DE60014941T2 - DISHWASHER CONTAINING COLOR-STABILIZING PHOSPHONATES - Google Patents

Description

technical area

The The present invention relates to liquid or gel dishwashing detergent compositions which for use in hand dishwashing methods are suitable. These compositions contain olefin derived Amine oxide surfactants, organic diamines, fragrances and trace amounts at transition metal ions (present as impurities) as well as solvents and other detergent additives. These components are used in the combinations disclosed herein in addition, dishwasher products provide which preferred properties with regard to food soil cleaning, Handling and foaming, while also having a color, which is stable, i. which does not change over longer periods of time.

background the invention

For the manual Wash the dishes useful light liquid (light-duty liquid, LDL) or gel detergent compositions are well known in the art. Such products are generally so formulated that they a number of very different features and characteristics regarding the efficiency and aesthetics provide. First of all liquid or gelatinous Dishwashing products with types and amounts of surfactants and other cleaning aids which gives acceptable solubilization and removal food contaminants, in particular greasy soils, of dishes provided with such products or in such Products formed solutions is cleaned. Such are the manufacturers of liquid dishwashing detergent compositions constantly striving, additional Components in liquid To bring detergent for manual dishwashing to consumers to provide improved cleaning benefits.

diamines are nitrogenous compounds, which is the cleaning power of liquid Dishwashing detergent compositions in particular the cleaning of greasy hydrophobic soils Dishes and other kitchen appliances, improve can. examples for Dishwashing detergent compositions which include diamines and improved grease removal properties are described in WO 99/11746 and WO 98/28393. Liquid detergents for manual dishwashing, which is a combination of diamines together with amine oxide and perfumes contain not only excellent cleaning performance, but also have a pleasant scent that improves consumer acceptance.

It However, it has been found that liquid detergents for manual dishwashing, which this combination of a nitrogenous surfactant, a Diamine and a fragrance contain tend to be unstable Color, i. the color changes unpredictably over one Period, as within the period, which during the shipment and the Storage passes. Since the color is the aesthetic property, which is most easily perceived by the consumer is she is an extremely important one Property of liquid Manual dishwashing products, especially because the Consumers their preferred dishwashing product at least for Recognize part by its color. Also, a detergent manufacturer can Use a product color to help consumers distinguish between a variety of different liquid products for manual Wash the dishes to help the manufacturer, each one special or improved Provide a feature. For example, a manufacturer may choose his liquid product for manual dishwashing, which is particularly good at cleansing fat, a certain one Give color, and for a liquid Product for manual dishwashing, which across from the hands is particularly mild, provide a different color, as well as a product, which still provides antimicrobial and disinfecting benefits give a different color. in addition, although most finished liquid Manual dishwashing products for consumers can be put on the market, are specifically colored, the color may be the finished dyed liquid Also change products for manual dishwashing unpredictably, if the color, which for the composition itself is specific, unstable and different changed over time. From the foregoing, it can be seen that there is a continuing need for There are detergent products which are not only excellent Provide cleaning performance and cleaning benefits, but also are color stable.

One solution to the problem of color instability or discoloration in a liquid detergent composition is paste bleaching. In paste bleaching, a particular component of the detergent composition (usually a surfactant) that is the cause of the color instability or discoloration of the detergent composition is preferably in an oxidative bleaching process wherein Hydrogen peroxide is used as the oxidant, bleached. The bleaching process is typically carried out at high temperatures (> 100 ° C) in a pressure reactor. Although this bleaching process is very effective, it suffers from the disadvantage that it is costly, time-consuming and also presents a serious industrial hygiene and safety problem. There is another disadvantage in that the bleached surfactant may be unfavorably reactive with other detergent components when added to a liquid detergent. When the color instability in a detergent formulation is caused by the presence of a chemical contaminant, another solution is to take steps to reduce or eliminate the level of impurities in the formulation. However, any cleaning methods, like the paste bleaching method, are also costly and time consuming.

Out it is clear from the foregoing that there is a continuing need color stable liquid To formulate products for manual dishwashing, the diamines, nitrogen-containing surfactants, such as amine-derived amine oxide, and perfumes, without the paste bleaching process or Cleaning procedures are applied.

Accordingly, it is an advantage of the present invention that liquid light dishwashing detergent compositions which are derived from olefin-derived amine oxides, Contain fragrances and diamines, and which not only improved Provide cleaning benefits, but are also color stable.

relevant State of the art

The U.S. Patent Nos. 5,023,376 to Shehad et al., 5,442,113 to Blezard et al. and 5,498,791 to Blezard et al. discuss all procedures for the Preparation of amine oxide and amine oxide compositions and are discussed in the text below and by the present invention demarcated.

Summary the invention

It has now been found that a color stable liquid Detergent composition for manual dishwashing containing derived from olefin amine oxides, fragrances and diamines, by adding an alkylene amino methylene phosphonic acid or a salt thereof to the detergent composition can be prepared. The present invention has been discovered to be Color stabilization benefits by the addition of the above-mentioned acids or Salts are provided when the liquid detergent composition for manual dishwashing both transition metal ions which as an impurity, as well as an amine oxide which is present derived from an olefin, as well as containing diamines and perfumes.

worin X die Einheit -CH₂-PO₃M_y darstellt; R 2 bis 6 Kohlenstoffatome enthält und ein aliphatischer oder alicyclischer Di-Rest mit einer Länge von 2 oder 3 Kohlenstoffatomen ist; M entweder H oder ein Nicht-Übergangsmetallkation, welches die Wasserlöslichkeit erhöht, darstellt; y 1 oder 2 ist, n eine ganze Zahl zwischen 1 bis einschließlich 4 ist, und m eine ganze Zahl zwischen 4 bis einschließlich 6 ist; und ein anionisches Tensid. Gemäß diesem ersten Aspekt der vorliegenden Erfindung besitzt die Reinigungsmittelzusammensetzung einen pH (gemessen in einer 10%igen wäßrigen Lösung) von weniger als 12,5.Thus, according to a first aspect of the present invention, the detergent compositions of the invention comprise an effective amount of an organic diamine, an olefin-derived amine oxide surfactant, a fragrance, transition metal cations, and an alkylene amino methylene phosphonic acid or a salt thereof selected from the group consisting of:

wherein X represents the moiety -CH ₂ -PO ₃ M _y ; R contains from 2 to 6 carbon atoms and is an aliphatic or alicyclic di-radical of 2 or 3 carbon atoms in length; M represents either H or a non-transition metal cation which increases water solubility; y is 1 or 2, n is an integer between 1 and 4, inclusive, and m is an integer between 4 and 6, inclusive; and an anionic surfactant. According to this first aspect of the present invention, the detergent composition has a pH (measured in a 10% aqueous solution) of less than 12.5.

