SK156899A3 - Light-duty liquid or gel dishwashing detergent compositions having controlled ph and desirable food soil removal and sudsing characteristics - Google Patents

Abstract

Disclosed are light-duty liquid or gel dishwashing detergent compositions that are especially useful for the manual washing of heavily soiled dishware. Such compositions essentially contain an alkyl ether sulfate-based anionic surfactant, a polyhydroxy fatty acid amide-based nonionic surfactant component, a suds booster which is preferably an amine oxide, an aqueous liquid carrier and a pH control agent such as sodium carbonate to provide a relatively alkaline product.

Description

A pH-controlled, low-performance, aqueous, low-performance detergent with soil removal and foaming properties

Technical field

The present invention relates to an aqueous, low-performance pH-controlled detergent composition which has particularly suitable soil removal and foaming properties for manual dishwashing. These compositions contain detergent surfactants, suds boosters, pH agents, and other adjuvants, which together serve to provide the consumer with a convenient cleaning of food contaminants and which impart foaming properties to these dishwashing detergent products. .

BACKGROUND OF THE INVENTION

Low performance (LDL) or gel detergent compositions for manual dishwashing are well known in the art. These products are usually formulated to provide many different embodiments and to have aesthetic properties and features. First and foremost, liquid or gel products for washing

Dishes must also be formulated with such types and quantities of other surfactant adjuvant surfactants to provide acceptable solubilization and removal.

And food contaminants, in particular greasy contaminants from dishes, to be cleaned with aqueous solutions or in aqueous solutions formed from these products.

Heavily soiled dishes may present special problems with the manual dishwashing procedure. Products such as plates, dishes, pots, pans, porcelain dishes and the like can be heavily soiled in the sense that relatively large amounts of dirt and food debris may be present on the dish when this soiled dish is hand washed. The dishes may also be heavily soiled in the sense that residues of food contaminants are caught very firmly or are stuck to the surface of the dishes to be cleaned. This can occur due to the type of contamination by the food present or the nature of the cookware surface. The tough food stain residues may also come from the type of cooking for which the dishes were used.

When heavily soiled dishes are washed by hand, very concentrated or high concentrations of dishwashing detergent products are very often used. Often, they will involve direct application of the liquid or gel product in its undiluted or pure form on a soiled dish. During these applications, the properties of the dishwashing composition may have a significant effect on the ability of the composition to solubilize and remove food soils, such as greasy soils. The pH of the product may further determine the effectiveness of conventional aqueous dishwashing solutions to remove greasy soils from the dishes. Aqueous dishwashing solutions, which are more alkaline in nature, are generally more effective in removing these soils.

In addition to being useful for dishwashing, LDL or gel compositions will also have other desirable properties that enhance aesthetic properties or consumer perception of the efficiency of a manual dishwashing operation. Useful hand dishwashing liquids or gels should also use materials that increase the foaming of the washing solutions formed from these products. The foaming property means both the production of a suitable amount of foam in the wash vessel initially and the formation of foam that persists during the dishwashing process.

In view of the foregoing, there is a continuing need to prepare hand dishwashing liquids and gels that provide an acceptable and desirable balance between cleaning performance, both in concentrated direct applications and in suitable dishwashing solutions and product aesthetics. It is an object of the present invention to provide low-efficiency liquid or goal dishwashing compositions which are particularly effective in removing food soils from soiled dishes because they are used in hand dishwashing.

It is a further object of the present invention to provide compositions having desirable pH properties for use in either direct application to dishwashing or dishwashing in aqueous solution.

It is a further object of the present invention to provide such compositions which provide suitable and desirable foaming.

It has been found that some selected combinations of surfactants, suds boosters, pH regulating agents and other adjuvants can be made by providing dishwashing compositions that achieve the foregoing articles. The elements of these selected ingredient combinations are described below.

SUMMARY OF THE INVENTION

The present invention relates to aqueous low efficacy

PH controlled liquid, gel or gel detergent compositions having particularly desirable soil removal and foaming properties when used to wash heavily soiled dishes. These compositions comprise a) 20 to 40 wt. % of the specific type of anionic surfactant;

% of a certain type of nonionic surfactant, c) 2 to 6 wt. d) 50 to 75 wt. % of an aqueous liquid carrier; and e) 0.2 to 6 wt. a pH controlling agent, such as sodium carbonate, which is effective to control the pH of a 10% (w / w) aqueous solution in the range of from 9 to 11.

The anionic surfactant essentially comprises alkyl ether sulfates having 8 to 18 carbon atoms in the alkyl group. These alkyl ether sulfates also contain 1 to 6 moles of ethylene oxide per molecule.

The nonionic surfactant essentially comprises C8-C18 fatty acid amides. 0.2 to 2.0 wt.% May also be present in nonionic surfactants, such as polyhydroxy fatty acid amides. a nonionic surfactant composition. The nonionic surfactant is selected from the group consisting of an alcohol (up to 18 carbon atoms) of ethoxylate with 1 to 15 moles of ethylene oxide, surfactants of the ethylene oxide / propylene oxide block copolymer type, and combinations of these nonionic surfactants.

