CZ9904042A3 - Aqueous, low-effective detergent preparation with controlled pH and having properties consisting in removal of dirt and generation of foam - Google Patents

Abstract

An aqueous, low-performance detergent composition is disclosed pH-controlled, which has particularly desirable properties consisting in removing soiling and foaming used for washing heavily soiled dishes. This means contains anionic surfactants which they contain C 8 -C 18 alkyl ether sulfates of the alkyl group; 1 to 6 moles of ethylene oxide, nonionic surfactant an agent, a suds enhancer / stabilizer, an aqueous liquid carrier, and the pH regulating agent being substantially free of a source calcium or magnesium ions.

Description

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

Technical field

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

BACKGROUND OF THE INVENTION

Low performance (LDL) or gel detergent compositions useful for hand dishwashing are well known in the art. These products are typically formulated to provide numerous different designs and to have aesthetic properties and features. First and foremost, dishwashing liquid or gel products must be formulated with such types and amounts of surfactants of other adjuvant cleaning agents that will provide acceptable solubilization and removal of food contaminants, particularly fatty contaminants, from dishes to be cleaned with aqueous solutions or in aqueous solutions formed from these products.

Heavily soiled dishes may present special problems during the manual dishwashing procedure. Products such as plates, dishes, pots, pans, porcelain dishes and the like may be heavily soiled in the sense that relatively large amounts of soils and food debris may be present on the dishes when the soiled dishes are hand washed. The dishes may also be heavily soiled in the sense that residues of food soils adhere particularly stably or are baked to the surfaces of the dishes to be cleaned. This can happen as a result of the type of pollution •

the present food or the nature of the surfaces of the dishes. Tough residues of food soiling can also come from the type of cooking for which the soiled dishes were used.

When heavily soiled dishes are washed by hand, very concentrated or high concentrations of dishwashing detergent products are often used. Often, they will involve direct application of the liquid or gel product in its undiluted or clean form to soiled dishes. 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 desirable other properties that enhance aesthetic properties or perception by the customer of the effectiveness of the hand 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 an appropriate amount of foam in the wash water initially and the formation of foam that persists in the dishwashing process.

In view of what has been said herein, there is a continuing need to prepare hand dishwashing liquids and gels that provide an acceptable and desirable balance between performing cleaning, both in concentrated direct applications and aqueous dishwashing solutions, and product aesthetics. It is therefore an object of the present invention to provide low performance liquid or gel dishwashing compositions which are particularly effective in removing food stains from soiled dishes when 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 compositions which provide a suitable and desirable foaming performance.

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

SUMMARY OF THE INVENTION

The present invention relates to pH-controlled, low pH, liquid or gel detergent compositions having particularly desirable soil removal and foaming properties when used for washing heavily soiled dishes. These compositions comprise A) from 20 to 40 wt. % of the specific type of anionic surfactant, B) from 3 to 10 wt. % of a certain nonionic surfactant, C) from 2 to 6 wt. % of a suds / stabilizer, D) from 50 to 75 wt. % of an aqueous liquid carrier; and E) from 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 of the composition 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% by weight of nonionic surfactants, such as polyhydroxy fatty acid amides, may also be present. a nonionic surfactant composition. The nonionic surfactant is selected from the group consisting of an alcohol (8 to 18 carbon atoms) ethoxylate with 1 to 15 moles of ethylene oxide, ethylene oxide / propylene oxide block copolymer surfactants, and combinations of these nonionic surfactants.

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

The foregoing essential ingredients, as well as numerous other optional ingredients, may be combined in a conventional manner to form the low performance liquid or gel dishwashing detergent products of the present invention. One type of ingredient typically used in dishwashing detergent products, but which should not be used in the relatively high pH environments 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 invention comprise five types of essential ingredients. These components are:

1) certain type of anionic surfactant,

(2) certain non-ionic surfactants;

3) some foaming amplifiers / stabilizers,

4) an aqueous liquid carrier; and

5) a pH regulating agent.

