CZ53393A3 - Liquid or jellylike cleansing agent and method of washing dishes therewith - Google Patents

Abstract

Aqueous unbuilt liquid or gel-form detergent compositions are provided comprising, from 15 % to 65 % by weight of a core surfactant mixture, comprising from 5 % to 95 % by weight of the mixture of a water soluble anionic sulphate or sulphonate surfactant salt together and from 5 % to 95 % by weight of the mixture of one or more compounds of formula (I), wherein Z is a polyhydroxy hydrocarbyl moiety having a linear hydrocarbyl chain with at least three hydroxy groups connected directly to the chain, said moiety being derived from glucose and mixtures thereof with maltose, the maltose comprising not more than 33 % of the mixture, R is a C6-C16 hydrocarbyl radical and R1 is a C1-C4 alkyl or C2-C4 hydroxyalkyl group, a 0.12 % solution of the surfactant mixtures of the compositions having an interfacial tension (IFT) of less than 0.2 Pa.cm at 48 DEG C and a polypropylene cup (PPC) greasy soil removal value of at least 1.4 x that of the anionic surfactant component(s) alone. Preferred optional ingredients include amide, betaine and ethoxylated C9-C11 fatty alcohol suds modifiers.

Description

Technical field

The invention relates generally to aqueous liquid cleaners, and more particularly to liquid cleaners intended to remove greasy soil from hard surfaces such as plates, snacks and other items used in food preparation and in the consumption of food.

BACKGROUND OF THE INVENTION

Liquid dishwashing detergent compositions are generally in the form of aqueous solutions comprising a mixture of one or more sulfate and sulfonate anionic detergents forming the core of the surfactants together with a suds enhancer or stabilizing agent. The suds stabilizing agents may take a wide variety of forms, but are generally amide derivatives, amine oxide, ethoxylated aliphatic alcohol, zwitterionic surfactants such as betaine, or a mixture of several such agents. The amounts of such materials used are generally 2 to 8% by weight, in particular 3 to 5% by weight, based on the weight of the cleaning composition as a whole.

One type of amide derivatives that are suitable for promoting and stabilizing the foam are N-alkanoyl-N-alkyl glucamines. These compounds are derived from glucose and can be prepared by reacting a lower alkyl amine with glucose to form a glucamine and then reacting the glucamine with a fatty acid methyl ester of the desired chain length to provide N-alkanoyl-N-alkylglucamine.

Such compounds are known, for example, from US-A-2 703798, WO83 / 04412 and GB-A-8O9O6O. This British patent describes cleaning compositions comprising at least one water-soluble salt of an organic sulfur reaction product having a sulfuric acid or sulfonic acid group and an amine derivative in its molecular structure.

% of the above-mentioned type in a quantity of 5 to 60% by weight, based on the water-soluble organic sulfur reaction product. Amide derivatives have been reported to improve the foaming characteristics of detergent compositions at temperatures below 37 ° C, with dishes being washed at bath temperatures as low as 16 ° C, especially in Latin American countries. Although it is stated in this patent that the surfactant composition can be used alone, in preferred and exemplified embodiments these are granular compositions incorporating phosphate builders (the term builder is used herein for detergent builders) and sodium sulfate builders.

Surprisingly, it has now been found that liquid or gel-like buffy-free detergents containing as core surfactants mixtures of certain N-alkanoyl-N-alkylglucamines with sulphated or sulphonated surfactants are characterized by a significant improvement in the removal of greasy Spina from hard surfaces beyond concomitantly increased lathering and mildly acting on the skin as compared to known means for such purposes. However, mixtures of anionic sulphate or sulphonate surfactants and N-alkanoyl-N-alkylglucamines have been proposed to improve foaming of products with low temperature wash bath builders, grease removal performance and mild skin action, as in the composition of the invention were not yet known.

SUMMARY OF THE INVENTION

The essence of the builder-free liquid or gel cleanser in the physically stable aqueous solution of the invention is that it contains about 15 to 65% by weight of the composition as a whole of the core surfactant composition containing by weight

a) about 5 to about 95% of a mixture of at least one water-soluble salt of an anionic surfactant selected from the group consisting of sultates and sulfonates

b) about 95 to about 5% of a mixture of one or more

- 3 compounds of the general formula

R - CON - Ri i

OF

—— ** · - —- < -O -O r— > CD it = 5 O • -and <X; 2: p> O O o -H < ΓΠι < xc

Cř C"· O O . t— * I 00 c / x . ►— · <X> r— O ) OO

where it means

A linear hydrocarbon chain polyhydroxy hydrocarbon moiety having at least three straight chain-linked hydroxyl groups derived from glucose and its mixtures with maltose, with a maltose content of not more than approximately 33% by weight of the mixture,

R is a saturated or unsaturated alkyl group having 8 to 16 carbon atoms or a mixture thereof; and

R 1 is C 1 -C 4 alkyl and C 2 -C 4 hydroxyalkyl.

a 0.12¾ by weight aqueous solution of a surfactant composition of this composition has a water hardness equivalent to 28.5 mg calcium carbonate equivalent per liter with a 3 ^: 1 calcium to magnesium ratio and a temperature of 48 ° C

(i) a phase-to-phase voltage drop (IFT) of less than about 0.2 Pa cm using a 99.7% pure triolein dirt; (ii) a grease dirt removal value in the polypropylene cup test (PPC) of at least about 1.4 times the the value obtained in the same test under the same conditions, using a 0,12¾ solution of at least one anionic surfactant alone.

The term physically stable always refers to the preservation of a single-phase state without precipitation after three months of storage at

If the composition contains an opacifying agent, there should be no or minimal opacification of the opacifying agent. In addition, for the purposes of the IFT & PPC test measurements of the invention, the cationic or water-soluble anionic sulphate or sulphonate surfactants are such that they correspond to the cation or cations of the detergent composition and the optional cation mixtures are contained in weight proportions corresponding to each cation contained in the composition. *

AND

Preferred compositions according to the invention use as components (b) of compounds in which the polyhydroxy-hydrocarbon moieties are derived from glucose or mixtures thereof with maltose, the mixture containing less than 25% by weight of maltose. Commercially available technical glucose contains maltose as impurity in amounts up to 5% by weight. For the purposes of the invention, glucamines are mini-materials containing up to 5% by weight of maltose-derived components.

Suitable anionic sulfate or sulfonate surfactants include alkyl of 10 to 16 carbon atoms in the alkyl moiety containing moderate to 6 moles of ethylene oxide per mole of alkyl ethoxy sulfate, paraffin sulfonates of 10 to 18 carbon atoms and N-acyl-N-alkylglucamine sulfates of 9 to 17 atoms carbon in the acyl moiety and from 1 to 4 carbon atoms in the alkyl moiety.

