CZ76196A3 - Detergents comprising lipolytic and proteolytic enzymes intended for washing-up in wash machines - Google Patents

Abstract

According to one aspect of the present invention there is provided a composition containing a surfactant system, lipolytic enzyme and proteolytic enzyme suitable for use in a manual dishwashing method. Preferably said composition is in the form of a liquid or a gel. Preferably said composition contains no builder salts. Preferably said composition contains no bleaching components.

Description

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The hand dishwashing detergent composition meets the need for a composition that meets a number of different consumer requirements for adequate efficacy.

Firstly, such a composition should be effective in removing dirt from dirty "dishes" when manually washing dishes. The term utensils ^-1 is used herein in a generic sense to include virtually anything that belongs to the dishes, including Chinese products, glass containers, plastic containers, hollow dishes (china, glass and metal), knives and cutlery, including silver.

Dirt that can be encountered when washing dishes is considerable, but does not come exclusively from food. Particularly difficult to remove impurities include fats, burns and scalds, dried food residues, highly colored impurities such as those from very colorful vegetables such as beetroot and tomatoes, as well as non-food impurities such as lipstick on glass edges or nicotine stains on saucers used as an ashtray.

Contaminants that have already been removed from the dishes are treated by the detergent by suspending them in the wash solution to prevent them from returning to the dishes or the sink surface.

While good removal and antiredeposition are common to performance requirements for dishwashing detergents, hand dishwashing detergents also meet

--------— Additional efficiency requirements. -------------------------------------------------- ------------E.g. hand dishwashing agent should foam a lot and the foaming should last throughout the washing process. The foaming is used as an indicator for the person performing the wash that the wash solution still contains the active ingredients of the detergent. After the foam has subsided, the sink is drained, and a fresh wash solution is prepared. Foam persistence during the washing process is measured in industry by various foam performance indicators.

Hand dishwashing detergent should also be gentle on the skin, especially on the hands. It should not cause the skin to dry, crack or redden when it comes into contact with the product. Such drying, cracking or reddening of the skin results primarily from the removal of natural oils, more particularly epidermal lipids, from the skin. Thus, it is desirable that the hand dishwashing agent be effective in removing fat from the plates, but does not remove epidermal lipids from the skin.

Due to the different nature of the performance requirements for a manual dishwashing composition, such compositions are prepared in different ways, for example, from dishwashing detergents, laundry detergents and solid surface cleaners.

Hand dishwashing compositions are generally free of filler and may contain additional levels of calcium and magnesium to aid efficient cleaning. Detergent and automatic dishwashing compositions typically contain high levels of fillers.

Hand dishwashing compositions typically do not contain any bleaching components, which are in contrast to the detergent, dishwasher and dishwashing compositions.

Hand dishwashing compositions typically contain high levels of high sudsing surfactants and often suds boosters. Desirably and dishwashing detergent compositions are desirably low foaming and typically contain low surfactant levels.

Hand dishwashing compositions are formulated to function well in a region close to neutral pH. Detergents and dishwashing detergents are typically alkaline with a pH in the range of usually from 9 to 11. Solid surface cleansing compositions containing a bleaching agent are often acidic, with a pH of less than 6.

The key active ingredient of a hand dishwashing composition is most commonly a surfactant system, which typically comprises from 5 to 80% by weight of the composition. The primary objective of the surfactant system is to remove contamination, but it also acts to suspend impurities in the solution and prevent re-attachment of these impurities. In addition, the surfactant system should be effective in removing and suspending fatty impurities.

Amylolytic, proteolytic and lipolyphic enzymes are common ingredients in laundry detergent and dishwashing compositions prepared in either granular or liquid (liquid / gel) form. The use of enzymes is not commonly recognized for hand dishwashing detergents.

Amylolytic enzymes or amylase enzymes act as catalysts for thyroid-starch protein protection as well as catalysts for the hydrolysis of peptide bonds in proteins. Lipolytic enzymes or lipases act as catalysts for the hydrolysis of fats or oils, including glycerol and fatty acid esters, to these glycerols and fatty acids, in

BACKGROUND OF THE INVENTION

The Applicant has now found the value of including a lipolytic enzyme in combination with a proteolytic enzyme in compositions specifically formulated for use in hand dishwashing. The specific usefulness of a combination of a lipase with a protease in such compositions has not been previously known in the art. However, the broad field of use of such enzymes in combination in dishwashing detergents and dishwashing detergents does not disclose a clear way of their usefulness in hand dishwashing, which could indicate bias against the use of such enzymes in hand dishwashing detergents,

At the core of this indicated bias may be the well-established trust in surfactants to aid the removal of fats in the art regarding hand dishwashing. It is believed that at high concentrations of fat-removing surfactant, the inclusion of lipases that act hydrolytically on fats will not be successful. Another reason for the indicated bias may be due to the belief that fatty acid products obtained by lipase degradation of oils or fats can act as suds suppressors. , thereby jeopardizing the desired high foaming efficiency. ------------------------------ - ------------------- SUMMARY OF THE INVENTION

The Applicant has found that a combination of lipase and protease is particularly useful to aid in the removal of baked or burnt contaminants from dishes in solution. It is known that these impurities are particularly difficult to remove during manual dishwashing because they are solid and typically adhere strongly to the contaminated substrate.

The removal of such baked or burnt impurities is particularly enhanced when the lipase and protease compositions are used in a washing process including a soaking step. The soaking step may comprise immersing the soiled parts for a period of time in a dilute solution containing the detergent composition. Alternatively, a highly concentrated solution of the composition can be applied directly to the surface of the dishes and thus allowed to act for a certain period of time prior to subsequent rinsing / washing steps.

The Applicants have further found that hand dishwashing compositions comprising a proteolytic enzyme and an iipolytic enzyme can be prepared having desirable skin-softening properties.

In addition, the present inventors have found that a combination of lipase and protease is particularly advantageous in a liquid, particularly liquid, hand dishwashing composition containing certain surfactant systems that act to stabilize these enzymes.

Summary of the Invention

The composition of the present invention comprises a surfactant system, a lipolytic enzyme and a proteolytic enzyme suitable for use in hand dishwashing.

The present composition is preferably in the form of a liquid or gel.

The present composition contains no filler salts.

The present composition contains no bleaching ingredients.

The present composition preferably comprises from 5 to 80% by weight of a surfactant system, the surfactant system comprising a surfactant selected from nonionic, anionic, cationic, zwitterionic, ampholytic and amphoteric surfactants.

In one aspect of the present invention, the composition is highly foaming.