worin X die Einheit -CH₂-PO₃M_y darstellt; R 2 bis 6 Kohlenstoffatome enthält und ein aliphatischer oder alicyclischer Di-Rest mit einer Länge von 2 oder 3 Kohlenstoffatomen ist; M entweder H oder ein Nicht-Übergangsmetallkation, welches die Wasserlöslichkeit erhöht, darstellt; y 1 oder 2 ist, n eine ganze Zahl zwischen 1 bis einschließlich 4 ist, und m eine ganze Zahl zwischen 4 bis einschließlich 6 ist. Gemäß diesem ersten Aspekt der vorliegenden Erfindung besitzt die Reinigungsmittelzusammensetzung einen pH (gemessen in einer 10%igen wäßrigen Lösung) von weniger als 12,5.According to a second aspect of the present invention, the detergent compositions of the present invention comprise an effective amount of a low molecular weight organic diamine having a pK1 and a pK2, wherein the pK1 and pK2 of the diamine are both in the range of 8.0 to 11.5 and in An olefin-derived amine oxide surfactant, a fragrance, transition metal cations, and 0.0001 to 0.5% of an alkyleneamino-methylenephosphonic acid or a salt thereof selected from the group consisting of:

wherein X represents the moiety -CH ₂ -PO ₃ M _y ; R contains from 2 to 6 carbon atoms and is an aliphatic or alicyclic di-radical of 2 or 3 carbon atoms in length; M represents either H or a non-transition metal cation which increases water solubility; y is 1 or 2, n is an integer between 1 and 4, inclusive, and m is an integer between 4 and 6 inclusive. According to this first aspect of the present invention, the detergent composition has a pH (measured in a 10% aqueous solution) of less than 12.5.

worin X die Einheit -CH₂-PO₃M_y darstellt; R 2 bis 6 Kohlenstoffatome enthält und ein aliphatischer oder alicyclischer Di-Rest mit einer Länge von 2 oder 3 Kohlenstoffatomen ist; M entweder H oder ein Nicht-Übergangsmetallkation, welches die Wasserlöslichkeit erhöht, darstellt; y 1 oder 2 ist, n eine ganze Zahl zwischen 1 bis einschließlich 4 ist, und m eine ganze Zahl zwischen 4 bis einschließlich 6 ist; und wobei die Zusammensetzung Aminoxid, Diamine und Duftstoffe enthält und einen pH (gemessen als 10%ige wäßrige Lösung) von weniger als 12,5 besitzt.The present invention also encompasses a methodological aspect for improving the color stability of a liquid dishwashing detergent composition, comprising the step of adding to the detergent composition of an alkylene amino methylene phosphonic acid or a salt thereof, selected from the group consisting of:

wherein X represents the moiety -CH ₂ -PO ₃ M _y ; R contains from 2 to 6 carbon atoms and is an aliphatic or alicyclic di-radical of 2 or 3 carbon atoms in length; M represents either H or a non-transition metal cation which increases water solubility; y is 1 or 2, n is an integer between 1 and 4, inclusive, and m is an integer between 4 and 6, inclusive; and wherein the composition contains amine oxide, diamines and fragrances and has a pH (measured as a 10% aqueous solution) of less than 12.5.

All proportions, percentages and ratios used herein are expressed as weight percentages unless stated otherwise. Unless otherwise indicated, all pH values which apply to a composition are measured in a 10% aqueous solution.

Full Description of the invention

definitions

The Detergent compositions herein include an "effective amount" or "fat removal improving amount "of individual components defined herein. With an "effective amount" of the diamines herein and the additive ingredients herein is meant an amount which is sufficient to either directed or significant at one 90% degree of safety the performance of the cleaning composition across from at least some of the contraventions considered and To improve stains. Consequently, the manufacturer is in a composition whose target substrates include certain grease stains, one Use sufficient amount of diamine to at least direct the Cleaning performance compared to improve such spots.

With "color stability" is the property a detergent composition which means the tendency the detergent composition describes that the Color over changed a period. The change The color can be determined by successive measurements of the Hunter-b value the detergent compositions over a period of time become. Consequently, with "improvement the color stability "meant that by the addition of a particular component is the absolute order of magnitude the change in terms of the Hunter b value of the detergent composition over a specified period is less than the absolute order of magnitude the change in terms of the Hunter b value of the detergent composition over the same period before the addition of the specific component.

With "liquid light detergent composition (light-duty liquid (LDL) detergent composition) "is a detergent composition which is used in manual (i.e., by hand) dishwashing becomes.

worin X die Einheit -CH₂-PO₃M_y darstellt; R 2 bis 6 Kohlenstoffatome enthält und ein aliphatischer oder alicyclischer Di-Rest mit einer Länge von 2 oder 3 Kohlenstoffatomen ist; M entweder H oder ein Nicht-Übergangsmetallkation, welches die Wasserlöslichkeit erhöht, darstellt; y 1 oder 2 ist, n eine ganze Zahl zwischen 1 bis einschließlich 4 ist, und m eine ganze Zahl zwischen 4 bis einschließlich 6 ist. Aminopolyphosphonate, besonders Ethylendiamintetramethylenphosphonsäure und Diethylentriaminpentamethylenphosphonsäure, werden bevorzugt.The present liquid detergent compositions contain an alkylene amino methylene phosphonic acid or a salt thereof selected from the group consisting of:

wherein X represents the moiety -CH ₂ -PO ₃ M _y ; R contains from 2 to 6 carbon atoms and is an aliphatic or alicyclic di-radical of 2 or 3 carbon atoms in length; M represents either H or a non-transition metal cation which increases water solubility; y is 1 or 2, n is an integer between 1 and 4, inclusive, and m is an integer between 4 and 6 inclusive. Aminopolyphosphonates, especially ethylenediamine tetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid, are preferred.

As discussed above, increased the addition of an alkyleneaminomethylenephosphonic acid the color stability of detergent compositions, which diamines, olefin-derived amine oxide, perfumes and transition metal ions, which are present as an impurity contain, considerably. Without being bound by theory, it is assumed that the before mentioned color instability the result of complex color-forming reactions is which through the transition metal and the other components are catalyzed. By including Metal ion sequestrants such as the above-described phosphonic acids and Salts thereof, metal ions are bound in a complex, whereby only a very low concentration of metal ions for a reaction with the other components left free in the solution.

Phosphonic acids are have already been used in amine oxide-producing reactions. To the Example is known that the Presence of transition metal impurities a reduction in the efficiency of a peroxide / amine reaction to May have consequences and that the Inclusion of phosphonic can reduce this effect. See U.S. Patent No. 5,023,376 to Shehad et al., issued June 11, 1991. However, the phosphonic acids or their salts in the present invention not during the Peroxide / amine reaction is added, but rather directly to the detergent composition which derived from the olefin Contains amine oxide, added. Unlike the Shehad patent, the order is the addition is not a crucial or essential part of the present Invention.

US Patent No. 5,442,113 to Blezard et al., Issued August 15, 1995 (collectively U.S. Patent No. 5,449,791 to Blezard et al., issued Mar. 12 1996) also discusses processes for the preparation of amine oxide in the presence of phosphonic acid or salts thereof. However, mention The Blezard patents do not have the difficulty of color stability, nor discuss the problem of contamination by transition metal contaminants.

solvent

The The present invention can provide a variety of water-miscible liquids contained, e.g. can lower alkanols, diols, other polyols, ethers, amines and the like used in the present invention. Especially preferred become the C1-C4 alkanols.