The suds booster / stabilizer used in the compositions of the present invention is selected from betaine surfactants, hydroxyl-free fatty acid amides, amine-oxide semipolar nonionic surfactants, and C8 -C22 alkyl polyglycosides. Combinations of these suds boosters / stabilizers may also be used.

The foregoing essential ingredients, as well as many other optional ingredients, can be combined in a conventional manner to form low-performance liquid or gel-based dishwashing detergent products according to the present invention.

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One type of ingredient that is typically used in dishwashing detergent products but which should not be consumed in the relatively high pH compositions of the present invention comprises some source of calcium or magnesium ions.

In the following, the present invention will be described in detail. The low-performance liquid or gel detergent compositions of the present " low-performance detergent of the present invention include five types of essential ingredients. These components are:

1) some type of anionic surfactant,

(1) certain non-ionic surfactants;

1) some foaming boosters / stabilizers,

(1) an aqueous liquid carrier; and

1) pH regulating agent.

In addition to the rheological and / or aesthetic properties of the compositions of the present invention, a variety of optional ingredients may also be added.

The essential and optional ingredients of the present low-performance liquid or goal dishwashing detergents are further described herein in detail together with the composition and use of the compositions. When describing the compositions of the present invention, it should be noted that the term detergent dishwashing composition as used herein means those compositions which are used in the manual dishwashing process. These compositions are usually high-foaming or foam-forming in nature. When describing the compositions of the present invention, it should be noted that all concentrations and ratios are by weight unless otherwise indicated.

Anionic Surfactant: The compositions of the present invention essentially comprise from 20 to 40 wt. anionic surfactant. More preferably, the anionic surfactant comprises from 25 to 30 wt. compositions according to the invention.

The anionic surfactant substantially comprises alkyl ether sulfates. Alkyl ether sulfates are also known as alkyl polyethoxylate sulfates. These ethoxylated alkylsulfates are compounds of the general formula:

H '-O- (C 2 H 4 O) nSO 2 -J in which R' represents an alkyl group having 8 to 18 carbon atoms, n represents an integer from 1 to 6 and M represents a salt-forming cation. Preferably R 'is alkyl of 10 to 16 carbon atoms, n is 1 to 4 and M is sodium, potassium, ammonium, alkylammonium or alkanolammonium. Most preferably, R 'is 12 to 16 carbon atoms, n is 1 to 3, and M is sodium. Alkyl ether sulfates are generally used in the form of mixtures containing different R 'chain lengths and varying degrees of ethoxylation. Often, these compositions will inevitably also contain unethoxylated alkyl sulfate materials, i. surfactants of the above formula of ethoxylated alkyl sulfate wherein n is 0.

Nonionic Surfactants: The compositions of the present invention also contain substantially 3% to 10% by weight of the composition. nonionic surfactant of another type.

More preferably, the nonionic surfactant will be present in the compositions of the present invention in an amount of from 4 to 6% by weight.

One essential type of nonionic surfactant that is directly present in the compositions of the present invention are the polyhydroxy acid amides having 8 to 18 carbon atoms. These materials are fully described in Pan / Gosselink: U.S. Patent 5,332,528, issued June 26, 1994, which is incorporated herein by reference. These polyhydroxy fatty acid amides are compounds of the general formula:

R ² -C (O) -NZ

R ¹ wherein R ¹ is a hydrogen atom, a C 1 -C 4 hydrocarbon group, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R ² is a C 8 -C 18 hydrocarbon group and Z is a linear hydrocarbon chain polyhydroxy hydrocarbon group with at least three hydroxyl groups directly attached to the chain or an alkoxylated derivative thereof. Examples of such surfactants include N-methyl or N-hydroxypropylglucamides having 10 to 18 carbon atoms. The N-propyl to N-hexyl glucamides of 12 to 16 atoms can be used in the suds-reducing embodiment. The polyhydroxy fatty acid amides are preferably present in the compositions according to the invention in an amount of from 3 to 5% by weight. by weight of the composition.

In the nonionic surfactant component of the composition of the invention, the polyhydroxy fatty acid amides described above may be combined with some other types of nonionic surfactants. These other types include surfactants such as ethoxylated alcohols and a block copolymer of ethylene oxide with propylene oxide, as well as a combination of these nonionic surfactants.

The ethoxylated alcohol type surfactant materials useful in the nonionic surfactant component of the present invention are those of the formula:

R ¹ -O- (C ₂ H ₄ O) n SOaM, wherein R ¹ represents an alkyl group having 8 to 18 carbon atoms and n is an integer from 1 to 15. R ¹ preferably represents an alkyl group which may be primary or secondary and containing from 9 to 15 carbon atoms, more preferably from 10 to 14 carbon atoms. The ethoxylated fatty alcohols will preferably contain 2 to 12 ethylene oxide moieties per molecule, more preferably 8 to 12 ethylene oxide moieties per molecule. Nonionic surfactants of the ethoxylated fatty alcohol type will often have a ratio of hydrophilic to lipophilic moiety (HLB) in the range of 6 to 15, most preferably 10 to 15.

