HUT73758A - Manual dishwashing composition comprising lipase enzymes - Google Patents

Description

Priority: 08.08.1993 (EP 93870163.8)

International Application Number: PTC / US94 / 08415

International Publication Number: WO 95/04808

The present invention relates to a hand dishwashing detergent composition comprising lipase enzymes and a surfactant system. This formulation foams well and does not contain builder salts and bleach components. However, it contains an enzyme stabilization system, antifoaming agents, product stability ions, etc. This detergent may be in liquid or gel form. The pH of a 1% w / w solution is adjusted to 6-9.

The hand dishwashing detergents of the present invention can be used in hand dishwashing methods such as sink, dishwasher and direct application.

61 969 / BE

· S.B.G

International

PUBLISHED

Hand dishwashing liquid containing lipase enzymes

THE PROCTER & GAMBLE COMPANY, CINCINNATI, Ohio, US

Inventor:

GOLDSTEIN Alan Scott, BLUE ASH, OH, US

Date of filing: 22.07.1994

Priority: 10.08.1993. (EP 93870163.8)

International Application Number: PCT / US94 / 08415

International Publication Number: WO 95/04808

The manufacturer of a hand dishwashing detergent composition is faced with the many challenges of meeting different consumer demands for timely performance.

In a hand dishwashing process, such a preparation must primarily be effective in removing impurities from the dirty dishes. The term "utensils" is used here in a generic sense and can basically include all kinds of items found in a dishwasher, including porcelain, glass, plastic pots, hollow-ware and cutlery, including silverware.

The contaminants we need to consider when washing dishes are largely, but not exclusively, food-based. Particularly difficult to remove impurities are greasy impurities, burnt food impurities, very colored impurities such as: very colored vegetables such as beets and tomatoes, and non-food impurities such as lipstick on the edges of glasses or ashtrays. come.

If the dishes have already been removed from the dishes, the dishwashing liquid must work so that these

It is suspended in the dishwashing solution and thus prevents it from re-depositing on the dishes or on the sink surface.

However, since good soil removal and anti-rusting effects are a common performance requirement for dishwasher formulations, the hand dishwasher manufacturer will also have to meet other performance requirements.

For example, hand dishwashing detergent should be well foaming and the foaming should remain throughout the washing process. The person washing will use foaming as an indicator to indicate that the washing solution still contains active ingredients in the dishwashing liquid. When the foaming subsides, the sink is usually emptied and fresh washing solution is prepared. In the industry, the foam durability during the washing process is measured by various foam performance indices.

Hand dishwashing detergents should also be skin-friendly, especially hand-washable. That is, it will not cause dry skin, peeling or roughness, which is largely due to the removal of natural oils from the skin. Thus, hand dishwashing detergent compositions should desirably be effective in removing grease from the plates, but not in removing natural oils from the skin.

A hand dishwashing detergent reflects the needs of a different nature to form such compositions in different ways, such as dishwashing detergent, detergent and hard surface cleaning compositions.

Hand dishwashing detergent formulations are usually non-floating and may contain amounts of calcium and magnesium added to aid in cleaning performance. Detergents and automatic dishwashing detergents typically contain large amounts of builders.

Hand dishwashing detergent typically contains a large amount of a high-foaming surfactant and often an antifoaming agent. Machine detergents and detergents are desirably reduced • ·

........

they are frothy and typically contain less surfactant.

Hand dishwashing detergent formulations are formulated to provide good performance near neutral pH. Machine dishwashing detergents and laundry compositions are typically alkaline, usually at a pH of 9 to 11, and hard surface cleaning compositions are often acidic, at a pH of less than 6.

The active key component of a hand dishwashing detergent composition is most commonly a surfactant system, typically comprising 5 to 80% by weight of the composition. The surfactant system is primarily for the purpose of removing dirt and also plays a role in suspending the impurities in solution and preventing the re-deposition of these impurities. The surfactant system must be particularly effective in removing and suspending greasy impurities.

It is a common perception that dishwashing liquid is essentially a surfactant solution with some other insignificant ingredients. This view seems to be exemplified by the recent Market Report on Detergent Products by EIU, Retail Business No. 409, March 1992, in which the amount of surfactant in a product is essentially used as an indicator of product quality.

Enzymes are common ingredients in laundry and dishwashing detergent formulations. Such formulations are common constituents of amylolytic and proteolytic enzymes. The utility of enzymes in hand dishwashing detergent formulations is not generally recognized.

Lipolytic enzymes or lipases work by hydrolyzing fats or oils containing glycerol and fatty acid esters to these glycerol and fatty acid constituents. Prior art teaches the use of lipolytic enzymes in laundry and dishwashing detergent formulations, most commonly in combination with coenzymes such as amylolytic and proteolytic enzymes.

Applicants have recognized the value of including lipolytic enzymes in formulations specifically formulated for hand dishwashing. Previously, the use of lipolytic enzymes in such formulations has not been accepted in the art. In fact, the science of using such enzymes in dishwashing detergent formulations seems to include a prejudice against the use of these enzymes in hand dishwashing detergents, but neglects to provide a clear instruction on their use in hand dishwashing.

Deep down in this veiled prejudice, it is a well-known conviction that handwashing detergents help degrease. Because high concentrations of surfactant remove fat, it is believed that adding a fat hydrolyzing enzyme would not be useful. A further reason for the implicit prejudice is the belief that fatty acid products obtained from the breakdown of fats or oils may act as an antifoam, thereby threatening the desired high foaming performance.

Applicants also stated that lipolytic en • · ·

zim is a particularly useful ingredient in a hand dishwashing detergent composition containing certain surfactant systems which act to stabilize the enzyme in liquid formulations.

In one aspect of the invention there is provided a composition comprising a surfactant system and a lipolytic enzyme suitable for use in a hand dishwashing process.

Preferably, said composition is highly foaming.

Preferably, said composition is in liquid or gel form.

Preferably said composition does not contain builder salts.

Preferably, said composition does not contain bleach components.

Preferably, said composition comprises from 5% to 80% by weight of said surfactant system, wherein said surfactant system comprises a surfactant selected from nonionic, anionic, cationic, zwitterionic, ampholytic or amphoteric surfactants.

A 1% w / w solution of said composition preferably has a pH of 6 to 9.

The composition may be formulated so as not to contain other enzyme components.

According to the invention, the first essential ingredient of the compositions is a lipolytic enzyme (lipase), which is preferably 0.001 to 2% by weight of the compositions, more preferably 0.01 to 1% by weight, most preferably 0.05 to 0.5% by weight. is present in amounts of active lipolytic enzyme.

Preferably, the lipase is of bacterial origin, such as Humicola sp. or Thermomyces sp. or a lipase producing strain of Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens.

Lipase obtained from chemically or genetically modified mutants of these strains may also be included. Lipase mixtures from different strains may also be included, although not preferred.

Another preferred lipase of the invention is obtained by cloning a gene obtained from Humicola lanuginosa and expressing the gene in Aspergillus oryza as a host, as disclosed in EP-A-0258 068, commercially available under the trade name Lipolase under Novo Industri A. Available from / S, Bagsvaerd, Denmark. This lipase is disclosed in U.S. Pat. P. 4,810,414 (Huge-Jensen et al).

The lipases of the invention are preferably compatible with the surfactants. Preferably, they are stable in the presence of the compositions of the invention and improve purification when incorporated into the compositions of the invention.

Suitable lipases which exhibit a positive immunological cross-reaction with a lipase antibody produced by Pseudomonas fluorescence. These lipases are disclosed in Japanese Patent Publication No. 53-20487, published February 24, 1987. It is available under the Lipase P Amano brand. An immunoassay for Amano P antibody immunoassay is described in U.S. Pat. P. 4,707,291 to Thom et al.

lik.

A lipase unit (LU) is defined as the amount of lipase that produces 1 pmol of titratable butyric acid per minute at a pH of 7.0, a temperature of 30 ° C and a substrate for ributyrin and gum arabic, calcium ions and sodium chloride. emulsion in phosphate buffer.

The compositions according to the invention contain from 5 to 80% by weight, preferably from 10 to 60% by weight, most preferably from 15 to 50% by weight of a surfactant system.

Preferably, the surfactant system is formulated to be compatible with the lipolytic enzyme. Most preferably, the surfactant system in liquid or gel formulations is formulated to promote or at least not impair the stability of the lipolytic enzyme in these formulations.

The surfactant system comprises a surfactant selected from nonionic, anionic, cationic, zwitterionic, ampholytic, amphoteric surfactants, or mixtures thereof.

The surfactant system is preferably by weight

It contains from 5 to 90% by weight, more preferably from 30 to 70% by weight of anionic surfactant and from 5 to 60% by weight, more preferably from 15 to 50% by weight of nonionic surfactant.

The anionic surfactant can be essentially any anionic surfactant, including sulfate anionic, sulfonate or carboxylate surfactant.

The sulfate anionic surfactant can be any organic sulfate surfactant. This is preferably a C10-C16 alkyl ethoxylated with about 0.520 mol / molecule of ethylene oxide.

selected from the group consisting of sulfates, C 9 -C 17 sulfated acyl-N- (C 1 -C 4 alkyl) glutamine, -N- (C 2 -C 4 hydroxyalkyl) glutamine sulfate, and mixtures thereof. More preferably, the sulfate anionic surfactant is a C 10 -C 16 alkyl sulfate ethoxylated with about 0.5 to about 20, preferably about 0.5 to about 12 moles, per molecule of ethylene oxide.

The alkyl ethoxysulfate surfactant contains primary alkyl ethoxysulfate derived from a condensation product of a C 10 -C 16 alcohol with an average of from about 0.5 to about 20, preferably from about 0.5 to about 12, ethylene oxide. The C10-C16 alcohol itself is commercially available. Preferred is C12-C14 alkyl sulfate ethoxylated with about 3 to about 10 moles per molecule of ethylene oxide.

To obtain an average of 12 degrees of ethoxylation, conventional base-catalyzed ethoxylation processes result in a unique ethoxylate distribution in the range of 1 to 15 ethoxy groups / mol of alcohol, so that the desired average can be obtained in several ways. Mixtures may be prepared from materials of varying degrees of ethoxylation and / or special ethoxylation technology employed and subsequent treatment steps such as distillation.

Sulfate anionic surfactants include C 9 -C 17 acyl-N- (C 1 -C 4 alkyl) - and -N- (C 1 -C 2 hydroxyalkyl) glucamine sulfates, preferably those in which the C 9 -C 17 acyl group is derived from coconut or comes from palm kernel oil. These materials are disclosed in U.S. Pat. P. 2 717 894 (Schwartz).

···· ·· _Μ • · · · · ·

For the sulfate anionic surfactant, the counterion is preferably selected from calcium, sodium, potassium, magnesium, ammonium or alkanolammonium and mixtures thereof, with calcium and magnesium being preferred for purification and foaming.

Suitable anionic sulfonate surfactants for use in the present invention include basically any sulfonate surfactant, including, for example, C9-C20 linear alkylbenzene sulfonates, C8-C22 primary or secondary alkane sulfonates, C8-C24 olefin sulfonates, sulfonated polycarboxylic acids, salts of glycerol sulfonates, fatty acylglycerol sulfonates, fatty oleylglycerol sulfonates, paraffin sulfonates and any mixtures thereof (e.g., alkali metal salts).

Anionic Alkyl Ethoxycarboxylate Surfactants - Alkyl ethoxycarboxylates suitable for use in the present invention include compounds of the formula RO (CH ₂ CH ₂ O) _X CH ₂ COO M ⁺ wherein R is C 12 -C 16 alkyl, x and the ethoxylate partition by weight is such that the amount of material for which x is 0 is less than about 20%, preferably less than about 15%, most preferably less than about 10%, and wherein x is greater than 7, less than about 25%, preferably less than about 15%, most preferably less than about 10%, x having an average value of from about 2 to about 4 when R has an average of 13 carbon atoms or less, and x has an average value of about 3 to 6 if the R group has an average of 13: ..........

··· · · »·· • ··· ···· ..

and M represents a cation selected from alkali metals, alkaline earth metals, ammonium, mono-, di- and triethanolammonium, most preferably sodium, potassium, ammonium and mixtures thereof with magnesium ions. Preferred alkyl ethoxycarboxylates are those wherein R is C12-C14 alkyl.

Anionic alkyl polyethoxypolycarboxylate surfactants

Suitable alkyl polyethoxypolycarboxylates for use in the present invention include compounds of formula (I) wherein:

R is C 6 -C 18 alkyl, x is 1 to 25,

H Rj ^ and _R2 groups, methyl acid radical, selected from succinic acid, hydroxy succinic acid radical, and mixtures thereof, at least one of R _x or R ₂ group is a succinic acid radical or hydroxy succinic acid radical, and R ₃ -at which hydrogen, C 1 -C 8 substituted or unsubstituted hydrocarbons or mixtures thereof.

Anionic Secondary Soap Surfactants - Secondary soap surfactants (aka alkylcarboxylic surfactants) useful in the present invention are those containing a carbonyl unit attached to a secondary carbon atom. It should be noted that the secondary carbon atom may be in a ring structure such as p-octylbenzoic acid or substituted alkylcyclohexylcarboxylates. Secondary soap surfactants must not contain etheric linkages or ester linkages

or hydroxyl groups. There should be no nitrogen atoms in the main group (amphiphilic moiety). Secondary soap surfactants generally contain a total of 11 to 13 carbon atoms, although slightly more (e.g., about 14 to 16) may be tolerated if the soap contains a ring structure such as p-octylbenzoic acid, as noted above.

Some of the secondary soap surfactants (or their precursor acids) useful in the present invention are further illustrated by the following general structures.

A. A very preferred group of secondary soaps for use in the present invention comprises secondary carboxylic compounds of the formula R ³ CH (R ⁴ ) COOM wherein R ³ is CH ₃ (CH ₂ ) _X and R ⁴ is

CH ₃ (CH ₂ ) _y , wherein y may be an integer from 0 to 1 to 4, x is an integer from 4 to 10, and (x + y) is from 6 to 10, preferably from 7 to 9, most preferably 8.

B. Another class of secondary soaps useful in the present invention include carboxylic compounds wherein the carboxyl substituent is on a cyclic hydrocarbon moiety, i.e., secondary soaps of the formula R ⁵ -R ⁶ -COOM wherein R ⁵ is C 7 -C 10, preferably C 8 -C 9 alkyl or alkenyl; and R ^{6 is} a ring structure such as benzene, cyclopentane and cyclohexane. (Note: R ⁵ may be ortho, meta or para to the ring relative to the carboxyl group.)

C. Another group of secondary soaps a

CH ₃ (CHR) _k - (CH ₂ ) _m - (CHR) _n -CH (COOM) (CHR) _o - (CH ₂ ) _p - (CHR) _q -CH ₃

containing secondary carboxylic compounds of the formula wherein each R is a C 1 -C 4 alkyl group wherein k, n, o, q are integers from 0 to 8, provided that the total number of carbon atoms (including the carboxylate) is 10- It is in the range of 18.

In each of the foregoing formulas A, B and C, M may be any suitable counterion, particularly water-soluble, such as hydrogen, alkali metal, alkaline earth metal, ammonium, alkanolammonium, di-, trialkanolammonium and C 1-5 substituted alkylammonium . Sodium is as suitable as diethanol ammonium.

The water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid are preferred secondary surfactants for use in the present invention. can be selected from a group.

Other anionic surfactants useful for cleaning purposes may also be included in the compositions of the present invention.

These may be soaps, fatty oleyl glycerol sulfates, (alkyl phenol) ethylene oxide ether sulfates, alkyl phosphates, izetio- sodium such as acyl isethionates, N-acyl taurates, methyl- tauride fatty acid amides, alkyl succinic acid and sulphonated

succinates (especially saturated and unsaturated C12-C18 monoesters), sulfosuccinate diesters (especially saturated and unsaturated C6-C14 diesters), N-acyl sarcosinates, sulfates of alkyl polysaccharides such as alkyl polyglycoside * ·· * e · Sulfates (here nonionic non-sulfated compounds), branched primary alkyl sulfates, alkyl polyethoxycarboxylates such as RO (CH ₂ CH ₂ O) _k CH ₂ COO-M ^{+ in} which R is 8-22 C is alkyl, k is an integer from 0 to 10, and M is a water-soluble salt cation, and salts of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and trietanolaminokat). Resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin and resin acids and hydrogenated resin acids present in or derived from tall oil may also be used. Further examples are provided by Schwartz, Perry and Berch in Surface Active Agents and Detergents I and II. Vol. USP 3,929,678 (Laughlin et al) also discloses a number of such surfactants in general from column 23, line 58 to column 29, line 23.

Suitable nonionic detersive surfactants are generally disclosed in the U.S. Pat. 3,929,678 (Laughlin et al.), From column 13, line 14 to column 16, line 6. Examples of non-limiting groups of nonionic surfactants that may be used are listed below.

Nonionic Polyhydroxy Fatty Acid Amide Surfactants - The polyhydroxy fatty acid amides of general formula (II), which have the formula:

• ·

R ¹ is hydrogen, C 1 -C 4 hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably C 1 -C 4 alkyl, more preferably C 1 -C 2 alkyl, most preferably C 1 -C 4 alkyl- i.e. methyl);

and

R is a C 5 -C 31 hydrocarbon group, preferably a straight-chain C 7 -C 19 alkyl or alkenyl group, more preferably a straight-chain C 9 -C 17 alkyl or alkenyl group, most preferably a straight-chain C 1 -C 17 alkyl or alkenyl group or a mixture thereof; and

Z is a linear polyhydroxy hydrocarbon radical having at least 3 hydroxyl groups directly attached to the chain or an alkoxylated (preferably ethoxylated or propoxylated) derivative thereof. Z is preferably derived from a reducing sugar, a reductive amination reaction; more preferably, Z is a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. High-glucose corn syrup, high fructose corn syrup and high maltose corn syrup as well as the individual sugars listed above may be used as raw materials. These corn syrups for Z can provide a blend of sugar ingredients. Preferably Z is -CH ₂ - (CHOH) _n -CH ₂ -OH ₂ , -CH (CH ₂ OH) - (CHOH) _n -, -CH ₂ OH, -CH ₂ - (CHOH) ₂ - (CHOR) ( CHOH) -CH ₂ OH wherein n is an integer from 3 to 5 inclusive and R is hydrogen or a cyclic or aliphatic monosaccharide and an alkoxylate derivative thereof. Most preferred is glycityl wherein n is 4, especially -CH ₂ - (CHOH) ₄ -CH ₂ OH.

In the formula (I), R ¹ can be, for example, N-methyl, Ν-ethyl, N-propyl, Ν-isopropyl, N-butyl, Ν-2-hydroxyethyl or Ν-2-hydroxypropyl.

Examples of the R-CO-N <group include cocamide, steroamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallow amide, and the like. group.

Z can be 1-deoxyglucityl, 2-deoxygro-frithityl, 1-deoxy-maltityl, 1-deoxy-galactityl, 1-deoxy-mannityl, 1-deoxy-maltotriethyl -, etc. group.

Most preferred is the polyhydroxy fatty acid amide of formula (III) wherein R is an alkyl or alkenyl group having 11 to 17 carbon atoms.

Nonionic Condensates of Alkyl Phenols Polyethylene, polypropylene and polybutylene oxide condensates of alkyl phenols are suitable for use in the present invention. Polyethylene oxide condensates are generally preferred. These compounds include the condensation products of alkyl phenols having from about 6 to about 12 carbon atoms in the alkylene oxide having either straight chain or branched alkyl configuration. In a preferred embodiment, the ethylene oxide is present in an amount of from about 5 to about 25 moles of ethylene oxide per mole of alkylphenol. These types of commercially available nonionic felületakz ^T M tive materials marketed by the GAF Corporation Igepal * CO-630;

TM and Triton X-45, X-114, sold by TM and Rhom & Haas Company ··· ··

X-100 and Χ-102.

Nonionic Ethoxylated Alcohol Surfactants - Alkyl ethoxylated condensation products of aliphatic alcohols with about 1 to about 25 moles of ethylene oxide are suitable for use in the present invention. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary and generally has from 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having from 10 to 20 carbon atoms having from about 2 to about 10 moles of ethylene oxide per mole of alcohol. Most preferred are condensation products of alcohols having one C 10 -C 14 alkyl group containing from about 6 to about 10 moles of ethylene oxide per mole of alcohol. Examples of such commercially available nonionic surfactants are Tergitol 15-S-9 (a condensation product of a C 11 -C 15 linear alcohol with 9 moles of ethylene oxide), Tergitol 24-L-6 NMW (12 to 14 A) condensation product of a primary alcohol with 6 moles of ethylene oxide with a narrow molecular weight distribution); Neodol 45-9 (condensation product of C14-C15 linear alcohol with 9 moles ethylene oxide), Neodol 23-6.5 (C12-13 linear alcohol condensation with 6.54 moles ethylene oxide) sold by Shell Chemical Company ), Neodol 45-7 (C14-15 linear alcohol condensation product with 7 moles ethylene oxide), Neodol 45-4 (C14-15 linear alcohol condensation product with 4 moles ethylene oxide), and Procter & Gamble Company-supplied Kyro ™ EOBN (Condensation of C13-C15 Alcohol with 9 Moles of Ethylene Oxide).:: · * ·,: ···.

··· ...

product).

Nonionic EO / PO (ethylene oxide / propylene oxide) condensates with propylene glycol - Ethylene oxide condensation products of a hydrophobic base formed by condensation of propylene oxide with propylene glycol. The hydrophobic moiety of these compounds is preferably from about 1500 to about 1800 molecular weights and is water insoluble. Addition of polyoxyethylene groups to this hydrophobic portion tends to increase the solubility of the molecule as a whole in water and maintains the liquid nature of the product to a point where the polyoxyethylene content is about 50% of the total weight of the condensation product, equivalent to condensation with a quantity. Examples of such compounds are certain commercially available Pluronic surfactants sold by BASF.

Nonionic EO Condensation Products with Propylene Oxide / Ethylene Diamine Adducts - Suitable condensation products of ethylene dioxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use in the present invention. The hydrophobic groups of these products consist of the reaction product of excess ethylenediamine and excess propylene oxide and generally have a molecular weight of about 2500-3000. This hydrophobic group is condensed with ethylene oxide to such an extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of about 5000 to about 11000. Examples of these types of nonionic surfactants are certain commercially available Tetronic compounds sold by BASF.

Nonionic Alkyl Polysaccharide Surfactants - Suitable for use in the present invention having from about 6 to about 30 carbon atoms, preferably from about

Alkyl polysaccharides having a C 10 -C 16 hydrophobic group and a polysaccharide, such as a polyglucoside, a hydrophilic group having from about 1.3 to about 10, from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing sugar having 5 or 6 carbon atoms, such as glucose, galactose and galactosyl groups, can be used to replace the glucosyl groups. (Optionally, the hydrophobic moiety is attached to the 2-, 3-, 4, etc. sites to give a glucose or galactose to a glucoside or galactoside). The saccharide linkages may be between the 1-position of the additional saccharide moieties and the 2, 3, 4, and / or 6-positions of the previous saccharide moieties.

Optionally and less desirably, there may be a polyalkylene oxide chain attached to the hydrophobic group and the polysaccharide group. A preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include saturated or unsaturated, branched or unbranched C8-C18 alkyl, preferably C10-C16 alkyl groups. The alkyl group is preferably a straight chain saturated alkyl group. The alkyl group may contain up to about 3 hydroxy groups and / or the polyalkylene oxide chain may contain up to about 10, preferably less than 5, alkylene oxide groups. Suitable alkyl polysaccharides include octyl, nonyl decyl, undecyl dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, di-, tri-tetra-, penta- and hexaglucosides. galactose. Suitable mixtures are coconut alkyl, di-, tri-, tetra- and pentaglucosides and tallow alkyl tetra-, penta- and hexaglucosides.

Preferred are the alkyl polyglucosides of formula (IV): wherein

R is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl groups contain from 10 to 18 carbon atoms, preferably from 12 to 14 carbon atoms; n is 2 or 3, x is 0-10, preferably about

1.3 to 3, most preferably about 1.3 to 2.7, t is from 0 to 10. The glucosyl group is preferably derived from glucose. These compounds are prepared by forming a polyethoxy alcohol, reacting the alcohol with a source of glucose first to produce glucose, or an alkyl and then a glucoside (1-linked). The additional glycosyl moieties are then coupled between their 1-position and the 2-, 3-, 4- and / or 6-positions of the previous glycosyl moieties, preferably the predominant 2-position.

Nonionic Fatty Amide Surfactants - Fatty acid amide surfactants of formula (V) are suitable for use in the present invention:

R ⁶ is C ⁷ -C 21, preferably C 9 -C 17 alkyl, and

R is selected from the group consisting of hydrogen, C 1-4 alkyl, C 1-4 hydroxyalkyl, and - (C ₂ H ₄ O) _X H, wherein x is in the range of 1-3.

Ampholytic surfactants may also be included in the detergent compositions of the present invention. These surfactants are generally described as aliphatic derivatives of secondary or tertiary amines, or as aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety may be straight or branched. One of the aliphatic substituents has at least about 8 carbon atoms, typically about 8 to 18 carbon atoms, and at least one contains an anionic water-solubilizing group such as carboxy, sulfonate, sulfate. For examples of ampholytic surfactants, see U.S.P. No. 3,929,678 to Laughlin et al

18, p. shows.

Suitable amphoteric surfactants for use in the present invention are alkyl amphocarboxylic acids of formula (VI):

R is a C8-C18 alkyl group, and

R _{T is} of formula (VII) or (VIII) - in which

R ¹ is a (CH ₂ ) _X COOM or CH ₂ CH ₂ OH group, and x is 1 or 2, and

Preferably, M is selected from the group consisting of alkali metal, alkaline earth metal, ammonium, mono-, di- and triethanolammonium, most preferably sodium, potassium, ammonium and mixtures thereof with magnesium ions. A preferred alkyl chain length R is a C 10-14 alkyl group. A preferred amphocarboxylic acid is prepared from fatty imidazolines in which the dicarboxylic acid functionality of the amphodicarboxylic acid is diacetic acid and / or dipropionic acid. Suitable alkyl amphocarboxylic acids for use in the present invention include, for example, Miranol (TM) C2M Conc., Manufactured by Miranol, Inc., Dayton, NJ.

amphoteric surfactant.

Zwitterionic surfactants may also be included in the detergent compositions of the present invention. These surfactants are generally described as derivatives of secondary or tertiary amines, or derivatives of heterocyclic secondary and tertiary amines, or as quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. For examples of zwitterionic surfactants, see U.S.P. 3,929,678 (Laughlin et al.) (Incorporated herein by reference) from column 18, line 18 to column 22, line 48.

Ampholytic, amphoteric and zwitterionic surfactants are generally used in combination with one or more anionic and / or nonionic surfactants.

Foaming Agents - The compositions of the present invention preferably further comprise from 1 to 20% by weight, preferably from 2 to 20% by weight, of an antifoaming agent selected from the group consisting of aminooxides, betaines, sultaines, complex betaines and certain nonionic compounds.

Amine oxides useful in the present invention include compounds of formula IX: wherein:

R is selected from the group consisting of C8-C26, preferably C8-C16-alkyl, hydroxyalkyl, acylamido-proponyl and alkylphenyl, or mixtures thereof;

^R4 represents a C2-3, preferably C2 alkylene or hydroxyalkylene group or mixtures thereof;

x is 0-3, preferably 0;

R ⁵ is a C 1-3, preferably C 1-2 alkyl or hydroxyalkyl group, or a group with 1-3, poly (ethylene oxide), preferably containing 1 ethylene oxide. The R ⁵ groups may be linked to each other to form a ring structure, e.g., through an oxygen or nitrogen atom.

These amine oxide surfactants include, in particular, C 10 -C 18 alkyldimethylamine oxides and C 8 -C 12 alkoxyethyl (dihydroxyethyl) amine oxides. Examples of such materials are dimethyl octylamine oxide, diethyl decylamine oxide, bis (2-hydroxyethyl) dodecylamine oxide, dimethyldodecylamine oxide, dipropyltetradecylamine oxide, methyl ethylhexadecylamine oxide, dodecylamidopropyldimethylamine oxide and dimethyl 2-hydroxyoctadecylamine oxide. C 10 -C 18 alkyldimethylamine oxides and C 10 -C 18 acylamidoalkyldimethylamine oxides are preferred.

+2

Betaines useful in the present invention are compounds of the formula R (R) ₂ NRCOO in which

R is a C 6 -C 18 hydrocarbon group, preferably a C 10 -C 16 alkyl group or a C 10 -C 16 acylamidoalkyl group, each R ¹ group being typically C 1 -C 3 alkyl, preferably methyl, and

R ² is a C 1 -C 5 hydrocarbon group, preferably a C 1 -C 3 alkylene group, more preferably a C 1 -C 2 alkylene group.

• ·

Suitable betaines include, for example, coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C 12 -C 14 acylamidopropyl betaine; C 8 -C 14 acylamido hexyl diethyl betaine; 4- (C 14 -C 16 acylmethylamido-diethylammonio) -1-carboxybutane; C 16 -C 18 acylamido-dimethyl betaine; C 12 -C 16 acylamidopentane diethyl betaine; C 12 -C 16 acylmethylamido dimethyl betaine. Preferred betaines are C 12 -C 18 dimethylammoniohexanoate and C 10 -C 18 acyl amidopropane (or ethane) dimethyl (or diethyl) betaines.

Sultans useful in the present invention are compounds of formula (R (R) ₂ NRSO ₃ ) wherein

R is a C 6 -C 18 hydrocarbon group, preferably a C 10 -C 16 alkyl group, more preferably a

C 1 -C 13 alkyl, each R ¹ is typically C 1 -C 3 alkyl, preferably methyl, and

R is a C 1 -C 6 hydrocarbon group, preferably a C 1 -C 3 alkylene or preferably a hydroxyalkylene group. Suitable sultans include, for example, C12-C14 dimethylammonio-2-hydroxypropylsulfonate,

C12-C14 amidopropylammonio-2-hydroxypropylsultain,

C 12 -C 14 dihydroxyethylammoniopropane sulfonate and a

C 16 -C 18 dimethylammoniohexane sulfonate, preferably a

C12-C14 amidopropylammonio-2-hydroxypropylsultain.