If present, contains the composition is preferably at least about 0.01% by weight, more preferably at least about 0.5% by weight, more preferably at least about 1% by weight of the composition of a solvent. The composition contains also preferably not more than about 20% by weight, more preferably not more than about 10% by weight, more preferably not more than about 8% by weight of the composition of a solvent.

These solvent can in conjunction with an aqueous liquid carrier such as Water or they can be used without any available aqueous liquid carrier used become. solvent are generally defined as compounds which are at temperatures are liquid from 20 ° C-25 ° C and which are not considered as surfactants. One of the distinguishing features is that solvent to it tend to be discreet units rather than extensive mixes of connections. Examples of suitable solvents for the present invention Ethanol, propanol, isopropanol, 2-methylpyrrolidinone, benzyl alcohol and morpholine n-oxide one. Of these solvents Ethanol and isopropanol are preferred.

Suitable solvents for use herein include ethers and diethers having 4 to 14 carbon atoms, preferably 6 to 12 carbon atoms, and more preferably 8 to 10 carbon atoms. Other suitable solvents are glycols or alkoxylated glycols, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated C1-C5 linear alcohols, C1-C5 linear alcohols, C8-C14 alkyl and cycloalkyl hydrocarbons and halocarbons, C6-C16 glycol ethers, and mixtures thereof.

The present liquid Detergent compositions may also be either diols or polymeric Glycols or a mixture of both diols and polymers Contain glycols. Diols and polymeric glycols for use in the present invention are disclosed in the PCT application WO 00/46331 to Clarke et al. Entitled "Diols and Polymeric Glycols for Improved Dishwashing Detergent Compositions ", disclosed in more detail.

Next Propylene glycol, polypropylene glycol and diols in the above included Registration is made of other glycols according to the formula: HO-CR1R2-OH, wherein R1 and R2 are independent H or a saturated one or unsaturated, are aliphatic and / or cyclic C 2 -C 10 -hydrocarbon chain, suitable and can used herein. One such suitable glycol is dodecane glycol.

Suitable alkoxylated glycols which can be used herein correspond to the formula R- (A) _n -R ¹ -OH wherein R is H, OH or a linear, saturated or unsaturated alkyl having 1 to 20, preferably 2 to 15 and more preferably 2 to 10 carbon atoms; wherein R ^{1 is} H or a linear, saturated or unsaturated alkyl of 1 to 20, preferably 2 to 15 and more preferably 2 to 10 carbon atoms; and A is an alkoxy group, preferably ethoxy, methoxy and / or propoxy, and n is 1 to 5 and preferably 1 to 2. Suitable alkoxylated glycols for use herein are methoxy octadecanol and / or ethoxyethoxyethanol.

suitable aromatic alcohols which may be used herein of the formula R-OH, wherein R is an alkyl-substituted or non-alkyl-substituted Aryl group of 1 to 20, preferably 1 to 15 and more preferred Represents 1 to 10 carbon atoms. A suitable aromatic Alcohol for use herein is, for example, benzyl alcohol.

suitable aliphatic branched alcohols used herein can, correspond to the formula R-OH, wherein R is a branched, saturated or unsaturated Alkyl group of 1 to 20, preferably 2 to 15 and more preferred 5 to 12 carbon atoms. Particularly suitable aliphatic Branched alcohols for use herein include 2-ethylbutanol and / or 2-methylbutanol.

Suitable alkoxylated aliphatic branched alcohols which can be used herein correspond to the formula R (A) _n -OH, wherein R is a branched, saturated or unsaturated alkyl group having 1 to 20, preferably 2 to 15 and more preferably 5 to 12 carbon atoms; wherein A represents an alkoxy group, preferably butoxy, propoxy and / or ethoxy; and n is an integer of 1 to 5, and preferably 1 to 2. Suitable alkoxylated aliphatic branched alcohols include 1-methylpropoxyethanol and / or 2-methylbutoxyethanol.

Suitable linear C ₁ -C ₅ -alcohols which can be used herein correspond to the formula R-OH, wherein R is a linear, saturated or unsaturated alkyl group having 1 to 5 and preferably 2 to 4 carbon atoms. Suitable linear C ₁ -C ₅ -alcohols are methanol, ethanol, propanol or mixtures thereof.

Other suitable solvents shut down, but are not limited to butyl diglycol ether (BDGE), butyl triglycol ether, tert-amyl alcohol and the like. Particularly preferred solvents, which can be used herein are butoxypropoxypropanol, butyl diglycol ether, benzyl alcohol, butoxypropanol, ethanol, Methanol, isopropanol and mixtures thereof.

Other suitable solvents for use herein include propylene glycol derivatives such as n-butoxypropanol or n-butoxypropoxypropanol, water soluble CARBITOL R solvents, or CELLOSOLVE R water soluble solvents. Water-soluble CARBITOL R 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 butyl carbitol. Water-soluble CELLOSOLVE R solvents are compounds of the 2-alkoxyethoxyethanol class in which 2-butoxyethoxyethanol is preferred. Other suitable solvents include benzyl alcohol and diols such as 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol and mixtures thereof. Some preferred solvents for use herein are n-butoxypropoxypropanol, butyl carbitol ^® and mixtures thereof.

The solvent can also chosen from the group of compounds containing ether derivatives of mono-, Di- and triethylene glycol, butylene glycol ether and mixtures thereof includes. The molecular weights of these solvents are preferably less than 350, more preferably between 100 and 300, and more preferably between 115 and 250. Examples preferred solvent shut down for example, monoethylene glycol n-hexyl ether, monopropylene glycol n-butyl ether and tripropylene glycol methyl ether. Ethylene glycol and propylene glycol ethers are commercially available from Dow Chemical Company under the trade name "Dowanol" and from Arco Chemical Company under the trade name "Arcosolv" available. Other preferred solvents including Mono- and diethylene glycol n-hexyl ethers are available from Union Carbide Company available.

diamines

As As noted above, the diamines herein are used in detergent compositions used in combination with detersive surfactants in sufficient proportions, at least a directed improvement in cleaning performance to achieve. In the context of a hand dishwashing detergent composition, such "use levels" may not only be dependent on the nature and severity of the stains and stains, but also from the wash water temperature, the volume of wash water and the time duration while the dishes are in contact with the wash water, vary.

There the habits and practices of users of detergent compositions show a considerable variation, the composition preferably contains at least 0.1 wt%, more preferably at least 0.2 wt%, still more preferably at least about 0.25 wt.%, more preferably also at least 0.5% by weight of the composition of a diamine. The Composition contains also preferably not more than 15% by weight, more preferably not more than 10% by weight, more preferably not more than 6% by weight, more preferably not more than 5% by weight, more preferably also not more than 1.5% by weight of the composition of a diamine.

According to one Of the several aspects of this invention, a means for enhancing the Removal of greasy / oily Dirt by combining the specific diamines of these Invention provided with surfactants. Greasy / oily "everyday" soiling are a mixture of triglycerides, lipids, complex polysaccharides, fatty acids, inorganic salts and proteinaceous Substances.