Embodiments of the invention

Lipolytic enzyme

The first essential component of the compositions of the present invention is a lipolytic enzyme (lipase), which is preferably present in amounts of active lipolytic enzyme from 0.001 to 2% by weight, more preferably from 0.005 to 1% by weight, most preferably from 0.01 to 0.5% by weight of the compositions .

The lipase is preferably of bacterial origin obtained, for example, from a strain producing ITpase Humicúía sp. or Thermamyces sp. or Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens.

Lipases from chemically or genetically modified mutants of these strains are also included herein. Mixtures of lipases from different strains are also included, but not preferably.

A preferred lipase is from the Pseudomonas pseudoalcaligenes strain. as described in Granted European Patent, EP-B-0218272.

Another preferred lipase is obtained by cloning the gene from Humicoia lanuginosa and expressing the gene in Aspergillus oryza as host, as described in European Patenr Application, EP-A-0258 068, and which is commercially available from Novo indusfri A / S, Bagsvaerd, Denmark , under the trademark Upolase. This lipase is also described in U.S. Pat. U.S. Patent 4,810,414 to Huge-Jensen et al. 1989.

Lipases are preferably compatible with surfactants herein. They are preferably stable in the compositions of the present invention and improve cleaning when included in the present compositions.

Suitable lipases include those that exhibit a positive immunological cross-reaction with the lipase antibody produced by Pseudomonas fluorescens. This lipase, described in Jaoanese Patent Application 53-20487, was filed February 24, 1987. It is available under the trademark Lipase P Amano. A method for testing an immunological cross-reaction with an Amano P antibody is described in U.S. Pat. Steam 4,707,291, Thom et al., Issued November 17. 1987.

The lipase unit (LU) is defined as the amount of lipase that is produced by trisubstituted butanoic acid at equilibrium pH where the pH is 7.0. 30 ° C and the substrate is an emulsion of ributyrin and acacia in the presence of Ca ² 'and NaCl in phosphate buffer.

Proteolytic enzyme

A second essential component of these compositions of the present invention is a proteolytic enzyme (protease), which is preferably present in an amount of active enzyme of from 0.005 to 2% by weight of the composition. The proteolytic enzyme is preferably included in an inflow amount such that the weight ratio of the active lipolytic enzyme to the active profeolytic enzyme is from 20: 1 to 1:20, preferably from 10: 1 to 1:10, more preferably from 5: 1 to 1: 5.

Preferred commercially available protease enzymes include the aforementioned sold under the trademarks Alcaiase and Savinase from Novo Industries A / S (Denmark) and Maxatase from International Bio-Synthefics, Inc. (Netherlands),

Amylolytic enzyme

The amylolytic enzyme (amylase) may be included in the compositions of the present invention in a preferred amount of active enzyme of from 0.005 to 2% by weight of the composition.

Preferred amylases include, for example, alpha-amylases obtained from a special strain of B licheniformis described in more detail in GB 1269 839 (Novo). Preferred commercially available amylases include, for example, Rapiclase from International Bio-Synthetics, Inc. and Termamyt from N o v tnd usf A / S. '

Enzyme stabilizing system

Preferred compositions comprising the enzyme of the present invention comprise from 0.001 to 10%, preferably from 0.005 to 8%, most preferably from 0.01 to 6% by weight of the enzyme stabilizing system. The enzyme stabilizing system may be any stabilizing system compatible with a detersive enzyme. Such stabilizing systems include calcium ions, orthoboric acid, propylene glycol, short chain carboxylic acid, boric acid, and mixtures thereof.

The compositions of the present invention may further comprise from 0 to 10%, preferably from 0.01 to 6% by weight, of chlorine bleach scavengers added to prevent attack and inactivation of the enzymes with chlorine bleaching agents present in many aqueous sources. While the amounts of chlorine in water are small, typically ranging from 0.5 to 1.75 parts per million, the available chlorine in the total amount of water that comes into contact with the enzyme during dishwashing is usually large; therefore, enzymatic stability when using the composition can be problematic.

Suitable chlorine scavenger anions are widely available, virtually ubiquitous, and examples include salts containing ammonium cations or sulfites, bisulfites, thiosulfites, thiosulfates, iodides, etc. Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetraacetic acid may also be used. EDTA.) Or an alkali metal salt thereof, monoethanolamine (MEA) and mixtures thereof. If desired, can other conventional scavengers such as hyphensulphate / nitrafe also be used? The peroxide-hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof. In general, since various ingredients listed separately in the description of the more recognizable functions (eg, other components of the present invention including oxygen bleaching agents) may exhibit the chlorine scavenger function, there is no requirement to add a separate chlorine scavenger unless embodiments comprising an enzyme of the present invention; even then the scavenger is added only for optimum results. In addition, routine chemical experience will be tested to avoid the use of any scavenger that is substantially incompatible with other suitable ingredients when used. E.g. the chemist will generally recognize that combinations of reducing agents such as thiosulfate with strong oxidizing agents such as percarbonate; it is not reasonably prepared unless the reducing agent is protected from the oxidizing agent such that the composition is in solid form. Similar to the use of ammonium salts, such salts can be simply mixed with the detergent composition, but are prone to water adsorption and / or ammonia release during storage. Therefore, such materials, if present, are suitably protected in the particles as described in U.S. Pat. U.S. Patent 4,652,392 to Baginski et al.

pH of the composition

The detergent compositions of the present invention are preferably prepared such that during use in aqueous cleaning operations, particularly when using a dilute detergent solution. of the composition, the wash solution will have a pH in the range of 5.0 to 8.0. Compositions intended for use in such aqueous cleaning operations preferably have a pH of 1¾ solution in water at a temperature of 20 ° C in the range of 5.5 to 8.5, most preferably from 6.8 to 7.8.

In another aspect of the present invention, the compositions can be prepared for use in a dishwashing process wherein the detergent composition is applied to the dishes in substantially concentrated form and preferably is thus left on the dishes for extended periods of time. Compositions intended for use in this manner may be prepared having a pH of a 1% solution in water in the range of from 3.5 to 4.5.

Techniques for controlling pH at recommended user levels include the use of buffers, bases, acids, etc., and are well known to those skilled in the art. Dilute hydrochloric acid is preferred for lowering the pH and sodium borohydride for increasing the pH.

Surfactant system

The compositions of the present invention comprise a surfactant system in amounts of from 5 to 80%, preferably from 10 to 60%, most preferably from 15 to 50% by weight of the composition

The surfactant system is preferably formulated to be compatible with the enzyme components. In liquid or gel formulations, the surfactant system is most preferably found to be

Uje Z enhances, or at least does not degrade, the stability of enzymes in such compositions; ’

The surfactant system includes a surfactant selected from the group of nonionic, anionic, cationic, zwitterionic, ampholytic and amphoteric surfactants and mixtures thereof.

