FI75597C - Liquid detergent compositions containing the mixture of anionic and ethoxylated, nonionic surfactants. - Google Patents

Abstract

Stable liquid dishwashing compositions are provided incorporating an alkyl benzene sulphonate and/or alkyl sulphate, an alkyl ethoxy sulphate and an ethoxylated C6-C13 alcohol containing an average of (Eav) from 1.5 to 25 moles of ethylene oxide per mole of alcohol and wherein the ethoxylated alcohol contains no more than 1% by weight of unethoxylated alcohol when Eav<9 and no more than 2% by weight of unethoxylated alcohol when 9<Eav<25.

Description

75597

This invention relates to aqueous liquid detergent compositions, and more particularly to dishwashing compositions comprising a mixture of anionic and ethoxylated nonionic surfactants. This invention relates to aqueous liquid detergent compositions, and more particularly to dishwashing compositions comprising a mixture of anionic and ethoxylated nonionic surfactants.

Liquid detergent compositions for use as dishwashing products are conventionally clear aqueous solutions containing a mixture of one or more anionic sulfate and sulfonate surfactants together with a foam stabilizer. When sulfonate surfactants are used in such mixtures, they may be of the olefin sulfonate, paraffin sulfonate or, most commonly, alkyl benzene sulfonate type, while alkyl sulfates and alkyl ether sulfates form commonly used sulfate compounds. Recently, there has been a trend to use magnesium cations in at least some of the anionic surfactants present, and GB Patent Application no. 2010893 A and EP patent application publication no. 0039110 represent the state of the art. It is advised in the art that these formulations have improved performance, especially when used in water with low mineral hardness. In any case, the pressure to improve the cost-effectiveness of liquid detergent compositions has meant that the search for compositions with improved economics, performance and performance has continued. Particularly vigorous efforts have been made to increase the concentration of liquid dishwashing detergent compositions and to lower the level of diluents such as water and soluble hydrotropes without compromising the storage stability of the compositions.

35 In most liquid dishwashing detergent compositions based primarily on anionic surfactants 2,75597, the use of anionic surfactant levels in excess of about 30% by weight of the composition (depending on the exact value of the surfactants used) requires an increase in the hydrotropic level. However, an exception to this general pattern of behavior is provided by paraffin sulfonates, the commercial sources of which contain disulfonate components that are thought to provide some hydrotroping properties. These components make paraffin sulfonate-containing compositions 10 more tolerant of otherwise poorly soluble ingredients such as inorganic salts and certain foam stabilizers such as alkanolamines. Examples of such mixtures are English Patent Nos. 1451228, 1567421 and 1382295. In the absence of a significant level (e.g. 5%) of paraffin sulfonates, the addition of foam stabilizers such as alkanolamines and amine oxides requires the addition of hydrotrope to maintain the phase stability of the mixture.

Ethoxylated nonionic surfactants 20 form a class of materials capable of solubilizing other components in aqueous media, but this ability is strongly dependent on their average degree of ethoxylation (E .. ,,). Highly ethoxylated nonionic surfactants (i.e., Eav> 20) are highly hydrophilic in nature and thus tend to degrade the oily soil removal ability of liquid dishwashing detergent compositions, which is not desirable because oil and grease removal is important for consumer acceptance. Highly ethoxylated nonionic substances with hydrocarbon chain lengths below C ^ 2 »are not readily available commercially, but with longer chain materials with high levels of ethoxylation and available as a tank delivery (e.g. tallow alcohol ethoxylates) tend to foam. properties and they also tend to be relatively poor oil and grease removers. On the other hand, nonionic surfactants with mail 3 75597 or ethoxylation levels (i.e., Eav> 2) are relatively hydrophobic and have a limited ability to solubilize other components without other active compounds.