Consequently offer diamines in combination with amphoteric and anionic surfactants in the specific ratios discussed below the benefit of improved cleaning of fat and stubborn food residues, thereby elimination or reduction of the amount of divalent ions in the preferred embodiments of the present formula becomes. This improved cleaning is a result of the tendency of Diamines as a buffering agent to increase the alkalinity of the dishwashing detergent composition to increase. The excellent dissolution rate, which is achieved by the elimination of the bivalent ions, even allows the manufacturer to produce hand dishwashing detergents. particularly compact formulations, with still significantly higher viscosities (e.g. 1000 centi poise or higher) as conventional Formulations while an excellent resolution and Cleaning performance is maintained. This has significant potential Benefits for the production of compact products with a higher viscosity, while a acceptable resolution is maintained. With "compact" or "Ultra" are detergent formulations with reduced levels of water compared to conventional ones liquid Meant cleaning agents. For "compact" or "Ultra" formulations is the proportion less than 70% by weight, preferably less than 40% by weight, of water, the liquid Dishwashing compositions. The concentrated products provide benefits to the consumer which one Owns product that can be used in smaller quantities, and also for the manufacturer, which has lower shipping costs. For compositions, which should not be concentrated, is a suitable proportion of water less than about 85 weight percent, more preferably less than about 70 weight percent, the liquid Dishwashing compositions.

It is preferred that the diamines of the invention are substantially free of impurities. By "substantially free" is meant that the diamines are greater than 95% pure, ie, preferably 97%, more preferably 99%, even more preferably 99.5%, free of impurities. Examples of impurities that may be present in commercially-prepared diamines include 2-methyl-1,3-di aminobutane and alkylhydropyrimidine. It is further believed that the diamines should be free from oxidation reactants to avoid diamine degradation and ammonia formation.

As in more detail below It is important that the compositions are free of hydrogen peroxide if the compositions contain an enzyme. Even small amounts of hydrogen peroxide may be present in enzyme-containing formulations Cause problems. However, the diamine can be present with any present React peroxide and be effective as an enzyme stabilizer and prevent the hydrogen peroxide from reacting with the enzyme. Of the only disadvantage of this stabilization of the enzymes by the diamine is the assumption that the produced nitrogen compounds which cause unpleasant odors, which may be present in diamine-containing compositions can. When the diamine is effective as an enzyme stabilizer, it can be prevented be that Diamine the benefits for the composition provides for which it originally was introduced, namely for fat purification, foaming, dissolution and stability at low temperatures. Therefore, it is preferred that the amount of hydrogen peroxide be as an impurity in the compositions of the invention is, either by the use of components, which essentially are free of hydrogen peroxide, or any other bleach species to minimize and / or use by non-diamine antioxidants, if the diamine can produce unpleasant-smelling compounds, and the available amount Diamine, which is present to make it its primary function exercise can decrease.

preferred Organic diamines are those in which the pK1 and the pK2 in the range of 8.0 to 11.5, preferably in the range of 8.4 to 11, and more preferably in the range of 8.6 to 10.75 lie. Preferred materials from the standpoint of performance and providing are 1,3-bis (methylamine) cyclohexane (pKa = 10 to 10.5), 1,3-propanediamine (pK1 = 10.5, pK2 = 8.8), 1,6-hexanediamine (pK1 = 11, pK2 = 10), 1,3-pentanediamine (Dytek EP) (pK1 = 10.5, pK2 = 8.9) and 2-methyl-1,5-pentanediamine (Dytek A) (pK1 = 11.2; pK2 = 10.0). Other preferred materials are the primary / primary diamines Alkylene spacer groups ranging from C4 to C8. In general, takes one thinks that primary diamines are secondary and secondary tertiary Diamines are preferred.

Definition of pK1 and pK2

So As used herein, "pKa1" and "pKa2" are quantities of one Type commonly known to those skilled in the art as "pKa" is. pKa is used herein in the same way as It is commonly known to those skilled in the chemical arts. The mentioned herein Values can from the literature, as described in "Critical Stability Constants: Volume 2, Amines "by Smith and Martel, Plenary Press, NY and London, 1975. Additional information about pKa's can out the relevant Company literature, such as the one by Dupont, a supplier of diamines, information provided.

When Working definition herein is the pKa of diamines in a wholly aqueous solution 25 ° C and for one ionic strength between 0.1 and 0.5M. The pKa is an equilibrium constant, which can vary with temperature and ionic strength; therefore vote the values described in the literature depending on the measuring method and the measuring conditions sometimes do not match. To dispel ambiguities, are the relevant conditions and / or references for pKa's of this invention may be used as described herein or in Critical Stability Constants: Volume 2, Amines "defined is. A typical measuring method is the potentiometric titration of the acid with sodium hydroxide and the determination of pKa's appropriate procedures, as in "The Chemist's Ready Reference Handbook "by Shugar and Dean, McGraw Hill, NY, 1990, and described is.

It it has been found that substituents and structural modifications involving pK1 and pK2 below of 8.0, undesirable are and cause losses in terms of efficiency. These can Include substitutions, which in ethoxylated diamines, hydroxyethyl-substituted diamines and diamines with oxygen in the beta (and less in the gamma) Position to the nitrogen atom in the spacer group (e.g. Jeffamine EDR 148). Furthermore are materials based on ethylenediamine unsuitable.

worin R_2-5 unabhängig gewählt sind aus H, Methyl, -CH₃CH₂ und Ethylenoxiden; C_x und C_v unabhängig gewählt sind aus Methylengruppen oder verzweigten Alkylgruppen, worin x + v 3 bis 6 ist; und A wahlweise vorliegt und gewählt ist aus elektronenschiebenden oder elektronenziehenden Einheiten, welche derartig gewählt sind, daß sie die pKa-Werte des Diamins auf den gewünschten Bereich einzustellen. Falls A vorliegt, dann müssen x und v beide 1 oder größer sein.The diamines useful herein can be defined by the following structure:

wherein R _{2-5 are} independently selected from H, methyl, -CH ₃ CH ₂ and ethylene oxides; C _x and C _{v are} independently selected are methylene or branched alkyl groups wherein x + v is 3 to 6; and A is optional and selected from electron donating or electron withdrawing units selected to adjust the pKa values of the diamine to the desired range. If A is present, then x and v must both be 1 or greater.