The surfactant system preferably comprises from 5 to 95% by weight, more preferably from 30 to 7% by weight of the anionic surfactant by from 5 to 95% by weight, more preferably from 30 to 70% by weight of the nonionic surfactant.

In preferred compositions of the present invention formulated to render the skin more gentle, the weight ratio of nonionic surfactant to anionic surfactant is preferably greater than 1: 1.

Anionic surfactant

The aninic surfactant may be substantially any anionic surfactant, including anionic sulfate, sulfonate or carboxylate surfactant.

Anionic sulfate surfactant

The anionic sulfate surfactant may be any organic sulfate surfactant. Is preferably selected from the group consisting of C _{LT-C l6} alkyl sulfate which has been efoxylován average of from 0.5 to 20 moles of ethylene oxide per molecule, a C, to C, acyl-N- (C, until CY alkyDglukaminsulfái and mixtures thereof.

Alkyletoxysultátové surfaktanfy suitable for use herein include primary oředkládaného alkyletoxysultát derived from the condensation product of C _{l ()} to C _ló alcohol with an average of from 0.5 to 20, preferably 0.5 to 12 ethylene oxide groups. C _i2 to C ₁₄ alkyl sulfate which has been ethoxylated with an average of 0.5 to 4'moly etylenoxfdu per molecule is especially preferred.

The counter-charged ion of the anionic sulfate surfactant component is preferably selected from the group consisting of calcium, sodium, potassium, magnesium, ammonium or alkanol-ammonium ion, and mixtures thereof, wherein calcium and magnesium are preferred for purification and foaming respectively.

Anionic sulfonate surfactant

Anionic suifonate surfactants suitable for use in the present invention include, for example, salts (e.g., alkali metal salts) of C ₉ to C ₂₀ linear alkylbenzene sulfonates, C ₃ to C ₂₂ primary or secondary alkanesulfonates, C ₃ to C ₂₄ olefinsulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates , fatty acid acylglycerol sulfonates, fatty acid oleyl glyceroisulfonates, paraffin sulfonates and mixtures thereof.

Anionic alkyl ethoxycarboxylate surfactant

Alkyl ethoxycarboxylates suitable for use in the present invention include compounds of the general formula

RO (CH ₂ CH ₂ O \ CH ₂ COOM wherein R ⁺ is C _,.; to C ₁₆ alkyl group, x ranges from 0 to 10 and the ethoxylate distribution is such that (by weight) the amount of material where x is 0 is less than 20%, preferably less than 15%.

most preferably less than 10%, and the amount of material wherein x is greater than -------- 24e-less than 25%; preferably - a cross-section of T 5% T most preferably less than ---- 10%, the average value of x being from 2 to 4, wherein on average R is C ₁₃ or less; and the average value of x is from 3 to 6, wherein on average R is greater than C ₁₃ , and M is a cation, preferably selected from the group consisting of alkali metals, alkaline earth metals, ammonium ion, mono-, di- and triethanolamine | an ion, most preferably comprising sodium, potassium, ammonium ion, and mixtures thereof with magnesium ions. Preferred alkyl ethoxycarboxylates are those wherein R is a C ₁₂ to C ₁₄ alkyl group.

Anionic alkylpolyethoxypolycarboxylate surfactant

Alkylpolyethoxypolycarboxylate surfactants suitable for use in the present invention include compounds of the general formula:

RO-CHR ^ CHR ^ -OVR ³ wherein R is a _C6 to _C18 alkyl group, x is 1 to 25, R ¹ and R ² are selected from the group consisting of hydrogen, methylacid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, wherein at least one R 1 or R ² is a succinic or hydroxysuccinic acid radical, and R ³ is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having from 1 to 8 carbon atoms, and mixtures thereof.

Anionic secondary soap surfactant

Secondary soap surfactants - (also known as alkyl carboxyl surfactants) useful in the present invention are those containing a carboxyl attached to the secondary carbon. Here, it is meant that this secondary carbon atom may be in the cycle structure of, for example, p-ocphylbenzoic acid or alkyl-substituted cyclohexylcarboxylates. The secondary soap surfactants should contain no ether linkages, no ester linkages and no hydroxyl groups. There should be no nitrogen atoms in the main group (amphiphilic portion). Secondary soap surfactants usually contain a total of 11 to 13 carbon atoms, but a little more can be tolerated (e.g., up to 16).

The following general structures further illustrate some of the secondary soap surfactants (or precursor acids thereof) useful in the present invention.

A. A particularly preferred class of secondary soaps useful in the present invention includes secondary carboxyl materials of the general formula

^R3 CH ^(R4) COOM wherein R ³ is CH 3 (CH?) X and ^R4 is CH3 _{(CH?) Y} where y is 0 or an integer of 1 to 4, x is an integer from 4 to 10 and the sum (χι-y) is 6 to 10, preferably 7 to 9, most preferably 8.

B. Another class of secondary soaps useful in the present invention includes those carboxyl compounds wherein the carboxy substituent is on a hydrocarbon cycle, i.e., they are secondary soaps according to the invention.

R ⁵ -R ⁶ -COOM wherein ^R is _a C to _{C] 0,} preferably C ₃ to C,., Alkyl or alkenyl and ^R² is a cyclic structure such as benzene, cyclopentane and cyclohexane. (Note: R ⁵ may be in the ortho-, meta- or para- position with respect to the carboxyl on the cycle.)

C. Yet another class of secondary soaps includes secondary carboxyl compounds of the general 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 to C ₄ alkyl, where k, n, o, q are integers ranging from 0 to 8, the total number of carbon atoms (including the carboxylate) is ranging from 10 to 18.

In each of the above formulas (A), (B) and (C), M may be any suitable, especially water-solubilizing, counter-charged ion such as hydrogen, alkali metal, alkaline earth metal, ammonium, alkanolammonium, di- and trialkanolammonium and C , up to C ₅ alkylsubstituted ammonium ion. Sodium as well as the diethanolammonium ion are suitable.

Preferred secondary soap surfactants for use in the present invention are water-soluble substances selected from the group consisting of 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-penphyl-1-heptanoic acid.