Examples of fatty alcohol ethoxylates suitable as the nonionic surfactant component of the composition of the invention include those made from an alcohol having 12 to 15 carbon atoms and containing up to 7 moles of ethylene oxide. These materials are commercially manufactured under the trade names Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company. Other useful Neodols include Neodol 1-5, an ethoxylated fatty alcohol of an average of 11 carbon atoms in its 5 moles of ethylene oxide alkyl chain, Neodol 23-9, an ethoxylated primary alcohol of 12 to 13 carbon atoms of 9 moles of ethylene oxide, and Neodol 91-10 is an ethoxylated primary alcohol of 9 to 11 carbon atoms with 10 moles of ethylene oxide. Alcohol ethoxylates of this type are also manufactured by Shell Company under the trade name Dobanol. Dobanol 91-5 is an ethoxylated fatty alcohol of 9 to 11 carbon atoms with an average of 5 moles of ethylene oxide and Dobanol 25-7 is an ethoxylated fatty alcohol of 12 to 15 carbon atoms with an average of 7 moles of ethylene oxide per mole of fatty alcohol.

Other examples of suitable ethoxylated alcohol nonionic surfactants include Tergitol 15-S-7 and Tergitol 15-S-9, both of which are secondary alcohol ethoxylates, which are commercially manufactured by Union Carbide Corporation.

The first is a mixed ethoxylation product of a linear secondary alcohol of 11 to 15 carbon atoms with 7 moles of ethylene oxide and the second is a similar product but with 9 moles of ethylene oxide reacted.

Other types of alcohol ethoxylate nonionic agents useful in the present compositions are high molecular weight

4th

nonionic agents such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol having 14 to 15 carbon atoms and a number of ethylene oxide groups per mole of about 11. These products are commercially manufactured by Shell Chemical Company .

Ethoxylated alcohol nonionic surfactants will often be present in the compositions of the invention in an amount of 0.2 to 2% by weight, more preferably in an amount of 0.5 to 1.5% by weight.

Another type of nonionic surfactant co-agent suitable for use in combination with polyhydroxy fatty acid amides in the nonionic surfactant component of the invention comprises ethylene oxide / propylene oxide block copolymers that function as polymeric surfactants. These block copolymers contain one or more groups which are hydrophobic and which contain mainly ethylene oxide moieties and one or more hydrophobic groups which contain mainly propylene oxide moieties. These groups are attached to the remainder of the compound containing one or more hydroxyl or amine groups. These polymeric surfactants have a molecular weight in the range of 400 to 60,000.

Preferred ethylene oxide-propylene oxide polymeric surfactants are those in which propylene oxide is condensed with an amine, especially a diamine, to form a base which is then condensed with ethylene oxide. Materials of this type are manufactured under the trade name Tetranic®. Similar structures in which ethylenediamine is replaced by a polyol, such as propylene glycol, are manufactured under the trade name "Pluronic ®". Preferred ethylene oxide propylene oxide polymeric surfactants have an HLB in the range of 4 to 30, more preferably 10 to 20.

The ethylene oxide-propylene oxide block copolymers used herein are described in more detail in Pancher / Mao: US Patent 5,167,872, issued December 2, 1992. This patent is incorporated herein by reference.

The ethylene oxide-propylene oxide block copolymers will often be present in the compositions of the invention in an amount of 0.1 to 2, more preferably 0.2 to 0.8% by weight. by weight of the composition.

Foam boosters / stabilizers: The compositions of the invention further comprise 2 to 6, preferably 3 to 6 wt. % of a suds booster or stabilizer component, such as betaine surfactants, hydroxyl-free fatty acid amides, amine oxide semipolar surfactants, and alkyl (C 8 -C 22) polyglycosides. Combinations of these suds boosters / stabilizers may also be used.

Betaine surfactants useful as suds boosters according to the invention are compounds of the general formula:

R-N ⁽⁺¹ (R ¹ ) 2-R ² COO ^(-) , wherein R is a hydrophobic group selected from alkyl of 10 to 22 carbon atoms / preferably of 12 to 18 carbon atoms, alkylaryl and arylalkyl groups with with a similar number of atoms with a benzene ring taken as equivalent to two carbon atoms and a similar structure interrupted by an amide or ether bond, each R ¹ represents an alkyl group having 1 to 3 carbon atoms and R ² represents an alkylene group having 1 to 6 carbon atoms.

Examples of preferred betaines include dodecyldimethylbetaine, cetyldimethylbetaine, dodecylamidopropyldimethylbetaine, tetradecyldimethylbetaine, tetradecylamidopropyldimethylbetaine and dodecyldimethylammonium hexanoate. Other suitable amidoalkyl betaines are described in U.S. Pat. 3,950,417.4 ₍ 137,191 and 4,375

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421, and GB patent no. No. 2,103,236, all of which are incorporated herein by reference.