The present invention is useful in the preparation of complex betaines of formula X in which

R is a hydrocarbon radical having from 7 to 22 carbon atoms,

A is [C (0)], n is 0 or 1,

R _x is hydrogen or lower alkyl, x is 2 or 3, y is an integer from 0 to 4,

Q is a -R ₂ COOM group in which R ₂ is a C 1-6 alkylene group and M is a hydrogen atom or an ion selected from the group consisting of alkali metals, alkaline earth metals, ammonium and substituted ammonium, and

B is hydrogen or Q as defined above.

An example of this category is the tallow phosphatohydroxyglycinate of formula XI.

Preferred amides are C8-C20 alkyl mono- or C2-C3 dialkanolamides, especially monoethanolamides, diethanolamides and isopropanolamides.

Preferred foaming agents include C 10 -C 18 acylamide alkyl dimethylamine oxides, betaines, sultaines, ethylene oxide condensation products of aliphatic alcohols, and alkyl polysaccharides and mixtures thereof.

Hydrotropes - Typically, a hydrotropic agent is added to the compositions of the invention, which may be present in an amount of 0.5 to 10% by weight, preferably 1 to 5% by weight.

Suitable hydrotropes include sodium, potassium and ammonium xylene sulfonates, sodium, potassium and ammonium toluene.

sulfonate, sodium, potassium and ammonium cumene sulfonates and mixtures thereof.

Other compounds useful as hydrotropes in the present invention are polycarboxylates. Some polycarboxylates have calcium chelating and hydrotropic properties.

Particularly useful hydrotropes are the type of alkyl polyethoxypolycarboxylate surfactant disclosed in the patent.

An example of a commercially available alkyl polyethoxypolycarboxylate for use in the present invention is POLY-TERGENT C, Olin Corporation, Cheshire, CT.

Another hydrotropic compound is the alkyl amphodicarboxylic acid of formula XII, wherein

R is C8-C18 alkyl, x is 1-2,

M is preferably selected from the group consisting of alkali metal, alkaline earth metal, ammonium, mono-, di- and triethanolammonium, more preferably sodium, potassium, ammonium and mixtures thereof with magnesium ions.

The preferred alkyl chain length (R) is a C 10 -C 14 alkyl group and the dicarboxylic acid functionality is diacetic acid and / or dipropionic acid.

A suitable example of an alkyl amphipodicarboxylic acid is Miranol, Inc., Dayton, Nj. manufactured by Miranol R 2CM Conc. amphoteric surfactant.

Lime soap dispersants. The compositions of the present invention are particularly useful when formulated to contain a lime soap dispersant which is an insoluble lime soap salt formed between any fatty acids produced by lipolytic hydrolysis of fats / oils and washable soluble calcium ions. dispersed, thereby preventing these salts from depositing on spots or films on the articles being washed or as an inappropriate ring around the drain hole. Certain lime soap dispersants may also provide improved product stability, particularly when the product is formulated as a liquid product containing calcium ions.

A lime soap dispersing compound of the invention is defined as a compound having a lime soap dispersing power (LSDP) of not more than 8, preferably not greater than 7, most preferably not greater than 6, as defined later in the patent. The lime-soap dispersing compound is typically present in the compositions in an amount of 0.1 to 40% by weight, more preferably 1 to 20% by weight, most preferably 2 to 10% by weight.

A lime-soap dispersant is a substance which prevents the precipitation of alkali metal, ammonium or amine salts of fatty acids by calcium or magnesium ions. The numerical measurement of the effectiveness of a lime soap dispersant is given by the lime soap dispersion force (LSDP), which is determined using a lime soap dispersion test as described by H.C. Borghetty and C.A. Bergman; a J.Am.Oil. Chem. Soc.

27, 1950, pp. 88-90. pages have to do with an article. This lime-soap dispersion test procedure is a matter of practical skill • · ♦ • ·

Berek is widely used in this professional field, for example in the following journal articles; W.N. Linfield; Surfactant Science Series, Volume 7, page 3; W.N. Linfield; Tenside Surf. Det., Vol. 27, pp. 159-161. (1990); and M.K. Nagajan, W.F. Masler; Cosmetics and Toiletries, Vol. 104, p. 7173 (1989). LSDP is the weight ratio of dispersant to sodium oleate required to disperse 0.025 g of sodium oleate in 30 ml of calcium carbonate (Ca: Mg = 3: 2) equivalent hardness.

In the Borghetty / Bergman Lime Soap Dispersion Test, 5 ml of a 0.5 wt% sodium oleate solution was added to a test tube, and then 10 ml of 600 ppm calcium ion and 400 ppm magnesium ion (1000 ppm calcium carbonate equivalent, 70 ° Clark hardness) were added. ) containing a hard aqueous solution which causes the formation of a lime soap deposit (or color soap). Thereafter, any amount (less than 15 ml) of a dispersant is added to the test tube as a 0.25% solution. The total volume of solution in the test tube is then made up to 30 ml and the test tube is closed, inverted 20 times and then allowed to stand for 30 seconds. The contents of the test tube are then inspected visually to determine if the lime soap deposits are intact or have already been dispersed in the solution. The experimental procedure is repeated using different amounts of dispersant solution until the minimum amount of dispersant solution that causes the lime soap deposits to disperse is obtained.

• · · · · ··· · · · · ··· ···

The lime soap dispersion power is then obtained as follows:

LSDP = (mass of lime soap dispersant) x 100 (mass of sodium oleate) Thus, in accordance with the experimental procedure described above, a lower LSDP material is a more effective lime soap dispersant than a higher LSDP value.

Calcium - 0.05 to 3%, more preferably 0.15 to 2%, of calcium ions may be included in the cleaning compositions of the present invention. In formulations containing polyhydroxy fatty acid amide, it has been found that the presence of calcium greatly improves the purification of fatty impurities. This is especially true when the formulations are used in softened water containing little divalent ions.

The calcium ions may be included, for example, as chloride, hydroxide, oxide, formate or acetate, or as the nitrate salt.

If the anionic surfactants are in acid form, the calcium ion may be added as an aqueous slurry of calcium oxide or calcium hydroxide to neutralize the acid.

The calcium ions may be present as salts in the compositions. The amount of calcium ion present in the compositions of the present invention may depend on the amount of total anionic surfactant present. The compositions of the invention preferably have a molar ratio of calcium ions to total anionic surfactants of from 1: 0.1 to 1:25, more preferably from 1: 2 to 1:10.