Other anionic surfactants

Other anionic surfactants suitable for detersive purposes may also be included in the compositions of the present invention. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di-triethanolamine salts) of soaps, oleyl glycerol sulfates of fatty acids, alkylphenolefylene oxide ether sulfates, alkyl phosphates, 2-hydroxyethanesulfonates such as acyl 2-hydroxyethanesulfonate -2-aminoefansulfonáfy, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated _C12-C18 monoesters) díesfery sulfosuccinate (especially saturated and unsaturated C-C _{M ft} diesters), N-acyl sarcosinates, sulfates of alkylpolysaccharides such as alkyl polyglucoside sulfates (nonionic non-sulfated compounds described herein), branched primary alkyl sulfates, alkyl polyethoxycarboxylates of the general formula

RO (CH ₂ CH ₂ O \ C ₂ COO IVT where R is C ₈ to C ₂ alkyl, k is an integer from 0 to 10 and M is a soluble cation forming salt, and fatty acids esterified with 2-hydroxyethanesulfonic acid and neutralized Resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin, and lunin are also suitable.

resin acids and hydrogenated resin acids present in or derived from tall oil. Other examples are listed in the book Surface Active Agents and Detergenis (Vol. I and II, Schwartz, Perry and Berch). A number of such surfactants are also generally described in U.S. Pat. No. 3,929,678, issued Dec. 30. 1975, Laughlin et al., From column 23, line 58 to column 29, line 23.

Nonionic surfactant

Suitable nonionic detergent surfactants are generally described in U.S. Pat. U.S. Patent 3,929,668, Laughlin et al. 1975, from 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 - polyhydroxy fatty acid amide

The polyhydroxy fatty acid amides suitable for use in the present invention are those having the general Formula I:

(I) R ² -CO-NR -Z wherein R 1 ^; is H, a C to C 8 hydrocarbyl residue, 2-hydroxyethyl, 2-hydroxypropyl or mixtures thereof, preferably a C 1 to C 4 alkyl, more preferably a C, or a C 1 -C 4 alkyl; alkyl, most preferably C 1, alkyl (ie methyl); and R ^? is a C5 to C _3i uhlovodkový radical, preferably a C, to C, alkyl or alkenyl snerozvěfveným chain, preferably a C ₉ to C _{| Z} alkyl or an unbranched chain alkenyl, most preferably C 1 to C 3, straight chain alkyl or alkenyl or mixtures thereof; and Z is a polyhydroxyhydrocarbyl residue having a linear hydrocarbon chain of at least 3 hydroxyls directly bonded to the chain or an alkoxylated derivative thereof (preferably alkoxylated or propoxylated). Z is preferably derived from a reducing saccharide in a reductive amination reaction; more preferably Z is glycity. Suitable reducing sugars include glucose, rructose, lactose, galactose, mannose, and xylosis. Concentrated glucose corn syrup, concentrated fructose corn syrup and concentrated maitose corn syrup as well as the individual carbohydrates listed above can be used as raw materials. These corn syrups can provide a mixture of carbohydrate components for the Z group. It should be noted that this list does not exclude other suitable raw materials. Z is preferably selected from the group consisting of -CH ₂ - (CHOH) _n -CH ₂ -OH ₂ , -CH (CH ₂ OH) - (CHOH) _r -, -CH ₂ OH, -CH ₂ - (CHOH) ₂ (CHOR ') (CHOH) -CH ₂ OH, wherein n is an integer from 3 to 5 inclusive and R 6 is H or a cyclic or aliphatic monosaccharide, and their aicoxylaphs. Most preferred are glycityls wherein n is 4, especially -CH ₂ - (CHOH) ₄ -CH ₂ OH.

In the general formula (I), R 'can be, for example, N-methyl, N-ethyl, N-propyl. N-isopropyl, N-butyl, N-2-hydroxyphyl or N-2-hydroxypropyl. R ^? it can be, for example, cocamide, spearylamide, oleylamide, laurylamide, myristylamide, decanylamide, palmityiamide, tallow amide and the like.

Z may be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymalfityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl,

1-deoxymaltotriotifyl etc.

The most preferred polyhydroxy fatty acid amide has the general formula:

--- R ^ CO-NICC.p-CH .- ^ HOH ^ GHpH -------------------------------- -------------------- wherein R ² is a C ,, to C _1Z alkyl or alkenyl group having a straight chain.

Non -opic condensates of alkylphenols

Polyethylene, polypropylene and polybutylene oxide condensates are suitable for use in the present invention. Polyethylene oxide condensates are generally preferred. These compounds include the condensation products of alkylphenols having an alkyl group containing from 6 to 12 carbon atoms in either a straight or branched chain with an alkylene oxide.

Nonionic ethoxylated alcohol surfactants

Alkyl ethoxylate condensation products of aliphatic alcohols with 1 to 25 moles of ethylene oxide are suitable for use in the present invention. The alkyl chain of the aliphatic alcohol may be either unbranched or branched, primary or secondary and generally contains from 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 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 with an alkyl group containing from 10 to 14 carbon atoms with 6 to 10 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergifol ™ 15-S-9 (the condensation product of C _{H 1} and _C, of a linear alcohol with 9 moles ethylene oxide), Tergitol 24-L ^M-O NMW (the condensation product of C _i2 -až.C _T4 primary alkanol (narrow molecular weight ethylene oxide), both traded by Union Carbide Corporation; Neodol ™ 45-9 (condensation product of C ₄ to C ₁₅ linear alcohol with 9 moles of ethylene oxide), Neodol ™ 23-δ, 5 (condensation product of C ₁₂ to C ₁₃ linear alcohol with 6.54 moles of ethylene oxide), Neodol ™ 45 -7 (condensation product of C ₁₄ to C ₁₅ linear alcohol with 7 moles of ethylene oxide), Neodol ™ 45-4 (condensation product of C ₁₄ to C ₁₅ linear alcohol with 4 moles of ethylene oxide), traded by Shell Chemical Company, and Kyro ™ EOBN (condensation product C ₁₃ to C ₁₅ alcohol with 9 moles of ethylene oxide) traded by The Procter & Gamble Company.

Nonionic EO / PO condensates with propylene glycol

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use in the present invention. Examples of compounds of this type include those commercially available as Pluronlc ™ surfactants marketed by BASF.

Nonionic EO condensation products with propylene oxide / ethylenediamine adducts

Ethylene oxide condensation products with a product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use in the present invention. Examples of this type of nonionic surfactant include the commercially available Tefronic ™ compounds marketed by BASF.

Nonionic afkylpolysaccharide surfactants

[0007] A suitable phosphoraccharide for use in the present invention is described in U.S. Patent 4,565,647, Llenado, issued January 21, 2001. 1986, having a hydrophobic group containing from O to 30 carbon atoms, preferably 10 to 16 carbon atoms and a polysaccharide, e.g. polyglucoside, hydrophilic group containing from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1 _γ 3 to 2.7 carbohydrate units. Any reducing carbohydrate containing 5 or 6 carbon atoms may be used, e.g., glucose, galactose or galactosyl groups may replace glucosyl groups. (Optionally, the hydrophobic moiety is attacked at positions 2-, 3-, 4-, etc., so that glucose or galactose is then in position against the glucoside or galactoside.) Bonds between carbohydrates may be, e.g., between one position of other carbohydrate units and positions 2 -, 3-, 4a / or 6- on the preceding saccharide units.