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Non-hydroxyl amide surfactants useful as suds boosters according to the invention include the ammonium monoethanol and diethanolamides of fatty acids having an acyl moiety of 8 to 18 carbon atoms. These materials are characterized as "non-hydroxylic" in order to distinguish them from polyhydroxy fatty acid amides substantially used in the aforementioned nonionic surfactants. Accordingly, "non-hydroxyl amides for purposes of this invention ^" means those amides in which the acyl moiety contains no hydroxyl substituents. These materials are compounds of the general formula:

R ¹ -CO-N (H) m_i (R ^Z OH) 3_m, wherein R ¹ is a saturated or unsaturated non-hydroxy aliphatic hydrocarbon group having from 7 to 21, preferably 11 to 17 carbon atoms, R ² is methylene or ethylene am 1, 2 or 3, preferably 1. Specific examples of these amides are coconut fatty acid monoethanolamine amide and diethanolamine-fatty dodecylic acid amide. These acyl moieties may be derived from naturally occurring glycerides, e.g. coconut oil, palm oil, soybean oil and tallow, but can also be derived synthetically, e.g. by oxidation of petroleum or by hydrogenation of carbon monoxide by the Fischer-Tropsch process. Preferred are C 12 -C 14 monoethanolamides and diethanolamides.

The amine oxide semipolar nonionic surfactants useful as suds boosters / stabilizers comprise compounds and mixtures of the following compounds of the general formula:

'R ² ''I ¹

R ¹ (C ₂ H ₄ O) _n -N-O,

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R ³ wherein R ¹ is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl or 3-alkoxy-2-hydroxypropyl group wherein the alkyl or alkoxy group is an 8 to 18 carbon atom, R ² and R ³ are methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl; and n is 0-10.

Particularly preferred amine oxides of the formula:

Λ ²

R ¹ - N 0,

R ³ wherein R ¹ is C 12 -C 16 alkyl and R ² and R ³ are methyl or ethyl. The above non-hydroxyl amides and amine oxides are described in more detail. in U.S. Patent 4,316-82-4, which is incorporated herein by reference.

Other surfactants suitable for use as suds boosters / stabilizers in the compositions of the present invention are nonionic fatty alkyl polyglycosides of the formula

R ² O (C _n H _{2 n} O) _y (Z) _x in which Z is derived from glucose, R ² is a hydrophobic group selected from alkyl, alkylphenyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl group is a group of 8 to 22, preferably 12 to 14 carbon atoms, n is 2 or

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3, preferably 1, y is 0 to 10, preferably 0, and x is 1.5 to 8, preferably 1.5 to 4, most preferably 1.6 to 2.7. U.S. Patents 4,393,203 and 4,732,704, incorporated herein by reference, disclose these alkyl polyglycoside surfactants.

Aqueous Liquid Carrier: The low-performance dishwashing detergent compositions of the present invention further comprise from about 50% to about 75%. an aqueous liquid carrier in which other essential and optional components of the compositions are dissolved, dispersed, or suspended. The compositions according to the invention more preferably comprise 47 to 64 wt. the aqueous liquid carrier.

However, one essential component of the aqueous liquid carrier is water. However, the aqueous liquid carrier may contain other materials which are liquid or which dissolve in the liquid carrier at room temperature with which they may also have, in addition to being a simple filler, some other functions. Such materials include, for example, hydrotropes, solvents and electrolytes for phase stability.

a) Hydrotropic Agents: The aqueous liquid carrier may contain one or more materials which are hydrotropic agents. Hydrotropic agents for use in the compositions of the invention include alkyl (C 1 -C 3) arylsulfonates, C 6 -C 12 alkanols, carbocyclic sulfates and C 1 -C 6 sulfonates, urea, C 1 -C 6 hydrocarbylates, carboxylates C 1-C, organické, C di-C organické organické di organic diacids and mixtures of these hydrotropic materials.

Suitable alkyl (C 1 -C 3) arylsulfonates include sodium, potassium and ammonium xylene sulfonate, sodium, potassium and ammonium toluenesulfonate, potassium and ammonium cumenesulfonate, substituted or unsubstituted sodium, potassium and ammonium naphthalenesulfonates, and mixtures thereof.

Suitable carboxylic sulfate or sulfonate salts of 1 to 8 carbon atoms are any water-soluble salts or organic compounds of 1 to 8 carbon atoms (except for substituent groups) which are substituted with sulfate or sulfonate and have at least one carboxyl group. The substituted organic compound may be acyclic or aromatic, i. these are benzene derivatives. Preferred alkyl compounds have 1 to 4 carbon atoms substituted with sulfate or sulfonate and one to two carboxyl groups. Examples of hydrotropes of this type include sulfosuccinate salts, sulfophthalic salts, sulfoacetate salts, m-sulfobenzoic acid salts, and sulfosuccinate diesters, preferably sodium or potassium salts, as described in U.S. Pat. 3,915,903.

Suitable C1-C4 hydrocarbylates and C1-C4 carboxylates for use herein include acetates, propionates and citrates. Suitable C 2 -C 4 diacids for use herein include succinic, glutaric and adipic acids.

Other compounds which impart hydrotropic effects suitable for use in the present invention as hydrotropic agents include C 6 -C 12 alkanols and urea.