Examples preferred diamines are disclosed in U.S. Patent No. 6,589,926 to Phillip Kyle Vinson et al., Entitled "Dishwashing Detergent Compositions Containing Organic Diamines for Improved Grease Cleaning, Sudsing, Low Temperature Stability and Dissolution ".

anionic surfactants

The useful in the invention anionic surfactants are preferably selected from the group consisting of linear alkyl benzene sulphonate, alpha olefin sulphonate, paraffin sulphonates, Alkyl ester sulfonates, alkyl sulfates, alkyl alkoxy sulfate, alkyl sulfonates, Alkylalkoxycarboxylate, alkylalkoxylated sulphates, sarcosinates, Taurinates and mixtures thereof. In the present invention may be an effective amount, typically 0.5 to 90% by weight, preferably 5 to 50% by weight, more preferably 10 to 30% by weight, of an anionic detersive surfactant be used.

suitable Examples of anionic surfactants are in PCT application WO 99/27058 by Chandrika Kasturi et al., titled "Liquid Detergent Compositions Comprising Polymeric Suds Enhancers ", to find. Further examples of suitable anionic surfactants are in "Surface Active Agents and Detergents "(vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants is also disclosed in U.S. Patent 3,929,678 issued to On December 30, 1975 to Laughlin et al., In column 23, lines 58 to Column 29, line 23, generally disclosed. Suitable anionic surfactants can further in U.S. Patent No. 5,415,814, issued May 16, 1995 to Ofosu-Asante et al., can be found.

amphoteric surfactants

The amphoteric according to the invention Surfactants are selected from amine oxide surfactants. Amine oxides are semipolar nonionic surfactants and include water-soluble amine oxides which an alkyl group of 10 to 18 carbon atoms and two units, selected from the group consisting of alkyl groups and hydroxyalkyl groups with 1 to 3 carbon atoms. Water-soluble phosphine oxides which are a Alkyl group of 10 to 18 carbon atoms and two units, selected from the group consisting of alkyl groups and hydroxyalkyl groups containing 1 to 3 carbon atoms; and water-soluble sulfoxides, which is an alkyl group having 10 to 18 carbon atoms and a Unit, selected from the group consisting of alkyl and hydroxyalkyl groups with 1 to 3 carbon atoms, may also be used.

worin R³ eine Alkyl-, Hydroxyalkyl- oder Alkylphenylgruppe mit 8 bis 22 Kohlenstoffatomen oder Mischungen hiervon ist; R⁴ eine Alkylen- oder Hydroxyalkylengruppe mit 2 bis 3 Kohlenstoffatomen oder Mischungen hiervon ist; x 0 bis 3 ist; und jedes R⁵ eine Alkyl- oder Hydroxyalkylgruppe mit 1 bis 3 Kohlenstoffatomen oder eine Polyethylenoxidgruppe mit 1 bis 3 Ethylenoxidgruppen ist. Die R⁵-Gruppen können unter Bildung einer Ringstruktur z.B. über ein Sauerstoff- oder Stickstoffatom miteinander verbunden sein.Semi-polar nonionic detersive surfactants include the amine oxide surfactants of the formula:

wherein R ^{3 is} an alkyl, hydroxyalkyl or alkylphenyl group having 8 to 22 carbon atoms or mixtures thereof; R ^{4 is} an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms or mixtures thereof; x is 0 to 3; and each R ^{5 is} an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or a polyethylene oxide group having 1 to 3 ethylene oxide groups. The R ⁵ groups may be linked together to form a ring structure, for example via an oxygen or nitrogen atom.

In particular, these amine oxide surfactants include C ₁₀ -C ₁₈ alkyl dimethyl amine oxides and C ₈ -C ₁₂ alkoxyethyl dihydroxyethyl amine oxides.

worin R¹ ein Alkyl-, 2-Hydroxyalkyl-, 3-Hydroxyalkyl- oder 3-Alkoxy-2-hydroxypropylrest ist, worin das Alkyl bzw. Alkoxy 8 bis 18 Kohlenstoffatome enthält, R² und R³ jeweils Methyl, Ethyl, Propyl, Isopropyl, 2-Hydroxyethyl, 2-Hydroxypropyl oder 3-Hydroxypropyl sind, und n 0 bis 10 ist.Also suitable are amine oxides, such as propylamine oxides, which are represented by the formula:

wherein R ^{1 is} an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl or 3-alkoxy-2-hydroxypropyl radical in which the alkyl or alkoxy contains 8 to 18 carbon atoms, R ² and R ^{3 are} each methyl, ethyl, propyl, Isopropyl, 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl, and n is 0 to 10.

worin R₁ ein Alkyl-, 2-Hydroxyalkyl-, 3-Hydroxyalkyl- oder 3-Alkoxy-2-hydroxypropylrest ist, worin das Alkyl bzw. Alkoxy 8 bis 18 Kohlenstoffatome enthält, R₂ und R₃ jeweils Methyl, Ethyl, Propyl, Isopropyl, 2-Hydroxyethyl, 2-Hydroxypropyl oder 3-Hydroxypropyl sind, und n 0 bis 10 ist.Another suitable species of semi-polar amine oxide surfactant compounds include compounds and mixtures of compounds having the formula:

wherein R _{1 is} an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl or 3-alkoxy-2-hydroxypropyl radical in which the alkyl or alkoxy contains 8 to 18 carbon atoms, R ₂ and R _{3 are} each methyl, ethyl, propyl, Isopropyl, 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl, and n is 0 to 10.

worin R₁ ein C_10-14-Alkyl ist, und R₂ und R₃ Methyl oder Ethyl sind. Da diese Spezies geringschäumend sind, kann es auch wünschenswert sein, langkettige Aminoxid-Tenside, welche in den US-Patenten Nrn. 4,316,824 (Pancheri), 5,075,501 und 5,071,594 ausführlicher beschrieben sind, zu verwenden.Particular preference is given to amine oxides having the formula:

wherein R _{1 is} a C _10-14 alkyl, and R ₂ and R _{3 are} methyl or ethyl. Since these species are low foaming, it may also be desirable to use long-chain amine oxide surfactants, which are described in more detail in U.S. Patent Nos. 4,316,824 (Pancheri), 5,075,501 and 5,071,594.

Other suitable non-limiting examples of amphoteric detersive surfactants which useful in the present invention are close Amidopropylbetaines and derivatives of aliphatic or heterocyclic, secondary and ternary Amines, wherein the aliphatic moiety straight or branched and wherein one of the aliphatic substituents 8 to Contains 24 carbon atoms and at least one aliphatic substituent is an anionic water-solubilizing Group contains.

Further Examples of suitable amphoteric surfactants are described in "Surface Active Agents and Detergents" (Volumes I and II of Schwartz, Perry and Berch), incorporated herein by reference, specified.

Preferably For example, the amphoteric surfactant in the composition is effective Amount, more preferably 0.1 to 20 wt .-%, even more preferably 0.1 to 15 wt .-%, even stronger preferably also 0.5 to 10 wt .-% before.

Secondary surfactants

The secondary Detersive surfactant can be chosen be from the group consisting of nonionic, cationic, ampholytic and zwitterionic surfactants and mixtures thereof. By selecting the type and amount of detersive surfactant together with other additional ingredients disclosed herein, the present detergent compositions formulated in such a way they will in connection with the laundry cleaning or in other different cleaning applications, especially including the Wash the dishes, can be used. The individual surfactants used can therefore be dependent vary greatly from the particular use contemplated. Suitable secondary surfactants are in PCT application WO 99/27058 to Chandrika Kasturi et al., titled "Liquid Detergent Compositions Comprising Polymeric Suds Enhancers ", described in detail.