Optionally and less appropriately, the polyalkylene oxide chain may link the hydrophobic and polysaccharide moieties. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include alkyls, either saturated or unsaturated, branched or unbranched, containing from 8 to 18, preferably from 10 to 10 carbon atoms. Preferably, the alkyl group is a branched saturated chain. The alkyl group may contain up to 3 hydroxyl groups and / or the polyalkylene chain may contain up to 10, preferably less than 5, alkylene oxide groups. tri-, fetra-, penfa- and hexa glucosides, galatoses. Suitable mixtures include alkyl di. ni-, flow and pentaglucosides from coconut oil ...... and alkyl Tatra-, penta- o tallow hexaglucosides.

Preferred alkyl polyglucosides have the general formula:

R ² O (C _n H 2 _n O) t (glycosyl) _x wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl groups contain from 10 to 13, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. Glycosyl is preferably derived from glucose. These compounds are prepared by first preparing an alcohol or an alkylpolyethoxy alcohol and then reacting with glucose or a source of glucose to form a glucoside (attack on-position). Further glycosyl units can then be attacked between their 1-position and the previous 2-, 3-, 4- and / or 6-position glycosyl units, preferably the 2-position prevails.

Nonionic surfactant fatty acid amide

Fatty acid amides as surfactants suitable for use in the present invention are compounds of the general formula:

R ^o -C (O) -N (R ^{z) O} ₂ where R is an alkyl group containing from 7 to 2 l, preferably from 9 to 17 carbon atoms and each R is selected ^{from a} / the group consisting of H, C to alkyl, C, to C, _and hydroxyalkyl, and - (C ₂ H ^ O \ H, where x is' wóžahuo3Tdo37 ------------------- ------ -------------------------- Ampholytic surfactant

Ampholytic surfactants may be included in the detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of heterocyclic secondary and tertiary amines, wherein the aliphatic radical may be branched or unbranched. One of the aliphatic substituents contains at least 8 carbon atoms, typically from 8 to 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Pat. Patent No. No. 3,929,678, Laughlin et al., Issued Dec. 30, 1975, column 19, lines 18-35, for examples of ampholytic surfactants.

Amphoteric surfactant

Suitable amphoteric surfactants for use in the present invention include alkylamphocarboxylic acids of the general formula:

RC (O) -NHCH ₂ CH, R ₁ wherein R is a C ₃ to C ₁₃ alkyl group and R; has the general formula:

(CH ₂ \ COO- (CH ₂ ) _x COON or N () - CH ₂ CH ₂ OH

R 1 R wherein R ¹ is (CH ₂ ) _X COOM or CH ₂ CH ₂ OH and x is 1 or 2 and M is preferably selected from the group of alkali metals, alkaline earth metals, ammonium ion, mono-, di-, tri-ammonium ion, most preferably sodium, potassium, ammonium ion and mixtures thereof with magnesium ions. Preferred R DEIK aikylového chain C _{l0-C 14} alkyl group. A preferred amphocarboxylic acid is formed from an imidazine fatty acid wherein the dicarboxylic function of the amphodicarboxylic acid is diacetic acid and / or dipropionic acid. A suitable example of an alkylamphodicarboxylic acid for use in the present invention is the amphoteric surfactant Miranol (TM) C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.

Amine surfactant

Amine oxides suitable for use as the amphoteric surfactants of the present invention include compounds having the general formula:

R ³ (OR ' ¹ ) _X N (O) (R% wherein R ³ is selected from the group consisting of alkyl, hydroxyalkyl, acylamidopropoyl and alkylphenyl groups or mixtures thereof containing from 8 to 26 carbon atoms, preferably from 8 to 16 carbon atoms -atomů; R ⁴ is ..... - - alkylene-or hydroxyalkylene group containing from 2 to 3 carbon atoms, preferably 2 carbon atoms, or mixtures thereof; x is from 0 to 3, preferably 0; and each R ^s is an alkyl or hydroxyalkyl group containing from 1 to 3, preferably from 1 to 2, carbon atoms, or a polyethylene oxide group containing from 1 to 3, preferably 1, ethylene groups. R ⁶ groups can attack each other, e.g., through an oxygen or nitrogen atom to form ring structure. These amine oxide surfactants in particular include C _{K.-C 18} alkyldimethylamine oxides and C ₈ to C _i2 alkoxyetyldihydroxyefylaminoxidy. Examples of such materials include dimetyloktyaminoxiá, dietyídecylaminoxid b is- (2-hydroxyethyl) dodecylamine oxide, dimethyldodecylamine oxide, dipropyltetradecylamine oxide, methylhexadecylamine oxide, dodecylamidopropyldimethylamine oxide and dimethyl-2-hydroxyoctadecylamine oxide. Preferred are C ₁₀ -C ₁₈ alkyldimethylamine oxide and C ₁₀ -C ₁₃ acylamidoalkyldimethylamine oxide.

Zwítterionický surfaktanf

Zwitterionic surfactants may also be included in the detergent compositions of the present invention. See U.S. Pat. Patent No. No. 3,929,678, Laughlin et al., Issued Dec. 30. 1975, from column 19, line 38 to column 22, line 48, which are examples of zwitterionic surfactants.

Betaine surfactant The betaines suitable for use as the Zwitterionic surfactants of the present invention are those compounds having the general formula:

R (R ') ₂ I \ TR ² COOkde R is a C6 to C18 hydrocarbyl, preferably C, C to ClO alkyl or C10 to C16 acylamidoalkylová group, each ^R1 is typically -C3 alkyl, preferably methyl, and R ² is A C ₁ to C ₅ hydrocarbon residue, preferably a C 1 to C ₃ alkylene group, more preferably a C 1 to C ₂ alkylene group. Examples of suitable betaine include coconut acylamidopropyldimethyl betaine; hexadecyldimefylbetain; _C12 to _C14 acylamidopropylbepain; C ₈ to C ₁₄ acylamidohexyldiethyl betaine;

4 (C acylmetylamidodíefylamonio] -L-karboxybutan; C _ló acylamidodimetylbefain to _{C18; C12 16} acylamidopenfandietylbetain; _{C12 16} acylmetylamidodimetylbetain. Preferred betaines are _{C12] 8} dimetylamoniohexanoát and C, _o to C ₁₈ acylamidopropane (or ethane) dimethyl (or di-betaine).

