaming agent, the hydroxypropyl-guar gum derivative.

In all these cases it must be possible to keep the product obtained from a relatively narrow-necked bottle (1.5 cm diameter) or narrow opening, but the viscosity of the detergent composition must not be so low that it resembles water.

The viscosity of the detergent should be at least 100 cP at room temperature and up to about 1000 cP. The viscosity may be about the same as that of the commercially accepted detergent compositions. The viscosity of the detergent and the detergent as such remain stable during storage for long periods of time, without color changes or precipitation of insoluble materials.

This composition preferably has a neutral pH value, about 6-8.

The products exhibit unexpectedly beneficial properties.

For example, the foam quality is superior to that of ordinary mild liquid detergents, despite the lower content of active ingredients.

The following examples are given for the purpose of illustrating the invention only and may not be construed as a limitation thereof.

Examples 1 and 2 Ingredients Example 1 Example 2 HP-601 o 0.5 g Citric acid 0 '1.0 g Deionized water 36.06 g 34.56 g Å Alkyl ether sulphate (AEOS, 58.3% AI) 20.6 g 20, 6 g Ethyl alcohol 5 g 5 g Ammonium xylene sulfonate (40% AI) o 5 g 5 g Ammonium lauryl sulphate (ALS, 30% AI) 26.67 g V 26.679 AKocos-amidopropyl betaine (30% AI) 6.67 g 6.67 g 453 399 13 "1 nonionic hydroxypropyl guar gum derivative (9% H 2 O) 2 ammonium C 12 -C 15 alkyl (C 2 H 4 O) 3 sulfate The ratio of the surfactants AEOS / ALS / betaine was 12/8/2.

AEOS, alcohol and ammonium xylene sulfonate were mixed to a homogeneous and clear product, at room temperature or slightly elevated temperature (not more than 100 ° C). The ammonium lauryl sulfate and betaine were then added with stirring, followed by the addition of the water while stirring the mixture to provide an aqueous solution of the surfactant three-component system. In Example 2, the guar gum derivative and the citric acid, which are involved in the dissolution of the guar gum, were added last and slowly with stirring.

The resulting product was a thickened solution with no evidence of suspended particles or precipitation.

Foam experiments with Tergotometer on Crisco dirt using sample solutions of Examples 1 and 2 showed that 16 plates were washed with the composition of Example 1 and 19 plates of the composition of Example 2 (containing the guar gum derivative), which markedly improved the foam properties. (the foam was maintained to plate 19). It was further noted that the dirt in the container containing the composition of Example 1 (without the guar gum derivative) became visible more quickly (after the addition of the eighth plate) on top of the solution than in the container containing the solution of the composition of Example 2. Example 1 had a viscosity of 22.5 cP, which is too watery for a suitable consumer product; whereas Example 2 had a viscosity of 407.5 cP, which is within the range of a suitable mild liquid detergent product. 453 399 14 "Changes in the above compositions may occur. For example, other alkyl sulfates may be substituted for the ammonium lauryl sulfate, such as sodium lauryl sulfate, potassium lauryl sulfate, ammonium, sodium and potassium myristyl sulfates, etc. Other alkylene ethoxy ether sulfates may be substituted for ammonium alkyl ethylene oxide sulfate, e.g. alkyl ethoxy etersulfate, etc. In addition, other betaines may be substituted for coconut amidopropyl betaine, e.g. eg coconut amidoethyl betaine, coconut concrete and the like.

Furthermore, the amounts of each of the anionic components can be varied provided that the total sum of the special groups of anionic surfactants constitutes about 20-30% by weight of the composition. The amount of betaine can also vary up to a maximum of about 5% by weight of the composition. The amount of the nonionic hydroxypropyl guar gum derivative may also be varied between 0.01 to about 1% by weight and preferably 0.025-0.6% by weight of the composition, depending on the desired viscosity of the resulting liquid detergent product. A composition containing 1% by weight of the guar gum derivative has been found to give an overly viscous product. The invention has been described here with reference to various examples and embodiments, but these do not constitute a limitation since a person skilled in the art which is confronted with the present patent application can of course use other components and quantities without therefore departing from the scope of the invention.

Claims (10)

10 15 20 25 15 P a t e n t k r a v Liquid detergent composition, consisting essentially of an aqueous vehicle containing a three-component mixture of a water-soluble salt of a C8-C18-alkylene ethoxy ether sulfate containing 1 to 12 moles of ethylene oxide, a water-soluble salt of a C8-C18-alkyl sulfate and a hybrid ionic betaine surfactant of the formula in which R 1 represents an alkyl group having 10 to 20 carbon atoms or an amido radical of the formula RC (O) N (H) (CH 2) a, wherein R represents an alkyl group having 9 to 19 carbon atoms and a is an integer between 1 and 4, R 2 and R 3 each represent an alkyl group having 1 to 3 carbon atoms and R 4 represents an alkylene or monohydroxyalkylene group having 1 to 4 carbon atoms, characterized in that the three-component mixture constitutes up to 40% by weight. of the composition, wherein the weight ratio of alkyl sulfate to alkylene ethoxy ether sulfate is from 1:29 to 29: 1, the concentration of betaine is not greater than 5% by weight of the composition, and the composition further contains 0.01 - 1% by weight of a complexion droxypropyl guar gum having a molar substitution value in the range 0.2 - 0.8 to improve the foaming properties of useful concentrates of the composition. x Liquid detergent composition according to claim 1, characterized in that the water-soluble salt of the alkylene ethoxy ether sulfate and the alkyl sulfate is selected from the group consisting of the alkali metal, ammonium and alkylol ammonium salts. 10 15 20 25 30 * 4553 5359 1 6 Liquid detergent composition according to claim 2, characterized in that the mixture of alkyl sulphate and alkylene ethoxy ether sulphate constitutes about 20 - 30% by weight and the betaine about 2 - 5% by weight of the composition. Liquid detergent composition according to claim 2, characterized in that the guar gum constitutes 0.1 - 0.6% by weight of the composition. 5. A liquid detergent composition according to claim 2, characterized in that the hybrid ionic surfactant is an amido betaine. Liquid detergent composition according to claim 2, characterized in that the alkyl sulphate is ammonium lauryl sulphate, the alkyletheneoxy ether sulphate is ammonium C12-C15-alkyl- (C2H4O) 1-5 sulphate and the betaine is coconut amidopropyl dimethyl betaine. Liquid detergent composition according to claim 1, characterized in that the water vehicle additionally contains about 1% by weight of citric acid. A method of preparing a liquid detergent according to claim 1, characterized in that an aqueous solution of the three-component mixture of surfactants is first prepared by mixing the solution at a temperature of up to 100 ° C; then slowly, with stirring, adds the guar gum in the form of particles of such size that at least 90% of them pass through a 140 mesh screen according to American screen standard; and continue stirring until the guar gum is dissolved in the aqueous solution. 9. A method according to claim 8, characterized in that the aqueous solution of the three-component mixture of surfactants is prepared by mixing aqueous solutions of the alkyl sulphate and the alkylene ethoxy ether sulphate, then adding the betaine with stirring, and then adding it with stirring. remaining water. 10. A method according to claim 8, characterized in that the aqueous solution of the three-component mixture of surfactants further includes a hydrotropic solubilizing agent and that up to 1% by weight of citric acid is slowly added together with the guar gum to facilitate the dissolution of this rubber.