Preferred hydrotropic agents for use herein are sodium cumene sulfonate. potassium and ammonium, sodium, potassium and ammonium xylene sulfonate, sodium, potassium and ammonium toluenesulfonate, and mixtures thereof. Most preferred are sodium cumene sulfonate, sodium xylene sulfonate, and mixtures thereof. These preferred hydrotropic materials may be present in the composition in an amount of 3 to 8 wt.

b) Solvents: A variety of water-miscible liquids such as lower alkanols, diols, other polyols, ethers, amines, and the like can be used as part of the aqueous liquid carrier. Especially preferred are alkanols having 1 to 4 carbon atoms. These solvents may be present in the compositions of the invention in an amount of 3 to 8% by weight.

c) Electrolytes: Various water-soluble salts can be used as electrolytes in the aqueous t-liquid carrier component of the compositions of the invention. These include salts such as sodium chloride, potassium chloride, sodium citrate, sodium acetate, sodium sulfate, potassium sulfate, and the like. The most preferred electrolyte is sodium or potassium chloride.

If used, the electrolytes may be present in the composition in an amount of 2.5 to 8, more preferably 1.5 to 4.5% by weight. by weight of the composition.

PH Controlling Agents: Alkaline pH products and alkaline aqueous dishwashing solutions made therefrom containing an appropriate combination of surfactants of the compositions of the invention are particularly effective in removing fatty contaminants from the dishes, particularly heavily soiled dishes. The compositions of the present invention will essentially comprise a pH controlling agent sufficient to maintain the pH of a 10% (w / w) aqueous solution of the composition in the range of 9-11. More preferably, the compositions of the invention will be in a 10% (w / w) alkaline solution with pH 10.0 to 10.5.

It is particularly preferred that the pH controlling agent is capable of maintaining the pH of the dilute solutions containing the aqueous dishwashing solutions of the present invention. The pH controlling agent is preferably effective to maintain a pH of a 3% (w / w) solution of the composition in the range of 9.5 to 10.8, preferably

9.8 to 10.5. Even more preferably, the pH controlling agent is effective to maintain the pH of a 0.3% (w / w) aqueous solution of the composition in the range of 9.8 to 11, preferably 10.0 to 11.0.

The pH control agent used for the respective pH of the dishwashing detergents of the invention may be any low molecular weight organic or any organic material that provides alkalinity. Useful inorganic salts include water-soluble carbonates, bicarbonates, borates, phosphates, chlorides, or silicates. Useful organic materials for increasing alkalinity include i

alkanolamines. Highly preferred pH control agents include alkali metal carbonates, especially sodium or potassium carbonate.

The pH-regulating agents will generally be present in the compositions of the invention in an amount of 0.2 to 6, preferably 2 to 5 wt. by weight of the composition.

Omission of divalent metal ions: The alkaline nature of the liquid dishwashing detergent compositions of the invention creates the need to avoid the inclusion of any divalent metal ions that can form dihydroxide precipitates at the pH conditions specified for the detergent products of the invention. The compositions of the present invention will then not essentially comprise any source of calcium and / or magnesium ions. This is also the case where the sources of Ca and / or Mg are conventionally contained in lower pH liquid dishwashing detergent compositions.

Improved Thermal Stability: Liquid dishwashing detergent compositions of the present invention having particularly desirable high and / or low temperature stability can be prepared by selecting the types and amounts of ingredients from those described above. By using potassium electrolyte salts and / or a pH regulating agent, it is possible to improve the stability of the products at room temperature and at high temperature, since these potassium salts have a reduced tendency to form visible precipitates at higher temperatures. By using relatively low concentrations, the anionic surfactant component, i. a concentration of 31% or less by weight, the tendency of the surfactant system to form visible precipitates at lower temperatures is reduced.

Optional Ingredients: Preferred optional ingredients in the dishwashing compositions of the invention include adjuvants such as protease, enzyme stabilizing system and thickeners. These and other optional ingredients are described below. ¹

a) Surfactant Auxiliaries: The compositions of the invention may comprise a variety of surfactant auxiliary agents in addition to the substantially used surfactants described above. These auxiliary surfactants include, for example, C 8 -C 22 alkyl sulfates, C 9 -C 15 alkyl benzene sulfonates, C 8 -C 22 olefin sulfonates, C 8 -C 22 paraffin sulfonates, C 8 -C 22 alkyl (glycol) ether sulfonates , fatty acid sulfonate esters, secondary alcohol sulphates, alkyl (12 to 16 carbon atoms) -ethoxycarboxylates, 11 to 16 carbon secondary soaps, ampholytic detergent surfactants and both detergent surfactants.

a) Proteases and / or other enzymes: The compositions according to the invention may optionally also contain 0.001 to 5, more preferably 0.003 to 4 and most preferably 0.005 to 3% by weight. proteases, i. proteolytic enzyme. Protein activity can be expressed in Anson units (AU) per kilogram of detergent composition. It has been found that an acceptable amount in the compositions of the present invention is an amount of 0.01 to 150, preferably 0.05 to 80, most preferably 0.1 to 40 AU per kilogram.

Useful proteolytic enzymes may be of animal, vegetable or (preferably) microbiological origin. More preferably, the serine proteolytic enzyme is of bacterial origin. Purified or unpurified forms of enzymes may be used. Proteolytic enzymes produced by chemically or genetically modified mutants are, by definition, included as close structural variants of the enzyme. A particularly preferred proteolytic enzyme is a bacterial serine proteolytic enzyme derived from Bacillus subtilis and / or Bacillus licheniformis.