Complex betaines suitable for use in the present invention have the general formula:

R- (A) _n - (N- (CHR ') _x ) _y -NQ (1) k * R wherein R is a hydrocarbon radical having from Ί to 22 carbon atoms, A'is a group CC ( (O) 1, n is 0 or t, R 1 - ^; is hydrogen or a lower alkyl group, x is 2 or 3, y is an integer from 0 to 4, Q is a group -R ² COOM, wherein R ² is an alkylene group having from 1 to 6 carbon atoms and M is hydrogen or an ion from the group of alkali metals, alkaline earth metals, ammonium ion, substituted ammonium ion, and B is hydrogen or a group Q as defined above.

Sultainy

Sultains suitable for use in the present invention are compounds having the general formula:

(R (R ¹⁾ 2 NR ² SO 3 · wherein R is a C ₆ to C ₁₈ hydrocarbyl, preferably C _lo to C ₆ alkyl, more preferably C ₁₂ to C ₁₃ alkyl group, each R 'is typically a C, to C ₃ alkyl, preferably methyl, and R ² is a C 1 to C ₃ hydrocarbon radical, preferably a C ₁ to C ₃ alkylene or more preferably a hydroxyalkylene group.

Organic solvent

Compositions of the present invention comprise an organic solvent system is preferably present in amounts from 1 to 30% by weight, preferably 3 to 25% by weight, preferably 5 to 20 wt% organic solvent prostředku.Vhodné to use the PoC ^e present invention has the formula:

CH _{; J}

RO _(CH? CHO) _n H wherein R is an alkyl, alkenyl or alkylaryl group having 1 to 8 carbon atoms and n is an integer from 1 to 4. Preferably, R is an alkyl group containing 1 to 4 carbon atoms and n is 1 or 2 Particularly preferred R groups are n-butyl or isobutyl. Preferred solvents of this type are 1n-butoxypropan-2-ol (n = D; and 1- (2-n-butoxy-1-methylethoxy) propan-2-ol (n = 2) and mixtures thereof.

Other solvents useful in the present invention include water-soluble CARBITOL solvents or water-soluble CELLOSOLVE solvents. Water-soluble CARBITOL solvents are compounds of the 2- (2-alkoxyethoxy) ethanol class wherein the alkoxy group is derived from ethyl, propyl or butyl; a preferred water-soluble carbitol is 2- (2-butoxyethoxy) ethanol also known as butylcarbitol. Water-soluble CELLOSOLVE solvents are compounds of the 2-alkoxyethoxyethanol class, 2-butoxyethoxyethanol being preferred.

Other suitable solvents are benzyl alcohol and diols such as 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.

Low molecular weight liquid-soluble liquid polyethylene glycols are also suitable for use in the present invention.

Also suitable are alkane mono- and diols. especially C to C, alkane mono- and diols. Preferred are C1 to C dihydrogen alcohols including propylene glycol. It is preferred that the monohydrogen alcohols.

in particular ethanol, are present in an amount of less than 6% by weight of the composition.

Foaming agents

The compositions of the present invention may comprise from 1 to 20%, preferably from 2 to 20%, by weight of a suds booster selected from the group consisting of amine oxides, betaines, sultains, complex betaines and certain nonionic substances.

Preferred amides are _C, to _C alkyl mono- or _di-C? up to C ₃ alkanolamides, especially monoethanolamides, diethanolamides and isopropanolamides.

Preferred suds enhancing agents are C _L0 to _L3 acylamidalkyldimetylaminoxidy C, betaines, condensation products of aliphatic alcohols with ethylene oxide, alkylpolysaccharides, and mixtures thereof.

Hydrotropic compounds

The hydrotropic compound is typically added to the compositions of the present invention in amounts of from 0.5 to 10%, preferably from 1 to 5% by weight.

Useful hydrotropic compounds include sodium, potassium and ammonium xylene sulfonates, sodium, potassium and ammonium toluene sulfonates, sodium, potassium and ammonium cumene sulfonates, and mixtures thereof.

Other compounds useful as hydrotropes include polycarboxylates. Some polycarboxylates chelate calcium, but have hydrotropic properties. Particularly suitable hydrotropic compounds are alkylpolyethoxypolycarboxylate surfactants of the type described above. An example of a commercially available alkylpolyethoxypolycarboxylate which can be used according to the present invention is POLYDETERGENT C, Olin Corporation, Cheshire, CT.

Another compound useful as hydrotropic is an alkyl amphodol carboxylic acid of the general formula:

(CH ₂ ) _X COO ₂

(CH ₂ ) _x COOM wherein R is a C ₈ to C ₁₈ alkyl group, x is from 1 to 2, M is preferably selected from the group consisting of alkali metals, alkaline earth metals, ammonium ion, mono-, di- and triethanolammonium ion , most preferably sodium, potassium, ammonium ion and mixtures thereof with magnesium ions. A preferred length of the alkyl chain (R) is a C ₁₀ to C ₁₄ alkyl group and the dicarboxylic acid functional group is diacetic acid and / or dipropionic acid.

A suitable example of an alkylamphodicarboxylic acid is the amtoteric surfactant MiranolR2CM Conc., Manufactured by Miranol, Inc, Dayton, NJ.

Dispersing agents based on calcium salts of fatty acids

The compositions of the present invention are particularly suitable when formulated to contain a calcium-based fatty acid dispersant which acts in such a manner. by dispersing any insoluble calcium salts of fatty acids that are formed between the fatty acids produced by lipolytic hydrolysis of fats / oils and calcium ions in the washing solution, thereby preventing the deposition of these salts in the form of stains or films on parts of dishes or unpleasant circles around the edges of the sink. Certain calcium fatty acid dispersants also exhibit improved product stability, especially where the product is prepared in liquid form containing calcium ions.

A calcium fatty acid dispersant is defined herein as a compound having a calcium fatty acid (DS) dispersing capacity of not more than 8, preferably not more than 7, most preferably not more than 6.

DS is the ratio by weight of dispersing agent to sodium oleate required to disperse calcium fatty acid deposits of 0.025 g sodium oleate in 30 ml of water of 333 parts per million CaCO ₃ equivalent (Ca: Mg = 3: 2). The calcium fatty acid dispersant is present in the composition of the present invention typically in an amount of from 0 to 40% by weight, more preferably from 1 to 20%, most preferably from 2 to 10% by weight of the composition.

Calcium

The detergent compositions of the present invention may contain from 0 to 3%, more preferably from 0.15 to 2% calcium ions. It has been found that for compositions containing polyhydroxy fatty acid amide, the presence of calcium greatly improves the cleaning of fatty contaminants. This is particularly true when the compositions are used in softened water containing few divalent ions.

For example, calcium ions can be added as chloride, hydroxide, oxide, formate or acetate, or nitrate salt. As anionic acid surfactants, calcium can be added in the form of a suspension of calcium oxide or calcium hydroxide in water to neutralize the acid.