A variety of optional ingredients may also be added to complement the rheological and / or aesthetic properties of the compositions of the invention.

• ·

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

Anionic surfactant: The compositions of the invention essentially comprise from 20 to 40 wt. anionic surfactants. More preferably, the anionic surfactant comprises from 25 to 35 wt. compositions according to the invention.

The anionic surfactant component essentially comprises alkyl ether sulfates. Alkyl ether sulfates are also known as alkyl polyethoxylate sulfates. These ethoxylated alkyl sulfates are compounds of formula

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

Nonionic Surfactants: The compositions of the present invention also contain substantially from 3 to 10 wt. nonionic surfactants of a certain 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 present in the compositions of the invention is the C8 -C18 fatty acid amide. These materials are fully described in Pan / Gosselink: U.S. Patent 5,332,528, issued July 26, 1994, which is incorporated herein by reference. These polyhydroxy fatty acid amides are compounds of formula

R ² -C (O) -NZ wherein R ¹ represents a hydrogen atom, a C 1 -C 4 hydrocarbon group, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R ² represents a C 8 -C 18 hydrocarbon group and Z is a linear hydrocarbon chain polyhydroxy hydrocarbon group having 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 of 10 to 18 carbon atoms. The C 12 -C 16 N-propyl to N-hexyl glucamides can be used for the foamed-down 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 compositions.

In the nonionic surfactant component of the compositions of the invention, the polyhydroxy fatty acid amides described herein may be combined with some other types of nonionic surfactant co-agents. These other types include ethoxylated alcohol surfactants and ethylene oxide-propylene oxide block copolymers, as well as combinations of these nonionic surfactants.

♦ · · «·« · · · * * * * * * * *

Ί

The ethoxylated alcohol surfactant materials useful in the nonionic surfactant component of the present invention are those of the formula: ## STR3 ##

R 1 -O- (C ₂ H ₄ O) nSO 3 M, wherein R ¹ is 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 which contains from 9 to 15 carbon atoms, more preferably from 10 to 14 carbon atoms. The ethoxylated fatty alcohols will preferably contain from 2 to 12 ethylene oxide moieties per molecule, more preferably from 8 to 12 ethylene oxide moieties per molecule. Nonionic surfactants of the ethoxylated fatty alcohol type will often have a hydrophilic to lipophilic (HLB) ratio ranging from 6 to 15, most preferably from 10 to 15.

Examples of fatty alcohol ethoxylates useful as the nonionic surfactant component of the compositions of the invention include those made from C 12 -C 15 alcohols 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 having an average of 11 carbon atoms in its alkyl chain of 5 moles of ethylene oxide, Neodol 23-9, an ethoxylated primary alcohol of 12 to 13 carbon atoms with 9 moles of ethylene oxide, and Neodol 91-10 , 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 Chemical 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 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 the number of ethylene oxide groups per mole being These products are commercially manufactured by Shell Chemical Company.

The ethoxylated alcohol nonionic surfactant co-agents will often be present in the compositions of the invention in an amount of from 0.2 to 2% by weight, more preferably from 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 ranging from 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 Tetronic ^(R) . Similar structures in which ethylenediamine is replaced by a polyol, such as propylene glycol, are manufactured under commercial

• 4 ·· • 4 · 4 • 4 4 4 with the name Pluronic ^(R) . Preferred ethylene oxide-propylene oxide (EO-PO) polymeric surfactants have an HLB in the range of 4 to 30, more preferably 10 to 20.

The ethylenexoid-propylene oxide block copolymers used herein are described in more detail in Pancheri / Mao: U.S. 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 from 0.1 to 2, more preferably from 0.2 to 0.8% by weight. by weight of the composition.

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

The betaine surfactants useful as the suds boosters of the invention are compounds of the general formula

R - N ⁽⁺⁾ (R ¹ ) ₂ - R ² COO ^w , wherein R is a hydrophobic group selected from alkyl groups of 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms, alkylaryl and arylalkyl groups with similar numbers benzene ring atoms taken as the equivalent of two carbon atoms and similar structures 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.

·· ·· * 4 44 44 • 44 44 44 4444 «· 4 · 4 4444

4 «4» · «44444

4 4 4 4 4 5

4444 44 4 · 4 · ♦ · 44 44

Examples of preferred betaines include dodecyldimethyl betaine, cetyl dimethyl betaine, dodecylamidopropyldimethyl betaine, tetradecyldimethyl betaine, tetradecylamidopropyldimethyl betaine and dodecyldimethylammonium hexanoate. Other suitable amidoalkyl betaines are described in U.S. Patent Nos. 3,950,417, 4,137,191 and 4,375,421, and British Patent No. 2,103,236, all of which are incorporated herein by reference.

Non-hydroxyl amide surfactants useful as the suds boosters of the present invention include ammonium monoethane and fatty acid diethanolamides having an acyl moiety of from about 8 to about 18 carbon atoms. These materials are characterized as non-hydroxylic to distinguish them from polyhydroxy fatty acid amides substantially used in the nonionic surfactants hereinabove. Accordingly, for the purposes of this invention, non-hydroxyl amides are 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 . ₁ (R ₂ OH) _{3. m} wherein R 1 is a saturated or unsaturated non-hydroxy aliphatic hydrocarbon group of 7 to 21, preferably 11 to 17 carbon atoms, R ₂ is a methylene or ethylene group and _m is 1, 2 or 3, preferably 1. Specific examples of these amides are the coconut fatty acid monoethanolamine amide and the diethanolamine fatty acid amide amide. These acyl moieties may be derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil, and tallow, but may also be derived synthetically, e.g., by oxidation of petroleum or hydrogenation of carbon monoxide by the Fischer-Tropsch process. Monoethanolamides and diethanolamides of C 12 -C 14 fatty acids are preferred.

Aminoxide semipolar nonionic surfactants useful as suds boosters / stabilizers contain compounds and mixtures of these compounds of the general formula 4 44 4 4 4

4 4 4

4 · 4,444 • 4

44

R ₂

Rf (C ₂ H ₄ O) _n N ~ O, R ₃ I wherein is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy groups means a group having 8 to R @ ₂ and R @ 3 are methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl; and n is from 0 to 10. Particularly preferred amine oxides of the formula

R ₂

AND

R _r N- ~ O,

AND

R ₃ wherein R 1 is C 12 -C 16 alkyl and R ₂ and R ₃ are methyl or ethyl. The above nonhydroxyl amides and amine oxides are described in more detail in U.S. Patent 4,316,824, which is incorporated herein by reference.

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

R ₂ O (C _n H 2 _n O) _y (Z) _x , wherein Z is derived from glucose, R is a hydrophobic group selected from alkyl, alkylphenyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl group is a group of 8 to 22, s preferably having 12 to 14 carbon atoms, n is 2 or 3, preferably 2, y is from 0 to 10, preferably 0, and x is from 1.5 to 8, preferably from 1.5 to 4, most preferably from 1.6 to 2.7. U.S. Patents 4,393,203 and

44 ·

444 444 444 4 • 4 4 4 4

4 4 4

4444 44 444 4 44 444

4

44

No. 732,704, incorporated herein by reference, disclose such alkyl polyglycoside surfactants.

Aqueous Liquid Carrier: The low-performance dishwashing detergent compositions of the present invention further comprise from 50 to 75 wt. an aqueous liquid carrier in which other essential and optional components of the compositions are dissolved, dispersed, or suspended. The compositions of the invention more preferably comprise from 47 to 64 wt. of 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 and which may also have, in addition to being a simple filler, some other functions. Such materials include, for example, hydrotropic agents, 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 1 -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 (excluding substituent groups) that are substituted with sulfate or sulfonate and have at least one carboxyl group. The substituted organic compound may be cyclic, acyclic or aromatic, i.e., benzene derivatives. Preferred alkyl compounds have 1 to 4 carbon atoms substituted with sulfate or sulfonate and one to two carboxyl groups. Examples of hydrotropic agents 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. Patent No. 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 acid.

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

Preferred hydrotropic agents for use herein are sodium, potassium and ammonium cumene sulfonate, sodium, potassium and ammonium xylene sulfonate, sodium, potassium and ammonium toluene sulfonate, 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 from 3 to 8 wt%.

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

c) Electrolytes A variety of water-soluble salts can be used as electrolytes in the aqueous liquid carrier component of the compositions of the invention. These include such salts as sodium chloride, potassium chloride, sodium citrate, sodium acetate, sulfate • 00 · 0 0 · • · 0

000 00 »

Sodium, potassium sulphate and the like. Most preferably, the electrolyte is sodium or potassium chloride.

If used, the electrolytes may be included in the composition in an amount

% 2.5 to 8, more preferably 1.5 to 4.5 wt. by weight of the composition.

PH Controlling Agents: The alkaline pH products and the alkaline aqueous dishwashing solutions formed therefrom containing the appropriate surfactant combination of the compositions of the invention are particularly effective in removing greasy soils from dishes, particularly heavily soiled dishes. Thus, 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 to 11. More preferably, the compositions of the invention will be in a 10% (w / w) solution with a pH of 10.0 to 10.5.

It is particularly preferred that the pH controlling agent is able to maintain the pH of the dilute solutions containing the aqueous dishwashing solutions of the present invention. The pH control agent is preferably effective to maintain a pH of a 3% (w / w) solution of the composition in the range of from 9.5 to 10.8, preferably from 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 from 9.8 to 11, preferably from 10.0 to 11.0.

The pH control agent used for the respective pH of the dishwashing detergent compositions 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 adding alkalinity include alkanolamines. Highly preferred pH control agents include alkali metal carbonates, especially sodium or potassium carbonate.

9 9

9 9

999

99 9 99

9 999

The pH-regulating agents will generally be present in the compositions of the invention in an amount of from 0.2 to 6, preferably from 2 to 5% by weight. 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 hydroxide precipitates under the pH conditions specified for the detergent products of the invention. Thus, the compositions of the present invention will not substantially comprise any source of calcium and / or magnesium ions. This is also the case when the sources of Ca and / or Mg are conventionally contained in lower pH liquid dishwashing detergent compositions.

Improved Thermal Stability: The 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. The use of potassium electrolyte salts and / or pH control agents can improve product stability 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 of the anionic surfactant, i.e., concentrations 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, enzymes such as protease, enzyme stabilizing system, and thickeners. These and other optional ingredients are described below.

a) Surfactant Adjuncts: The compositions of the invention may contain a variety of surfactant adjuvants in addition to the surfactants described above. Such auxiliary surfactants include, for example, C 8 -C 22 alkyl sulfates, C 9 -C 15 alkylbenzene sulfonates, C 8 -C 22 olefin sulfonates, C 8 -C 22 paraffin sulfonates. · 9 9

9 9

98 9 99 9

99

9 9 · 9 9 999 999

Carbon atoms, alkyl (8 to 22 carbon atoms) glyceryl ether sulfonates, fatty acid sulfonate esters, secondary alcohol sulfates, alkyl (12 to 16 carbon atoms) ethoxycarboxylates, 11 to 16 carbon secondary soaps, ampholytic detergent surfactants and zwitterionic detergent surfactants.

b) Proteases and / or Other Enzymes: The compositions of the invention may optionally also contain from 0.001 to 5, more preferably from 0.003 to 4, and most preferably from 0.005 to 3% by weight. active proteases, i.e. proteolytic enzyme. Protease activity can be expressed in Anson units (AU) per kilogram of detergent composition. It has been found that acceptable amounts in the compositions of the present invention are from 0.01 to 150, preferably from 0.05 to 80, most preferably from 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 uncleaned forms of the enzyme 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 ^(R) (preferred), Esperase ^(R) , Savinase ^(R) (Copenhagen, Denmark), Gist's Maxatase ^(R) , Maxacal ^(R) and Maxapem 15 ^(R) ( protein assembled by Maxacal ^(R) (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 251 446, issued December 28, 1994 and published January 7, 1988 (especially pages 17, 24, and 98), and referred to herein as Protease B. U.S. Pat. No. 5,030,378, Venegas, issued July 9, 1991, which relates to a modified bacterial serine proteolytic enzyme (Genencor International), fl 99. · 9 9 *.........

This is called Protease A (same as BPN ') in the present invention. For a complete description, including amino acid sequence of protease A and variants thereof, see especially columns 2 and 3 of U.S. Patent 5,030,378. Preferred proteolytic enzymes are then selected from the group consisting of Alcalase ^(R) (Novo Industri A / S), BPN ', Protease A and Protease B (Genencor) 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 different amino acids for multiple amino acid residues at a position at said carbonyl hydrolase equivalent to +76, preferably 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 by numbering Bacillus amyloliquefaciens subtilisin as described in WO 95/10615, published Apr. 20, 1995, Genencor International.

Useful proteases are also described in PCT publications: WO 95/30 010, published November 9, 1995, The Procter and Gamble Company, WO 95/30 011, published November 9, 1995, The Procter and Gamble Company, and WO 95/29 979, published Nov. 9, 1995, The Procter and Gamble Company,

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

c) Enzyme Stabilizing System: Preferred compositions of the invention may further comprise from 0.001 to 10, preferably from 0.005 to 8, most preferably from 0.01 to 6% by weight. 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 contain boric acid.

0 00 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 , boric acid, polyhydroxyl compounds, and mixtures thereof, as described in U.S. Patents 4,261,868, Hora et al., issued April 14, 1981; 4,404,115; Tai, issued September 13, 1983; 4,353,818; Letton et al. Guildert et al., Issued Jan. 6, 1981; 4,462,922; Boskamp, issued July 31, 1984; 4,532,064; Boskamp, issued July 30, 1985; and 4,537,707; Severson, Jr. August 27, 1985; all of which are incorporated herein by reference.

Further, 0 to 10, preferably 0.01 to 6 wt. chlorine bleach scavengers and oxygen bleach to prevent the chlorine bleach particles present at many water suppliers to attack and inactivate enzymes, particularly under alkaline conditions. Although the amounts of chlorine in water may be small, typically in the range of 0.5 ppm to 1.75 ppm, the available chlorine in the total amount of water that comes into contact with the enzyme during dishwashing is usually large. The stability of the enzyme in its use can therefore be problematic.

Suitable anionic 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 etc., antioxidants such as carbonate, ascorbate, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or a salt thereof with alkali metal and monoethanolamine (MEA) and mixtures thereof.

d) Thickeners: The detergent dishwashing detergent compositions of the invention may also contain a thickening material. Many suitable polymeric thickening agents are known in the art. A preferred thickening agent for use in the compositions of the present invention is hydroxypropyl methylcellulose.

The hydroxypropyl methylcellulose polymer has a number average molecular weight of 50,000 to 125,000 and a viscosity of a 2% (w / w) aqueous solution at 25 ° C (ADTMD2363) of 50 to 100 Pa.s. A particularly preferred hydroxypropylcellulose pole is Methocel ^(R) J75MS-N, 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 such 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 hydroxypropyl methylcellulose polymer is used in the preparation of the dishwashing detergent compositions of the present invention, it will give the detergent composition a Brookfield viscosity of from 0.5 to 3.5 Pa.s at 25 ° C. More preferably, the hydroxypropyl methylcellulose material will be used to achieve a viscosity of 1 to 3 Pa.s at 25 ° C. For the purposes of the present invention, the viscosity is measured with a Brookfield LVTDV-11 viscosity meter with a RV # 2 needle at 12 rpm.