Ratio of the anionic surfactant to the amphoteric surfactant to the diamine

In the compositions of the invention is The relationship of the anionic surfactant to the amphoteric surfactant to the diamine 100: 40: 1 to 9: 0.5: 1; preferably The relationship of the anionic surfactant to the amphoteric surfactant to the diamine 27: 8: 1 to 11: 3: 1. It has been found that detergent compositions, which the anionic surfactant, the amphoteric surfactant and the diamine in this specific ratio range contain improved stability at low temperatures provide and better benefits for fat removal and the Cleaning persistent Food residues at a pH of less than 12.5 and improved cleaning in Provide hard water.

According to one another aspect of the present invention has been found the existence molar ratio of the anionic surfactant to the diamine greater than 9: 1, preferably greater than 20: 1, improved stability at low temperatures and better grease removal benefits and the cleaning of stubborn Food residues and provides improved cleaning in hard water.

Optional detergent ingredients

Polymeric foam stabilizer

• i) Homopolymeren von (N,N-Dialkylamino)alkylacrylatestern mit der Formel:
  
  worin jedes R unabhängig Wasserstoff, C₁-C₈-Alkyl und Mischungen hiervon ist, R¹ Wasserstoff, C₁-C₆-Alkyl und Mischungen hiervon ist, n 2 bis etwa 6 ist; und
• ii) Copolymeren von (i) und
  
  worin R1 Wasserstoff, C₁-C₆-Alkyl und Mischungen hiervon ist; mit der Maßgabe, daß das Verhältnis von (ii) zu (i) etwa 2 zu 1 bis etwa 1 zu 2 beträgt.

The compositions of the invention may optionally contain a polymeric foam stabilizer. These polymeric foam stabilizers provide increased suds volume and longer suds duration without sacrificing the grease separation ability of the liquid detergent compositions. These polymeric foam stabilizers are selected from:

• i) homopolymers of (N, N-dialkylamino) alkyl acrylate esters having the formula:
  
  wherein each R is independently hydrogen, C ₁ -C ₈ alkyl and mixtures thereof, R ^{1 is} hydrogen, C ₁ -C ₆ alkyl and mixtures thereof, n is 2 to about 6; and
• ii) copolymers of (i) and
  
  wherein R _{1 is} hydrogen, C ₁ -C ₆ alkyl and mixtures thereof; with the proviso that the ratio of (ii) to (i) is about 2 to 1 to about 1 to 2.

The Molecular weight of polymeric foam boosters determined by conventional Gel permeation chromatography, is about 1,000 to about 2,000,000, preferably about 5,000 to about 1,000,000, more preferably about 10,000 to about 750,000, stronger preferably about 20,000 to about 500,000, more preferably about 35,000 to about 200,000. The polymeric foam stabilizer may optionally in the form of a salt, either inorganic or organic Salt, for example as the citrate, sulfate, acetate or nitrate salt of (N, N-dimethylamino) alkyl acrylate ester.

One preferred polymeric foam stabilizer is an (N, N-dimethylamino) alkyl acrylate ester, in fact

If present in the compositions, the polymeric suds enhancer may be used in the co composition in about 0.01 to about 15% by weight, preferably about 0.05 to about 10% by weight, more preferably about 0.1 to about 5% by weight.

Builder

The Compositions of the invention can further comprising a builder system. Because builders like citric acid and Citrate the stability of enzymes in LDL compositions, it is desirable to the amounts of builder salts normally used in LDL compositions which include or include propylene glycol as a builder remove. When a detergent composition is a propylene glycol solvent as part or whole of the wearer of the Includes detergent, the enzymes are more stable and are lower levels or none Builder salts necessary.

If it desirable is to use a builder, then any is conventional Builder system suitable for use herein, including aluminosilicate materials, Silicates, polycarboxylates and fatty acids as well as materials such as Ethylenediaminetetraacetate. Although for obvious reasons of Environmental protection less preferred, may also include phosphate builder be used.

Suitable polycarboxylate builders for use herein include citric acid, preferably in the form of a water-soluble salt, and derivatives of succinic acid having the formula R-CH (COOH) CH ₂ (COOH) wherein R is C _10-20 alkyl or alkenyl, preferably C _12-16 , or wherein R may be substituted with hydroxyl, sulfosulfoxyl or sulfone substituents. Specific examples include laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate and 2-tetradecenylsuccinate. Succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts.

Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monobasic and tartrate disuccinic acid, such as in US Pat US 4,663,071 described.

Suitable fatty acid builders for use herein, especially for the liquid embodiment herein, are saturated or unsaturated C _10-18 fatty acids and the corresponding soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acid is oleic acid. Another preferred liquid composition builder system is based on dodecenyl succinic acid and citric acid.

If Detergent builders are included, they are in quantities from 0.5 to 50% by weight, preferably 5 to 30% by weight and most commonly 5 to 25% wt .-% of the composition introduced.

enzymes

The detergent compositions of the invention may further comprise one or more enzymes which provide cleaning performance benefits. These enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenol oxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases or mixtures thereof. A preferred combination is a detergent composition comprising a cocktail of conventional useful enzymes such as protease, amylase, lipase, cutinase and / or cellulase. If present in the compositions, the enzymes are present at a level of from about 0.0001 to about 5% active enzyme by weight of the detergent composition. Preferred proteolytic enzymes are then selected from the group consisting of Alcalase ^® thereof (Novo Industri A / S), BPN ', Protease A and Protease B (Genencor), and mixtures thereof. Protease B is most preferred. Preferred Amylaseenyzme close TERMAMYL ^®, DURAMYL ^® and Amylaseenyzme described to Genencor International and WO 9402597 to Novo in WO 9418314 A.

Further non-limiting examples of suitable and preferred enzymes in US Pat. No. 6,589,926, "Dishwashing Detergent Compositions Containing Organic Diamines for Improved Grease Cleaning, Sudsing, Low Temperature Stability and Dissolution ".

Since hydrogen peroxide and builders such as citric acid and citrates affect the stability of enzymes in LDL compositions, it is desirable to reduce the proportions of these compounds in co-products Compositions containing enzymes to reduce or omit. Hydrogen peroxide is often found as an impurity in surfactants and surfactant pastes. Therefore, the preferred amount of hydrogen peroxide in the amine oxide or in the surfactant paste of amine oxide is 0-40 ppm, and more preferably 0-15 ppm. Amine impurities in amine oxide and betaines, if present, should be minimized to the levels mentioned above for hydrogen peroxide.

magnesium ions

Even though it is preferred that bivalent Ions of those made in accordance with the present invention LDL compositions may be omitted other embodiments of the present invention include magnesium ions.

It is desirable that all divalent ions are removed from the present LDL compositions, since such ions have a slower resolution and inadequate properties in terms of rinsing off and stability at low temperatures can result. In addition, the wording of compositions containing such divalent ions, in matrices with an alkaline pH because of the incompatibility of the divalent Ions, especially magnesium, with hydroxide ions be difficult.