The calcium ions are present as salts in the compositions. The amount of calcium ions present in the compositions of the present invention depends on the total amount of anionic surfactants present in the composition. The molar ratio of calcium ions to total anionic surfactants is preferably from 1: 0.1 to 1:25, more preferably from 1: 2 to 1:10, for the compositions of the present invention.

Calcium ion stabilizing agent

Malic, maleic or acetic acid, their salts or a certain calcium-fatty acid dispersant can be added to a composition prepared to contain calcium so as to exhibit good product stability, and in particular to prevent the precipitation of insoluble calcium salts. If calcium is present, malic, maleic or acetic acid, or salts thereof, may be added in an amount of from 0.05 to 10% of the composition, and the molar ratio to calcium ranges from 0.01: to 1:10.

Magnesium

Preferably, from 0.01 to 3%, most preferably from 0.15 to 3%, may be added to the liquid detergent compositions of the present invention

0.9% by weight of magnesium ions to improve product stability as well as foaming. If the anionic surfactants are in the acid form, magnesium may be added by acid neutralization with magnesium oxide or a suspension of magnesium hydroxide in water. Calcium can be used similarly. This method minimizes the addition of chloride ions, which reduces the corrosive properties. The neutralized surfactant salts and the hydrotropic compound are then added to the final mixing tank and any suitable ingredients are added before adjusting the pH.

Form of resources

These compositions are of a naturally liquid nature, eg liquid, in the form of gels, creams, foams or whipped foams.

Liquid formulations

In a preferred embodiment, the detergent compositions of the present invention are liquid detergent compositions. These preferred liquid detergent compositions typically comprise from 35 to 94% by weight, preferably from 40 to 90% by weight, most preferably from 50 to 80% by weight of a liquid carrier such as water, preferably a mixture of water and an organic solvent.

Gel preparations

The detergent compositions of the present invention may also be in the form of gels. Such compositions are typically prepared in a polyalkenyl polyether and have a molecular weight of from 50,000 to 40,000,000.

Particularly preferred examples of these polycarboxylate polymeric thickeners are the Carbopoi 600 resins available from B.F. Goodrich. Particular preference is given to Carbopoiol 6 and Carbopoi 617. It is believed that these resins are much more crosslinked than the resin series 110 and have molecular weights of 1000000 and 4000000. Mixtures of the polycarboxylate polymers herein may also be used in the present invention. Particularly preferred is a resin mixture of the Carbopoi ol. And 617 series.

The polycarboxylate polymeric thickener is preferably used essentially free of clay thickening agents. It has been found that the use of the polycarboxylate polymers of the present invention together with clay in the compositions of the present invention results in a less desirable product in terms of the instability phase. In other words, the polycarboxylate polymer is preferably used in the compositions of the present invention as a thickening / stabilizing agent instead of clay.

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

Thickening agents are preferably used to provide a target value of from 50 to 350, and most preferably from 75 to 250. The target value is an indication of tangent stress at which the gel structure strength is exceeded and flow begins. The Brookfield RVT viscometer with T-stirrer and B screw at 25 ° C using Helipath is used for measurement.

Other suitable ingredients useful in the compositions of the present invention include colorants, perfumes, and opacifiers. ·

Hardening agents may be added, preferably as a last step, such as Lytron (Morton Thiokol, Inc), modified polystyrenelatex or ethylene glycol disulfate. Lytrone can be added directly as a dispersion with stirring. Ethylene glycol disulfate can be added in the molten state with vigorous stirring to form pearlescent crystals. The quenching agents used herein, particularly in the case of thin liquids, are typically present in amounts of from 0.2 to 10%, preferably from 0.5 to 6% by weight.

Manual dishwashing method

In accordance with aspects of the hand dishwashing process of the present invention, the soiled dishwashing agent is in contact with an effective amount, typically from 0.5 to 20 g (per 25 pieces of dishwashing item), preferably from 3 to 10 g of the composition of the present invention. The actual amount of detergent used will be based on the judgment of the user and will depend on factors such as, in particular, the formulation of the composition, the concentration of the composition, the amount of soiled dishwashing composition and the degree of soiling of the dishwashing composition.

Washing procedures using concentrated solution

In one preferred method of the present invention, a concentrated detergent solution solution is applied to the surface of the dishes to be washed. By a concentrated solution of the composition is meant not less than 20% by weight, preferably not less than 50% by weight of diluted prosredx, most preferably the composition is applied in undiluted form. —.........

Application of the detergent composition to the surface of the cookware may be accomplished using an applicator such as a sponge, cloth or brush to which the detergent has been previously applied, or the detergent composition may alternatively and preferably be sprayed onto the cookware surface. Typically, the detergent is distributed on the surface of the dishes such that heavily soiled surfaces are covered more heavily than areas with little soiling. The dishes can be rinsed or soaked in water before the detergent is applied, but this is not necessary.

The concentrated detergent solution is allowed to act on the surface of the dishes for a period of time. The exact length of this time depends on a number of factors including the degree of soiling of the dishes, the amount of detergent applied, the extent of previous rinsing or soaking in water and the nature of the subsequent rinsing or washing steps.

Subsequently, the dishes are washed or rinsed manually or in a dishwasher, including further washing steps and the use of detergent and / or rinsed manually or in a dishwasher. Preferably, the dishes are only rinsed manually or in a dishwasher.

Preferred methods of applying a concentrated detergent solution solution to the surface of the dishwashing liquid, herein referred to as "direct application method" and "method of using a soaking detergent composition", are further described.

Method of direct application

The method of direct application typically sums up a " beer " to moisten soiled dishes, e.g., by immersing the dishes in water without any liquid dishwashing detergent or by holding underwater flowing from the dishwasher. tap. Then, the liquid detergent-absorbent device, such as a sponge, is placed directly on a separate amount of the concentrated liquid or gel detergent composition for a period typically ranging from 1 to 5 seconds. The absorbent aid and the subsequently undiluted detergent composition are then applied individually to the surface of each piece of soiled dishware. The absorbent aid is applied to each piece of cookware for a time ranging from 1 to 10 seconds, but the actual application time depends on factors such as the degree of soiling of the cookware. This contact of the absorbent device with the surface of the dishes is preferably accompanied by simultaneous washing. Subsequently, the dishes are rinsed by hand by immersion in water or by holding them under a stream of running water, usually with manual washing of the surface of the dishes.

A method of using a soaking detergent composition In this method, a concentrated detergent solution is applied to the surface by any of the aforementioned methods and is allowed to act on the surface of the dishes for a period of from 30 seconds to 24 hours, usually from 5 minutes to 1 hour. minutes to 30 minutes. The dishes are then washed or rinsed by hand or in a dishwasher, preferably rinsing.