Preferred detergent compositions of the present invention comprise an anionic surfactant system containing from about 9% to about 18% by weight of the composition as a whole of a C12-14 primary alkyl ethoxy sulfate with an average of 0.4-4.0 ethylene oxide groups per mole of alkyl ethoxy sulfate 12 to 14 carbon atoms in the alkyl moiety, preferably 0.3 to 3.0 ethoxy groups, together with 9 to 15% by weight, based on the cleaning agent as a whole, of N-cocoacyl-N-methylglucamine.

In preferred detergent compositions of the present invention, the weight ratio of anionic surfactant to glucamine is 2: 1 to 1: 1. Particularly preferred detergent compositions of the present invention comprise from about 10% to about 18% C12-C14 alkyl ethoxy sulfate and 7 to 15% by weight. % glucamine surfactant. The alkyl ethoxysulfates themselves comprise a mixture of a material containing at least one mole of ethylene oxide per mole and a material containing an average of about 3.0 moles of ethylene oxide. per, mol per. by weight, a ratio of 2: 1 to 5 µl, preferably about 4: 1.

Preferred detergent compositions of the present invention also contain from about 1% to about 8%, preferably from about 2% to about 7%, of a suds booster selected from the group consisting of alkyl monoalkanolamides and alkyldlalkanolamides having from 10 to 16 carbon atoms in each alkyl moiety and 2 to 3 carbon atoms each. alkyl betaines or alkyls, lamidobetains each having from 12 to 14 carbon atoms in the alkyl moiety, alkylsulfobetaines having 12 to 14 carbon atoms in the alkyl moiety, alkyldialkylamine oxides having from 10 to 16 carbon atoms in the first alkyl moiety and from 1 to 4 carbon atoms in the second alkyl moiety; C 10 -C 16 alkyl dihydroxyalkylamine oxides having 2 to 4 carbon atoms in the hydroxyalkyl moiety, C 9 -C 12 primary alcohol ethoxylates and moderately 7 to 12 ethylene oxide groups per mole of alcohol, and mixtures thereof.

Preferred suds boosters contain mixtures of C 12 -C 14 alkyl betaine in the alkyl moiety in an amount of 1 to 5%, preferably 1.5 to 3%, by weight of the cleaning composition as a whole, together with a primary alcohol ethoxylate with 9%. up to 12 carbon atoms in the alcohol moiety (preferably with 10 carbon atoms and with 8 ethoxy groups) in an amount of 6-8% by weight, based on the cleaning composition as a whole.

Another preferred component of such detergent compositions is magnesium ions in an amount of up to 1.5% by weight, and in particular 0.5 to 1.0% by weight of the cleaning composition as a whole. Particularly preferred cleaning compositions also contain calcium in addition to magnesium ions in an amount of 0.3 to 0.5% by weight.

The cleaning compositions according to the invention thus contain a mixture of core surfactants in an amount of 15 to 65% by weight of the cleaning agent as a whole, preferably 20 to 50% and in particular 22 to 40%. % of a mixture of at least one water-soluble salt of an anionic sulfate or sulfonate surfactant together with 95 to 5% by weight of a mixture of an 8-C16 N-aoyl-Nalkylglucine nonionic surfactant and an C 1 -C 4 alkyl group . Preferably, the composition comprises 20 to 80% by weight of anionic surfactant and 80 to 20%. alkylglucamine and in particular 40 to 70% of an anionic surfactant and 60 to 30% of alkylglucamine.

The anionic surfactant may be substantially any organic sulfate or sulfonate surfactant.

a salt, but typically the anionic surfactant is selected from the group consisting of alkylbenzene sulfonates having 11 to 15 carbon atoms in the alkyl moiety, alkyl sulfates having 10 to 16 carbon atoms in the alkyl moiety, and ethoxy analogues thereof containing up to 6 moles of ethylene oxide per mole of alkylethoxysulfate; C uhlíku až,, až,,,,,,, Cef, 16 16 16 ol ol ol ,efef ol,,,, alkyl ol alkyl alkyl alkyl alkyl alkyl, Cgly alkyl alkyl 20 20 alkylglyglyglyglyglyglyglygly alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkyl alkylglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglyglygly. up to 17 carbon atoms in the aoyl moiety and from 2 to 4 carbon atoms in the hydroxyalkyl moiety and any mixtures thereof. Particularly preferred anionic surfactants are selected from the group consisting of alkyl ethoxy sulfates, alkyl glyoeryl ether sulfonates, and paraffin sulfonates.

The alkylbenzene sulfonates useful in the detergent compositions of the present invention preferably have an alkyl group substantially linear containing from about 10 to about 16 carbon atoms, preferably from about 11 to about 13 carbon atoms, most preferably the mean carbon chain length is about 11.8. The separation of the phenyl isomer, i.e. the point of attachment of the alkyl chain on the benzene ring, is not critical, but alkylbenzenes with a high 2-phenyl isomer content are preferred.

Suitable alkyl sulfates are primary alkyl sulfates having an alkyl moiety of from 10 to 16 carbon atoms, preferably from medium to 12 to 14 carbon atoms, preferably in a linear chain. Alcohols of 10 to 16 carbon atoms, derived from natural fats or from the Ziegler olefin synthesis or from the OX synthesis, are suitable sources of such alkyl groups. Examples of synthetically derived materials include Dobanol 23 (RTM. * Trade registered trademark) sold by Shell Chemicals (UK) Ltd., Ethyl 24 EthylCorporation company, a mixture of alcohols having 13 to 15 carbon atoms in the ratio 67% C _i3, 33% * Cis sold under the trade name Lutensol to BASF GmbH and Synperonio (RTM) to XCI Ltd. and Lial 125 of Llquichimica Italiana. Examples of naturally occurring materials from which such alcohols can be derived are coconut oil and palm oil and the corresponding fatty acids.

Alkyl ethoxylate surfactants include primary alkyl ethoxy sulfate derived from the condensation product of a C 10 -C 16 alcohol having medium to 6 ethylene oxide groups. The C 10 -C 16 alcohol itself can be obtained from any of the above sources for the alkyl sulfate component. Alkyl ether sulfates having from 12 to 13 carbon atoms in the alkyl moiety are preferred.

The conventional, basically catalysed ethoxylation process leads to an intermediate degree of ethoxylation of 6 by dividing the individual ethoxylates of 1 to 15 ethoxy groups per mole of alcohol so that the desired mean value can be obtained in various ways. Mixtures with different degrees of ethoxylation and / or different distribution of ethoxylates may be prepared in connection with specific ethoxylation procedures and subsequent distillation treatment. For example, it has been found that equivalent foaming and fatty soil removal characteristics for a given mixture of alkyl sulfates and alkyl triethoxy ether sulfates can be obtained by reducing the alkyl sulfates content and using alkyl ether sulfates with moderately about two ethoxy groups per mole of alcohol. In a preferred detergent composition of the invention, a mixture of alkyl ethoxy sulfates is used, a material having an average degree of ethoxylation of 0.4 to 1.0, preferably about 0.8, combined with a material having an average degree of ethoxylation of 2.0 to 4.0, preferably about 3, 0.