Calcium Stabilizer - For a calcium-based formulation to ensure good product stability, and especially to prevent the precipitation of insoluble calcium salts, malic acid or maleic acid, or certain dispersing compounds of lime soap. If calcium is present, the malic acid or maleic acid may preferably be added in an amount of 0.0510% and a calcium molar ratio of 0.01: 1 to 1:10.

Magnesium - Preferably 0.01 to 3% by weight, most preferably 0.15 to 0.9% by weight of magnesium ions are added to the liquid cleansing compositions of the present invention for improved product stability and improved foaming.

When the anionic surfactants are in acid form, the magnesium can be added by neutralizing the acid with aqueous magnesium oxide or magnesium hydroxide. Calcium can be treated similarly. This technology minimizes the addition of chloride ions, which reduces corrosion problems. The neutralized surfactant salts and the hydrotrope are then placed in a final mixing tank and all other ingredients are added before adjusting the pH.

PH of the Composition - Liquid cleaning compositions are preferably formulated in accordance with the invention so that the wash water is used at a pH of from about 5.0 to about 8.0 during use in aqueous cleaning operations. The liquid compositions themselves preferably have a pH of about 5.5 to about 8.5, most preferably about 6.8 to about 7.8 in 10% aqueous solution at 20 ° C.

At recommended rates of use, pH control technologies include buffers, alkalis, acids, and the like. and are well known to those skilled in the art. Diluted hydrochloric acid is preferred for adjusting the pH downward, and sodium hydroxide is preferred for adjusting the pH upwards.

Enzyme Stabilization System - Preferred compositions herein may further comprise from 0.001 to 10% by weight, preferably from 0.005 to 8% by weight, most preferably from 0.1 to 6% by weight of the enzyme stabilization system. The enzyme stabilization system may be any enzyme stabilization system that is compatible with the enzyme of the invention. Such stabilization systems may include calcium ion, boric acid, propylene glycol, lower carboxylic acid, boronic acid, polyhydroxyl compounds, and mixtures thereof, e.g.

a U.S.P. No. 4,318,818 (Letta et al); 4,462 922 No. (Boskamp); No. 4,532,064 (Boskamp); and 4,537 707 No. (Severson Jr.) communicate which patent

all of the descriptions herein are incorporated by reference.

Further, 0-10% by weight, preferably 0.01-6% by weight, of chlorine bleach can be added to the compositions of the present invention to prevent the chlorine bleaches present in many water supply systems from attacking and inactivating the enzymes, especially under alkaline conditions. While the amount of chlorine in the water may be small, typically in the range of 0.5 to 1.75 ppm, the amount of chlorine available in the total volume of water contacted with the enzyme during washing is usually high; consequently, enzyme stability during use may be problematic.

Suitable chlorine-depleting anions are salts containing ammonium cations. They are similar to sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. • 4 ·>

substances selected from the group consisting of substances, antiosidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or their alkali metal salts and monoethanolamine (MEA) and mixtures thereof. Other conventional inactivating anions may be used, such as sulfate, bisulfate, carbonate, bicarbonate, percarbonate, nitrate, chloride, borate, sodium perborate tetrahydrate, sodium perborate monohydrate, percarbonate, phosphate, condensate, phosphate, , maleate, tartrate, salicylate, etc. and mixtures thereof. Preferred ammonium salts or other salts of the specific chlorine deactivating anions can either replace the foam regulator or be added in addition to the foam regulator.

Although ammonium salts may be mixed with the cleaning composition, they tend to adsorb water and / or release ammonia gas. Therefore, it is better to protect them in a somewhat similar manner to that described in U.S. Patent No. 6,652,292 (Baginski et al), which is incorporated herein by reference.

Liquid or Gel Formulations - In a preferred embodiment, the cleaning compositions of the present invention are liquid cleaning compositions. These preferred liquid cleansing compositions are 94-35% by weight, preferably 90-40% by weight, most preferably 80-50% by weight of a liquid carrier such as water and a C 1-4 monovalent alcohol (e.g., ethyl alcohol, propyl alcohol, isopropyl alcohol). butyl alcohol and mixtures thereof), the preferred monovalent alcohol is ethyl alcohol or a mixture of water and a C1-C4 divalent alcohol (e.g., propylene glycol).

Gels - The cleaning compositions of the invention may also be in gel form. Such compositions are typically formulated in polyalkenyl polyether and have a molecular weight of about 750000400000000.

Very useful examples of these polycarboxylate polymer thickeners are B.F. Carbopol 600 Series resins available from Goodrich. Carbopol 616 and 617 are particularly preferred. It is believed that these resins are more crosslinked than the 900 series resins and have a molecular weight of about 1 million to 4,000,000. Mixtures of polycarboxylate polymers of the present disclosure may also be used in the present invention. A mixture of Carbopol 616 and 617 is particularly preferred.

The polycarboxylate polymer thickener is used essentially with a non-clay thickener. In fact, it has been found that using the polycarboxylate polymers of the invention with clay in the composition of the invention results in a less desirable product in terms of phase stability. In other words, the polycarboxylate polymer is preferably used in the compositions of the invention instead of clay as a thickener / stabilizer.

When a polycarboxylate polymer is used as a thickening agent in the compositions of the present invention, it is typically present in an amount of from about 0.1% to about 2%, preferably from about 0.2% to about 2%.

»» ** • ·

The thickeners are preferably used to provide yields of from about 50 to about 350 and most preferably from about 75 to about 250. The yield value is an indication of the shear stress at which it exceeds gel strength and begins to flow. This is measured here using a Brookfield RVT viscometer type T-bar, B axis, at 25 ° using a Helipath.

Other ingredients typically used in the compositions of the invention are paints, fragrances, and opacifiers.

Opacifying agents such as Lytron (Morton Thiokol, Inc.), a modified polystyrene latex or ethylene glycol distearate are preferably added as a final step. Lytron can be added directly as a dispersion with stirring. Ethylene glycol distearate may be added in a molten state to form pearl crystals by rapid mixing. The opacifying agents used in the present invention, particularly in high performance fluids, are typically present in about 0.2 to 10% by weight, preferably about 0.5 to 6% by weight.

Manual Dishwashing Method - According to the method of the manual dishwashing method of the invention, the contaminated dishes are contacted with an effective amount, typically about 0.5-20 ml (for 25 dishes to be treated), preferably about 3 to 10 ml. The actual amount of liquid cleansing composition used is based on the judgment of the user and depends on factors such as composition, concentration of the composition, number of contaminated dishes to be cleaned, and degree of soiling of the dishes.

The process of bringing contaminated dishes into contact with an effective amount of the composition of the present invention is essentially any dishwasher process generally known for hand dishwashing and commonly used in Northern Europe and the United States; it may be a process commonly used in Latin America and Japan, which contains a solution in a sink, and a direct use procedure generally used in southern Europe and developing countries.

Dilute solution sink method - In a typical dilute solution sink method, about 3-15 ml, preferably about 5-10 ml, of the liquid detergent composition in a 5000-20000 ml, more typically 10000-15000 ml sink, 1000-10000 ml, more typically 3000-5000 ml water. The detergent composition may contain from about 10% to about 60%, preferably from about 45% to about 50%, surfactant. Dirty dishes are immersed in a sink containing detergent and water, where they are cleaned by contacting the dirty surface of the dish with a cloth, sponge or similar article. The cloth, sponge or similar article may be submerged in a detergent / water mixture before contacting the dish surface and contacting the dish surface for a period typically of 1-10 seconds, although the actual time will vary with each application and user. Advantageously, contacting the cloth, sponge or the like with the surface of the container is accompanied by the simultaneous rubbing of the container surface.

Solution in a Sink Dish - In a typical solution in a sink dish, 1 to 50 ml, preferably 2 to 10 ml, of a dishwashing liquid is mixed in a 500 to 5000 ml, more typically 500 to 2000 ml dishwasher, more typically 100-1000 ml of water. The detergent composition may contain from about 10% to about 60%, preferably from about 15% to about 50%, surfactant. Contaminated containers are cleaned by contacting the contaminated surface of the container with a cloth, sponge or similar article. The cloth, sponge, or the like may be submerged in a mixture of detergent and water before being brought into contact with the container surface and typically exposed to the container surface for a period of from 1 to 10 seconds, although actual time will vary with each application and user. Advantageously, contacting the cloth, sponge or the like with the surface of the container is accompanied by the simultaneous rubbing of the container surface.

Direct Application Process - The direct application process typically involves the first step of immersing contaminated vessels in a water bath without any liquid detergent. A device for absorbing liquid detergent, such as a sponge, is then placed in a separate, undiluted, liquid or gel detergent amount for a period typically of about 1 to 5 seconds. The absorbent device and consequently the undiluted cleaning composition are then individually contacted with the surface of each contaminated vessel to remove said contaminant. Typically, the absorbent device is contacted with each vessel surface for a period of 1-10 seconds, although the vessel may be exposed to a period of 1-10 seconds. The actual application time depends on factors such as the degree of contamination of the vessel. Advantageously, contacting the absorbent device with the surface of the vessel is accompanied by simultaneous rubbing.

Examples

In accordance with the invention, the following compositions were prepared.

yo m e g%

I II III ARC V C 12/13 alkyl-ethoxy- (average 0.8) sulfate 10.0 10.0 9.0 5, 0 10.0 C 12/13 alkyl-ethoxy- (average 3) sulfate 7.0 7.0 8, 0 15.0 7.0 C12 / C14 alkylamine oxide 2.0 1.0 - 1.0 2.0 C12 / C14 alkyldimethyl- betaine 1.0 1.5 2.0 12/14 Carbon Ampholak (TM) - - 1.5 - - C12 alkyl N-methyl- glucamide 12.0 12, p 9.0 11.0 12.0 C10 alkyl ethoxylate (Avg. 8) 5.0 5, 0 5, 0 4.6 5, 0 Mg ion - 0, 6 - 0.3 0.6 _ + 4- Ca ion - - 0.3 0.15 0.1 maleic - - 0.2 0.3 - Miranol (TM) - - 2.0 - - Polytergent (TM) - - - 2, 0 - Lipolase (TM) 0.05 0.1 0.2 0.3 0.4

V ···· «« · »·· • e · · * ·» «« • ··· ······················································•

Q Ο ··· ··· 99 99 9

The formulations were prepared by mixing all the surfactants except glucamide. The magnesium and calcium salts were then pre-dissolved in a solution of maleic acid and added with the remaining ingredients to the surfactant mixture. Finally, the pH was adjusted to 7.3 using hydrochloric acid and the viscosity was checked.

·· ·· «·« 4 a · v ···· 4 • ·· • ····

Claims (10)

A composition comprising a surfactant system and a lipolytic enzyme for use in a hand dishwashing process. A composition according to claim 1, wherein said composition is highly foamy. Composition according to claim 1 or 2, characterized in that said composition is in liquid or gel form. 4. A composition according to any one of claims 1 to 4, wherein said composition does not contain builder salts. 5. A composition according to any one of claims 1 to 3, characterized in that said composition does not contain bleach components. 6. Composition according to any one of claims 1 to 5, comprising 5 to 80% by weight of said surfactant system, characterized in that the surfactant system comprises a surfactant selected from nonionic, anionic, cationic, zwitterionic, ampholytic and amphoteric surfactants. 7. A composition according to any one of claims 1 to 3, wherein the 1% w / w solution of said composition has a pH of 6-9. 8. A composition according to any one of claims 1 to 5 containing from 0.05 to 3% by weight of calcium ion. 9. A composition according to any one of claims 1 to 4 containing from 0.01% to 3% by weight of magnesium ion. 10. The foam according to any one of claims 1 to 20, • ·· ** * · ·· • • * 4 4 4 • • 44 · ♦ ·· • • 4 4 • · · · · · · · · you ·· Preparation containing a potentiating agent. The agent shall: 'Oat ^ dalmi / carrier »z S.B.O. KI International members ifit Afldrássy út 113. 5P, A-ax. 34-24-323 H-1062Bu Phone: 34 foo-íoüt 0 CH. II I R 8 - C - N - CH ₂ - (CHOH) - CH ₂ - OH R ² O (CH _2n O) t (glycosyl) _x 6 ¹ 7 -C- R ⁶ N (R ^z) ₂ II RC-NHCH ₂ CH ₂ R 1