If a dishwasher is used in a subsequent washing or rinsing process, it is preferred that the composition used in the form of the detergent composition soaked comprises a suds suppressor in an amount of 0.01 to 15% by weight. The suds suppressor may be any of the suppressors known in the art including silicone suds suppressors.

Washing methods using a dilute solution

In another preferred method of the present invention, a large volume of a dilute detergent solution solution is used. The dishes are preferably allowed to soak for a period of time in a dilute solution, usually from 5 seconds to 30 minutes.

Washing methods using a dilute solution include the method of "dilute solution in the sink" and "dilute solution in the tray" described below.

Method of dilute solution in the sink

Typically, the dilute solution in the sink is combined from 3 to 15 ml, preferably from 5 to 10 ml of liquid detergent composition with 1 to 10,000 ml, more usually 3,000 to 5,000 ml of water in the sink having a volume capacity ranging from 5,000 to 5,000 ml. 20000, more usually from 10,000 to 15,000 ml. The detergent composition has a surfactant concentration of from 10 to 60% by weight, preferably from 45 to 50% by weight. The soiled dishes are immersed in a sink containing detergent and water and are washed here by soaking in solution and manually washing the soiled surface of the dishes using a cloth, sponge, etc. Preferably the dishes are soaked in dilute detergent solution - sink for 5 seconds. up to 30 min Tue, - prefabricated-ed-30 seconds within 10 minutes, before hand washing. A cloth, sponge or the like can be dipped in a detergent / water mixture prior to contact with the cookware surface, and is typically in contact with the cookware surface for from 1 to 10 seconds, but the actual time varies for each application and user. Contact of the cloth, sponge or the like with the surface of the dishes is preferably accompanied by simultaneous washing of the surface of the dishes.

Method of dilute solution in the tray

Typically, the dilute solution in the tray is combined from 1 to 50 ml, preferably from 2 to 10 ml of the detergent composition with 50 to 2000 ml, more usually 100 to 1 COO ml of water in the tray having a volume capacity ranging from 500 to 5,000 ml more usually from 500 to 2000 ml. The detergent composition has a surfactant concentration of from 10 to 60% by weight, preferably from 15 to 50% by weight. The soiled dishes are immersed in a bath containing detergent and water and washed there by soaking in solution and manually washing the soiled surface of the dishes using a cloth, sponge, etc. Preferably, the dishes are soaked in a diluted detergent solution in the bath for 5 seconds to 30 seconds. minutes, preferably from 30 seconds to 10 minutes, prior to manual washing. A cloth, sponge, or the like can be dipped in a detergent / water mixture prior to contact with the cookware surface and typically is in contact with the cookware surface for from 1 to 10 seconds, but the actual time varies for each application and user. Contact of the cloth, sponge or the like with the surface of the dishes is preferably accompanied by simultaneous washing of the surface of the dishes.

Examples

The following detergent compositions of the present invention were prepared.

1 * / <, r.rr.oínoskni j 1 II III 1 iv IN VI i C ₁ to C ₁₃ alkylethoxy (dia 0.8) sulfate 10 10 9 ⁵ 1 10 10 I C ₁ to C ₁₃ alkylethoxy (dia. 3) sulfate 7 7 8 15 Dec 7 ¹⁰ i C ₁ to C ₁₄ alkylaminoxd 2 1 - 1 ΐ 2 5 i 1 C ₁₂ to C ₁₄ alkyldimethylbefain - 1 1.5 2 - j C, 2 to C ₁₄ Ampholac (TM) - - 1.5 - C, ₂ alkyl-N-methyl glucamide 12 12 9 11 '12 7 i C _l2 alkyl ethoxylate (ave. 8) 5 5 5 4.6 i 5 4 i Mg ²⁺ ions - 0.6 - 0.3 I 0,6 0,6 ΐ Ca ²⁺ ions - - 0.3 0.15 i 0,1 0.1 Maleic acid - - 0.2 0.3 and Miranol (TM) - - 2 - ¹ - Polytergenf (TM) - - - 2 - - Lipase 0.005 0.01 0.02 0.03 O O 0.03 Protease 0.01 0.02 0.01 0.02 0.03 0.02

Lipase is an iipolytic enzyme sold under the trademark

-iipoiáza - - -New -Industries-A / SR - The amount of active ........ ^{- "-} ------ enzyme in the compositions are given. Commercial samples typically have an activity of 2%.

The protease is a proteolytic enzyme sold under the trademark savinase, Novo Industries A / S. The amounts of active enzyme in the compositions are given. Commercial samples typically have an activity of from 1 to 4%. The compositions were prepared by mixing all surfactants except glucamide. The magnesium and calcium salts were then dissolved in maleic acid solution and added to the surfactant mixture with the remaining ingredients. Finally, the pH was adjusted to 7.3 using hydrochloric acid and the viscosity was measured.

Industrial applicability

The present invention provides a detergent composition comprising a surfactant system, a lipolytic enzyme and a proteolytic enzyme suitable for use in a manual dishwashing process. The preferred detergent composition is in the form of a liquid or gel. The preferred composition contains no filler salts. The preferred composition contains no bleaching components.

Claims (11)

PATENT CLAIMS What is claimed is: 1. A detergent composition comprising a surfactant system, a lipolytic enzyme and a proteolytic enzyme suitable for use in a manual dishwashing process. A detergent composition according to claim 1, characterized in that it is a high-foaming detergent composition. A detergent composition according to claim 1 or 2, characterized in that it is in liquid or gel form. A detergent composition according to any one of claims 1 to 3, characterized in that it contains no filler salts. 5. A detergent composition according to any one of claims 1 to 4, wherein no detergent composition is present. A detergent composition according to any one of claims 1 to 5 comprising from 5 to 80% by weight of a surfactant system, wherein the surfactant system comprises a surfactant selected from the group of nonionic, anionic, cationic, zwitterionic, ampholytic and amphoteric surfactants. 7. A detergent composition according to any one of claims 1 to 6 wherein the pH of the 1% w / w solution is from about 9 to about 9%. 8. A detergent composition according to any one of claims 1 to 7 comprising from 0.05 to 3% by weight of calcium ions. 9. A detergent composition according to any one of claims 1 to 8 comprising from 0.01 to 3% by weight of magnesium ions. A detergent composition according to any one of claims 2 to 9 comprising from 0.1 to 20% by weight of a sudsing agent. A detergent composition according to any one of claims 1 to 10, wherein the surfactant system comprises a nonionic surfactant and an anionic surfactant such that the weight ratio of nonionic surfactant to anionic surfactant is greater than 1: 1.