Suitable proteolytic enzymes include Novo Industri A / S Alcalase® (preferred), Esperase®, Savinase® (Copenhagen, Denmark),

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Gist's Maxatase ®, Maxac'al ® and Maxapem 15 ® (protein assembled by Maxacal ®) (Delft, The Netherlands) and subtilisin BPN and BPN '(preferred), which are commercially available; Preferred proteolytic enzymes also include modified bacterial serine proteases, such as those produced by Genencor International, Inc. (San Francisco, California), which are described in European patent B 251 466, issued December 28, 1994 and published January 7, 1988 (in particular pages 17, 24 and

98) and referred to herein as "Protease B." U.S. Patent 5,030,378, Venegas, issued June 9, 1991, to a modified bacterial serine proteolytic enzyme (Genecor International), which is called "Protease A" in the present invention. (same as BPN '). For a complete description, including amino acid sequence A and variants thereof, see, in particular, columns 2 and 3 of U.S. Patent 5,030,378. Preferred proteolytic enzymes are then selected from the group consisting of Alcalase® (Novo Industri A / S), BPN ', Protease A and Protease B (Gencor) and mixtures thereof. Most preferred is Protease B.

Another preferred protease, referred to as " Protease D, is a carbonyl hydrolase variant having a non-naturally occurring amino acid sequence that is derived from a carbonyl hydrolase precursor by substituting various amino acids of multiple amino acid residues at position in said carbonyl hydrolase equivalent to position +76, also in combination with one or more positions of amino acid residues equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265 and / or +274 the numbering of Bacillus amyloliquefaciens subtilisin as described in WO 95/10615, published April 20, 1995, by Genencor International.

Useful proteases are also described in PCT publications: WO 95/30010, published November 9, 1995, The Procter and Gamble Company, WO 95/30011, published November 9, 1995, The Procter and Gamble Company, and WO 95/29979, published November 9, 1995, The Procter and Gamble Company. %

Optional enzymes, such as lipase and / or amylase, may be added to the compositions of the present invention for additional cleaning effects.

c) Enzyme Stabilizing System: Preferred compositions according to the invention may further comprise 0.001 to 10, preferably 0.005 to 10

8, most preferably 0.01 to 6 wt. an enzyme stabilizing system. The enzyme stabilizing system may be a stabilizing system that is compatible with the protease or other enzymes used in the compositions of the invention. These stabilizing systems may include boric acid, propylene glycol, short chain carboxylic acid, boric acid, polyhydroxyl compounds, and mixtures thereof, as described in U.S. Patent 4,261,868, Hora et al., Issued April 14, 1981; , Tai, issued September 13, 1983, 4,313,818, Letton et al., 4,243,543, Guildert et al, issued January 6, 1981, 4,462,922, Boskamp, issued July 31, 1984, 4,532,064, Boskamp. , issued July 30, 1985, and 4,537,707, Severson Jr., issued August 27, 1985; all of which are incorporated herein by reference.

0 to 10% by weight, preferably 0.01 to 6% by weight, can be added to the compositions according to the invention. chlorine bleach scavengers and oxygen bleach to prevent chlorine bleach particles present in many water suppliers from attacking and deactivating enzymes, particularly under alkaline conditions. Although the amount of chlorine in the water may be small, typically in the range of from 0.5 ppm to 1.75 ppm, the available chlorine in the total amount of water that comes into contact with the enzyme during dish washing is usually large. The stability of the enzyme in its use can therefore be problematic.

Suitable anionic chlorine scavengers are salts containing ammonium cations. These salts may be selected from the group consisting of reducing materials such as sulfite, bisulfite, thiosulfite, thiosulfate, iodine and the like, antioxidants such as carbonate, ascorbate, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or its alkali metal salt and monoethanolamine (MEA) and mixtures thereof.

d) Thickening Agents: The detergent dishwashing detergent compositions of the invention may also contain a thickening material. Many suitable polymeric thickeners are known in the art. A preferred thickening agent for use in the compositions of the present invention is hydroxypropylmethylcellulose.

The hydroxypropylmethylcellulose polymer has a number average molecular weight of 50,000 to 125,000 and a viscosity of 2% (w / w) aqueous solution at 25 ° C (ADTMD2363) of 50 to 10 Pa.s. A particularly preferred hydroxypropylcellulose polymer is Metocel (R) J75MS-A, whose 2.0% (w / w) aqueous solution at 25 ° C has a viscosity of 75 Pa.s. Particularly preferred hydroxypropyl cellulose polymers are surface treated so that the hydroxypropyl cellulose polymer readily disperses at 25 ° C in an aqueous solution having a pH of at least 8.5.

When a thickening agent such as a hydroxypropylmethylcellulose polymer is used in the preparation of the dishwashing detergent compositions of the present invention, the detergent composition will have a Brookfield viscosity of 0.5 to 3.5 Pa.s at 25 ° C. More preferably, the hydroxypropyl methylcellulose material will be used to provide a viscosity of 1 to 3 cps at 25 ^e C. For purposes of this invention, viscosity is measured with the Brookfield viscosity measurement LVTDV-11-needle RV # 2 at 12 rpm.

The detergent dishwashing detergent compositions of the invention may contain 0.2 to 2, more preferably 0.5 to 2.5 wt.

a thickening agent, in particular a hydroxypropylmethylcellulose thickening agent.

I

e) Some optional ingredients: Other conventional optional ingredients that are commonly used in amounts below 5% by weight include opacifying agents, antioxidants, bactericides, colorants, perfumes, and the like. In addition, detergent builders may be present in the compositions of the invention in amounts up to 50%, preferably 2 to 30%, and most preferably 5 to 15% by weight. Typically, no detergent builder component is present in the low-performance liquid or goal detergent dishwashing compositions. Although sources of calcium and magnesium ions are excluded from the compositions of the invention, some compositions may contain trace amounts of magnesium or calcium ions as impurities. These compositions may require a further presence of low amounts, preferably up to 10, more preferably 0.5 to 3 wt. chelating agents selected from the group consisting of bi-tin / bis (2-ethanol) bycin, N- (2-hydroxyethyl) iminodiacetic acid citrate (HIDA), N (2,3-dihydroxypropyl) diethanolamine, 1,2-diamino2 -propanol, N, N'-tetramethyl-1,3-diamino-2-propanol, Ν, Ν-bis (2-hydroxyethyl) glycine (aka bicine) and N-tris (hydroxymethyl) methylglycine (aka tricine). Mixtures of any of the above agents are acceptable.

Preparation of the compositions: The liquid or gel detergent compositions of the invention may be prepared by combining the essential and optional ingredients in any suitable order using appropriate mixing to form a homogeneous product. Preferred methods of making detergent compositions of the type described herein and preparing various components thereof are described in more detail in U.S. Patent 5,474,710, Ofosu-Asante, issued December 12, 1995, which is incorporated herein by reference.

Dish Washing Method: Soiled dishes may be contacted with an effective amount, typically 0.5 ml to 20 ml (per piece of dish), preferably 3 ml to 10 ml, of the detergent composition of the present invention. The actual amount of liquid detergent used will depend on the judgment of the user and will typically depend on such factors as the particular composition of the composition, including the concentration of the active ingredient in the composition, the number of soiled dishes to be washed, the degree of soiling and similar factors. Furthermore, the composition of the product concerned will depend on a number of factors, such as the intended market (ie USA, Europe, Japan, etc.). The following are examples of typical processes in which the detergent compositions of the present invention can be used to clean dishes. These examples are for illustration only and are not intended to be limiting.

Typically in the USA, 3-15 ml, preferably 5-10 ml of liquid detergent composition is combined with 1000-10,000 ml of water, typically 3000-5000 ml of jersey with a volume of 5000-20,000 ml, more typically 10,000-15 000 ml. The detergent composition has a surfactant concentration of 21 to 44%, preferably 25 to 40% by weight. The soiled dish is immersed in a jersey containing detergent and water, where it is washed by contacting the soiled surface of the dish with a cloth, sponge or the like. The rag, sponge or the like can be immersed in a detergent / water mixture before being contacted with the dish surface and is typically in contact with the dish surface for a period of from 1 to 10 seconds, although the actual time may vary depending on use and by user. The contacting of the rag, sponge or the like with the surface of the dish is preferably accompanied by simultaneous wiping of the surface of the dish.

In a typical use on the European market, 3-15 ml, preferably 5-10 ml of liquid detergent composition is combined with 1000-10,000 ml of water, typically 3000-5000 ml of jersey with a volume of 5000-20,000 ml, more typically 10,000- 15,000 ml. The detergent composition has a surfactant concentration of 20 to 50%, preferably 30 to 40% by weight. The soiled dish is immersed in a jersey containing detergent and water, where it is washed by contacting the soiled surface with a cloth, sponge or the like. The rag, sponge or the like can be immersed in the detergent composition and water mixture before being contacted with the dish surface and is typically in contact with the dish surface for 1 to 10 seconds, although the actual time may vary depending on use and by user. The contacting of the dish, sponge or the like with the surface of the dish is preferably accompanied by simultaneous wiping of the dish surface.

Typically used in the Latin American market, 1 to 50 ml, preferably 2 to 10 ml of detergent composition is combined with 50 to 2000 ml of water, more typically 100 to 1000 ml of water in a bowl of 500 to 5000 ml, more typically 500 to 2000 ml. The detergent composition has a surfactant concentration of from 5 to 40%, preferably from 10 to 30% by weight. The soiled dish is cleaned by contacting the soiled surface of the dish with a cloth, sponge or the like. The rag, sponge or the like can be immersed in the detergent composition and water mixture before being contacted with the dish surface and is typically in contact with the dish surface for 1 to 10 seconds, although the actual time may vary depending on use and by user. The contacting of the cloth, sponge or the like with the surface of the dish is preferably accompanied by simultaneous wiping of the surface of the dish.