Yet The presence of magnesium ions can offer several advantages. It is noteworthy that the Inclusion of such divalent ions the purification of greasy Dirt for various LDL compositions, especially for compositions, which alkyl ethoxycarboxylates and / or polyhydroxy fatty acid amide included, improved. This is especially true when the compositions in softened Water containing few bivalent ions.

In of the present invention these advantages, however, without the inclusion of divalent ions to be obtained. In particular, the improved grease cleaning without divalent ions due to the inclusion of organic diamines in combination with amphoteric and anionic surfactants in the above-discussed specific circumstances be achieved while for enzymes has been shown to improve skin mildness of the present LDL compositions.

If Magnesium ions in another embodiment of the present invention LDL compositions included then they are in an active share of about 0.01 to 1 wt%, preferably about 0.015 to 0.5 wt% and more preferably about 0.025 to 0.1 wt .-% before. The in the compositions of the invention Existing amount of magnesium ions also depends on the amount of total surfactant present therein, including the Amount of alkyl ethoxycarboxylates and polyhydroxy fatty acid amide, from.

Preferably are the magnesium ions as a hydroxide, chloride, acetate, Sulfate, formate, oxide or nitrate salt to the compositions of the invention added. Because while storage stability these compositions due to the formation of hydroxide precipitates in the presence of compositions containing low concentrations contained in hydroxide ions, becomes insufficient, it may be necessary be to admit certain complexing agents. Suitable complexing agents are described below and in US Patent No. 5,739,092, issued on April 1998 to Ofosu-Asante, further discussed.

fragrances

fragrances and perfume ingredients used in the present compositions and methods useful are a big one Variety of natural and synthetic chemical constituents, including, but not limited to aldehydes, ketones, esters and the like. Also included are various natural extracts and essences, which complex mixtures of ingredients such as orange oil, lemon oil, rose extract, Lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar and the like. Finished fragrances can be extremely complex mixtures include such components. Finished perfumes typically include from about 0.01% to about 2% by weight of the detergent compositions herein, and individual perfume ingredients may be about 0.0001 to about 90% a finished perfume composition include.

Nonlimiting examples for useful herein Perfume ingredients are described in U.S. Patent No. 6,589,926, "Dishwashing Detergent Compositions Containing Organic Diamines for Improved Grease Cleaning, Sudsing, Low Temperature Stability and Dissolution ".

complexing

The Detergent compositions herein may also optionally include one or contain several iron and / or manganese complexing agents. Such Complexing agents can chosen from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally-substituted aromatic complexing agents and Mixtures thereof, all as defined below. Without one To be bound theory, it is believed that the advantage of these materials partly to their extraordinary ability is due Iron and manganese ions through the formation of soluble chelates from washing solutions remove.

aminocarboxylates, which are useful as optional complexing agents include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetrapropionates, Triethylenetetraaminehexaacetate, diethylenetriamine pentaacetate and Ethanoldiglycine, alkali metal, ammonium and substituted ammonium salts thereof and mixtures thereof.

Amino phosphonates are for use as complexing agents in the compositions of the invention also suitable if at least small amounts of phosphorus in total in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) like DEQUEST. Preferably, these amino phosphonates contain no Alkyl or alkenyl groups of greater than about 6 carbon atoms.

Polyfunctionally-substituted Aromatic complexing agents are also included in the compositions herein useful. See U.S. Patent 3,812,044, issued May 21, 1974 to Connor et al. Preferred compounds of this type in the acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

One preferred biodegradable complexing agent for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S, S] isomer, as in U.S. Patent 4,704,233, November 3 1987 to Hartman and Perkins.

The Compositions herein can be used also water-soluble methylglycine (MGDA) salts (or their acid form) as complexing agent or co-builder. In similar Way you can also the so-called "weak" builders like citrate be used as a complexing agent.

If When used, these complexing agents generally comprise about 0.1 to about 15% by weight of the detergent compositions herein. More preferably, if used, the complexing agents include about From 0.1% to about 3.0% by weight of such compositions.

pH of the composition

Of the pH of the present compositions (measured as 10% aqueous solution) is less as 12.5 and preferably less than 10.5. As the dishwashing detergent compositions according to the invention in use, i. dilute and applied to soiled dishes, one by food spills exposed to acid stress should be a composition, if they have a pH of greater than 7 is more effective, preferably containing a buffering agent which is capable one generally stronger provide alkaline pH in the composition and in dilute solutions. The dishwashing detergent compositions according to the invention thus contain about 0.1 to 15 wt .-%, preferably about 1 to 10% by weight, most preferably about 2 to 8% by weight, of a buffering agent. The pKa of this buffering agent should be about 0.5 to 1.0 pH units below the desired one pH of the composition (determined as described above) are. Preferably should pKa of the buffering agent is about 7 to about 12. Under In these conditions, the buffering agent most effectively regulates the pH, while the minimum amount of it is used.

preferred inorganic buffer / alkalinity sources shut down the alkali metal carbonates, alkali metal hydroxides and alkali metal phosphates on, e.g. Sodium carbonate, sodium hydroxide and sodium polyphosphate.

The optional buffering agent (which is used in compositions having a pH of greater than 7) may itself be an active cleaning agent or may be a low molecular weight, organic or inorganic material which is used in this composition solely to maintain an alkaline pH. Preferred buffering agents for compositions of the invention are nitrogen-containing materials. Some examples are amino acids like lysine or low Alcohol amines such as mono-, di- and triethanolamine. The diamines detailed above are also effective as buffering agents and are preferred buffering agents. Preferred buffering systems for use in the present detergent compositions include a combination of 0.5% diamine and 2.5% citrate and a combination of 0.5% diamine, 0.75% potassium carbonate and 1.75% sodium carbonate. Other preferred nitrogen-containing buffering agents are tri (hydroxymethyl) aminomethane (HOCH ₂ ) ₃ CNH ₃ (TRIS), 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methylpropanol, 2-amino-2-methyl 1,3-propanol, disodium glutamate, N-methyldiethanolamide, 1,3-diaminopropanol, N, N'-tetramethyl-1,3-diamino-2-propanol, N, N-bis (2-hydroxyethyl) glycine (Bicin ) and N-tris (hydroxymethyl) methylglycine (tricine). Mixtures of any of the above compounds are also acceptable. For further buffers cf. McCutcheon's Emulsifiers and Detergents, North America Edition, 1997, McCutcheon Division, MC Publishing Company Kirk, and WO 95/07971.

Other ingredients

The detergent compositions preferably further comprise one or more detergent ingredients selected from the following: soil release polymers, polymeric dispersants, polysaccharides, abrasives, bactericides and other antimicrobials, tarnish inhibitors, builders, enzymes, dyes, buffers, fungal or mildewicides, insect repellants, perfumes, hydrotropes, Thickeners, processing aids, foam boosters, brighteners, anti-corrosion aids, stabilizers, antioxidants and complexing agents. A wide variety of other ingredients useful in detergent compositions may be included in the compositions herein, including other active ingredients, carriers, hydrotropes, antioxidants, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc. If any strong foaming is desired, foam boosters such as the C ₁₀ -C ₁₆ alkanolamides can be incorporated into the compositions in proportions of typically 1 to 10%. The C ₁₀ -C ₁₄ monoethanol and diethanolamides illustrate a typical class of such suds boosters. The use of such suds boosters together with high sudsing auxiliary tides such as the amine oxides, betaines and sultaines mentioned above is also advantageous.

One Antioxidant may optionally be added to the detergent compositions of the invention be added. It can be any conventional antioxidant which is used in detergent compositions, such as 2,6-di-tert-butyl-4-methylphenol (BHT), carbamate, ascorbate, thiosulfate, Monoethanolamine (MEA), diethanolamine or triethanolamine. It will preferred that the Antioxidant, if present, in the composition in about 0.001 to about 5 wt .-% is present.

Various Detergent ingredients used in the present compositions can optionally by absorbing the constituents on a porous hydrophobic Substrate, then coating of the substrate with a hydrophobic coating, further stabilized become. Preferably, the detergent ingredient becomes a surfactant mixed before it is in the porous Substrate is recorded. In use, the detergent ingredient becomes from the substrate into the aqueous wash liquor released where he wanted his Cleansing effect exerts.

For example, to exemplify this technique, a porous hydrophobic silica (registered trademark SIPERNAT D10, DeGussa) is mixed with a proteolytic enzyme solution containing 3% to 5% of a nonionic surfactant in the form of an ethoxylated C _13-15 alcohol (EO7) , Typically, the enzyme / surfactant solution accounts for 2.5 times the weight of silica. The resulting powder is dispersed in silicone oil with stirring (various silicone oil viscosities in the range of 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. In this way, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric care agents, and hydrolyzable surfactants can be "protected" for use in cleaners, including liquid laundry detergent compositions.

Further include these hand dishwashing detergent embodiments preferably still a hydrotrope. Suitable hydrotropes include sodium, Potassium, ammonium or water-soluble substituted ammonium salts of toluenesulfonic acid, naphthalenesulfonic acid, cumene sulfonic acid and xylene sulfonic acid one.

Non-aqueous liquid detergents

The preparation of liquid detergent compositions containing a nonaqueous carrier can be described in the disclosures in US Pat. Nos. 4,753,570; 4,767,558; 4,772,413; 4,889,652 and 4,892,673; in GB-A-2,158,838; GB-A-2,195,125; GB-A-2,195,649; US 4,988,462 ; US 5,266,233; EP-A-225,654 (16/6/87); EP-A-510,762 (28/10/92); EP-A-540,089 (5/5/93); EP-A-540,090 (5/5/93); US 4,615,820; EP-A-565,017 (13/10/93); and EP-A-030,096 (10/6/81). Such compositions may contain various particulate detergent ingredients which are stably suspended therein. Thus, such nonaqueous compositions comprise a liquid phase and optionally, but preferably, a solid phase, each of which is described in more detail below and in said documents.

The Compositions of the invention can used to aqueous washing solutions for Use in dishwashing to form by hand. In general, an effective amount of such Compositions added to water to provide such aqueous cleaning or soaking solutions form. The aqueous solution formed in this way is then mixed with the dishes, Tableware and the kitchen appliances in contact brought.

A effective amount of the detergent compositions herein which for the formation of aqueous cleaning solutions Water is added may include sufficient amounts to about 500 to 20,000 ppm of the composition in an aqueous solution form. More preferably, about 800 to 5,000 ppm of the detergent compositions herein in an aqueous cleaning liquor intended.

The the following examples illustrate the present invention, but should not limit the scope of protection hereof or in others Define way. All proportions, percentages and ratios used herein are expressed as weight percentages unless stated otherwise.

Examples

Table I

Liquid light dishwashing detergents are as follows. Composition II contains a phosphonate and is used in Made consistent with the present invention. composition I is identical except that she contains no phosphonate.

The perceived visible color and analytically measured color each of the above compositions was measured in a color stability test about the relative color stability of compositions I and II.

The Color can be measured analytically by a Hunter colorimetry test be, taking the color of a solution is determined by reflection spectrometry. For the purposes of the present Tests only the Hunter "b value" is given.

test results

The change the Hunter b value after aging for compositions which Containing phosphonates was significantly lower than for compositions which did not contain phosphonates, demonstrating that phosphonate-containing compositions a greater color stability than compositions without Phosphonates had. This result is due to the visual appearance of the products before and after aging.

Claims (8)

A liquid or gel dishwashing detergent composition suitable for use in hand dishwashing, the composition characterized by: a) an effective amount of an organic diamine; b) an olefin-derived amine oxide surfactant; c) a fragrance; d) transition metal cations present as an impurity; and e) an alkylene amino methylene phosphonic acid or a salt thereof selected from the group consisting of:

wherein X represents the moiety -CH ₂ -PO ₃ M _y ; R contains from 2 to 6 carbon atoms and is an aliphatic or alicyclic di-radical of 2 or 3 carbon atoms in length; M represents either H or a non-transition metal cation which increases water solubility; y is 1 or 2; n is an integer from 1 to 4 inclusive and m is an integer from 4 to 6 inclusive; f) an anionic surfactant, and wherein the detergent composition has a pH (measured at a 10% aqueous solution) of less than 12.5. liquid or gelatinous dishwashing according to claim 1, wherein the transition metal cations Iron cations are. liquid or gelatinous dishwashing according to one of the claims 1 to 2, wherein the composition by 0.0001% to 0.5% Alkylenaminomethylenphosphonsäure or a salt thereof is characterized. A liquid or gel dishwashing detergent composition according to any one of claims 1 to 3, wherein the transition metal cations are Fe ³⁺ cations. A liquid or gel dishwashing detergent composition according to any one of claims 1 to 4, wherein the organic diamine is selected from the group consisting of:

wherein R _{2-5 are} independently selected from H, methyl, ethyl and ethylene oxides; C _x and C _{v are} independently selected from methylene groups or branched alkyl groups wherein x + v ranges from 3 to 6; and A is optional and selected from electron donating or electron withdrawing units selected to adjust the pKa values of the diamine in the range of 8.0 to 11.5; where both x and y must be 1 or greater if A is present. A process for increasing the color stability of a liquid detergent composition characterized by: a) transition metal cations present in trace amounts as an impurity; b) an olefin-derived amine oxide surfactant; c) an organic diamine; d) a perfume; wherein the detergent composition has a pH (measured at a 10% aqueous solution) of less than 12.5; which is characterized by the step of adding, preferably from 0.0001% to 0.5%, of an alkylene amino methylene phosphonic acid or a salt thereof selected from the group consisting of:

wherein X represents the moiety -CH ₂ -PO ₃ M _y ; R contains from 2 to 6 carbon atoms and is an aliphatic or alicyclic di-radical of 2 or 3 carbon atoms in length; M represents either H or a non-transition metal cation which increases water solubility; y is 1 or 2; n is an integer from 1 to 4 inclusive and m is an integer from 4 to 6 inclusive. The method of claim 6, wherein the transition metal cations Iron cations are. A method according to any one of claims 6 to 7, wherein the liquid detergent composition is characterized by anionic surfactants and solvents and is suitable for use in hand dishwashing is net.