A common feature of all ethoxylated nonionic surfactants is the presence of a certain level of non-ethoxylated material, the magnitude of which depends on the degree of ethoxylation, but which may constitute up to 20% by weight of the nonionic surfactant. Non-ethoxy-aliphatic primary C8-C18 alcohols 10 are odorless materials with low water solubility and these properties are detectable in ethoxylated alcohols to an extent that depends on the level of ethoxylation as the effect decreases as Eav increases. The relatively low utility of ethoxylated alcohol surfactants, especially in laundry detergent compositions, makes the odor properties of ethoxylated alcohol relatively insignificant in such products, especially granular products intended for use in automatic washing machines. However, consumers 20 tend to be well aware of the physical properties of liquid detergent compositions, especially those used in dishwashing, due to the manual nature of the matter and the greater degree of consumer exposure to the hot detergent solution. Liquid dishwashing detergent compositions containing paraffin sulfonate as the main anionic compound together with ethoxylated nonionic surfactants having an Eav in the range of λ 2-6 are commercially available, so that such compositions have a certain degree of aesthetic acceptance by consumers. However, with detergent compositions that do not contain paraffin sulfonate, the detrimental effect of the non-ethoxylated components in the nonionic surfactant on the phase stability properties of liquid dishwashing detergents has been found to be unacceptable.

75597

In particular, liquid dishwashing detergent compositions containing alkyl sulphates and / or alkyl benzene sulphonates have been found to cause odor and storage stability problems / when mixed with ethoxylated non-ionic surfactants containing a more normal distribution of ethoxylated compounds and this effect is when the mixture also contains magnesium ions. However, it has now been found that certain alcohol ethoxylates containing less than 10 specified amounts of non-ethoxylated compounds, and preferably at least some of the monoethoxylated compounds have been removed, can be incorporated into liquid benzene sulfonate or alkyl sulfate-containing liquid dishwashing compositions without detrimental effect on the latter.

According to the present invention there is therefore provided a physically stable liquid detergent composition comprising 20-85% of an anionic surfactant system consisting essentially of a C 1 -C 4 alkylbenzenesulfonate-20 salt and / or a primary C 1 -C 4 alkyl sulfonate salt together with a primary C 1 -C 4 alkyl sulfonate salt. With a -C 1-6 alkyl ethoxy sulfate salt containing an average of up to 6 ethyl oxide groups per alkyl group in the alkyl ether sulfate, and optionally containing a foam stabilizer, the mixture also containing 1-10% of ethoxylated aliphatic C 8 -C 18 alcohol. containing an average of 1.5 to 25 moles of ethylene oxide per mole of alcohol, said ethoxylated alcohol containing not more than 1% by weight of unoxylated alcohol, the ethoxylated alcohol containing on average less than 9 moles of ethylene oxide and not more than 2% by weight of unoxylated alcohol, when the ethoxylated alcohol contains an average of 9 to 25 moles of ethylene oxide per mole of k threw alcohol.

The HLB number of the ethoxylated aliphatic alcohol is preferably between 8.0 and 17.0, more preferably between 11.0 and 17.0, and most preferably between 11.0 and 15.0.

Il 5 75597

In preferred compositions of the invention, the ethoxylated aliphatic alcohol is a primary C 8 -C 4 alcohol condensed with an average of 6 to 10 moles of ethylene oxide per mole of alcohol. Preferably, the ethoxylated alcohol contains less than 0.7% and most preferably less than 0.5% non-ethoxylated material, and in highly preferred compositions, the amount of monoethoxylated C 8 -C 4 alcohol is up to 5% by weight of the nonionic surfactant.

Preferred liquid detergent compositions according to the present invention contain an alkyl sulfate surfactant and magnesium ions in a molar amount corresponding to at least half the molar amount of alkyl sulfate present and containing 1 to 5% by weight of ethoxylated alcohol.

A preferred group of compositions comprises a three component anionic surfactant system comprising 8-12% by weight of a mixture of primary C 1 -C 6 alkyl sulfate, 9-11% of a primary C 1 -C 4 alkyl ethoxy sulfate containing an average of 1.5 - 3 ethoxy groups per alkyl group 20, and 13-17% qC 1-4 alkylbenzenesulfonate. The cations of this system are a mixture of ammonium and magnesium ions, with the amount of magnesium corresponding to approximately half the molar amount of alkyl sulfate present.

Another preferred group of compositions uses a two-component anionic surfactant system with 4-8% primary C 1-6 alkyl sulfate and 20-25% C 1-6 alkyl ethoxy sulfate containing 0.5 to 2.0 ethoxy groups per alkyl group. .

Preferred compositions according to the present invention also contain 2-8% and most preferably 3-4% by weight of a foaming agent selected from C 1 -C 6 mono- and di-C 2 -C 3 alkanolamides and C 8 -C 8 alkanolamides. alkyl di-C ^ -C ^ -alkyyliamiinioksideista.

The detergent compositions of this invention consist of a mixture of 35 anionic surfactants of a specified composition in an amount of 20-50% by weight of the composition, 6,75597, together with an ethoxylated nonionic surfactant having a low content of non-ethoxylated material.

All mixtures of this invention contain 5 alkyl sulfate and / or alkyl benzene sulfonate components together with alkyl ethoxysulfate.

The alkyl sulfate component is a primary alkyl sulfate in which the alkyl group contains 10 to 16 carbon atoms, more preferably an average of 12 to 14 carbon atoms. The alkyl group 10 may be linear or branched in structure.

C10-C16 alcohols derived from natural fats or Zieleger olefin synthesis or oxosynthesis provide suitable sources for the alkyl group. Examples of synthetically derived materials are Dobanol 23, 15 sold by Shell Chemicals (UK) Ltd, Ethyl 24, sold by Ethyl Corporation, a mixture of C 1-4 alcohols in a ratio of 67%, C. GmbH sells under the trade name Lutensol and ICI Ltd under the name Synperonic'0 'and Liguichimica Italiana under the name Lial 125. Examples of naturally occurring materials from which alcohols can be derived are coconut oil, palm kernel oil and similar fatty acids.

When the alkyl sulfate component is present in the compositions of this invention, the level of the alkyl sulfate component is between 4-20% by weight of the mixture and more generally between 4-16% by weight. In a preferred embodiment of the invention, which also contains an alkyl benzene sulfonate, the amount used is between 8 and 12% by weight and most preferably between 8 and 11% by weight. In another embodiment of the invention in which the sulfonate component is not present, the alkyl sulfate t-30 is between 12-20% by weight and more preferably 14-18% by weight.

For the purposes of this invention, any alkali metal, alkaline earth metal, ammonium or substituted ammonium cation may be used in conjunction with an alkyl sulfate. However, in the highly preferred compositions of the invention, the alkyl sulfate is attached to a source of magnesium ions which, as shown below, can be fed as either an oxide or hydroxide to neutralize the acid or can be added to the mixture as a water soluble salt. The addition of significant amounts of magnesium salts to the dishwashing compositions of the invention raises the temperature at which the inorganic salt crystals form in the compositions upon cooling and is therefore disadvantageous.

In mixtures consisting of a mixture of alkylbenzenesulfonate, alkyl sulfate and alkyl ether sulfate, the molar amount of magnesium ion in the mixtures is adjusted to correspond to a value of 0.20 to 0.70X, preferably 0.45 to 0.55X, where X is the number of moles of alkylCl sulfate present. . Most preferably, the magnesium ion content is adjusted to provide the stoichiometric equivalence of the alkyl sulfate present. In practice, magnesium ion is present in an amount of about 0.15 to 0.70 wt% and preferably 0.25 to 0.55 wt% of the mixture.

In contrast, mixtures containing only alkyl sulfate and alkyl ether sulfate as anionic surfactants preferably contain up to about 0.90 wt% of the magnesium ion in the mixture, and some of the alkyl ether sulfate is also neutralized with magnesium ion.

Alkylbenzene sulfonates useful in the compositions of this invention are those in which the substantially linear alkyl group contains from 10 to 16 carbon atoms, preferably from 11 to 13 carbon atoms, with the most preferred material having an average carbon chain length of 11.8. The phenyl isomer distribution, i.e., the point of attachment of the alkyl chain to the benzene nucleus, is not critical, but alkyl benzenes having a high 2-phenyl isomer content are preferred. When alkylbenzenesulfonate is used in the compositions of this invention, it is required to have a concentration of 10-28% by weight and generally 12-26% by weight. In a preferred aspect of the invention, an alkylbenzenesulfonate content of 13-17% by weight is used and the highly preferred compositions of this aspect of the invention contain 14-17% g of alkylbenzenesulfonate.

8 75597

The alkyl ethoxysulfate surfactant component consists of a primary alkyl ethoxysulfate derived from the condensation product of a C 1 -C 4 alcohol having an average of 6 ethylene oxide groups.

The C 1 -C 6 alcohol itself can be obtained from any of the sources described above for the alkyl sulfate component. However, it has been found advantageous to use alkyl sulfate and alkyl ether sulfate having the same carbon chain length distributions. C 1 -C 2 β-allyl alkyl ether sulfates are preferred and the amount of alkyl ethoxy sulfate in the mixture is between 8-25% by weight of the mixtures, generally between 10-25% by weight. In a preferred aspect of the invention containing an alkylbenzene sulfonate surfactant, the amount is between 9 and 15% by weight and most preferably between 9 and 11% by weight.

Conventional ethoxylation processes result in a distribution of individual ethoxylates ranging from 1 to 10 ethoxy groups per mole of alcohol, so that the desired average can be achieved in a number of different ways.

Mixtures can be made from a material with different degrees of ethoxylation and / or different ethoxylate distributions due to the ethoxylation technique used in each case and the subsequent processing steps, such as distillation. For example, it has been found that foaming and degreasing performance similar to that provided by a mixture of alkyl sulfate and alkyl triethoxy ether sulfate can be obtained by reducing the amount of alkyl sulfate and using an alkyl ether sulfate having an average of approximately two ethoxy groups per mole of alcohol.

In the preferred compositions of this invention, the average degree of ethoxylation is 0.5 to 4, and more preferably 0.8 to 2.0.

The counterion of the alkyl ethoxysulfate may be any of sodium, potassium, ammonium or alkanol ammonium ions or a mixture thereof. However, in order to obtain the lowest possible solidification point temperature (the temperature at which inorganic salt crystals separate), it is desirable that at least 30% of the Alkyl Ethoxy Sulfate Counterparts be ammonium ions.

In mixtures containing an alkylbenzenesulfonate component, it is highly preferred that the alkyl ethoxy sulfate be completely neutralized with ammonium ions.

In the case of an alkyl benzene sulfonate, the counterions are independently selected in the same manner as the counterions of the alkyl ethoxysulfate, preferably with at least 50% ammonium ions. In order for the compositions of the invention to have a pour point of 0 ° C, at least 70% of the neutralizing cations of the anionic surfactants must be ammonium ions, and most preferably ammonium forms the only cation present other than magnesium.

The ethoxylated, nonionic surfactant component of the invention is an aliphatic C 1 -C 4 alkyl alcohol ethoxylate containing an average of 1.5 to 25, more preferably 2 to 15, and most preferably 6 to 10 moles of ethylene oxide per mole of alcohol. The aliphatic alcohol ethoxylate si-20 contains up to 1% by weight of non-ethoxylated alcohol when the ethoxylated alcohol contains on average less than 9 moles of ethylene oxide and up to 2% by weight of non-ethoxylated alcohol when the ethoxylated alcohol contains on average 9-25 moles of ethylene oxide per mole of alcohol.

The starting alcohol may be a primary or secondary alcohol, but is preferably a primary alcohol which may be derived from natural or synthetic sources. Thus, natural fats or oils or products of Ziegler olefin synthesis reactions or oxosynthesis 30 can all be used as a source of a hydrocarbon chain, which can be of a linear or branched structure.

The preferred range of alcohol chain length is C8-C18, as it has been found that performance, namely foam volume and yield, is optimal for ethoxylates made from such alcohols. The average degree of ethoxylation (Eo) is between 1.5 and 25 moles per mole of alcohol, but is preferably between 2 and 15 and most preferably between 6 and 10 moles per mole of alcohol. For performance reasons, it is also desirable that the hydrophilic-5 lipophilic balance (HLB) of the ethoxylated alcohol be between 8.0 and 17.0, more preferably between 11.0 and 17.0, and most preferably between 11.0 and 15.0.

As described for the alkyl ethoxy sulfate component, the normal (base catalyzed) ethoxylation process results in a wide distribution of ethoxylate compounds.

With an average degree of ethoxylation of 6 to 10 moles per mole of alcohol, this range ranges from one to at least 15 moles of ethylene oxide per mole of alcohol, and with an average range of 20 to 25 moles per mole of alcohol, the range can range up to 50 moles per mole of alcohol. Increases in Eav degree cause the ethoxylate distribution to focus less around the mean and also lead to a decrease in the level of non-ethoxylated material. Condensation products with an E 1 v between 3 and 9 moles per mole of alcohol contain 3-20% non-ethoxylated material, while products with an E 1 v between 10 and 20 moles av per mole of alcohol still contain up to 2% non-ethoxylated material.

In the liquid dishwashing detergent compositions of the invention, amounts of non-ethoxylated material in the ethoxylated nonionic surfactant in excess of 2% by weight cause phase stability / solidification point problems and / or result in a product with a fatty alcohol odor that is not acceptable to consumers and difficult to mask. . It has been found that for reasons of phase stability, the maximum amount of unoxylated alcohol that can be tolerated in the ethoxylated alcohol component is 1% by weight of the alcohol ethoxylate when the ethoxylation level is less than 9 moles per mole of alcohol and 2% by weight when the ethoxylation level is 9-25 moles per mole. moles per alcohol. Preferably, the level of non-ethoxylated alcohol is at most

II

11,75597 0.70% and most preferably it is less than 0.5% by weight of the ethoxylated alcohol component.

Vacuum distillation is used to remove undesirable material and this also removes some of the monoethoxylate fraction-5, which increases the E grade of the remaining material.

dV

In preferred embodiments of the invention, where the ethoxylated alcohol is a primary C 1 -C 4 alcohol ethoxylate, the level of monoethoxylate is up to 5% by weight of the ethoxylated alcohol.

The level of use of the ethoxylated alcohol component in the compositions of the invention is 1-10% by weight, more preferably 1-5% and most preferably 2-4% by weight. The liquid dishwashing detergent compositions of the invention having 3-5% by weight of a primary alcohol containing 9-11 carbon atoms condensed with an average of 5-10 moles of ethylene oxide per mole of alcohol to give an HLB value of 12-15, with alcohol ethoxylate containing <0.5 wt% non-ethoxylated alcohol, has freezing points <0 ° C and improved foamability and performance compared to previous blends in the art.

A highly preferred ingredient of the composition of the invention is a foaming agent present in an amount of 2-8% by weight of the mixture, preferably 3-6% and most preferably 3-4%.

The foaming agent can be any C 1 -C 6 mono- and di-C 2 -C 8 alkanolamide and a tertiary amine oxide containing a C 1 -C 6 alkyl group.

Examples of alkanolamides are coconut alkyl monoethanolamide, coconut alkyl alkyl diethanolamides and palm kernel-30 and coconut alkyl mono- and diisopropanolamides. The palm kernel or coconut alkyl residue can be either the "whole region" containing the C18 and C18 fractions or the so-called "narrow region", the C12-C14 fraction. Synthetic sources of the q-C 1-6 alkyl group may also be used.

75597 Amine oxides useful in this invention have one hydroxyalkyl moiety of 8 to 18 carbon atoms, preferably 8 to 16 carbon atoms, and two moieties selected from alkyl groups of 1 to 3 carbon atoms and hydroxyalkyl groups. Examples of such materials are dimethyloxylamine oxide, diethyldecylamine oxide, bis- (2-hydroxyethyl) dodecylamine oxide, methylethylhexadecylamine oxide and dimethyl-2-hydroxyoctadecylamine oxide.