The detergent dishwashing detergent compositions of the invention may contain from 0.2 to 2, more preferably from 0.5 to 2.5 wt. a thickening agent, in particular a hydroxypropylmethylcellulose thickening agent.

e) Certain optional ingredients: Other conventional optional ingredients that are typically used in amounts below 5 wt% 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 of from 0 to 50, preferably from 2 to 30, and most preferably from 5 to 15% by weight. It is typical that no detergent builder is present in the low-performance liquid or gel 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 0 to 10, more preferably 0.5 to 3 wt. chelating agents selected from the group consisting of bicine / bis (2-ethanol) blycine, N- (2-hydroxyethyl) iminodiacetic acid citrate (HIDA), N- (2,3-dihydroxypropyl) diethanolamine, 1,2-diamino-2- propanol, N, N'-tetramethyl-1,3-diamino-2-propanol, N, N-bis (2-hydroxyethyl) glycine (aka bicin) and N-tris (hydroxy)

I · · · · · ♦

Methyl) methylglycine (a.k.a. tricin). 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.

Dishwashing method: Dirty dishes may be contacted with an effective amount, typically 0.5 ml to 20 ml (per 25 items), 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 in question will depend on numerous factors such as the intended market (ie USA, Europe, Japan, etc.). The following are examples of typical methods in which the detergent compositions of the present invention can be used for cleaning dishes. These examples are for illustrative purposes only and are not intended to be limiting.

In a typical use in the USA, from 3 to 15 ml, preferably 5 to 10 ml of liquid detergent composition is combined with 1000 to 10,000 ml of water, typically 3000 to 5000 ml of water in a sink of 5,000 to 20,000 ml, more typically 10,000 to 10,000 ml. 15,000 ml. The detergent composition has a surfactant composition concentration of from 21 to 44%, preferably from 25 to 40% by weight. The soiled dishes are immersed in a sink containing detergent and water, where they are washed by contacting the soiled surface of the dishes with a cloth, sponge or the like. The rag, sponge, or the like may be immersed in a detergent / water mixture before being introduced.

contacting the cookware surface and is typically in contact with the cookware surface for a period of from about 10 seconds, although the actual time may vary depending on usage and 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.

Typically used in the European market, from 3 to 15 ml, preferably 5 to 10 ml of liquid detergent composition is combined with 1000 to 10,000 ml of water, typically 3000 to 5000 ml of water in a sink of 5000 to 20,000 ml, more typically 10,000 up to 15 000 ml. The detergent composition has a surfactant composition concentration of from 20 to 50%, preferably from 30 to 40% by weight. The soiled dishes are immersed in a sink containing detergent and water, where they are washed by contacting the soiled surface of the dishes 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 cookware surface and is typically in contact with the cookware surface for from 1 to 10 seconds, although the actual time may vary according to use and per 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.

Typically used in the Latin American market, from 1 to 50 ml, preferably up 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. Soiled dishes are cleaned by contacting the soiled surface of the dishes with a cloth, sponge or similar product. The rag, sponge or the like can be immersed in the detergent composition and water mixture before it is contacted with the cookware surface and is typically in contact with the cookware surface for from 1 to 10 seconds, although the actual time may vary according to use and per 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.

• · · ·

4 4 4

Another method of dishwashing used worldwide includes direct application of the detergent compositions of the invention, either clean or diluted in a storage bottle, to the soiled dishes to be washed. This may be accomplished by a device that absorbs a liquid dishwashing detergent, such as a sponge or dishcloth, which is placed directly into a separate amount of undiluted or somewhat diluted liquid dishwashing detergent for typically from 1 to 5 seconds. The adsorption device, and thus the undiluted or somewhat diluted liquid dishwashing composition, is then individually contacted with the surface of each soiled dish to remove food soiling. The adsorbing device is typically in contact with each cookware surface for from 1 to 10 seconds, although the actual application time will depend on factors such as the degree of soiling of the cookware. The contacting of the adsorption device with the cookware surface is preferably accomplished 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 (12 to 13 carbon atoms) sodium ethoxy (1-3) sulfate 34 C 12 -C 14 glucose amide 4 coconut amine oxide 5 EO / PO block copolymer - Tetronic ^(R) 704 0.3 ethanol 7 sodium xylene sulfonate 5 alcohol (C11) ethoxylate (Eg) Neodol ^(R) 1 perfume 0.2 sodium chloride 4.0 sodium carbonate 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 stability of the following composition is prepared:

component concentration (% by weight) alkyl (12 to 13 carbon atoms) sodium ethoxy (1-3) sulfate 31 C 12 -C 14 glucose amide 4 coconut amine oxide 4 EO / PO block copolymer - Tetronic ^(R) 704 0.4 ethanol 5 sodium xylene sulfonate 5 alcohol (C11) ethoxylate (Eg) Neodol ^(R) 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

«4 ♦ · ·

Claims (3)

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, characterized in that it comprises: A) from 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, B) from 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 to 2.0 wt. a nonionic surfactant composition selected from the group consisting of an alcohol (C8-C18) ethoxylate with 1-15 moles of ethylene oxide, ethylene oxide / propylene oxide block copolymer surfactants, and combinations of these nonionic surfactants, C) from 2 to 6 wt. a suds booster / stabilizer selected from the group consisting of betaine surfactants, hydroxy fatty acid amides, amine oxide semipolar nonionic surfactants, C8 -C22 alkyl polyglycosides, and combinations of these suds boosters / stabilizers, D) from 45 to 75 wt. an aqueous liquid carrier; and E) from 0.2 to 6 wt. a pH controlling agent effective to maintain a pH of a 10% (w / w) aqueous solution of the composition in the range of from 9 to 11, wherein the composition is substantially free of calcium or magnesium ion sources. li vy2 99 99 99 99 9 9 9 9 9 9 9 • 9 · 999,999 9 999 999 99 99 9 9 9 9 99 9 9 9 • 999 99 2. 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) from 25 to 35 wt. (C až-C 16) alkyl ether sulfate and from 1 to 3 moles of ethylene oxide, B) from 3 to 5 wt. polyhydroxy fatty acid amides of 10 to 16 carbon atoms, C) from 0.5 to 1.5 wt. C 10 -C 14 alcohol ethoxylates having from 8 to 12 moles of ethylene oxide, D) from 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 from 4000 to 6000 and an HLB of from 10 to 20; E) from 3 to 6 wt. coconut alkyldimethylamine oxide, F) from 2.0 to 5.0 wt. 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 to 11, and G) from 50 to 65 wt. % of an aqueous liquid carrier comprising from 3 to 8 wt. % by weight of a hydrotropic agent composition selected from xylene to alkali metal toluenesulfonates; and from 3 to 8 wt. by weight of the solvent composition, which is selected from C 1 -C 4 alkanols, wherein the composition is substantially free of calcium or magnesium ion sources. Composition according to claims 1 to 2, characterized in that it is stable at high and low temperatures, wherein: A) said anionic surfactant is 31% or less by weight. the weight of the device, (B) the aqueous liquid carrier comprises electrolytes in the form of a potassium salt; and 0 0 · 0 0 0 0 ♦ ··· • 0. 49 8 ty - • 0 00 00 * 0 0 · 0 0 0 0 0 0 0 0 0 0 0 0 0 0 000 000 0 0 0 0 000 000 00 00 C) pH regulating agent is potassium carbonate.