The secondary alkanesulfonates suitable for use in the detergent compositions of the present invention have 13 to 18 carbon atoms per molecule, especially 13 to 15 carbon atoms per molecule. These sulfonates are preferably prepared by subjecting a paraffinic cross-section of the corresponding chain length, as described above, to a treatment of sulfur dioxide and oxygen with a known sulfoxidation process. The reaction product is a secondary sulfonic acid which is then neutralized with a suitable base to form a water-soluble secondary alkyl sulfonate. Similarly, the secondary alkyl sulfonates can be obtained by other methods, for example, the sulfochlorination method, wherein chlorine and sulfur dioxide are reacted with paraffins in the presence of actinic light, whereby the obtained sulfonyl chlorides are hydrolyzed and neutralized to form secondary alkyl sulfonates. Whichever method is used, it is generally desirable to prepare

a sulfonate as a monosulfonate, free from unreacted starting hydrocarbons or having only a limited content thereof and a low amount of inorganic salts as by-product or free of inorganic salts. Similar proportions of disulfonate or of the above sulfonated material are minimized, but some may be present. The monosulfonate is to be sulfonated at the end, or the sulfonate group can bind to carbon 2 or another carbon of the linear chain. Similarly, any concomitant disulfonate, typically produced using an excess sulfonating agent, may have sulfonate groups distributed on different paraffin base carbon atoms, and mixtures of monosulfonates and disulfonates may be included.

Mixtures of monoalkane sulfonates wherein the alkanes have 14 to 15 carbon atoms are particularly preferred, wherein the sulfonates are contained in a weight ratio of paraffins with 14 to 15 carbon atoms in the range of 1: 3 to 3: 1.

The olefin sulfonates useful in the detergent compositions of the present invention are mixtures of alkene-1-sulfonates, alkene hydroxy sulfonates, alkene disulfonates and hydroxy disulfonates and are described in US-A-3 332880 (PF Pflaumer & A. Kessler, issued July 25, 1967). ).

Suitable alkyl glyceryl ether sulfonates are derived from coconut oil and tallow ethers.

Other sulfate surfactants include N-acyl-N-alkylglucamine sulfates having from 9 to 17 carbon atoms in the acyl moiety and from 1 to 4 carbon atoms in the alkyl moiety, preferably from 9 to 17 carbon atoms in the acyl moiety, derived from coconut or palm kernel oil. These materials can be prepared by the method of US-A-2,717894.

The ion for the anionic surfactant may be any cation selected from sodium, potassium, magnesium, ammonium or alkanolammonium, and mixtures thereof. Sodium is the preferred counterion for the liquid detergent compositions of the present invention, but potassium is even more preferred when it is important that the compositions of the present invention are perfectly clear and have high resistance to clot formation.

In the gelled detergent compositions of the invention, sodium is more preferred than potassium or ammonium for gel formation. Preferred liquid cleaning compositions of the invention have a cloud point temperature of less than 8 ° C, preferably less than 5 ° C, and are at least partially neutralized with ammonium ions. (The cloud point temperature refers to the temperature at which inorganic salts precipitate as crystals in a liquid.)

If calcium and / or magnesium ions are present, they can be introduced either in the form of an oxide or hydroxide to neutralize the surfactant acid or added to the composition in the form of a water-soluble salt. However, the addition of a considerable amount of such salts to the dishwashing compositions of the invention raises the temperature at which inorganic salt crystals are formed in the detergent composition upon cooling, and the addition of such salts should therefore be minimized.

In preferred cleaning compositions. according to the invention mixtures of calcium and magnesium ions may be added to achieve up to 1% by weight of calcium ions, based on the cleaning composition as a whole, in particular 0.3 to 0.5% calcium ions and up to 1.5% by weight magnesium ions, in particular 0, 5 to 1.0% of magnesium ions. Preferred mixtures are magnesium-rich and the more preferred calcium to magnesium ion weight ratio is 1: 1 to 1: 4. and calcium ions are particularly suitable for very low water hardness conditions (less than 28.5 mg calcium carbonate equivalent per liter) and also for product concentrations greater than 0.5 weight percent

The second core builder-free liquid surfactant component is a compound of the formula:

R-C-N-R 1

Z where means ·

A polyhydroxy hydrocarbon moiety having a linear hydrocarbon chain having at least three hydroxyl groups bonded directly to the chain, the latter being derived from glucose and its mixtures with raaltose, the content by weight of

Μ maltose is not more than approximately 33% of the mixture,

R 1 is selected from the group consisting of saturated and unsaturated C 1 -C 16 alkyl groups and mixtures thereof, and R 1 is selected from the group consisting of C 1 -C 4 alkyl and C 2 -C 4 hydroxyalkyl.

The group R may be derived from any source of the hydrocarbon groups mentioned above in connection with the anionic surfactant, but preferably is of natural origin. The R group preferably has a mean chain length of 12 to 14 carbon atoms and is derived from coconut oil or palm kernel oil. Preferably R1 is methyl.

The preparation of glucamine compounds is known in the art and is not part of the present invention. As described above, a representative process for the preparation of N-alkanoyl-N-alkylglucamines having two major steps is described in US-A2 703798. The first step involves the reaction of glucose and a primary alkyl amine in the presence of hydrogen and a hydrogenation catalyst under elevated conditions. temperature and at elevated pressure to form glucamine. This glucamine is then reacted with the ester at an elevated temperature to form N-alkanoyl-N-alkylglucanain. It appears advantageous to add a low amount of sodium methoxide as a catalyst in this second step.

The preferred concentration of N-alkanoyl-A-alkylglucamine in the liquid or gel-formulated detergent compositions of the present invention is from about 8% to about 25%, in particular from about 9% to about 18%, and more preferably from about 10% to about 15%.

Physically stable purifiers The compositions of the invention may be formulated with calcium ions in the absence of magnesium ions, but require the use of high purity N-alkanoyl-N-alkylglucamines in which the concentration of unreacted starting materials, impurities and by-products, particularly fatty acids, is minimized.

Balancing of the liquid cleaning compositions of the present invention is possible with water or, in the case of gel-like compositions, with a gelling agent and water. However, preferred detergent compositions of the invention may also contain other functional ingredients and the content by weight of the mixture of anionic surfactant or anionic surfactants and glucamine components is 20 to 40%, especially 22 to 30%.

A highly desirable component is one or more suds modifiers or promoters, generally present in an amount of 1-8% by weight based on the weight of the cleaning composition as a whole.

Some of these substances also have additional functional significance, such as soil suspending agents. One such foam-promoting agent is an alkyl monoalkane amide or an alkyl dialkanolamide having from 10 to 16 carbon atoms in each of the alkyl moieties and from 2 to 3 carbon atoms in the alkanol moiety. Examples are coconut alkyl monoethanolamide, coconut alkyl diethanolamine and palm kernel and coconut alkyl monoisopropanolamide and alkyl diisopropanolamide. The palm kernel or coconut alkyl moiety may be either a full cut including a C 10 and C 16 fraction, or it may be a so-called narrow cut with a C 12 -C 14 fraction. Synthetic sources of C 10 -C 16 alkyl groups may also be used.

Other useful suds enhancers are zwitterionic surfactants of the formula

Rí

AND

R - (Y) n - N + - (R ₃₎ »Xi R ₂ wherein

R 1 is C 1 -C 16 alkyl,

R ₂ is alkyl having 1 to 3 carbon atoms,

R _{3 is a} group of formula

- (CH ₂ ) ₃ or - (CH ₂ -CH-CH ₂ )

OH

Y a group of formula

O

Η

- C - Ν - (CH ₂ ) ₃

Η m & n zero or 1 a

X- is CH2COO or SO3, provided that when X- is CH2COO, m is zero and when X1 is SO3, n is zero and m is 1.

In particular, R 1 is a group having a mean carbon chain length of 12 to 16 carbon atoms, which can be derived from synthetic sources, which may then have some branching or natural fats and oils, the chain being linear and may contain fewer proportions of 8 up to 10 carbon atoms and 14 to 18 carbon atoms. The synthetic sources for the R 1 group may be the same as above for the alkyl group of the anionic surfactant.

Another class of suds boosters useful in the present invention are amine oxides of the formula

R1R2R3N -> O where is

R 1 is C 1 -C 16 alkyl

R ₂ and R _{3 are} each independently C 1 -C 3 alkyl and C 2 -C 3 hydroxyalkyl.

Preferred members of this group are dimethyldodecyl amine oxide, dimethytetradecyl amine oxide, bis- (2-hydroxyethyl) dodecylamine oxide and analogues thereof, wherein their dodecyl or tetradecyl moieties are derived from natural sources such as coconut oil or palm kernel oil. Preferred foaming modifying agents are ethoxylated alcohol or mixtures of ethoxylated alcohols of defined composition.

The ethoxylated alcohol comprises an aliphatic alcohol ethoxylate having 6 to 13 carbon atoms, containing moderately 1.5 to 25, in particular 2 to 15, and most preferably 6 to 10 moles of ethylene oxide per mole of alcohol. The aliphatic alcohol ethoxylate contains no more than 1% by weight of nonethoxylated alcohol when the ethoxylated alcohol contains moderately less than 8 moles of ethylene oxide and no more than 2% by weight of nonethoxylated alcohol when the ethoxylated alcohol contains moderately 8 to 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. Natural fats or oils or Ziegler olefin synthesis or OXO synthesis products may be used as sources of the hydrocarbon chain, which may be linear or branched.

The alcohol chain length of 9 to 11 carbon atoms is preferred, since it has been found that the foam volume and foam characteristics of the detergent compositions of the invention are optimal when incorporating ethoxylates of such alcohols. It is also desirable for performance characteristics that the hydrophilic-lipophilic balance (HLB) of the ethoxylated alcohol be 8.0 to 17.0, especially 11.0 to 17.0, and especially 11.0 to 15.0. A preferred alcohol ethoxylate is a primary alcohol ethoxylate containing medium C 10 alkyl atoms condensed with medium C 8 ethylene oxide groups per mole of alcohol. <·

As mentioned above in connection with alkyl ethoxy sulfate as an anionic surfactant, the normal (basicly catalyzed) ethoxylation process to produce an intermediate degree of ethoxylation of E _v 6 results in the distribution of ethoxylated portions of 1 to 15 moles of ethylene oxide per mole of alcohol. The increase in E _av causes a certain change in distribution, essentially reducing the concentration of the nonethoxylated material, but the increase in E _av from 3 to 5 still leaves about 5 to 10% of such material in the ethoxylated product.

In the liquid dishwashing detergent composition of the present invention, this content of nonethoxylated material increases the problems of phase stability and freezing point temperature and / or results in a fatty alcohol odor product which is unacceptable to the consumer and cannot be masked by conventional perfumes for detergent compositions. It has been found that the maximum permissible content of nonethoxylated alcohol in the ethoxylated alcohol component is 1% by weight. In particular, it should be at most 0.7% and most preferably at most

0.5% of the non-ethoxylated alcohol, based on the ethoxylated alcohol component.

Vacuum distillation is used to remove the undesirable material, which also removes a portion of the monoethoxylated fraction with an increase in the E value _{and the} remaining material. According to a preferred embodiment of the invention, the monoethoxylate content by weight is not more than 5 based on the weight of the ethoxylated alcohol.

In the preferred cleaning compositions of the present invention, a suds modifying and promoting composition is used in an amount by weight of each component of 1 to 10%, preferably 2 to 8%. One such preferred composition is a mixture of C12 -C14 alkyldimethyl betaine and a C9 -C11 alcohol condensed with an average of 7-9 moles of ethylene oxide per mole of alcohol, each of which is present in an amount of 2 to 8% by weight. %, based on the cleaning agent as a whole.

In preferred cleaning compositions of the present invention, a hydrotropic component-water system is used for balancing, wherein the hydrotropic component may be urea, a C 1 -C 3 aliphatic alcohol, a lower alkyl benzene sulfonate or a lower dialkyl benzene sulfonate salt, for example a fluorosulfonate, xylenesulfonate or cumene sulfonate. Generally, one hydrotropic compound is sufficient to achieve the desired phase stability, but the detergent compositions of the invention preferably comprise a urea-alcohol-water mixture, an alcohol-lower alkylbenzene sulfonate-water mixture, a urea-lower alkylbenzene sulfonate-water mixture to achieve the desired viscosity. suitable casting characteristics. In the case of detergents having an organic active substance concentration of less than about 40% by weight, the preferred hyrotropic agent is ethanol, which is used in an amount of 3 to 10% by weight of the detergent composition as a whole, preferably in an amount of 4 to 8 %, generally in admixture with urea. In the case of cleaning compositions with an organic active ingredient concentration greater than about 40% by weight, mixtures of ethanol with urea and / or lower alkylbenzene sulfonate are preferred. Furthermore, mixtures of hyrotropic agents can be used for economic reasons without regard to considerations regarding the stability and viscosity of the detergent compositions of the present invention.

Optional components of the liquid cleansing compositions of the present invention include opacifying agents such as ethylene glycol distearate, thickeners such as guar gum, antibacterial agents such as glutaraldehyde and Bronopol (RTM), anti-conditioning agents such as benzoxytriazole, chelating agents for heavy metals such as ethylenediaminetetraacetic acid (EDTA) or ETDMF, perfumes and dyes. The pH of the detergent compositions of the present invention may be any one in the range of 6.0 to 6.5, but after preparation, the detergent compositions typically have a pH of 6.5 to 7.3, which is subsequently adjusted to achieve the desired pH of the finished detergent composition. In the case of colored detergents, a pH of 6.5 to 7.2 is preferred to maintain color stability.

The detergent compositions of the present invention can be produced in a variety of ways, but it is preferred to introduce any zwitterionic surfactants at the end of the manufacturing process as the last ingredient added. This minimizes the risk of any degradation of the zwitterionic surfactant under acidic conditions at the beginning of the manufacturing process and also facilitates the control of the viscosity of the final cleaning composition. The glucamine surfactant should not be exposed to a pH of less than 4 or more than 10 to prevent hydrolysis of the surfactant.

Thus, anionic surfactants can be prepared as aqueous solutions of an alkali metal salt or ammonium salt of pH 4 to 10, which are mixed with N-alkanoyl-N-alkylglucamine, followed by any ethoxylated nonionic surfactant and other foaming agents foaming foams. and a hydrotropic agent, after which any calcium or magnesium ions can be introduced in the form of a water-soluble salt such as chloride or sulfate. Any zwitterionic surfactant and components added in small amounts are then added at the same time as the pH and viscosity are adjusted. This method has the advantage of using known techniques and equipment, but introducing additional chloride and sulfate ions which may increase the turbidity temperature (i.e., the temperature at which the inorganic salts precipitate as crystals in the liquid).

In the preferred detergent compositions of the invention containing an alkyl ethoxy sulfate as an anionic surfactant, the desired alcohol and the alkanol ethoxylate may be mixed together, and one sulfation and neutralization may then be performed on the two materials. For this purpose, the alcohol and the alcohol ethoxylate should be mixed in a weight ratio of 4: 3 to 1: 6. According to the most preferred process, a single alcohol ethoxylate feed is prepared in which the concentration of alcohol and ethoxylated alcohol is controlled to achieve the desired ratio of these starting materials.

Any sulfating or sulfonating agent such as sulfur trioxide or chlorosulfonic acid can be used to sulfate or sulfonate the alcohol and alcohol ethoxylate. Neutralization of the alkyl ether sulfuric acid and the alkyl sulfuric acid is then carried out using a suitable alkali or magnesium or calcium or magnesium / calcium oxide or hydroxide slurry. If the amount of anionic surfactant is not sufficient to allow the addition of the desired amount of calcium and magnesium ions by this route, the remaining magnesium and calcium ions may be added in the form of a water-soluble salt.

The gel cleansing compositions of the present invention can be prepared as generally described in U.S. Patent 4,615,819.

The detergent compositions of the invention are characterized by low interfacial tension (IFT), which is an indication of the ability to emulsify greasy and oily Spina, high weight loss in the PPC test, which demonstrates the ability to remove greasy dirt from the surface and suspend dirt in solution with gentle effect on the skin. The combination of these properties is not known in the prior art liquid cleaning compositions.

In addition, the detergent compositions of the present invention exhibit higher foaming in both hard and soft water compared to prior art detergents.

The test procedures used to assess these parameters are described below.

1) Between Phase Voltage (IFT)

The interfacial tension is an indication of the ability of a surfactant sample to emulsify dirt under defined test conditions. A spinning drop tensiometer and a Model 500 Texas University strain gauge manufactured at the University of Texas Austin, Texas, United States are used to determine the interfacial voltage. Two devices are used. Model Site 04 of Kriiss GmbH, Vissenschaftliche Laboratorate, Borsteler Chausses 85-99a, D2000 Hamburg 61 FRG under conditions corresponding to the European dishwashing process. Measurements shall be carried out using a specimen at 48 ± 1 ° C using a 0,12% concentration of detergent; in water having a hardness corresponding to either 28.5 or 254.5 mg calcium carbonate equivalent per liter with a calcium to magnesium weight ratio of 3 = 1, on a molar basis. As model dirt, triolein having a purity of 99.7% (the remaining 0.3% being a mixture of free fatty acids) of Aldrich Chemical Company Ltd., New Road, Gillingham, Dorset, England is used. Results are recorded in Pa cm (1 Pa cm »10 dynes / cm).

2) Weight loss test of polypropylene cup (PPC)

The Polypropylene Cup (PPC) Weight Loss Test is a measure of the overall ability of a detergent to remove greases under conditions simulating manual dishwashing. The test involves measuring the amount of solid fats removed from the bottom of the polypropylene *

cup at a temperature below the melting point of the fats.

Oily dirt is prepared by mixing the following fats (percentages are by weight):

100% solid 100% vegetable fat (Spry CRISP NORY,

Van den Berghs, Burgess Hill, V. Sussex, England) and 30% liquid 100% corn oil (Mazzola Company

CPC (UK> Ltd .. Claygate House, Esher, Surrey, England) _____________________

The mixture is heated until miscible, then cooled and stored below 0 ° C. For use, approximately 150 ml of this fat is melted in a glass beaker and kept at a temperature of 0 ° C.

Fifteen clean, dry, 250 ml polypropylene cups are weighed and poured directly into the bottom of each cup.

fox 6,00 ± 0,03 g of fat without wetting the side walls. The cups are kept at 21 ± 1 ° C for 2 to 3 hours to solidify the fat.

Prepare a solution of 0.12 l of the test detergent at a temperature of 50 to 55 ºC and 100 ± 0,1 g into each of the five glass containers which are sealed with a wolf. The sealed containers are placed in a water bath in a constant temperature room and the water bath temperature is set to 45-46 ° C so that the temperature of the solution in each vessel is 43.8 ± 0.1 ° C. The procedure is similar for each detergent tested and for the standard detergent used for comparison.

The contents of the glass container are then poured into the cup along the side wall, taking care not to disturb the bottom fat, and then the cup is allowed to stand horizontal for 21 hours at 21 ° C before being transferred to an ice bath for 10 minutes. After cooling, a deposit line forms on the surface of the solution in the cup. This combination of spillage and subsequent cooling is performed for each cup and glass container. After 10 minutes, each cup is rapidly emptied and the inside of the cup is dried to remove any material adhering to the walls of the cup between the rim and the fat line. The cup is then placed upside down on the kitchen absorbent roll material to be emptied for 10-15 minutes before drying in the shoulder for two hours at 30 ° C and for an additional hour at 50 ° C. Then the cups are weighed again. The average weight difference between the original fat weight and the weight remaining! after the test, it is then calculated for five samples. This difference was divided by the weight difference obtained with the standard product to give a value that expresses the efficiency factor between the test product and the standard product. The products of the invention exhibit an efficiency factor of greater than about 1.3, preferably at least about 1.4.

For the purpose of the test, the standard product should have a fat removal efficiency at the same general level as the test product at the same concentration. This can be achieved by adjusting the weight ratio of liquid and solid grease composition so that the standard (reference) product provides 20-35% grease removal

The test sample may have a fat removal of 20 to 80.

3) Total foaming and foaming

Total foaming is the total volume of foam produced in the standard dishwashing test and is a measure of the foam's ability to form the detergent. Suds mileage is a measure of the amount of dirt required to reduce the foam of a test solution to a defined minimum under standard conditions of product concentration, temperature and water hardness. It expresses the observed useful life of the hand dishwashing solution. The foaming of the detergent composition under identical test conditions was obtained by using a prepared mixture of food soils and prepared fatty soils in the described mechanical foaming test method.

Test conditions Product concentration 0.12¾ Water temperature 45 C Water hardness corresponding to either 28.5 or 254.5 mg calcium carbonate equivalent per liter

Rice / Chopped / Egg Food Mix Real food x 392 g meat roast with onion ¹ x 439 g rice pudding ² eggs ml 2¾ mixed fatty acids (MFFA) in corn oil * ml corn oil Grease dirt cake mixed slurry 30 g sponge mix ³ g 2 MFFA in corn oil * ........-..............____________ _____________ __________ __________________ ¹ Master Foods product, Kings Lynn, Norfolk, England ² company product Ambrosia Creamery, Lifton, Devon, England ³ product by McDougalls Catering Foods Ltd, Imperial VayVarton Grange, Reading, England * 4 g oleic acid, 4 g linoleic acid, 2 g acid

stearic acid, 5 g palmitic acid, 735 g pure corn oil

Test method

Four cylinders of 300 mm in length and 100 mm in diameter are used side by side and rotate around the central axis at 24 revolutions per minute. Each cylinder is filled with 500 ml of a 0.12% solution at 48 C. The outer two cylinders serve one of the products being compared and the inner two cylinders serve another product.

The rollers are allowed to rotate for 2 minutes, stopped and the initial foam is measured, and then a portion of dirt is typically added in 2 ml aliquots. After 1 minute, the rollers are again rotated and the rollers are allowed to rotate for 1 minute. The height of the foam is recorded and 2 ml of dirt is added to each roll. After 1 minute, the rollers are started again. This process is continued until the height of the foam in the cylinder drops below 6 mm. The sum of all measured foam heights in each test (i.e., until the foam height drops below 6 mm) constitutes the total foam measured.

One product is designated as a control and the foam and foaming index values are calculated for the other products in relation to the control product as follows:

Foam index of the test product = total foam of the test product

----—— x 100 total foam of control product

Suds Mileage of the test product = number of dirt additions to the test product to reduce foam height below 6 mm ____________ a -—-) - ._________________________ _______________ _ - .X 100 number of dirt additions to the control product to reduce foam height below 6 mm

The invention is illustrated in more detail by the following examples

Examples of the invention o

Example 1

A variety of core surfactant systems are prepared comprising a mixture of an alkyl ethoxy sulfate surfactant and N-lauroyl-N-methylglucamine. Alkyl ethoxysulfate is derived from a C 12 -C 14 primary alcohol condensed with an average of 0.8 moles of ethylene oxide per mole of alcohol and neutralized with a mixture of ammonium and magnesium ions to a content of 0.22 moles of magnesium per mole of alkyl ethoxysulfate. The reagents are first prepared in distilled water. A 0.12% by weight solution of this product is then formed either in soft water (hardness equivalent to 28.5 mg calcium carbonate equivalent per liter) or in hard water (hardness equivalent to 254.5 mg calcium carbonate equivalent per liter) and tested. with respect to IFT and in water having a hardness corresponding to a content of 28.5 mg calcium carbonate equivalent per liter with respect to PPC greasy dirt removal using the methods described above. This procedure is performed for the ratio of alkyl ethoxysulfate (AES) to alkylglucamine (GA) 100 0, 75-25, 65 = 35, 50: 50, 25 = 75 and 0 = 100, the results are shown in the following table.

IFT (Pa.cm) Weight ratio AES = GA Water hardness 100 = 0 75 = 25 65 = 35 50 = 50 25 = 75 0 = 100 28.5 mg CaCO 3 0.35 0.12 0.12 0.14 0, 16 0.10 254.5 mg CaCO ₃ 0.21 0.09 0.07 0.12 0.06 0.07 PPC 28.5 mg CaCO 3 1.00 - 1.60 1.50 - 1.30 From these values it is obvious that - Addition of alkylglucamine to of anionic surface active reagents substantially improves emulsion

of the fat, as evidenced by the IFt values of the greasy dirt treatment, as evidenced by improved PPC soil removal values.

The above co-surfactant mixtures are also evaluated for overall foam height and suds mileage using the methods described above. However, the results are not compared with the comparative product, but are directly reported as total foaming / suds / suds mileage).

In the first paragraph, the letters have the following meaning:

A hardness equivalent to 28.5 mg calcium carbonate equivalent per liter. a real pin of food

B oily pin

C hardness equivalent to 256.5 mg calcium carbonate equivalent per liter, actual Spina from food

D oily 100 = 0 dirt Weight ratio AES = GA 0 = 100 95 = 5 90 = 10 75 = 25 65 = 35 50 = 50 AND 260 / 5.0 6.5 416 / 7.5 567/10 657/10 604 / 10.5 458 / 10.0 (B) 4.5 / 4.5 277 / 4.8 333 / 5.5 407 / 8.0 524 / 8.5 355 / 6.5 100 / 2.0 C 300 / 5.5 415 / 6.8 498 / 8.0 595 / 9.5 600 / 9.7 621/10 400 / 10.0 D 302 / 4.8 316 / 5.0 369 / 6.0 380 / 6.0 348 / 5.5 283 / 4.7 64 / 1.0

From the assessment of both greasy soil removal and foaming under greasy soil loading conditions, it is clear that the preferred blend ratio for both greasy soil removal and foaming is the ratio of 75-25 alkyl ethoxysulfate = alkylglucamine to 50 '50 alkyl ethoxysulfate · alkylglucamine with optimum results at a ratio of 65 = 35-100%, the alkylglucamine system provides comparable fat removal values but a severe overall foaming and foaming deficiency especially under greasy dirt conditions.

Example 2

The following detergent compositions A to E are prepared = composition A is a comparable commercial liquid dishwashing detergent composition, while compositions B, C, D and E are in accordance with the invention.

Cn.e linear alkyl- AND (B) C D E benzensu1f onát 6.5 - - - - N-Cocoylkanoyl-N-methyl 1- glucamine - 12.5 ίο, n 0.0 12.3 C 12-13 alkyl (E10), sulfate 20.5 11.0 15.0 '16 .0 10.0 C 12-13 alkyl (C 1-3) sulfate - - . - - 2.7 primary alcohol ethoxylate ¹ 4.0 6.0 4.0 8.0 7.0 magnesium and onty 0.35 0.20 0.25 0.5 -

23 - C12-1448 imidylbetaine 1.5 4.0 3.0 kokomonoethano1am i d 3.8 - - C 12-14 alkyl dimethylamine oxide - - 4.0 paint umkumensu1f oná t 1.0 1.0 2,0 ethano1 4,5 5.0 5.0 urea 0.5 - - water «3 O 100 ALIGN! ¹ predominantly 1 and non-linear mixture s 9 to 11 atoms t

2,0

2,0

5.0

2,0

2,0

5.0 moderately 10 ethylene oxide units per mole of alcohol and containing less than 2% by weight of nonethoxylated alcohol

IFT, PPG and foaming values have been determined for all detergents and are as follows:

IFT (Pa.cm)

Water hardness AND (B) C D E 28.5 mg CaCO 3 0.15 0.08 0.08 0.09 0.03 254.5 mg CaGlZb 0.11 0.06 0.06 0.07 0.09 PPC 28.5 mg CaCO 3 1.00 1.60 1.70 1.70 ON

total foaming

mixed dirt Water hardness AND (B) C D E 28.5 mg CaCO3 100/100 189/167 186/170 135/128 142/129 254.5 mg CaCCb 100/100 145/140 177/153 121/119 138/150 greasy dirt 28.5 mg CaCO3 100/100 132/129 130/132 123/122 150/150 254.5 mg CaCO 3 100/100 95/113 98/115 108/107 102/99 Industrial applicability Aqueous, effective and strong foaming liquid or gelový čist icí pro-

Builder-free medium in the form of a physically stable aqueous solution, suitable for washing dishes and hard surfaces --------------------

Claims (21)

PATENTOVÉ A builder-free liquid or gel-like detergent composition in the form of a physically stable □ aqueous solution, characterized in that it contains from 15 to 65% by weight of the composition as a whole, core surfactant compositions containing by weight (a) 5 to 95% of a mixture of at least one water-soluble anionic surfactant sulphate or sulphonate salt b) 95 to 5% of a mixture of at least one compound of the formula R-CON-Ri Z where means A linear hydrocarbon chain polyhydroxy hydrocarbon moiety having at least three hydroxyl groups bonded directly to the chain, said moiety being derived from glucose and mixtures thereof with maltose, the maltose content by weight being at most 33 based on the mixture. R is a saturated or unsaturated alkyl group having 8 to 16 carbon atoms or a mixture thereof; and R1 alkyl having 1 to 4 carbon atoms and hydroxyalkyl having 2 to 4 carbon atoms, wherein a 0.12¾ by weight aqueous solution of a surfactant composition of this composition has a water hardness equivalent to 28.5 mg calcium carbonate equivalent per liter with a calcium ratio to magnesium 3 = 1 and a temperature of 48 ° C i> the interfacial voltage drop (IFT) less than about 0.2 Pa cm using tri-oline dirt with a purity of 99.7¾. (ii) a greasy soil removal value in a polypropylene cup (CPPC) assay of at least about 1.4 times the value obtained in the same assay under the same conditions using a 0.12µ solution of at least one anionic surfactant alone. * Liquid or gel detergent composition according to claim 1, characterized in that. That the polyhydroxy hydrocarbon moiety as component (b) is derived from glucose and mixtures thereof with maltose, said mixture containing not more than 25% maltose by weight. Liquid or gel detergent composition according to claim 1, characterized in that it contains 20 to 50% by weight of the mixture of core surfactants. 4. A liquid or gel detergent composition according to claim 3 comprising from about 22% to about 40% by weight of the core surfactant mixture. 5. A liquid or gel detergent composition according to claim 1 wherein the core surfactant mixture comprises 20 to 80% by weight of component (a) and 80 to 20% by weight of component (b). 6. A liquid or gel detergent composition according to claim 1 wherein the core surfactant mixture comprises 40 to 70% by weight of component (a) and 60 to 30% of component (b). 7. A builder-free liquid or gel cleanser composition in the form of a physically stable aqueous solution according to claim 1 comprising 20 to 50% by weight of the composition as a whole of a core surfactant composition containing by weight (a) 5 to 95% of a mixture of at least one water-soluble anionic surfactant selected from the group consisting of C 10 -C 16 alkyl ethoxy sulfates containing up to 6 moles of ethylene oxide per mole of C 10 -C 18 alkyl ethoxy ether sulfonates , C 10 -C 16 paraffin sulphonates, C 9 -C 17 acyl-N-alkylglucamine sulphates and C 1 -C 4 alkyl acyl and any mixtures thereof, υ 50 < what σ> 7Ζ. D co 1 '* O <m < to i · »o re σ O 05 / c / x IC r— O Λ. o n b) 95-5 t of a mixture of at least one compound of the formula R-CON-R 1 Z where means Of polyhydroxyhydrocarbon, derived from glucose and mixtures thereof with maltose, the maltose content by weight not exceeding 25% of the mixture. R is selected from the group consisting of a saturated or unsaturated alkyl group having 8 to 16 carbon atoms, or a mixture thereof, and R 1 is C 1 -C 4 alkyl or C 2 -C 4 hydroxyalkyl. a 0.12¾ by weight aqueous solution of a surfactant composition of this composition has a water hardness corresponding to a content of 28.5 mg calcium carbonate equivalent per liter with a calcium to magnesium ratio of 3 J 1 and a temperature drop of 48 C t> Pa.cm using triolein dirt with a purity of 99.7¾. (ii) a greasy dirt removal value in the polypropylene cup test (CPPC) of at least 1.4 times the value obtained in the same test under the same conditions using a 0.12 µl solution of at least one anionic surfactant alone. Liquid or gel cleaning composition according to claim 7, characterized in that. The composition of claim 1, wherein the composition comprises from about 22% to about 40% by weight of the core surfactant mixture. 9. A liquid or gel detergent composition according to claim 7, wherein the core surfactant mixture comprises 20 to 80 &lt; 3 &gt; of the component Ca) and 80 to 20 &lt; 3 &gt; of the component Cb). 10. A liquid or gel detergent composition according to claim 7 wherein the core surfactant mixture comprises from 40 to 70% by weight of component (Ca) and up to 30% of component (b). 11) a PPP value of at least 1.4 times the value obtained in the same test under the same conditions using a 0.12% solution of at least one anionic surfactant alone. 21. A detergent composition according to claim 1 comprising a mixture of nonionic and anionic detergent surfactants, wherein the nonionic surfactant is a polyhydroxy fatty acid amide selected from the group consisting of N-acyl-N-alkylglucamine sulfates of 9 to 17 atoms % of an acyl moiety having from 1 to 4 carbon atoms in an alkyl moiety. 22. The detergent composition of claim 21 additionally comprising a suds booster additive selected from alkanolamides, betaine surfactants, sulfobetaine surfactants, amine oxide surfactants, and mixtures thereof. A liquid cleaning composition according to claim 21. A dishwashing liquid composition according to claim 22. 25. A dishwashing liquid composition according to claim 22 further comprising calcium ions, magnesium ions, or mixtures thereof. A method of washing dishes, comprising contacting the dishes with a water bath containing the liquid dishwashing composition of claim 21. A liquid or gelled detergent composition according to claim 7, wherein component (a) comprises a C 12 -C 14 primary alkyl ethoxy sulfate surfactant having an average of at most 1.5 ethoxy groups per mole of alkyl ethoxy sulfate. 12. A liquid or gel detergent composition according to claim 7, wherein component (a) comprises a primary alkyl ethoxy sulfate surfactant having 12 to 14 carbon atoms in the alkyl moiety and having a moderate 0.4 to 1.0 ethoxy groups per mole of alkyl ethoxy sulfate . 13. A liquid or gel detergent composition as claimed in claim 7, comprising magnesium ions in an amount of up to 1.5% by weight of the composition as a whole. 14. A liquid or gel detergent composition according to claim 7 comprising calcium ions in an amount of up to 1.0% by weight of the detergent composition as a whole. Liquid or gel cleaner according to claim 7, characterized in that the suds booster is selected from the group consisting of alkyl monoalkanolamides and alkyl dialkanoamides having in each case 10 to 16 carbon atoms in the alkyl portion and in each case having 2 to 3 carbon atoms in the alkanol portion. alkylsulfobetaines having 12 to 16 carbon atoms in the alkyl moiety, alkyldialkylamine oxides having 10 to 16 carbon atoms in the first alkyl moiety and having 1 to 4 carbon atoms in the second alkyl moiety, or alkyl dihydroxyalkylamine oxides having 10 to 16 carbon atoms in the alkyl moiety and having 2 to 4 carbon atoms in hydroxyalkyl moieties, primary alcohol ethoxylates having from 9 to 12 carbon atoms in the alcohol moiety and having moderate 7 to 12 ethylene oxide groups per mole of alcohol, and mixtures thereof. , ι.> 16, confines 8.5. 16. A builder-free liquid cleaning composition in the form of a physically stable aqueous solution according to claim 1, characterized in that it comprises from 20 to 50% by weight of the composition as a whole. Core surfactant compositions containing by weight a) 40 to 70% of a mixture of at least one water-soluble anionic surfactant selected from the group consisting of C 10 to C 16 alkyl ethoxy sulfates containing up to 6 moles of ethylene oxide per mole of alkyl ethoxy sulfate. C 10 -C 18 alkyl glyceryl ether sulfonates, C 10 -C 16 paraffin sulfonates, C 9 -C 17 acyl N-alkylglucamine sulfates and C 1 -C 4 alkyl groups, and any mixtures thereof. b> 60 to 30% of a mixture of at least one compound of the formula R - CON - R 1 AND Z where means A polyhydroxy hydrocarbon moiety derived from glucose and mixtures thereof with maltose, the maltose content by weight being not more than 5 per mixture, R is a saturated or unsaturated alkyl group having 8 to 16 carbon atoms or a mixture thereof; and R1 has a C1-C4 alkyl group or a C2-C4 hydroxyalkyl group, and the composition contains from 2 to 8% by weight each as a foaming agent of betaine and a primary alcohol condensed with an average of 7-9 phol moles of ethylene oxide per mole alcohol, a 0.12¾ by weight aqueous solution of a surfactant composition of this composition has a water hardness equivalent to 28.5 mg calcium carbonate equivalent per liter with a 3: 1 calcium to magnesium ratio and a temperature of 48 ° C (i) an interfacial voltage decrease (IFT) of less than 0,2 Pa.cm using a trilineine dirt of purity of 99,7 $; (ii) a grease spinning value in a PPC at least approximately 1,4-fold with respect to to a value obtained in the same test under the same conditions using a 0.12% solution of at least one anionic surfactant alone. 17. A liquid cleaning composition according to claim 16, wherein: The composition of claim 1, further comprising a hydrotropic additive selected from the group consisting of urea, a C 1 -C 3 aliphatic alcohol, a lower alkyl benzene sulfonate, a lower dialkyl benzene sulfonate, and mixtures thereof. 18. Liquid He's lurking here. 19. A liquid detergent composition according to claim 16 comprising an opacifying agent supplying composition according to claim 16 having a pH of 6.0 to 5.0. 20. A builder-free liquid detergent composition in a physically stable aqueous solution as claimed in claim 1 comprising 20 to 50% by weight of the composition as a whole of core surfactant compositions containing by weight. (a) 40 to 70% of a mixture of water-soluble C 10 to C 16 alkyl ethoxy sulphates containing up to 6 moles of ethylene oxide per mole of alkyl ethoxy sulphate; b) 60 to 30% of a mixture of at least one compound of the formula R - CON - Rj -------------------------------- -------------------------------------------------- ------ Z where means A polyhydroxy hydrocarbon residue derived from glucose and a mixture thereof with maltose, the maltose content by weight not exceeding 5%, based on the mixture, A linear or substantially linear C 12 -C 14 alkyl group; R 1 is a methyl group, and the composition comprises 0.3 to 0.5% by weight of calcium ion and 0.5 to 1.0% by weight of magnesium ion, and in each case 2 to 8% by weight, as a suds booster of betaine and primary alcohol. condensed with moderately 7 to 9 mol% ethylene oxide per mole of alcohol, a 0.12% by weight aqueous solution of the surfactant composition of this composition having a water hardness equivalent to 28.5 mg calcium carbonate equivalent per liter at a calcium to magnesium ratio of 3 = 1 and 48 ° C (i) an interfacial voltage drop (IFT) of less than 0,2 Pa-cm using 99.7% purity triolein dirt, 2 ¹ ?. A method of washing dishes, characterized by. wherein the dishes are contacted with a water bath containing the liquid dishwashing composition of claim 22.