A very preferred example of a tertiary amine oxide is 2-C 1-4 alkyldimethylamine oxide in which the C 1 -C 14 alkyl group is derived from coconut oil.

The remainder of the assembly consists of hydrotropic-water systems, wherein the hydrotrope may be urea, a C 1 -C 4 aliphatic alcohol, or a lower alkyl benzene sulfonate, or a mixture of any of these. Normally one hydrotrope is sufficient to provide the required phase stability, but in the compositions of this invention it is preferred to use a mixture such as a urea-alcohol lower alkyl benzene sulfonate-water mixture to achieve the desired viscosity and to keep the mixture stable and easy to pour. For mixtures with an active organic content of less than about 40% by weight, the preferred alcohol hydrotrope is ethanol, which is used in 3-10% by weight of the mixtures, preferably 4-8%, usually mixed with urea. Mixtures of hydrotropes can, of course, be used for cost-effectiveness reasons, regardless of any stability / viscosity considerations.

Optional ingredients in the liquid detergent compositions of the invention include opacifiers such as ethylene glycol dististerate, bactericides such as glutaraldehyde and Bronopol®, corrosion inhibitors such as benzoxytriazole, heavy metal chelating agents such as ETDA, or ETDMP, perfumes, and colorants. The pH of the blends may be in any range of 6 to 7.5, but when prepared, the pH of the blends is normally in the range of 6.6 to 7.3 and they are subjected to a final pH adjustment of 13,75597 to obtain the desired final product pH. For colored products, the pH is preferably between 6.6 and 6.9 to maintain color stability.

The compositions of the invention may be prepared in a number of ways, but it is preferred that the ethoxylated nonionic surfactant be added near the end of the manufacturing process, unless it actually forms the last ingredient to be added. This is particularly important when the ethoxylated nonionic surfactant has an HLB value of 9.5, which is considered to be below which such materials are in principle insoluble in water.

Thus, individual anionic surfactants can be prepared as aqueous solutions of alkali metal or ammonium salts, which are then mixed with foaming agents and hydrotropes, after which any magnesium ion can be added as a water-soluble salt, such as chloride or sulfate. The ethoxylated nonionic surfactant and any optional minor ingredients are then added simultaneously as the pH and viscosity are adjusted. The advantage of this method is that conventional technique and equipment are used, but it actually results in the supply of additional chloride or sulphate ions, which may raise the solidification point temperature (the temperature at which inorganic salts precipitate as crystals in the liquid).

An alternative and preferred method is to mix the alcohol and alcohol ethoxylate together and perform a single sulfation and neutralization. To this end, the alcohol and the alcohol ethoxylate must be mixed in a weight ratio of between 4: 3 and 1: 6. The sulfation can be carried out with any of the conventional sulfating agents, such as sulfur trioxide or chlorosulfonic acid. The neutralization of the alkyl ether sulfuric acid and the alkyl sulfuric acid is carried out with an appropriate alkali or magnesium oxide or hydroxy slurry, thus avoiding the addition of chloride or sulphate ions. In preferred embodiments of this technique 14 75597 using a magnesium hydroxide slurry, it is appropriate to use a mixture of these acids because the magnesium salt of the alkyl ether formic acid has relatively better water stability than the alkyl sulfuric acid component. The foaming agent is then dissolved in this basic solution of the active alkyl sulfate and alkyl ether sulfate.

The separately neutralized alkyl benzene sulfonate salt and neutralized alkyl and alkyl ether sulfate salts containing a foaming agent and a hydrotrope are then added to the final mixing tank and the ethoxylated nonionic surfactant and any optional ingredients are added before adjusting the pH as above.

Preferred ingredients of the invention are clear single phase liquids, but the invention also encompasses turbid products containing dispersed phases, provided that such products are physically stable (i.e., not separable) upon storage.

The invention is illustrated by the following non-limiting examples in which all parts and percentages are by weight unless otherwise indicated.

Il 15 75597

Example 1

The following mixtures were prepared:

5 A B C d E

Ammonium linear C 1-8 alkyl-benzenesulfo- 14.2 14.2 14-2 14.2 14 2

naatti f * J

Ammonium C 12 -C 13 alkyl 10.4 10.4 10.4 10.4 10.4 10 (E0) 2 sulphate

Magnesium C12-C13-alkyl-8r6 8.6 8.6 8.6 8.6 sulphate - 1 ·

Primary alcohol ethoxy - - 3.5 * 3.52 3.53 3.5 ^ plate 'f

Coconut monoethanolamide 4/0 4 / ° 4 / ° 4 / ° 4 ^ 0 15 Ethanol V 99.1 9/1

Water _ up to 100_ 1) Dobanoi® 91Eg, a predominantly linear C8-C18 alcohol mixture containing an average of 5 ethylene oxide groups per 20 moles of alcohol, manufactured by Shell International Ltd and "truncated" the amount of non-ethoxylated C8-C18 alcohol to 0.5% by weight of the ethoxylate, increasing the average degree of ethoxylation to approximately 6.

2) Dobano ^ 91E2 5, a mainly linear C8-C18 alcohol mixture containing on average 2,5-ethylene oxide units per mole of alcohol.

3) Dobano] ®23Eg is a mainly linear ci2-C13-α2-alcohol mixture containing an average of 6.5 ethyleneoxy-30 diunits per mole of alcohol.

D

4) Dobanol 45 E ?, a predominantly linear C 1 -C 4 -alcohol mixture containing an average of 7 ethylene oxide units per mole of alcohol.

16 75597

In the preparation of mixture A, a mixture of alcohol and alcohol ethoxylate was sulfated using SO 2 air sulfation and then neutralized in an alcoholic ammonium hydroxide solution to which magnesium hydroxide had been added in an amount corresponding to half the molar amount of alkyl sulfate present. Separate alkylbenzene sulfonation was used to produce alkylbenzenesulfonic acid, which was added to an alkaline solution of the other active ingredients and neutralized with excess ammonia to pH 7. The monoethanolamide was then added before final pH adjustment to 6.8. The pour point of mixture A was -5 ° C. Mixtures B-E were prepared in the same manner except that ethoxylated nonionic surfactant was added during the final pH adjustment operation.

The pour point of the different mixtures was measured and each mixture was evaluated for the odor of the solution. Comparison of the foam yield of the mixtures was also performed using the mechanical foaming test described below under the following conditions.

Product content 0.12%

Water temperature 47 ° C Water hardness 2 ° H and 18 ° H

Dirt: Cake mix / free fatty acids (MFFA) 25 The cake mix is a McDougall dough mix

Free fatty acids contain 2 parts oleic acid 2 parts linoleic acid 1 part stearic acid 2.5 parts palmitic acid 30 367 parts corn oil to give a 2% MFFA mixture.

The method uses four cylinders 30 cm long and 10 cm in diameter, mounted side by side and rotatable at a speed of 35 24 rpm about a central axis. Each cylinder is charged with 500 ml of a solution of 0,12% li 17 7559 7 and a temperature of 45 ° C. The two outer cylinders are used for one of the products to be compared and the two inner ones for the other product.

The cylinders are rotated for 2 minutes, stopped, the initial foam is measured and the dirt charge is added. The greasy dirt consists of a mixture of fatty acids in a cooking oil base and 1 ml of this mixture. (MFFA) is added to each cylinder. Any particulate dirt is also added at this point. After one minute, the cylinders are restarted for 10 minutes and allowed to rotate for one minute. The foam height is determined and 1 ml of 2% MFFA is added to each cylinder. After one minute, the cylinders are restarted. This process continues until the height of the foam in the cylinder is less than 0.5 cm.

15 Product A is defined as a control product and foam yield figures are calculated for another product against a "control" product on the following basis.

Test product yield = number of additions of dirt to the test product 20 solution to reduce the foam height to 0.5 cm _ x 100 number of dirt additions to the control product to calculate the foam height to 0.5 cm The results of solidification point measurements and odor evaluations and yield comparisons using mixture A as 100% were the following: 18 75597

Mixture Sufficiency Freezing point Odor type

2 ° H 18 ° H

B 114 120 -5 Mild 5 C 113 100 +24 Strong shade of fatty alcohol D 100 100 -1.5 Shade of fatty alcohol E 91 80 -4 Fat alcohol- 10 Iin shade

It can be seen that only mixture B showed a uniform yield advantage in both hard and soft water, a combination of an acceptable pour point and an acceptable odor.

Example 2

The following mixtures are in accordance with this invention Magnesium 2 "C 1-3 alkyl sulfate Magnesium 2" C 1-3 alkyl (EO) ^ sulfate Magnesium 2 "C 1-3 alkyl (EO) 2 sulfate

Ammonium 2-C 1-3 alkyl (EO) 2 sulfate Ammonium 2 C 1 -C 13 alkyl (¢ 0) 2 sulfate

Primary linear C 1 -C 4 alcohol (EO) g containing <1% non-ethoxylated alcohol C 1-2 monoethanolamide C 12 -C 12 alkyldimethylamine oxide

ethanol

Urea 30 Sodium xylene sulfonate

Water up to 100

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19 75597

Example 3

The mixtures were prepared according to Example 1 except that the type, amount and HLB of the surfactant ethoxylated primary alcohol X were as follows:

Non-ionic type Amount HLB

H commercial C 1-4 alcohol (EO) ^ 4.95% 14.7 L commercial C 6 -C 10 alcohol (EO) g 3.5 12.5 (truncated to remove non-ethoxylated Ia-10) to give an (EO) value of 6 , 5) J C8 (EO) 4 g 2.7 12.4 K C8-C8-C4-alcohol mixture (EO) g 3.5 12.2 L C10 (EO) 20 8.7 16.9 15 M C6 (EO ^ 5 1.45 8.3 N Cg (EO) 3 2.11 12.0 O Cg (EO) 2 1.90 8.7 A Reference mixture, no non-ionic surfactant at all.

X) The amounts were adjusted to give the same molar amount as in mixture 2.

The foam coverage of the above mixtures was compared using the procedure of Example 1 to give the following results:

Particulate ° S dirt ° H

Greasy ° S

lika ° H

All mixtures H-0 show advantages over reference mixture A, which does not contain an ethoxylated nonionic component. It can also be seen that mixtures H and I, which represent preferred embodiments of the invention, provide better performance than other less preferred embodiments, such as mixtures L and M.

Claims (8)

1. Physically stable, liquid detergent composition containing 20-80% of an anionic surfactant system consisting essentially of a C ^-C alkyl alkyl alkylbenzenesulfonate salt and / or a primary CCCC ^ alkyl sulfate salt. together with a primary C 1 of an aliphatic ethoxylated C6 ~ C13 "alcohol containing on average 1.5-25 moles of ethylene oxide per mole of alcohol, wherein the ethoxylated alcohol contains at most 1% by weight of unethoxylated alcohol where the average ethoxylated alcohol contains less than 9 and not more than 2% by weight of unethoxylated alcohol where the ethoxylated alcohol contains an average of 9-25 moles of ethylene oxide per mole of alcohol. Detergent composition according to claim 1, characterized in that the ethoxylated aliphatic alcohol has an HLB of 8.0-17.0. Detergent composition according to claim 25 or 2, characterized in that the ethoxylated aliphatic alcohol contains on average 6-10 moles of ethylene oxide per mole of alcohol. Detergent composition according to any one of claims 1-3, characterized in that the ethoxylated aliphatic alcohol has an HLB of 11.0-17.0, preferably 11.0-15.0. Detergent composition according to any one of claims 1-4, characterized in that the alcohol ethoxylate contains less than 0.7, preferably less than 0.5% by weight of unethoxylated alcohol. Il