Another method of dishwashing used worldwide is the direct application of the detergent compositions of the invention, either clean or diluted in a storage bottle, to the soiled dish to be washed. This can be done by a device that absorbs a liquid dishwashing detergent, such as a sponge or dish cloth, which is placed directly into a separate amount of undiluted or slightly diluted liquid

Detach the dishwashing agent for 1 to 5 seconds. The adsorption device and the undiluted or slightly dilute liquid dishwashing composition are then contacted with the surface of each soiled dishware to remove food soiling. The adsorbing device is typically in contact with each surface of the cookware for 1 to 10 seconds, although the actual application time will depend on such factors as the degree of soiling of the cookware. The contacting of the adsorption device with the surface of the dish is preferably done by simultaneous wiping. Prior to contacting and wiping, the method comprises immersing soiled dishes in a water bath without any liquid dishwashing detergent. After wiping, the dishes can be rinsed under running water.

The following examples illustrate the invention and facilitate its understanding.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

A low-performance liquid dishwashing detergent composition is prepared having the following composition:

component concentration (% by weight) Alkyl (C12-C13) ethoxy (1-3) - 34 sodium sulfate C 12 -C 14 glucose amide 4 Coconut amine oxide 5 EO / PO block copolymer - Tetronic ® 704 0.3 ethanol 7 Sodium xylene sulfonate 5 Alcohol (C11) ethoxylate (Eg) Neodol® 1 perfume 0.2 Sodium chloride 4.0 Sodium carbonate V 3,0 Water and minor components add to 100 PH of 10% (w / w) solution (after preparation) 10.1

Example 2

A low-performance liquid dishwashing detergent composition having a particularly desirable high and / or low temperature composition of the following composition is prepared;

component concentration (% by weight) Alkyl (C12-C13) ethoxy (1-3) - 31 sodium sulfate C 12 -C 14 glucose amide 4 Coconut amine oxide 9 '* EO / PO block copolymer - Tetronic ® 704 0.4 ethanol 5 Sodium xylene sulfonate 5 Alcohol (C11) ethoxylate (Eg) Neodol® 1 perfume 0.2 Potassium chloride 2.5 Potassium carbonate 2.5 Water and minor components add to 100 PH of 10% (w / w) solution (after preparation) 10.5

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Claims (1)

PATENT CLAIMS A pH-controlled, low-performance aqueous detergent composition having particularly desirable soil removal and foaming properties when used for washing heavily soiled dishes, comprising: a) 20 to 40 wt. an anionic surfactant containing alkyl ether sulfates of 8 to 18 carbon atoms in the alkyl group and 1 to 6 moles of ethylene oxide, a) 3 to 10 wt. % of a nonionic surfactant comprising surfactants selected from the group consisting of C8-C18 fatty acid amides and a combination of these polyhydroxy fatty acid amides with 0.2-2.0 wt. a nonionic surfactant composition selected from the group consisting of an alcohol (C8-C18) of ethoxylate with 1 to 15 moles of ethylene oxide, surfactants of the ethylene oxide / propylene oxide block copolymer type, and a combination of these nonionic surfactants, a) 2 to 6 wt. a suds booster / stabilizer selected from the group consisting of betaine surfactants, hydroxy fatty acid amides, amine oxide semipolar and nonionic surfactants, C8 -C22 alkyl polyglycosides, and combinations of these suds boosters / stabilizers, a) 45 to 75 wt. an aqueous liquid carrier; and a) 0.2 to 6 wt. a pH regulating agent effective to maintain the pH of a 10% (w / w) aqueous solution of the composition in the range of 9-11, wherein the composition is substantially free of calcium or magnesium ion sources. A pH-controlled, low-performance aqueous detergent composition having particularly desirable soil removal and foaming properties when used for washing heavily soiled dishes, characterized in that it comprises: a) 25 to 35 wt. (C až-C 16) alkyl ether sulphate and 1 to 3 moles of ethylene oxide, a) 3 to 5 wt. polyhydroxy fatty acid amides of 10 to 16 carbon atoms, a) 0.5 to 1.5 wt. C 10 -C 14 alcohol ethoxylate having 8 to 13 moles of ethylene oxide, a) 0.2 to 0.8 wt. a polymeric surfactant comprising ethylene oxide and propylene oxide condensed with ethylenediamine to form a block copolymer having a molecular weight of 4000 to 6000 and an HLB of 10 to 20, a) 3 to 6 wt. % of coconut alkyldimethylamine oxide; sodium carbonate as a pH controlling agent effective to maintain the pH of a 10% (w / w) aqueous solution of the composition in the range of 10-11; a) 50 to 65 wt. % of an aqueous liquid carrier comprising 3 to 8 wt. by weight of the composition of a hydrotropic agent selected from alkali metal xylenes and toluenesulfonates; and 3-8 wt. by weight of the solvent composition selected from alkanols having from 1 to 4 carbon atoms, said composition substantially free of calcium or magnesium ion sources. Composition according to claims 1 to 2, characterized in that it is stable at high temperature, wherein: a) said anionic surfactant is 31% or less by weight of the composition; from the weight of the composition, (a) the aqueous liquid carrier comprises electrolytes in the form of a potassium salt; and (a) pH regulating agent means potassium carbonate. Represented by: