CZ38896A3 - Preparation containing lipase enzymes for hand washing of dishes - Google Patents

Abstract

There is provided a composition containing a surfactant system and lipolytic enzyme suitable for use in a manual dishwashing process. Preferably said composition is high sudsing and in the form of a liquid or a gel. Preferably said composition contains no builder salts and no bleaching components.

Description

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Means for manual dishwashing ^and ggaŤmšP ^ <k .1. i.pžae

Technical field

The present invention relates to a novel detergent composition for hand dishwashing comprising 1-phase enzymes.

BACKGROUND OF THE INVENTION

The task of the manufacturer of hand dishwashing detergents is to create a formulation that meets a number of important and often contradictory consumer requirements.

First, the dishwashing detergent must effectively remove dirt from dirty dishes during manual use. The term dishes includes articles for washing, including porcelain, glass and plastic dishes and cutlery, including silverware.

Dishes for washing are contaminated mostly (but not only) with food residues. Very difficult to remove impurities include greasy impurities, burnt food scraps, dry food scraps, colored impurities such as colored vegetables such as beetroot and tomato, or other impurities such as lipstick on the edge of a glass or nicotine stains on a saucer. was used as an ashtray.

Once the impurities have been removed from the dishes, the detergent composition should suspend the impurities in the wash solution to prevent them from being redeposited on the dishes or on the sink surface.

While removing dirt and preventing redeposition are properties common to both hand dishwashing products and dishwashing products, hand dishwashing products have to meet other requirements.

Handwashing products should be highly foaming and retain foam throughout the wash. The presence of the foam is an indicator of the presence of the effective for the person washing the dishes

-Λ.? »» »·

of detergent ingredients. When the foams decrease, the washing solution is usually replaced by fresh. The ability of the foam to persist during the entire wash time is determined in the industry using various foam and moisture indicators.

Hand dishwashing products should not damage the skin, especially on the hands. This means that they should not dry the skin on contact, causing it to crack or collapse. Drying, cracking or coarsening of the skin results from the removal of natural fats in the skin. Therefore, a hand wash should effectively remove greasy dirt from dishes, but not natural fats from the skin.

In view of the other operational requirements for hand dishwashing products, the preparation of these products differs from the preparation of eg dishwasher detergents, detergents and solid surface cleaners.

Hand dishwashing products usually do not contain builders, but may contain additional amounts of Ca and Mg, which improves their cleaning properties. Laundry and dishwasher formulations usually contain large amounts of builders.

Hand dishwashing products usually do not contain bleach, which are common ingredients in dishwashing detergents, laundry detergents and hard surface cleaners.

Hand dishwashing compositions typically contain a large amount of high sudsing surfactants and often sudsing agents. Laundry and dishwasher formulations are generally low foaming and contain low surfactants.

The composition of hand dishwashing compositions is selected so that the compositions are effective at neutral pH. Laundry and dishwashing detergents are usually alkaline, have a pH of 9 to 11, and detergents for solid surfaces are often acidic with a pH of less than 6.

The key active ingredient of hand dishwashing compositions is most commonly a surfactant system, typically 5 to 80% by weight. preparation. The primary purpose of the surfactant system is to remove impurities and further suspend the released impurities in the solution and prevent their redeposition. In particular, the system must effectively remove and suspend fatty contaminants.

In general, washing solutions contain only surfactants and certain minor ingredients. This is stated in Intel's latest Economist Business Report! According to this report, the quantity in the surface of the device is a criterion of their quality.

Enzymes are common ingredients in dishwashing detergents, 409, March 1992. Active ingredients for washing and amylolytic and proteolytic hand dishwashing enzymes lipase enzymes, hydrolyze fats or dishwashers. These are usually enzymes. They are usually not included in conventional preparations.

Lipolytic enzymes, or oils containing glycerol fatty acid esters per component, glycerol and fatty acids. It is known from the field of the use of 1 ipolytic enzymes in laundry and dishwasher formulations to use 1 ipolytic enzymes as coenzymes in combination with, for example, amylolytic and proteolytic enzymes.

Applicants have recognized the sense of incorporating 1 ipolytic enzymes in dishwashing compositions of a specific composition with respect to manual use. Lipolytic enzymes have not been used in the art to date. An extensive field of technology devoted to the use of these enzymes in dishwashing preparations, while neglecting their possible use in hand dishwashing preparations, could raise prejudice against their possible use in the field of hand dishwashing preparations.

The essence of this prejudice may lie in the well-known connection between surfactants and the ability of the hand wash composition to remove greasy impurities. With a high concentration of greasy soil removal surfactants, it could be assumed that the simultaneous introduction of fat-hydrolyzing enzymes would not make sense. Another cause of this prejudice may be the belief that fatty acids, products of oil and fat hydrolysis, may reduce foaming and thus counteract the desirable high foaming performance of the wash.

Applicants have further found that a lipolytic enzyme is a particularly suitable component of liquid dishwashing compositions containing certain surfactant kits that stabilize the enzyme.

SUMMARY OF THE INVENTION

The present invention provides a hand dishwashing composition comprising a surfactant system and a lipolytic enzyme.

Said composition is preferably highly foaming.

Said preparation is preferably in the form of a liquid or gel.

Said composition preferably contains no salts as builders.

Said composition preferably contains no bleach.

Said formulation contains 5 to 80 wt. said surfactant assemblies comprising surfactants selected from the group of nonionic, anionic, cationic, zwitterionic, ampholytic and amphoteric surfactants.

The pH of a 1% solution of said formulation is 6-9.

The preparation may no longer contain any other enzymatic components.

The first essential component of the composition of the present invention is a lipolytic enzyme (lipase), preferably present in an amount of 0.001 to 2% by weight, more preferably 0.01 to 1% by weight, most preferably 0.05 to 0.5% by weight. % of active enzyme after the lytic enzyme with respect to the weight of the preparation.

Preferred are lipases of bacterial origin, e.g. from a strain producing Humicola sp. or Thermomyces sp. or Pseudomonas pseudoa 1 and 1 igenes or Pseudomonas fluorescens.

Lipases derived from the chemically or genetically modified strains mentioned above are also suitable. However, mixtures of lipases from different strains as mentioned herein are not suitable.

Preferred is an ipase derived from the Pseudomonas pseudoa leaigigenes strain described in the European patent granted, EP-B-02 1 8272.

Another preferred Aspergillus oryza base in which Humicola lanuginosa, as EP-A-0258 068, which from Novo Industri A / S, Bagsvaerd, is derived from a host strain was expressed by the cloned gene described in European patent enzyme is commercially available Denmark , under the trade name is

Lipolase. This lipase is also described in U.S. Pat. No. 4,810,414, Huge-Jensen et al., Issued Mar. 7, 1989.

Of the patents suitable for surface treatment, the presently preferred purposes are preferably active agents. In the present stable and increase their purification which give a positive anti-lipase antibody

Lipazes are compatible with the formulation.

Suitable lipases are those immunologically cross-reactive with the produced Pseudomonas fluorescens strain. Such lipases are disclosed in Japanese Patent Application 53-20487, published February 24, 1987. They are commercially available under the trade name Lipase P Amano. A method for testing an immunological cross-reaction with an Amano P antibody is disclosed in U.S. Pat. No. 4,707,291, Thom et al., Issued November 17, 1987.

A lipase unit is defined as the amount of lipase that produces 1 µmol of titratable butyric acid per minute at pH 7.0 and 30 ° C from a ributyrin-arabic gum emulsion substrate in the presence of Ca ⁺⁺ and NaCl in phosphate buffer.

System of surfactants

The compositions of the present invention comprise a surfactant system in an amount of 5 to 80% by weight, preferably 10 to 60% by weight, most preferably 15 to 50% by weight. relative to the weight of the preparation.

The composition of the surfactant system is preferably selected with respect to compatibility with the lipolytic enzyme. In liquid or gel formulations, the surfactant system is selected to increase or at least not decrease the stability of the present polyolytic enzyme ..........

The surfactant system includes surfactants selected from nonionic, anionic, cationic, zwitterionic, ampholytic, amphoteric surfactants and any mixtures thereof.

The surfactant system preferably comprises 5 to 90 wt%, more preferably 30 to 70 wt%. % of anionic surfactants and 5 to 60 wt.%, more preferably 15 to 50 wt. nonionic surfactants.

Anionic surfactants

Any anionic surfactant may be used as anionic surfactant, including anionic sulfate, sulfonate, or carboxylate surfactants.

Anionic sulfate surfactants

The anionic sulfate surfactants may be any organic sulfate surfactants. It is preferred to choose from the group consisting of C 10 -C 16 alkyl sulfates ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule, sulfated C 9 -C 17 acyl-N- (C 1 -C 4 alkyl) glucamine, -N- (C 2 -C 4 hydroxyalkyl) glucamine sulfate and mixtures thereof. A more preferred anionic sulfate surfactant is a C 10 -C 16 alkyl sulfate ethoxylated with 0.5 to 20 moles, preferably 0.5 to 12 moles of ethylene oxide per molecule.

Alkyl ethoxysulfate surfactants contain primary alkyl ethoxy sulfates derived from the C10-C1B alcohol condensation product with an average of 0.5 to 20, preferably 0.5 to 12, ethylene oxide groups. The C10-C16 alcohol itself is commercially available. C12-C14 alkyl sulfate ethoxylated with 3 to 10 moles of ethylene oxide per molecule is preferred.

Conventional base-catalyzed ethoxylation, resulting in an average degree of ethoxylation of 12, results in a mixture of individual ethoxylates bearing 1 to 15 ethoxy groups per 1 alcohol molecule so that the desired average ethoxylation degree can be achieved in various ways. Mixtures of materials of varying degrees of ethoxylation can be prepared and / or directed to a different distribution of ethoxylates by introducing specific ethoxylation processes and other manufacturing steps such as distillation.

Anionic sulfate surfactants include C9-C17 acyl-N- (C1-C4 alkyl) and -N- (C1-C2 hydroxyalkyl) glucamine sulfates, preferably those whose C9-C17 acyl group is derived from coconut or palm oil. These materials can be prepared as described in U.S. Pat. No. 2,717,894, Schwartz, issued March 1, 1955.

The anionic sulfate surfactant vapor ion is preferably selected from the group of calcium, sodium, potassium, magnesium, ammonium, alkanolammonium ions, and mixtures thereof, of which calcium and magnesium ions are more preferred due to the cleaning or foaming properties.

Anionic sulfonate surfactants

The anionic sulfonate surfactants may be any sulfonate surfactant, including, for example, salts (e.g., alkali metal salts) of C9-C20 linear alkylbenzene sulfonates, C8-C22 primary or secondary and 1 channel sulfonates, C8-C24 olefinic sulfonates, sulfonylated polycarboxylic acids alkyl glycerol sulfonates, oleyl glycerol sulfonates, paraffin sulfonates, and any mixtures thereof.

Anionic and 1-ethoxycarboxylate surfactants

Suitable alkyl ethoxycarboxylates include those of the present invention

R 0 (CH 2 CH 2 O) x CH 2 COO-M ⁺ , wherein R is a C 12 -C 16 alkyl group, x and a ethoxylate distribution by weight of less than 20% by weight, preferably less than 15%, 10%; for x> 7: less than 25% by weight, is in the range 0 to 10 for x = 0: less most preferably less than preferably less than 15%, most preferably less than 10% by weight; is on average C 13 or less, and the average value of x is 3 to 6 for R is greater than C 13; and M is a cation, preferably selected from alkali metal, alkaline earth metal, ammonium, mono-, di- and triethanolammonium ions, the most preferred ions being sodium, potassium, ammonium and mixtures thereof with magnesium ions. Preferred α-alkyloxycarboxylates are those wherein R is a C 12 -C 14 alkyl group.

Anionic alkyl polyethoxy polycarboxylate surfactants

Suitable alkyl polyoxyethoxycarboxylates for use herein include those of the formula

R-O- (CH-CH-O) x-R 3

R 1 R 2 wherein R is C 6 -C 18 alkyl, x is 1 to 25, R 1 and R 2 are selected from hydrogen, methyl, succinic, hydroxysuccinic, and R 3 is selected from hydrogen, substituted or unsubstituted C 1-8 The hydrocarbon and mixtures thereof.

Anionic secondary surface-active soaps

Secondary surfactant soaps (and alkyl carboxylate surfactants) suitable for the present purposes are those whose carboxyl unit is attached to a secondary carbon atom. This secondary carbon may be part of a ring structure, such as in p-octylbenzoic acid, or in alkyl-substituted cyclohexylcarboxylates. Secondary surfactant soaps should not contain any ether or ester linkages, nor hydroxyl groups. The head (amphiphilic) portion of the molecule should not contain nitrogen atoms. Secondary surfactant soaps typically contain a total of 11 to 13 carbon atoms, and a slight number of about 14 to 16 is allowed to be noted (e.g., a ring such as p-octyl benzoic).

The following general structures of secondary surface-active precursor acid) suitable for the present invention.

if the structure above, e.g.

further illustrate soaps (or include acid at some of the appropriate

A. A very preferred class of secondary soaps suitable for the present purposes are 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 is 0 or whole the number from 1 to 4 and x is an integer from 4 to 10 and the sum of x + y is 6 to 10, preferably 7 to 9, most preferably 8.

B. Another class of secondary soaps useful herein are the carboxylic acids whose carboxylic substituent is bonded to a ring hydrocarbyl unit, i.e. sekunární soaps of the formula ^{R5 -R6} -COOM, wherein ^R5 is C7 -C10, preferably C8 -C9 alkyl or alkenyl and R ® is a ring structure such as benzene, cyclopentane and cyclohexane. (Note: R ⁵ may be in the ortho, meta or para position relative to the ring carboxyl.)

C. Another preferred class of secondary soaps are secondary carboxylic compounds of formula

CH 3 (CHR) k - (CH 2) m - (CHR) n -CH (COOM) (CHR) o - (CH 2) p - (CHR) q -CH 3, wherein each R is C 1 -C 4 alkyl, k, n, o, q are integers from 0 to 8, provided that the total number of carbon atoms (including carboxyl) is between 10 and

18.

In each of formulas A, B and C above, M is any suitable paired ion, especially compounds in water, e.g. an alkaline earth, an ion that enhances the solubility of H, an alkali metal, ammonium, alkanolammonium, dia tri and 1 canolammonium ion. and ammonium substituted with C 1 -C 8 alkyl.

Sodium ion and diethanolammonium are suitable.

Anionic secondary surface-active soaps preferred for the present purposes are water-soluble substances derived from the group of water-soluble acid salts

2-methyl-1-undecene, 2-ethyl-1-decene, 2-propyl-1-nonanoic, 2-butyl-1-octane and 2-pentyl-1-heptane.

Other anionic surfactants

The present compositions may also contain other anionic surfactants suitable for cleaning purposes. These are the salts (eg, sodium, potassium, ammonium and substituted ammoniums, eg, mono-, di- and triethanolammonium) of soaps, fatty oleylglycerol sulfates, and alkylphenoxyethyl ether sulfate, and alkyl phosphates, isethionates such as acyl isethionate, N-acyltalate. fatty acid amides, and alkyl succinates and sulfosuccinates, sulfosuccinate monoesters (particularly saturated and unsaturated C12-C18 monoesters), sulfosuccinate diesters (especially saturated and unsaturated Ce-C1 4 diesters), sulfosylsalkylate sarcosides such as sulfates and alkyl groups (nonionic unsulfated compounds are described herein), branched primary alkyl sulfates, alkylpolyethoxycarboxylates such as those of the formula R0 (CH2CH2O) kCH2COO-M +, wherein R is C8-C22 alkyl, k is an integer from interval 0 to 10 and M is a cation of the soluble salt, and isethionic acid esterified fatty acid ester sodium hydroxide. Also suitable are acidic resins and hydrogenated acidic resins such as rosin, hydrogenated rosin, and acidic resins and hydrogenated acidic resins derived from or derived from tall oil. Other examples are Surface Active Agents and Detergents (Vol. I and II by Schwarz, Perry and Berch). Many other similar surfactants are also generally described in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975 to Laughlin et al., Column 23, r. 58 to column 29, r. 23.

Nonionic Surfactants -------------- Suitable nonionic surfactants are generally described in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975 to Laughlin et al., Column 13, line 14 to column 16, line 6, incorporated herein by reference. Examples of non-limiting classes of useful nonionic surfactants are given below.

Nonionic surfactant amides of polyhydroxy fatty acids

The polyhydroxy fatty acid amides suitable for the present purposes are compounds of the structural formula:

R ¹

AND

CNZ-R2 wherein ^R1 is H, Ci-C4 hydrocarbyl, 2-hydroxyethyl 1, 2-hydroxypropyl, or a mixture thereof, preferably Ci-C4 alkyl, more preferably Cl or C2 alkyl, most preferably on whether the alkyl (i.e., methyl); and R 2 is a C 5 -C 31 hydrocarbon, preferably a C 7 -C 19 straight chain alkyl, more preferably a C 9 -C 17 straight chain alkyl or alkenyl, most preferably a straight chain C 11 -C 17 alkyl or alkenyl, or a mixture thereof; and Z is a polyhydroxyl hydrocarbon whose linear hydrocarbon chain carries at least three directly bonded hydroxyl groups, or an alkoxylated derivative of these compounds (preferably ethoxylated or propoxylated). Z is preferably derived from a reducing sugar by a reductive amination reaction; more preferably glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. Raw materials such as high dextrose corn syrup, high fructose corn syrup and high maltose corn syrup, or individual sugars as mentioned above may also be used. A mixture of sugar components for Z can be obtained from said cereal syrups.

Τ’-T?

- 12 suitable raw materials. Z is preferably selected from the group consisting of -CH 2 - (CHOH) n -CH 2 OH, -CH (CH 2 OH) - (CHOH) n -, -CH 2 OH, -CH 2 - (CHOH) 2 (CHO 2); (CHOH) -CH 2 OH, wherein n is an integer from 3 to 5 inclusive, and R 1 is H or a cyclic or aliphatic monosaccharide and an alkoxy derivative thereof. Most preferred are glycityls wherein n is 4, particularly -CH 2 - (CHOH) 4 -CH 2 OH.

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

R ² -CO-N může can be eg cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.

Z may be 1-deoxyglucityl, 2-deoxyfructyl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactity 1,1-deoxymanityl, 1-deoxymaltotriotityl, etc.

The most preferred amyl polyhydroxy fatty acid amide is:

O CHa

AND

R 2 -CN-CH ₂ - (CHOH) 4 CH ₂ OH wherein R ² is a straight chain C 11 -C ¹⁷ alkyl or alkenyl.

Nonionic condensates of alkylphenols

Alkylphenol condensates with polyethylene, polypropylene and polybutylene oxide are also suitable for use in the present invention. Polyethylene oxide condensates are more preferred. These compounds include the condensation products of alkylphenols whose alkyl group contains from 6 to 12 carbon atoms and can be straight or branched, with and alkylene oxide. According to a preferred embodiment of the condensation, the ethylene oxide is present in an amount of 5 to 25 moles of ethylene oxide per mole of alkyl phenols. Commercially available surfactants of this type are Igepal ™ CO-630, sold by GAP Corporation; and Triton ™ X-114, X-100 and X-102, all sold by the Rohm & Haas Company.

Nonionic surfactant ethoxylated alcohols

Other suitable materials for the present invention are alkyl ethoxylates, the condensation products of aliphatic alcohols with 1 to 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary, and usually contains 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols whose alkyl group contains 10 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per mole of alcohol. Most preferred are the condensation products of alcohols whose alkyl group contains 10 to 14 carbon atoms with 6 to 10 moles of ethylene oxide per mole of alcohol. Commercially available nonionic surfactants of this type are, for example, Tergitol (TM) 15-S-9 (condensation product of linear C11-C15 alcohol with 9 moles of ethylene oxide), Tergitol (TM) 24-L-6 NMW (condensation product of primary C12-C14 alcohol with 6 moles of ethylene oxide of narrow molecular weight distribution), both sold by Union Carbide Corporation; Neodol ™ 45-9 (condensation product of linear C14-C15 alcohol with 9 moles of ethylene oxide), Neodol ™ 23-6,5 (condensation product of linear C12-C13 alcohol with 6.54 moles of ethylene oxide), Neodol ™ 45-7 (condensation product) linear C14-C15 alcohol with 7 moles of ethylene oxide), Neodol ™ 45-4 (condensation product of linear C14-C15 alcohol with 4 moles of ethylene oxide), all sold by Shell Chemical Company and Kyro ™ EOBN (condensation product of C13-C15 alcohol with 9 moles of ethylene oxide) ), sold by The Procter & Gamble Company.

Non-ionic EO / PO condensates with propylene glycol

Other suitable substances for the present invention are the condensation products of ethylene oxide with a hydrophobic base prepared by condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds preferably has a molecular weight of 1500 to 1800 IU. and is insoluble in water. Attachment of polyoxyethylene groups to this hydrophobic base

14 increases the solubility of the resulting molecule in the water-liquid character of the compound persists up to 50% by weight. the polyoxyethylene content of the total weight of the condensate, corresponding to condensation with an amount of up to 40 moles of ethylene oxide. Examples of compounds of this type are the commercially available Pluronic ™ surfactants sold by BASF.

Non-ionic EO condensation products with propylene oxide / ethylene amine adducts

Other suitable materials for the present invention are the condensation products of ethylene oxide with the products of the reaction of propylene oxide with ethylenediamine. The hydrophobic portion of these, the product of the reaction of ethylenediamine with an excess of propylene oxide, typically has a molecular weight of 2,500 to 3,000 IU. . This hydrophobic moiety is condensed with ethylene oxide to such an extent that the resulting compound contains 40 to 80 wt. polyoxyethylene and had a molecular weight of 5,000 to 10,000 h. . Examples of compounds of this type are the commercially available Tetronic ™ surfactants sold by BASF.

Nonionic alkyl polysaccharide surfactants

Alkylpolysaccharides suitable for the present invention are described in U.S. Pat. No. 4,565,647, Llenado, issued January 21, 1986. The hydrophobic alkyl group of these alkylsaccharides contains 6 to 30 carbon atoms, preferably 10 to 16 carbon atoms, and the 1ysaccharide, e.g., the polyglycoside forming the hydrophilic portion of the molecule, contains 1.3 to 10, preferably 1.3 to 3, most preferably

1.3 to 2.7 carbohydrate units. Any reducing carbohydrate containing 5 to 6 carbon atoms is suitable, e.g., glucose and galactose, the galactose moiety may be substituted for glucose. The hydrophobic groups may be attached at positions

2-, 3-, 4-, etc., which builds glucose or galactose as opposed to glucoside or galactoside). Intersaccharide linkages may occur, for example, between any of the positions of the accessing carbohydrate unit and the 2-, 3-, 4- and / or 615 position of the preceding unit.

Possible but less preferred is the linkage of the hydrophobic and the lysaccharide portion of the molecule to the lyacene oxide chain. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, saturated and unsaturated, branched and unbranched, containing from 8 to 18, preferably 10 to 16, carbon atoms. Preferred is a straight chain saturated alkyl group. The alkyl group may contain up to 3 hydroxyl groups and / or the polyaclylene oxide chain may contain up to 10, preferably less than 5, alkylene oxide units. Suitable alkylpolysaccharides are octyl, nonyldecyl, undecyl dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl octadecyl, di-, tri-, tetra-, penta- and hexaglucoside-, galactose. Suitable mixtures include alkyl (coconut) di-, tri-, tetra-, and pentaglcosides and alkyl (tallow) tetra-, penta, and hexaglides.

Preferred alkyl polyglycosides have the general formula

R ²⁰ (C 11 H 10 n) glycosyl) x, wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof with alkyl groups containing 10 carbon; n is 2 or 3, x most preferably 1.3 to 2.7, t to 18, preferably 12 to 14 atoms is 0 to 10, preferably 1.3 to 3, is 0 to 10. Glycosyl is preferably derived from glucose. The preparation of these compounds involves first the formation of an alcohol or alkylpolyethoxyalkyl, and further its reaction with glucose or a source thereof to form a glucoside (attachment at the 1- position). Additional glycosyl units can then be linked at the 1-position to the 2-, 3-, 4- and / or 6-position of the preceding unit, predominantly to the 2-position.

Nonionic surfactant fatty acid amide

The surfactant fatty acid amides suitable for the present invention are those of the formula

..... o .....................................-...... ................-........-................... ..... ....-.............................- ~

R 6 -CN- (R 7) ₂ wherein R ⁸ is an alkyl group containing 7 to 21, preferably 9 to 17 carbon atoms, and each R ⁷ is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl and - (C 2 H 4 O) ) xH, wherein x is 1 to 3.

Ampholytic surfactants

The present detergent compositions may contain ampholytic surfactants. These surfactants can generally be described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary or tertiary amines whose aliphatic radical may have a straight or branched chain. One of the aliphatic substituents contains at least 8 carbon atoms, typically 8 to 18 carbon atoms, and at least one contains a water-solubility facilitating group, such as a carboxyl, sulfonate or sulfate. Examples of ampholytic surfactants are disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975 to Laughlin et al., Column 19, lines 18-35.

Amphoteric surfactants

Amphoteric surfactants suitable for the present invention include alkylamphocarboxylic acids of the general formula

II

RC-NHCH 2 CH 2 R 1 wherein R is a C 6 -C 16 alkyl group and R 1 is a group of formula (CH 2) x COO-M (CH 2) x COO-M or N ⁺ CH 2 CH 2 OH

R ¹

R ¹ wherein R ¹ is (CH 2) x COO M or CH 2 CH 2 OH and x is 1 or 2 and M is preferably selected from alkali metal, alkaline earth metal, ammonium, mono-, di- and triethanolammonium ions, sodium, potassium, ammonium and their mixture with ions is C10-C14 alkyl. is derived from magnesium amphodicarboxylic acid. Preferred alkyl chain R Preferred amphoteric carboxylic acid of imidazolines wherein the dicarboxylic function of the acid is diacetic acid and / or dipropionic acid. An example of an amphodicarboxylic acid suitable for the present invention is the amphoteric surfactant Miranol ™ C2M Conc. manufactured by Miranol Inc., Dayton, NJ.

Zwitterionic surfactants

The present detergent compositions are zwitterionic surfactants.

These surfactants may in general and tertiary amines, and tertiary amines, be described as derivatives of secondary derivatives of heterocyclic secondary or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Examples of zwitterionic surfactants are disclosed in U.S. Pat. No. 3,929,678, issued December 30, 1975 to Laughlin et al., Column 19, line 38 to column 22 line 48 (incorporated by reference).

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

A long owing foam

The present compositions preferably further comprise 1 to 20%, preferably 2 to 20% by weight. sudsing agents. These agents may be selected from the group consisting of amine oxides, betaines, sultaines, complex betaines, and some nonionic compounds.

Suitable amine oxides for the present invention are compounds of formula

O

AND

R ³ (OR ⁴ ) x N (R ⁵ ) ₂ wherein R ³ is alkyl, hydroxyalkyl, acylamidopropoyl, alkylphenyl or a mixture thereof, a group containing 8 to 26, preferably 8 to 16 carbon atoms; R ⁴ is an alkylene or hydroxyalkylene group having 2 to 3, preferably 2 carbon atoms, or a mixture thereof, x is 0 to 3, preferably 0, and each R ⁵ is an alkyl or hydroxyalkyl having 1 to 3, preferably 1 to 2 carbon atoms or a polyoxyethylene group containing 1 to 3, preferably 1, ethylene oxide group. The R ⁵ groups may be bonded to each other by, for example, an oxygen or nitrogen atom to form a ring structure.

These amine oxide surfactants include C 10 -C 16 alkyl dimethylamine oxides and C 6 -C 12 alkoxy-ethyldihydroxyethylamine oxides. Examples of such materials are dimethyl octyl amine oxide, diethyldecyl amine oxide, bis- (2-hydroxyethyl) dodecylamine oxide, methyl ethyl hexadecylamine oxide, dodecylamidopropyldimethylamine oxide and dimethyl-2-hydroxyoctadecylamine oxide. Preferred are C10-C18 alkyl dimethylamine oxides and C10-C18 acylamido-alkyl dimethylamine oxides.

Betaines suitable for the present invention are compounds of formula

R (R ¹ ) ² N ⁺ R ² C0019 wherein R is a C 6 -C 18 hydrocarbon group, preferably a C 1 -C 18 alkyl or C 1 -C 18 acylamidoalkyl, each R ¹ is typically C 1 -C 3 alkyl, preferably methyl, and R ² is C 1 -C 5 a hydrocarbon group, more preferably C 1 -C 2 alkylene. An example of betaine is presented

C 1 -C 3 alkylene suitable for acylamidopropyldimethyl betaine; C12-C14 acylamidopropylbetaine;

diethylbetain; 4 [C 14 -C 18

-carboxybutane; C16-C18 of the invention are coconut hexadecyldimethyl betaine; C8-C14 acylamidohexylacylmethylamidodiethylammonio] -1acylamidomethylbetaine; C12-C16 acylamidopentanediethylbetaine; [C 12 -C 18 acylmethylamidodimethyl betaine. Preferred betaines are C 12 -C 18 dimethylammonium hexanoate and C 10 -C 18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.

Sultains suitable for the present invention are compounds of formula

R (R ¹ ) ² N * R ² SO ³ where R is a C 6 -C 16 hydrocarbon group, preferably C 10 -C 16 alkyl more preferably C 12 -C 13 alkyl, each R ¹ is typically C 1 -C 6 alkyl, preferably methyl, and R ² is C 1 -C 6 hydrocarbon group, preferably a _C1-C3 alkylene or, preferably, hydroxy ky1en 1. Examples of sultains suitable for the present invention are C12-C14 dimethylammonio-2-hydroxypropyl sulfonate, C12-C14 amidopropylammonio-2-hydroxypropyl sulfide, C12-C14 dihydroxyethyl ammonium propane sulfonate, and C12-C14 dimethyl ammonium hexyl sulfonate; 2-hydroxypropylsulfoline.

Complex betaines suitable for the present invention are compounds of formula

R (A) n - [N- (CHR 1) x] y-N-Q (I)

I I

Kde B where R is a C 7 -C 22 hydrocarbon group, A is a (C (O)) group, n is 0 or 1, R 1 is hydrogen or lower alkyl, x is 2 or 3, y is an integer from 0 to 4, 6? is the group -R 2 COOM, wherein

- 20 CH2 COON /

R 2 is an alkylene group having 1 to 6 carbon atoms and M is hydrogen or an ion derived from the group of alkali metal, alkaline earth metal, ammonium and substituted ammonium ions and B is hydrogen or a group Q as defined above. An example of this category is tallowamphopolycarboxyglycinate of the formula;

CH2C00Na CH2C00Na CH2COONa

I I I

R-N-CH2CH2 CH2-N-CH2 CH2 CH2-N-CH2 CH2 CH2 N \

CH2 COONa

Preferred amides are C8-C20 alkyl mono- or di-C2-C3 and canoamides, especially monoethanolamides, diethanolamides and sopropanolamides.

Preferred sudsing agents are C10-C18 acyl-amide-alkyl-dimethylamides, betaines, sultaines, condensation products of aliphatic alcohols with ethylene oxides, and alkanes to polysaccharides and mixtures thereof.

Hydrotropic substances

Hydrotropic substances are typical components of the present compositions and are 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, such as sodium, potassium and ammonium sulfonates, sodium, potassium and ammonium cumonates, and mixtures thereof.

Other substances which can be used as hydrotropic agents are polycarboxylates. Some polycarboxylates have the ability to chelate calcium ions in addition to hydrotropic properties.

Particularly preferred hydrotropic agents are alkyl polyethoxy polycarboxylate surfactants of the type described above.

of the compounds is

An example of suitable commercially available alkyl polyethoxy polycarboxylates is POLY-TERGENT C, 01in Corporation, Cheshire, CT.

Another suitable hydrotrope is an alkyl amphodicarboxylic acid of the formula:

(CH2) xC00 ~ /

RCNHCH2CH2N \

_(CH2) xC00M wherein R is Ca-Cie alkyl group, x is 1-2, M is selected from the group consisting of alkali metal ions, alkaline earth metal, ammonium, mono-, di- and tri-ethanolammonium, most preferably from sodium , potassium, ammonium and mixtures thereof with magnesium ions. A preferred alkyl chain R is C 10 -C 11 alkyl and the dicarboxylic function is diacetic acid and / or dipropionic acid.

An example of an amphodic carboxylic acid suitable for the present invention is the amphoteric surfactant Miranol R 2CM Conc. manufactured by Miranol Inc., Dayton, NJ.

Lime soap dispersing agents

It is highly preferred that the present compositions comprise lime soap dispersing agents, i.e., agents that disperse all insoluble salts of lime soaps formed from fatty acids by lipolytic hydrolysis of fats / oils in the presence of calcium ions contained in the wash solution. Dispersing agents thus prevent the deposition of these salts as stains or coatings on the articles to be washed, or as a discreet circle at the edge of the sink. Some dispersing agents may also enhance the stability of the formulation, particularly by dispersing from the dispersing agent to determine Borghetty, H. C., (1989). LSDP is the weight by weight of sodium oleate as a reagent that, when in liquid form, contains calcium ions.

The lime soap dispersing agent of the present invention can be defined as a lime soap dispersing power LSDP as defined below, not exceeding 8, preferably not exceeding 7, most preferably not exceeding 6. The lime soap dispersing agent is typically present in an amount of 0.1 to 40 wt.%, More preferably 1 to 20 wt.%, Most preferably 2 to 10 wt. relative to the weight of the preparation.

The lime soap dispersing agent is a material that prevents the precipitation of sodium, ammonium or amine salts of fatty acids by calcium or magnesium ions. Numerically, the efficacy of the lime soap dispersant is expressed by the force (LSDP) of the assay as described in Bergman, C.A., J. Am.Chem.Soc., Vol. 27, p. 88-90 (1950). This test is widely used in the art, see review articles: L inf i Id, W. N .; Surfactant Science Series, vol. 7, p.3; Linfield, W. N., Tenside Surf. Det., Vol. 27, p.

159-161 (1990); Nagarajan, M. K., Masler, W. F., Cosmetics and

Toi letr ies, vol. 104, p. 71-73 dispersant ratio to percent, for the amount of dispersant needed to disperse deposits formed from 0.025 g sodium oleate in 30 ml of water containing 333 ppm of CaCO3 (Ca: Mg = 3: 2) equivalents hardness.

According to Borghetta / Bergman dispersion test, to 5 ml 0.5 wt. of sodium oleate solution in the test tube add 10 ml of hard water containing 600 ppm Ca ²⁺ and 400 ppm Mg ²⁺ (1000 ppm equivalent to CaCO 3, 70 ° Clark hardness scale) to form lime soap deposits (or precipitate). Any amount (less than 15 ml) of 0.25 wt. of a dispersing agent solution. The total volume of the solution in the test tube is adjusted to 30 ml, capped, inverted 20 times and allowed to stand for 30 seconds. It is visually determined whether the deposits in the tube remain intact or have been dispersed in the solution. The test is repeated with varying amounts of dispersing agent until the minimum amount of agent required to disperse the lime deposits is determined.

The LSDP dispersion force can then be calculated from:

LSDP = (weight of lime soap dispersing agent) x 100 (weight of sodium oleate)

This test shows that a low LSDP material is a more efficient dispersant than a higher LSDP material.

Calcium

The present compositions contain 0.05 to 3% by weight, preferably 0.15 to 2% by weight. calcium ions. It has been found that the presence of calcium iotones in formulations containing amides of polyhydroxyl fatty acids substantially increases the ability to remove fatty impurities. This is particularly noticeable when using formulations in softened water that contains few divalent iotons.

Calcium ions can be added, for example, as chloride, hydroxide, oxide, formate, acetate or nitrate.

When anionic surfactants are used in acid form, calcium can be added as a suspension of calcium oxide or hydroxide in water, neutralizing the acid present.

The calcium ions may be included as salts in the formulation. Their amount in the formulation depends on the total amount of anionic surfactants present in the formulation. The molar ratio of calcium ions to total amount of anionic surfactants in the composition of the present invention is preferably 1: 1.0 to 1:25, more preferably 1: 2 to 1:10.

Calcium stabilizing agent

For a calcium-containing product, stabilization can be carried out, and in particular the precipitation of calcium salts can be prevented by the addition of malic or maleic acid or certain types of reagents.

- 24 dispersing lime soaps. Malic acid or maleic acid is added to the calcium-containing formulations in an amount of 0.05 to 10% by weight, in a molar ratio to calcium of 0.01: 1 to 1:10.

Magnesium

0.01 to 3% by weight, most preferably 0.15 to 0.9% by weight, are added to the liquid preparations of the present invention. magnesium ions, which increases their stability and foaming.

. When anionic surfactants are used in acid form, as with calcium, magnesium can be added as a suspension of magnesium oxide or hydroxide in water, neutralizing the acid present to the amount of chloride chloride added to the formulation.

This procedure reduces the ions and thereby reduces the neutralized surfactants and the hydrotropic components are then added to the final mixture in the mixing tank and all other components are added before the final pH adjustment.

PH value of the preparation

The composition of the liquid detergent compositions of the present invention is selected such that the pH of the wash solution is in the range of 5.0 to 8.0 during use in an aqueous wash. The liquid preparations themselves have a pH (10% aqueous solution at 20 ° C) preferably of 5.5 to 8.5, most preferably 6.8 to 7.8.

Methods for maintaining the pH at the recommended level include the use of buffers, bases, acids, etc., as is well known in the art. Dilute hydrochloric acid is useful for lowering the pH, sodium hydroxide for increasing.

System of enzyme stabilizing substances

Formulations 0.001 to 10%, w / w; The systems of the present invention further preferably contain preferably 0.005 to 8%, most preferably 0.1 to 6% enzyme stabilizing agents. This enzyme stabilizing system is any enzyme-compatible stabilizing system of the present invention. Such a system includes calcium ion, boric acid, short-chain carboxylic acid, propylene glycol, boron water, polyhydroxy compounds, and mixtures thereof, as described in U.S. Ser. Boskamp, eds. And 4,537,707.

U.S. Patent 4,318,818 to Letton et al .; 4,462,922, Jul 31, 1984; 4,532,064, Boskamp, issued July 30, 1985;

Severson Jr., issued August 27, 1985, all incorporated herein by reference.

It is further preferred to add 0 to 10%, preferably 0.01 to 6% by weight of the present compositions. chlorine scavenging agents, which are present as chlorine bleach in many water sources and can, in particular in an alkaline environment, attack and inactivate the enzymes of the composition. Although the chlorine content of the water is usually low, typically 0.5 to 1.75 ppm, the total amount of chlorine that comes into contact with the enzyme is significant due to the large volume of water used; thus, the stability of the enzyme present may be problematic.

Suitable chlorine scavenging anions are ammonium salt anions. They may be selected from the group consisting of reducing compounds such as sulfite, bisulfite, thiosulfite, thiosulfate, iodide etc., antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or its alkali salt and monoethanolamine (MEA), and a mixture of said substances. Other conventional anion-absorbing anions such as sulfate, hydrogen sulfate, carbonate, bicarbonate, percarbonate, nitrate, chloride, borate, sodium perborate tetrahydrate, sodium perborate monohydrate, phosphate, polyphosphate, acetate, benzoate, citrate, formate, lactate, malate, malate, malate, malate, lactate , salicylate, etc., and mixtures thereof. Suitable ammonium or other salts of specific anionic scavengers may be added to or used in place of the suds boosters.

Although ammonium salts can be incorporated into the detergent composition, they tend to absorb water and / or release ammonia. Therefore, it is preferable that they are protected in particulate form, as described in U.S. Pat. No. 4,652,392 to Baginski et al.

asesasasw®ss

- 26 included in references.

Preparations in the form of liquids or gels

According to a preferred embodiment of the invention, the present detergent compositions are liquid. A preferred liquid formulation comprises 94 to 35%, preferably 90 to 40%, most preferably 80 to 50% by weight. a liquid carrier, eg water, preferably a mixture of water with a C 1 -C 4 monohydroxyl alcohol (eg ethanol, propanol, isopropanol, butanol and a mixture thereof), preferably with ethanol, or a mixture of water with a C 1 -C 4 dihydroxyl alcohol (eg propylene glycol).

Ge 1 y

Further, the present detergent compositions may be in the form of a gel. Such formulations typically contain polyalkenyl polyethers having a molecular weight of 750,000 to 4,000,000 hj. .

An example of a highly preferred polymeric polycarboxylate thickener is the range of Carbopol 600 resins available from B.F. Goodrich. Particularly preferred are Carbopol 616 and 617. It is believed that these polymers are more crosslinked than a series of 900 resins and have a molecular weight ranging from 1,000,000 to 4,000,000, i. . Mixtures of said polycarboxylate polymers can also be used in the present invention. Particularly preferred is a mixture of Carbopol 616 and 617 resins.

Polycarboxylate thickeners are preferably used without the clay thickener. It has been found that the simultaneous presence of polycarboxylate and clay thickeners in the formulations of the present invention results in poor product quality due to phase instability. In other words, polycarboxylate polymers are used in the present compositions preferably instead of clay thickeners as thickening / stabilizing agents.

When used as a thickener in the present composition, the carboxylate polymer is typically present in an amount of 0.1 to 10%, preferably 0.2 to 2% by weight.

The thickening agents are preferably selected to give a shear stress value of 50 to 350, most preferably 75 to 250. This value is a measure of the shear stress at which the cohesive gel forces are overcome and flow begins. In the present work, this value is measured by a Brookfield RVT model viscometer with a T-bar B shaft at 25 ° C using Helipath.

Other suitable components of the present compositions are dyes, perfumes

Opalescing agents, e.g.

Inc.), the modified polystyrene latex or ethylene glycol distearate can be added to the formulation preferably in the final preparation step. Lytron can be added directly as a dispersion during mixing. Ethylene glycol distearate can be added as a melt with rapid stirring, resulting in the formation of pearlescent crystals.

In particular, opalescent substances are present in amounts of not very dense preparations in an amount of 0.2 to 10%, preferably 0.5 to 6% by weight. .

and opalescent agents. Lytron (Morton Thiocol,

Manual dishwashing procedure

The hand dishwashing process of the present invention contemplates contact of the soiled dishware with an effective amount of the present composition, typically 0.5 to 20 ml (25 plates), preferably 3 to 10 ml. The actual amount of liquid preparation used depends on the choice of the user and the particular composition of the preparation, its concentration, the amount of soiled dishes and the degree of soiling.

The particular manual dishwashing process may be arbitrary and includes options such as washing with a dilute solution of the detergent in a sink, usually performed in Northern Europe and the USA; washing with a dilute solution of the product in a scrub, usually performed in Latin America and Japan, and a direct application procedure, usually performed in southern Europe and developing countries.

- 28 Dilution washing with the spray liquid in the sink

In a process based on the use of a dilute solution of a preparation in a wash sink, 3-15 ml, preferably 5-10 ml of liquid preparation are mixed with 1,000-10,000 ml, more often 3,000-5,000 ml of water in a sink of 5,000 up to 20,000 ml, more often 10,000 to 15,000 ml. The detergent composition comprises surfactants in a concentration of 10 to 60% by weight, preferably 45 to 50% by weight. The soiled dish is immersed in a sink containing detergent and water and is washed with a piece of cloth, sponge or the like. A piece of cloth, sponge, or the like can be immersed in a solution in the sink before the dishwashing process begins, and the surface of the dishwashing is then most often washed for 1 to 10 seconds, although the actual time depends greatly on the user's habit. Washing the surface of the dishes with a piece of cloth, sponge or the like is preferably accompanied by scrubbing.

Washing with a dilute solution of the product in a pot

In a method based on the use of a dilute solution of the formulation in a vial, 1 to 50 ml, preferably 2 to 10 ml of the liquid formulation are mixed with 50 to 2,000 ml, more often 100 to 1,000 ml of water in a vial of 500 to 5,000 ml. , more often 500 to 2000 ml. The detergent composition comprises surfactants in a concentration of 10 to 60% by weight, preferably 15 to 50% by weight. Dirty dishes are washed with a piece of cloth, sponge or the like. A piece of cloth, sponge or the like can be immersed in the washing solution before the dishwashing process begins, and the surface of the dishwashing is then most often washed for 1 to 10 seconds, although the actual time depends greatly on the user's habit. Washing the surface of the dishes with a piece of cloth, sponge or the like is preferably accompanied by scrubbing.

Direct application procedure

In the direct application procedure, the dishes are first immersed in a sink with water without detergent. The article capable of absorbing a liquid detergent composition, such as a sponge, is then immersed directly into a separate amount of undiluted liquid or gel detergent composition for 1 to 5 sec. With this detergent item, the soiled dishes are then washed individually. The surface of the dishes is then washed most often for 1 to 10 seconds, although the actual time depends greatly on the user's habit. Washing the surface of the dishes with an absorbent article is preferably accompanied by scrubbing.

DETAILED DESCRIPTION OF THE INVENTION

The following formulations were prepared according to the present invention.

% wt.

AND II III IV IN C12 / 13 alkyl ethoxy (dia. 0.8) sulfate 10.0 10.0 9.0 5.0 10.0 C12 / 13 alkyl ethoxy (dia. 3) sulfate 7.0 7.0 8.0 15.0 7.0 C12 / 14 alkyl amine oxide 2,0 1.0 - 1.0 2,0 C12 / 14 alkyldimethyl beta i n - 1.0 1.5 2,0 - C12 / 14 Ampholak (TM) - - 1.5 - - C12 and alkyl-N-methyl glucamide 12.0 12.0 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 Ca ⁺⁺ ion - - 0.3 0, 15 0.1 Kys. maleic - - 0.2 0.3 - M i morning 1 ™ - - 2,0 - - Polytergent ™ - - - 2,0 - L even after lasso ™ 0.05 0.1 0.2 0.3 0.4

Preparation of the formulation involved mixing all surfactants except glucamide. The magnesium and calcium salts were previously dissolved together with maleic acid and added with the remaining ingredients to the surfactant mixture. Finally, the pH was adjusted to 7.3 with hydrochloric acid and the viscosity of the formulation checked.

Industrial applicability

The present invention provides a liquid, high sudsing, dishwashing composition comprising a surfactant system and a lipolytic enzyme.

Claims (1)

Claims A composition comprising a polyolytic enzyme suitable for use in hand dishwashing. A composition according to claim 1, characterized in that it is highly foaming. Composition according to claim 1 or 2, characterized in that it is in the form of a liquid or a gel. Composition according to any one of claims 1 to 3, characterized in that it contains no salts as builders. The composition of any one of the ingredients comprises no bleach. claims 1 to 4 as building Composition according to any one of claims 1 to 5, characterized in that it comprises from 5 to 10% 80 wt. said surfactant assemblies comprising surfactants selected from nonionic, anionic, cationic, zwitterionic, ampholytic and amphoteric surfactants. Composition according to any one of claims 1 to 6, characterized in that the pH is 1% by weight. of said solution is 6-9. The composition of any one of: