ES2228468T3 - DETERGENT COMPOSITIONS TO WASH THE DISH THAT CONTAIN PHOSPHONATES THAT STABILIZE THE COLOR. - Google Patents

Abstract

A liquid or gel dishwashing detergent composition suitable for use in manual dishwashing, said composition characterized by: a) an effective amount of an organic diamine; b) an olefin-derived amine oxide surfactant; c) a perfume; d) transition metal cations, present as impurities; and e) an alkylene-aminomethylene phosphonic acid or salt thereof selected from the group consisting of: where X is the moiety ¿CH2¿PO3My; R contains 2 to 6 carbon atoms and is an aliphatic or alicyclic diradical of 2 or 3 carbon atoms in length; M is H or a non-transition metal cation that improves 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; f) an anionic surfactant, and wherein the detergent composition has a pH (measured as 10% aqueous solution) of less than 12.5.

Description

Detergent compositions for dishwashing containing phosphonates that stabilize the color.

Technical field

The present invention relates to compositions liquid or gel dishwashing detergents suitable for your use in dishwashing operations. These compositions contain surfactants derived from oxide-type olefins of amine, organic diamines, perfumes and trace amounts of ions from transition metals (present as impurities) as well as solvents and other detergent adjuvants. These components, in the combinations described in the present invention serve to provide dishwashing detergent products with preferred characteristics of food dirt cleaning, handling and foaming while having a color that is stable, that is, it does not change over extended periods of weather.

Background of the invention

Liquid detergent compositions for use do not Intensive (LDL) or gel useful for manual dishwashing are well known in the art. Such products are formulated generally to provide features and properties Aesthetic and very varied performance. First, and most important, is that liquid dishwashing products or in gel should be formulated with types and amounts of surfactants and others cleaning aids that provide solubilization and a removal of acceptable food stains, especially stains from grease, from the dishes being cleaned, with, or in solutions aqueous formed from said products. There is therefore a continuous effort by the formulators of compositions dishwashing liquids to incorporate additional components to manual liquid dishwashing detergents to offer Consumers better washing benefits.

Diamines are a type of nitrogen compound which can improve the cleaning behavior of compositions liquid dishwashing detergents, particularly in the cleaning of fatty and hydrophobic stains on dishes or other Cookware. Examples of detergent compositions of dishwashing comprising diamines, and presenting Enhanced fat removal properties are described in the WO 99/11746 and WO 98/28393. Liquid washing compositions Manual crockery containing a combination of diamines, together With amine oxide and perfumes, they will not only have excellent cleansing performance, but also a pleasant fragrance that Improves consumer acceptance.

However, it has been observed that liquid dishwashing liquid compositions containing this combination of a nitrogen-containing surfactant, a diamine and a perfume, tend to have an unstable color, that is, the color changes unpredictably over a period of time, such as the time that elapses during shipping and the storage. Since color is the most aesthetic property easily perceived by the consumer, it is a property extremely important of liquid washing compositions tableware manual. Specifically, because consumers can get to identify your manual dishwashing product preferred, at least in part, by color. In addition, a manufacturer of detergents can use the color of the product to help the consumers to distinguish between several of the different liquid manual dishwashing compositions from the manufacturer, offering each of them a particular characteristic or improved For example, a manufacturer can give a certain color to your manual dishwashing liquid product that is especially good for cleaning grease, another color to a product manual dishwashing liquid that is especially smooth with hands, and another color to a product that provides benefits antimicrobials and disinfection. In addition, although most of liquid finished manual dishwashing compositions made available to consumers are colored with a color specific, if the intrinsic color of the composition itself is unstable and changes over time, it will also change mode unpredictable the color of liquid manual wash compositions of colored tableware. Given the above, there is a need permanent detergent products that not only provide a detersive performance and excellent cleaning benefits, but They also have a stable color.

A solution to the problem of instability of color or fading in a liquid detergent composition is the bleaching of the paste. In the bleaching of the paste, it is bleached a particular component of the detergent composition (often a surfactant) causing instability of the color or discoloration of the detergent composition, preferably in an oxidative bleaching process in which peroxide is used of hydrogen as oxidizing agent. The bleaching process takes typically performed at high temperatures (> 100 ° C) in a pressure reactor. While this bleaching process is very effective, it has the disadvantages of being expensive and time consuming, also presenting serious safety and hygiene problems industrial. It also has the additional disadvantage that the bleached surfactant may react adversely with others detergent components when added to a liquid detergent. When the color instability a detergent formulation It is caused by the presence of a chemical impurity, another solution is to take the necessary measures to reduce or eliminate the level of impurities in the formulation. However, as in the paste blasting process, any purification process is Also expensive and time consuming.

Given the above, there is a continuing need for formulate liquid dishwashing liquid compositions stable containing diamines, surfactants containing nitrogen, such as amine oxide and perfumes derived from olefins without resort to pulp bleaching or purification procedures of processes

Therefore, it is a benefit of the present invention provide liquid dishwashing compositions non-intensive use containing amima oxides derived from olefin, perfumes and diamines and that not only provide better cleaning benefits, but also have colors stable.

Relevant prior art

U.S. Patent Nos. 5,023,376, granted to Shehad et al., 5,442,113, granted to Blezard et al. and 5,498,791, granted to Blezard et al. they treat methods for the production of amine oxide and amine oxide compositions, and are discussed and they differ from the present invention in the text below.

Summary of the invention

It has recently been determined that a liquid dishwashing liquid detergent composition stable containing amine oxides, perfumes and derived diamines Olefin can be produced by adding to the detergent composition alkylene aminomethylene phosphonic acid or a salt of same. Through the present invention it has been discovered that the addition of the mentioned acids or salts will provide these benefits of color stabilization when the composition liquid dishwashing detergent containing both ions of transition metals present as impurity and an amine oxide derived from an olefin, as well as diamines and perfumes.

Therefore, in accordance with a first aspect of the present invention, the detergent compositions of the present invention comprise an effective amount of a diamine organic, an amine oxide surfactant derived from olefin, a perfume, transition metal cations and an acid alkyl-aminomethylene phosphonic or leave the same one selected from the group consisting of:

\delm{N}{\delm{\para}{X}}

---(R---

\delm{N}{\delm{\para}{X}}

)_{n}---XX ---

 \ delm {N} {\ delm {\ para} {X}} 

--- (R ---

 \ delm {N} {\ delm {\ para} {X}} 

) n --- X

where X is the rest -CH2 -PO3 {M} {y}; R contains from 2 to 6 carbon atoms and is an aliphatic or alicyclic diradical of 2 or 3 carbon atoms in length; M is H or a cation of a metal not of transition that improves water solubility; and is 1 or 2, n is a integer between 1 and 4, inclusive and m is an integer between 4 and 6, inclusive, and an anionic surfactant. In this first aspect of the present invention, the detergent composition has a pH (measured in a 10% aqueous solution) of less than 12.5

In 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 with a pK1 and a pK2, where ek pK1 and pK2 of said diamine are both in the range of 8.0 to 11.5, a surfactant of type amine oxide derived from olefin, a perfume, metal cations transition and 0.0001% to 0.5% of an alkylene acid aminomethylene phosphonic or salt thereof of the group consisting of:

\delm{N}{\delm{\para}{X}}

---(R---

\delm{N}{\delm{\para}{X}}

)_{n}---XX ---

 \ delm {N} {\ delm {\ para} {X}} 

--- (R ---

 \ delm {N} {\ delm {\ para} {X}} 

) n --- X

where X is the rest -CH2 -PO3 {M} {y}; R contains from 2 to 6 carbon atoms and is an aliphatic or alicyclic diradical of 2 or 3 carbon atoms in length; M is H or a cation of a metal not of transition that improves water solubility; and is 1 or 2, n is a integer between 1 and 4, inclusive and m is an integer between 4 and 6, inclusive. In this first aspect of the present invention, the detergent composition has a pH (measured in an aqueous solution at 10%) of less than 12.5

The present invention also encompasses one aspect. of the method to improve the color stability of a composition liquid manual dishwashing detergent comprising the step of adding an acid to the detergent composition alkyl aminomethylene phosphonic or salt thereof selected from the group consisting of:

\delm{N}{\delm{\para}{X}}

---(R---

\delm{N}{\delm{\para}{X}}

)_{n}---XX ---

 \ delm {N} {\ delm {\ para} {X}} 

--- (R ---

 \ delm {N} {\ delm {\ para} {X}} 

) n --- X

where X is the rest -CH2 -PO3 {M} {y}; R contains from 2 to 6 carbon atoms and is an aliphatic or alicyclic diradical of 2 or 3 carbon atoms in length; M is H or a cation of a metal not of transition that improves water solubility; and is 1 or 2, n is a 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 perfumes, and has a pH (measured as an aqueous solution at 10%) of less than 12.5

All parts, percentages and relationships used herein are expressed as percentage by weight, at unless otherwise specified. Unless another one is specified thing, all the pH values given for a composition are the measured as 10% aqueous solution.

Detailed description of the invention Definitions

The present detergent compositions they comprise an "effective amount" or an "amount that improves fat removal "of individual components defined in the present invention. For an "effective amount" of the diamines in this memory and adjuvant ingredients in this memory is meant to mean an amount that is enough to improve, either directionally or significantly at a level of 90% confidence, the behavior of the cleaning composition face at least some of the spots and target dirt. So in a composition whose objectives include certain spots of fat, the formulator will use enough diamine to improve, by less directionally, the cleaning behavior against such spots

By "color stability" you want to give understand the property of a detergent composition that describes the tendency of the detergent composition to change color throughout of a period of time. The color change can be followed by successive measurements of Hunter's b-value of the compositions detergents over a period of time. Therefore for "improvement of color stability" means that by adding a certain component, the magnitude absolute of Hunter's change in value b detergent over a fixed period of time is less than the absolute magnitude of the change in Hunter's b-value of the detergent composition over the same period of time before of the addition of a certain component.

By detergent composition "liquid use no Intensive (LDL) "means a composition detergent used in a manual dishwashing (i.e. hand).

The present liquid detergent compositions contain an alkyl aminomethylene phosphonic acid or leave the same one selected from the group consisting of:

\delm{N}{\delm{\para}{X}}

---(R---

\delm{N}{\delm{\para}{X}}

)_{n}---XX ---

 \ delm {N} {\ delm {\ para} {X}} 

--- (R ---

 \ delm {N} {\ delm {\ para} {X}} 

) n --- X

where X is the rest -CH2 -PO3 {M} {y}; R contains from 2 to 6 carbon atoms and is an aliphatic or alicyclic diradical of 2 or 3 carbon atoms in length; M is H or a cation of a metal not of transition that improves water solubility; and is 1 or 2, n is a integer between 1 and 4, inclusive and m is an integer between 4 and 6, inclusive. Amino polyphosphonates are preferred, particularly tetramethylene phosphonic ethylenediamine acid and the diethylenetriamine acid pentamethylene phosphonic.

As discussed above, the addition of an alkyl aminomethylene phosphonic acid improves in greatly the color stability of detergent compositions containing diamines, amine oxide derived from olefins, perfumes or transition metal ions, one or more of which It is present as an impurity. Without being limited by theory, it believes that the color instability mentioned above is the result of complex catalyzed color forming reactions by the transition metal and the other components. By means of the inclusion of metal ion sequestrants such as acids phosphonic and its salts described above, the ions are complexed metallic, which leaves a very low concentration of metal ions free in the solution to react with others components.

Phosphonic acids have been used previously in reactions producing amine oxide.

For example, it is known that the presence of Transition metal impurities can have the effect of reducing the efficiency of a peroxide / amine reaction and that the inclusion of Phosphonic acids can lessen this effect. See the patent of USA no. 5,023,376, granted to Shehad et al., Published 11 June 1991. However, in the present invention, they are not added phosphonic acids or their salts during the reaction peroxide / amine, but rather are added directly to the detergent composition containing the amine oxide derived from the olefin Unlike the Shehad patent, the order of addition It is not a critical or essential part of the present invention.

U.S. Pat. no. 5,442,113, granted to Blezard et al., Published on August 15, 1995 (together with its US Patent No. 5,449,791, granted to Blezard and col., published March 12, 1996) also discusses methods of production of amine oxide in the presence of phosphonic acid or salts of the same. However, Blezard's patents do not mention the problem of color stability, nor discuss the problem of contamination by impurities of transition metals.

Solvents

The present invention may contain various water miscible liquids, such as lower alkanols; they can used in the present invention diols, other polyols, ethers, Amines, and the like. Particularly preferred are the alkanols. C1-C4.

When present, the composition will contain preferably at least about 0.01%, more preferably at least about 0.5%, even more preferably, at least about 1% by weight of the solvent composition The composition will also contain preferably not more than about 20%, more preferably not more than about 10%, even more preferably, no more than about 8% by weight of the solvent composition

These solvents can be used together with a aqueous liquid carrier, such as water, or can be used without no aqueous liquid carrier being present. Solvents liquid compounds are broadly defined at temperatures of 20ºC - 25ºC and which are not considered to be surfactants. One of the distinguishing features is that solvents tend to exist as discrete entities rather than as approximate mixtures of compounds. Examples of solvents suitable for the present invention include ethanol, propanol, isopropanol, 2-methyl pyrrolidinone, benzyl alcohol and morpholin n-oxide Preferred among these solvents are ethanol and isopropanol

Suitable solvents for use herein invention include ethers and diesters having 4 to 14 atoms of carbon, preferably 6 to 12 carbon atoms, and more preferably from 8 to 10 carbon atoms. In addition, others Suitable solvents are glycols or alkoxylated glycols, alkoxylated aromatic alcohols, aromatic alcohols, alcohols aliphatic branched, branched aliphatic alcohols alkoxylated, C1-C5 linear alkoxylated alcohols, C1-C5 linear alcohols, hydrocarbons and C8-C14 alkyl and cycloalkyl halohydrocarbons, glycol C6-C16 ethers and mixtures thereof.

The present liquid detergent compositions they can also contain either diols or polymeric glycols or a mixture of both diols and polymeric glycols. The diols and the polymeric glycols suitable for use in the present invention are described in greater detail in PCT Application WO 00/46331, Clarke et al., Entitled "Diols and Polymeric Glycols for Improved Dishwashing Detergent Compositions. "

Apart from propylene glycol, polypropylene glycol and the diols in the application incorporated above, other glycols according to the formula: HO-CR1R2-OH in where R1 and R2 are independently H or a saturated chain or aliphatic unsaturated hydrocarbons C2-C10 and / or cyclic, are suitable, and can be used herein invention. One of such suitable glycols is dodecanoglycol.

Suitable alkoxylated glycols that can be used in the present invention they conform to the formula

R- (A) n -R1 -OH

where R is H, OH, an alkyl linear saturated or unsaturated from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, wherein R1 is H or a saturated or unsaturated linear alkyl of 1 to 20 carbon atoms, preferably 2 to 15 and more preferably from 2 to 10, and A is an alkoxy group preferably ethoxy, methoxy, and / or propoxy and n ranges from 1 to 5, preferably 1 to 2. Alkoxylated glycols suitable for use in the present invention are the methoxyoctadecanol and / or ethoxyethoxyethanol.

Suitable aromatic alcohols that can used in the present invention conform to the formula R-OH, where R is an aryl group alkyl-substituted or not alkyl-substituted 1 to 20 carbon atoms, preferably from 1 to 15 and more preferably from 1 to 10. By example, an aromatic alcohol suitable for use herein Invention is benzyl alcohol.

Suitable aliphatic branched alcohols which can be used in the present invention are in accordance with the formula R-OH where R is an alkyl group saturated or unsaturated branched from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5 to 12. The aliphatic branched alcohols particularly suitable for use in the present invention include the 2-ethylbutanol and / or the 2-methylbutanol.

Alkoxylated aliphatic branched alcohols suitable that can be used in the present invention are according to the formula R (A) n-OH where R it is a saturated or unsaturated branched alkyl group of 1 to 20 carbon atoms, preferably 2 to 15 and more preferably from 5 to 12, wherein A is an alkoxy group, preferably butoxy, propoxy and / or ethoxy, and n is an integer from 1 to 5, preferably 1 to 2. Suitable alkoxylated aliphatic branched alcohols include 1-methylpropoxyethanol and / or the 2-methylbutoxethanol.

C1-C5 linear alcohols suitable that can be used in the present invention are according to the formula R-OH where R is a group linear saturated or unsaturated alkyl of 1 to 5 carbon atoms, preferably 2 to 4. Linear alcohols Suitable C 1 -C 5 are methanol, ethanol, Propanol or mixtures thereof.

Other suitable solvents include, but are not limited to, butyl digliycol ether (BDGE), butyl triglycol ether, tert-amyl alcohol and the like. Solvents particularly preferred that can be used herein invention are the butoxy-propoxy-propanol, butyl diglycol ether, benzyl alcohol, butoxy propanol, ethanol, methanol, isopropanol and mixtures thereof.

Other suitable solvents for use herein invention include propylene glycol derivatives such as the n-butoxy propanol or the n-butoxy-propoxy-propanol, CARBITOL R water-soluble solvents or water-soluble solvents from CELLOSOLVE R; CARBITOL R water-soluble solvents are compounds of the class of 2- (2-alkoxyethoxy) ethanol, where the group alkoxy is derived from ethyl, propyl or butyl; a carbitol preferred water soluble is the 2- (2-Butoxyethoxy) ethanol, also known like butyl carbitol. The water-soluble solvents of CELLOSOLVE R they are compounds of the 2-alkoxyethoxy class ethanol, 2-butoxyethoxyethanol being preferred. Other suitable solvents include benzyl alcohol, and diols like 2-ethyl-1, 3-hexanediol and the 2,2,4-trimethyl-1,3-pentanediol and mixtures thereof. Some preferred solvents for use in the present invention are the n-butoxy-propoxy-propanol, the BUTIL CARBITOL® and mixtures thereof.

The solvents can also be selected from the group of compounds comprising mono-, di- and triethyl glycol ether derivatives, butylene glycol ether, and mixtures thereof. The molecular weights of these solvents are preferably less than 350, more preferably between 100 and 300, even more preferably between 115 and 250. Examples of preferred solvents include, for example, mono-ethylene glycol n-hexyl ether, mono-propylene glycol n -butyl ether, and tri-propylene glycol methyl ether. Ethylene glycol and propylene glycol ethers are marketed by Dow Chemical Company under the "Dowanol" brand and by Arco Chemical Company under the "Arcosolv" brand. Other preferred solvents that include mono- and diethylene glycol n- hexyl ether are marketed by Union Carbide.

Diamines

As already mentioned, the diamines used in the present invention in detergent compositions in combination with detersive surfactants at levels are effective in achieving At least one directional improvement in cleaning performance. At context of a manual dishwashing composition, said "levels of use" may vary, depending not only on the type and severity of stains and dirt, but also of the temperature of the washing water, the volume of washing water and the duration of the time when the dishes are in contact with the wash water.

Since the habits and practices of users of detergent compositions show a variation considerable, the composition will preferably contain at least one 0.1%, more preferably at least 0.2%, even more preferably, at least 0.25%, even more preferably still, at least 0.5% by weight of said diamine composition. The composition too it will preferably contain no more than 15%, more preferably not more than 10%, even more preferably, not more than 6%, even more preferably still, no more than 5%, even more preferably, no more than 1.5% by weight of said diamine composition.

In one of its various aspects, this invention provides means to strengthen the removal of dirt fat / oily when combining the specific diamines of this invention with surfactants. "Daily" oily / oily dirt is formed by a mixture of triglycerides, lipids, polysaccharides complexes, fatty acids, inorganic salts and matter protein

Therefore, the diamines, in combination with amphoteric and anionic surfactants in specific proportions that are discussed then offer the benefit of a better cleaning of fats and resistant foods, which allows elimination or reduction in the amount of divalent ions in the Preferred embodiments of the present formula. This better cleaning It is a result of the propensity of diamines to act as buffering agent to increase the alkalinity of the composition of dishwashing The highest dissolution rate achieved by the Elimination of divanlent cations allows the formulator to even manufacture manual dishwashing detergents with formulations especially compact, even at significantly viscosities higher (e.g., 1,000 centipoise or more) than formulations conventional, while maintaining excellent performance of dissolution and cleaning. This has potential advantages. significant to prepare compact products with a higher viscosity, while maintaining an acceptable solution. By "compact" or "Ultra" is meant detergent formulations with reduced water levels compared with conventional liquid detergents. For formulations "compact" or "Ultra", the water level is less than 70%, preferably less than 40% by weight of the compositions liquid dishwashing detergents. Such products concentrates provide advantages to the consumer, who has a product that can be used in smaller quantities, and at producer, who has lower transportation costs. For the compositions that are not expected to be concentrated, an adequate level of water is less than about 85%, more preferably less than about 70% by weight of the compositions liquid dishwashing detergents.

It is preferred that the diamines used in the The present invention is substantially free of impurities. Is to say, by "essentially exempt" it is meant that diamines are pure in more than 95%, that is preferably in 97%, more preferably 99%, even more preferably 99.5% free of impurities. Examples of impurities that can be present in commercially supplied diamines include 2-methyl-1,3-diaminobutane and alkylhydropyrimidine. In addition, it is thought that the diamines they should be free of oxidation reactants to avoid diamine degradation and ammonia formation.

As discussed in greater detail below, make hydrogen peroxide free compositions is important when the compositions contain an enzyme. Even small amounts of hydrogen peroxide can cause Problems with enzyme-containing formulations. Without However, the diamine can react with any peroxide present and act as an enzyme stabilizer and prevent the hydrogen peroxide react with the enzyme. It is thought that the only drawback of this stabilization of enzymes by of the diamine is that the nitrogen compounds produced cause the odors that may be present in compositions with Diamine content. Let the diamine act as a stabilizer Enzymatic can prevent diamine from providing the benefits to the composition for which it was originally included, namely fat cleaning, foaming, dissolution and stability low temperature. Therefore, it is preferred to minimize the amount of hydrogen peroxide present as an impurity in the compositions of the invention either using components that are substantially free of hydrogen peroxide or any other species bleach and / or by using antioxidants not yet diamine when the diamine can produce smelly compounds and the reduction in the amount of available diamine present for Perform its main function.

Preferred organic diamines are those in the that pK1 and pK2 are in the range of 8.0 to 11.5, preferably in the range of 8.4 to 11, even more preferably 8.6 to 10.75. Preferred materials considering performance and supply are the 1,3-bis (methylamine) -cyclohexane (pKa = 10 to 10.5), 1.3 propane diamine (pK1 = 10.5; pK2 = 8.8), 1.6 hexane diamine (pK1 = 11; pK2 = 10), 1,3 pentane diamine (Dytek EP) (pK1 = 10.5; pK2 = 8.9), 2-methyl 1.5 pentane diamine (Dytek A) (pK1 = 11.2; pK2 = 10.0). Other preferred materials are the primary / primary diamines with C4 to alkylene spacers C8 In general, primary diamines are believed to be preferable to secondary and tertiary diamines.

Definition of pK1 and pK2

As used herein, "pKa1" and "pKa2" are amounts of a type collectively known as Those skilled in the art such as "pKa". pKa is used in this memory in the same way as is usually known by Chemistry experts. The values cited in the present invention can be obtained from the literature, as per example of "Critical Stability Constants: volume 2, Amines" by Smith and Martel, Plenum Press, NY and London, 1975. Information Additional information about pKa's can be obtained from the relevant bibliography provided by companies, such as the information provided by Dupont, a supplier of diamines.

As a definition of work in the present memory, the pKa of the diamines is specified in a solution completely aqueous at 25 ° C and for an ionic strength between 0.1 and 0.5 M. The pKa is a constant in equilibrium that can change with the temperature and ionic strength: thus, the values outlined in the bibliography sometimes disagree depending on the method and The measurement conditions. To eliminate ambiguities, the relevant conditions and / or references used for pKa's of this invention are as defined herein or in "Critical Stability Constants: volume 2, Amines ". A measurement method typical is the potentiometric titration of acid with hydroxide of sodium and the determination of pKa by appropriate methods as describe and reference in "The Chemist's Ready Reference Handbook "by Shugar and Dean, McGraw Hill, NY, 1990.

It has been determined which substituents and structural modifications that reduce pK1 and pK2 below approximately 8.0 are undesirable and cause losses in the behavior. These may include substitutions that lead to ethoxylated diamines, hydroxyethyl substituted diamines, diamines with oxygen in the beta position (and to a lesser extent gamma) with with respect to nitrogen in the spacer group (for example Jeffamine EDR 148). In addition, materials based on ethylenediamine

The diamines useful herein can be Define by the following structure:

one

where R_ {2-5} are independently selected from H, methyl, -CH 3 CH 2, and ethylene oxides; C_ {x} and C_ {v} are independently selected from methylene groups or from branched alkyl groups where x + y is about 3 to about 6; and A is optionally present and selected of the electron donor or acceptor moieties chosen for adjust the pKa of the diamine to the desired range. If A is present, then x and y must be both 1 or higher.

Examples of preferred diamines may found 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 anionic surfactants useful herein invention are preferably selected from the group consisting of linear alkylbenzene sulfonate, alpha olefin sulfonate, sulphonates paraffin, alkyl ester sulphonates, alkyl sulfates, alkyl alkoxysulfate, alkyl sulphonates, alkyl alkoxy carboxylate, alkoxylated alkyl sulfates, sarcosinates, taurinates, and mixtures of the same. An amount may be used in the present invention. effective, typically 0.5% to 90%, preferably 5% to 50%, more preferably 10 to 30%, by weight, of surfactant anionic detersive.

Suitable examples of anionic surfactants can be found in PCT Application WO 99/27058 of Chandrika Kasturi et al., Entitled "Liquid Detergent Compositions Comprising Polymeric Suds Enhancers ". Additional examples of surfactants Suitable anionics are given in "Surface Active Agents and Detergents "(Vol. I and II by Schwartz, Perry and Berch). Several of said surfactants are also generally described in the U.S. Patent no. 3,929,678, granted on December 30, 1975 to Laughlin et al. in Column 23, line 58 to column 29, line 23. Additional anionic surfactants can be found in U.S. Patent No. 5,415,814 granted on May 16, 1995, Ofosu-Asante et al.

Amphoteric surfactants

Amphoteric surfactants useful herein invention are selected from oxide type surfactants of amine. Amine oxides are semipolar nonionic surfactants, and include water-soluble amine oxides containing a alkyl structure of 10 to 18 carbon atoms and 2 structures selected from the group consisting of alkyl groups and groups hydroxyalkyl containing 1 to 3 carbon atoms. Oxides of Water-soluble phosphine containing an alkyl structure of 10 to 18 carbon atoms and 2 structures selected from the group that It consists of alkyl and hydroxyalkyl groups containing 1 to 3 carbon atoms; and water-soluble sulfoxides containing a alkyl structure of about 10 to about 18 atoms carbon and a structure selected from the group consisting of alkyl and hydroxyalkyl structures of about 1 to approximately 3 carbon atoms.

Nonionic detergent surfactants semi-polar include oxide surfactants of amine with the formula

2

where R 3 is a group alkyl, hydroxyalkyl, or alkylphenyl or mixtures thereof that they contain from 8 to 22 carbon atoms; R 4 is an alkylene group or hydroxyalkyl containing from 2 to 3 carbon atoms or mixtures thereof; x is 0 to 3; and each R 5 is an alkyl group or hydroxyalkyl containing from about 1 to about 3 carbon atoms or a group of polyethylene oxides containing from 1 to 3 groups of ethylene oxide. R 5 groups may be linked together, for example through an oxygen atom or nitrogen, to form a structure cancel.

These amine oxide surfactants include, in particular, alkyl oxides C 10 -C 18 -dimethyl-amine and alkoxy oxides C 8 -C 12 -ethyl-hydroxy-ethyl-amine.

Also suitable are amine oxides such as the amine propyl oxides, represented by the formula:

3

where R_ {1} is a radical alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxy-propyl wherein the alkyl and alkoxy, respectively, contain from 8 to 18 carbon atoms, R2 and R3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl, and n ranges from 0 to 10.

Additional suitable species of agents semipolar amine oxide surfactants comprise compounds and mixtures of compounds with the formula:

4

where R_ {1} is a radical alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxy-propyl wherein the alkyl and alkoxy, respectively, contain from 8 to 18 carbon atoms, R2 and R3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxy-propyl and n is 0 to 10. Particularly preferred are the amine oxide of the formula:

5

where R 1 is an alkyl C 10-14 and R 2 and R 3 are methyl or ethyl. Because they are low foam it may also be desirable to use described long chain amine oxide surfactants of more fully in U.S. Patent No. 4,316,824 (Pancheri), 5,075,501 and 5,071,594.

Other suitable, non-limiting examples of amphoteric detergent surfactants useful in the present invention include amidopropyl betaines and derivatives of secondary amines or tertiary, aliphatic or heterocyclic in which the structure aliphatic can be a linear or branched chain and where one of the aliphatic substituents contain 8 to 24 carbon atoms and at least one aliphatic substituent contains an anionic group water soluble.

Other examples of amphoteric surfactants suitable are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch), incorporated here for reference.

Preferably, the amphoteric surfactant is present in the composition in an effective amount, more preferably from 0.1% to 20%, even more preferably from 0.1% to 15%, still more preferably still from 0.5% to 10%, by weight.

Secondary Surfactants

A secondary detergent surfactant can be select from the group consisting of nonionic surfactants, cationic, ampholytic, ion hybrids and mixtures thereof. To the select the type and amount of detergent surfactant together with other attached ingredients described herein, the present detergent compositions may be formulated to be used in the context of laundry cleaning applications or in other different cleaning applications, in particular including dishwashing The particular surfactants used may vary, therefore, widely depending on the intended particular end use. They are described in detail suitable secondary surfactants in PCT WO Application 99/27058 by Chandrika Kasturi et al., Entitled "Liquid Detergent Compositions Comprising Polymeric Suds Enhancers ".

Proportion of anionics to amphoteric diamine

In the compositions of the present invention, the proportion of anionic surfactant: amphoteric: diamine ranges from 100: 40: 1 to 9: 0.5: 1, per mole; preferably, the coefficient of anionic surfactant: amphoteric: diamine ranges from 27: 8: 1 to 11: 3: 1, by mol. It has been found that detergent compositions that contain anionic surfactant, amphoteric surfactant and diamine in this specific ratio provides improved stability to low temperature, provides better fat removal and Cleaning benefits of food resistant to an internal pH of 12.5, and better cleaning with hard waters.

In another aspect of the present invention, the molar ratio of anionic surfactant to diamine of more than 9: 1, preferably greater than 20: 1, it has been observed that provides better stability at low temperature, provides better fat removal and food cleaning benefits resistant, and better cleaning with hard waters.

Optional detergent ingredients Polymer foam stabilizer

The compositions of the present invention may optionally contain a polymeric foam stabilizer. These polymeric foam stabilizers provide greater volume foam and longer foam life without sacrificing the grease removal ability of the compositions liquid detergents These polymeric foam stabilizers are select from:

i)

homopolymers of (N, N-dialkylamino) alkyl acrylate esters with the formula:

6

where each R it's independently hydrogen, alkyl C 1 -C 8, and mixtures thereof, R 1 is hydrogen, C 1 -C 6 alkyl, and mixtures of the themselves, n ranges from 2 to about 6; Y

ii)

copolymers of (i) and

7

where R 1 is hydrogen, C1-C6 alkyl, and mixtures thereof, provided that the proportion of (ii) to (i) is approximately 2 to 1 a about 1 to 2; The molecular weight of the enhancers foaming polymers, determined by a Conventional gel permeation chromatography is about 1,000 to about 2,000,000, preferably from about 5,000 to about 1,000,000, plus preferably from about 10,000 to about 750,000, more preferably from about 20,000 to about 500,000, even more preferably from about 35,000 to Approximately 200,000 Polymeric foam stabilizer can optionally be present in the form of a salt, be it a salt inorganic or organic, for example citrate salts, sulfate, (N, N-dimethylamino) alkyl acetate or nitrate acrylate ester.

A preferred polymeric foam stabilizer they are the (N, N-dimethylamino) alkyl acrylate esters, namely

8

When present in the compositions, the polymeric foam forming enhancer may be present in the composition of about 0.01% to about 15%, preferably from about 0.05% to about a 10%, more preferably about 0.1% at approximately 5%, by weight.

Detergent builder

The compositions according to the present invention may further comprise an additive system detergent booster. Because reinforcing additives of the detergent, such as citric acid and citrates, interfere With the stability of enzymes in LDL compositions, it is desirable reduce the amount or completely eliminate additive salts detergent builder normally used in LDL compositions incorporating propylene glycol as a reinforcing additive of the Detergent. When a detergent composition includes solvent of propylene glycol as part or total of the detergent carrier, Enzymes are more stable, requiring smaller amounts of, or None, detergent booster additive salt.

If it is desirable to use a reinforcing additive of the detergent, any system of conventional detergent builder additive for use herein invention, including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate. Although they are less preferred for obvious environmental reasons, they can also used in this invention detergent builder additives of phosphate.

Detergent builder additives Suitable polycarboxylate for use in the present invention include citric acid, preferably in the form of a water-soluble salt, succinic acid derivatives of the formula

R-CH (COOH) CH2 (COOH) wherein R is C 10-20 alkyl or alkenyl, preferably C 12-16, or where R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents. Specific examples include lauryl succinate, succinate myristyl, palmityl succinate, succinate 2-dodecenyl succinate 2-tetradecenyl. The reinforcing additives of Succinate detergent are preferably used in the form of their water soluble salts, including sodium, potassium, ammonium and alkanolammonium

Other suitable polycarboxylates are oxodisuccinates and acid mixtures tartrate-monosuccinic acid tartrate-disuccinic, as described in the US 4,663,071.

Especially for the liquid realization in the present invention, acid detergent builder additives Fatty suitable for use in the present invention are fatty acids saturated or unsaturated C 10-18, as well as corresponding soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain. Fatty acid Preferred unsaturated is oleic acid. Another preferred system of detergent booster additive for liquid compositions se based on dodecenyl succinic acid and acid citric.

If salts of reinforcing additive are included detergent, should be included in quantities ranging from 0.5% to 50% by weight of the composition, preferably from 5% to 30% and more usually from 5% to 25% by weight.

Enzymes

The detergent compositions herein invention may additionally comprise one or more enzymes that Provide cleansing performance benefits. These enzymes include selected enzymes of cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, Phenoloxidases, lipoxygenases, ligninases, pululanases, tanases, pentosanases, malanases, β-glucanases, arabinosidases or mixtures thereof A preferred combination is a detergent composition that has an applicable enzyme cocktail Conventional such as protease, amylase, lipase, cutinase and / or cellulase When enzymes are present in the compositions, of approximately 0.0001% to approximately 5% active enzyme by weight of the detergent composition. Proteolytic enzymes Preferred are then selected from the group consisting of Alcalase® (Novo Industri A / S), BPN ', protease A and protease B (Genencor) and their mixtures Protest B is the most preferred. Amylase Enzymes Preferred include TERMAMYL®, DURAMYL® and the amylase enzymes that are described in WO 9418314 granted to Genencor International and WO 9402597 granted to Novo.

Other additional non-limiting examples of Suitable and preferred enzymes are described 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 additives detergent booster such as citric acid and citrates interfere with the stability of enzymes in LDL compositions, it is desirable to reduce or eliminate the levels of these compounds in Compositions containing enzymes. Hydrogen peroxide is frequently found in the form of impurity in surfactants and surfactant pastes. As such, the preferred level of peroxide of hydrogen in the amine oxide or in the surfactant paste of amine oxide is 0-40 ppm, more preferably 0-15 ppm. Amine oxide and amine impurities betaines, if present, should be minimized to levels referred to above for hydrogen peroxide.

Magnesium ions

While it is preferred that the ions divalents are omitted from LDL compositions prepared according to the present invention, alternative embodiments of the present invention may include magnesium ions.

It is desirable to exclude all divalent ions from the present LDL compositions because such ions can give place for a slower dissolution as well as a bad rinse, and to Bad stability properties at low temperature. Besides, the formulation of such compositions containing divalent ions in alkaline pH matrices can be difficult due to the incompatibility of divalent ions, particularly of magnesium, with hydroxide ions.

Anyway, the presence of magnesium ions It offers several advantages. It is remarkable that the inclusion of such Divalent ions improves the cleaning of fatty stains for several LDL compositions, in particular compositions containing alkyl ethoxycarboxylates and / or fatty polyhydroxy acid amide. This is especially true when the compositions are used in water softened that contains few divalent ions.

However, in the present invention, they can Obtain these benefits without the inclusion of divalent ions. In in particular, a better cleaning of the grease without ions can be obtained divalents by including organic diamines in combination with anionic and amphoteric surfactants in specific proportions discussed above, while has shown that enzymes improve the softness of the skin of present LDL compositions.

If they are to be included in one embodiment Alternative of the present LDL compositions, magnesium ions they are present at an active level of approximately 0.01% at 1%, preferably from about 0.015% to 0.5%, more preferably from about 0.025% to 0.1%, by weight. The amount of magnesium ions present in the compositions of the invention will also depend on the amount of total surfactant present in them, including the amount of alkyl ethoxycarboxylates and fatty polyhydroxy acid amide.

Preferably, magnesium ions are added as hydroxide, chloride, acetate, sulfate, formate, oxide or salt of nitrate to the compositions of the present invention. Given the during storage the stability of these compositions is bad, due to the formation of hydroxide precipitates in presence of compositions containing moderate concentrations of hydroxide ions, it may be necessary to add certain agents chelators Suitable chelating agents are discussed at continued and in U.S. Patent No. 5,739,092, granted on April 14, 1998, to Ofosu-asante.

Aromas

Perfumes and perfume ingredients useful in The present compositions and procedures comprise a broad diversity of natural and synthetic chemical ingredients, included but not limited to aldehydes, ketones, esters and Similar. Various extracts and essences are also included natural that can comprise complex mixtures of ingredients such as orange oil, lemon oil, rose extract, washing, musk, patchouli, balsamic essence, wood oil Sandalwood, pine oil, cedar and the like. The finished perfumes they can comprise extremely complex mixtures of such ingredients. Finished perfumes typically comprise of about 0.01% to about 2%, by weight, of the detergent compositions of this invention, and ingredients of individual perfumes can comprise from about 0.0001% to approximately 90% of a finished perfume composition.

Non-limiting examples of ingredients of perfumes useful in the present invention can be seen in the patent from the USA UU. no. 6,589,926: "Dishwashing Detergent Compositions Containing Organic Diamines for Improved Grease Cleaning, Sudsing, Low temperature stability and Dissolution ".

Chelating agents

The detergent compositions herein invention may also optionally contain one or more agents iron and / or manganese chelators. The chelating agents of this type can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally aromatic chelating agents substituted and mixtures thereof, all of them as defined herein to continuation. Without being supported by theory, it is thought that the benefit of these materials is due, in part, to its exceptional ability to separate iron and manganese ions from solutions washing by the formation of soluble chelates.

Suitable aminocarboxylates as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminotriacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylenetetraamine-hexacetates,
diethylenetriamine and ethanoldiglycine pentaacetates, alkali metals, ammonium and substituted ammonium salts, as well as mixtures thereof.

Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when detergent compositions allow at least low total phosphorus levels, and include ethylenediaminetetrakis (methylene phosphonates) such as DEQUEST. Preferably, these aminophosphonates contain alkyl or alkenyl groups with more than approximately 6 carbon atoms.

Aromatic chelating agents Polyfunctionally substituted are also useful in Compositions of this invention. See US Pat. 3,812,044, issued May 21, 1974 to Connor et al. Preferred compounds of this type in acid form are the dihydroxydisulfobenzenes such as the 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use in The present invention is ethylenediamine disuccinate ("EDDS"), especially the [S, S] isomer as described in U.S. Patent 4,704,233, of November 3, 1987, granted to Hartman and Perkins.

The compositions of this invention may also contain water-soluble salts of methyl glycine acid di-acetic acid (MGDA) (or acid form) as chelating agent or detergent builder. By way of similar, the so-called detergent booster additives "weak", such as citrate, can also be used as chelating agents.

If used, these chelating agents they will generally comprise about 0.1% to approximately 15% by weight of the detergent compositions in The present invention. More preferably, if agents are used chelators these will comprise between approximately 0.1% and 3.0% by weight, of such compositions.

pH of the composition

The pH of the present compositions (measured as 10% aqueous solution) is less than 12.5, preferably less to 10.5. Since the dishwashing compositions of the present invention will undergo acidic stress created by spots of meals at the time of use, that is, diluted and applied to dirty dishes, if a composition with a pH greater than 7 should be more effective, preferably it should contain a buffering agent capable of providing a generally more alkaline pH in the composition and in dilute solutions. The dishwashing compositions of the The present invention will therefore contain approximately 0.1% at 15%, preferably from about 1% to 10%, maximum preference of about 2% to 8%, by weight, of an agent buffering The pKa value of this buffering agent should be approximately 0.5 to 1.0 pH units below the value of Desired pH of the composition (determined as described more above). Preferably, the buffer agent pKa should be of about 7 to about 12. Under these conditions, the buffering agent controls pH at maximum efficiency which makes use of the least possible amount of it.

Inorganic buffers / alkalinity sources include alkali metal carbonates, hydroxides of alkali metals and alkali metal phosphates, p. eg sodium carbonate, sodium hydroxide, sodium polyphosphate.

The optional buffering agent (used in compositions with a pH greater than 7) can be an active detergent in itself, or it can be an organic or inorganic material of low molecular weight used in this composition only for Maintain an alkaline pH. Preferred buffering agents for Compositions of this invention are materials containing nitrogen. Some examples are amino acids such as lysine, or lower alcohol amines such as mono-, di- and tri-ethanolamine. The diamines, described in detail above, they also act as buffering agents and are preferred buffering agents. The buffering system Preferred 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 buffering agents which contain nitrogen are Tri (hydroxymethyl) amino methane (HOCH2) 3CNH3 (TRIS), the 2-amino-2-ethyl-1,3-propanediol, he 2-amino-2-methyl-propanol, he 2-amino-2-methyl-1,3-propanol, disodium glutamate, N-methyl diethanolamide, 1,3-diamino-propanol N, N'-tetra-methyl-1,3-diamino-2-propanol, the N, N-bis (2-hydroxyethyl) glycine (bicin) and the N-tris (hydroxymethyl) methylglycine (tricine). Are also acceptable mixtures of any of the above. For other tampons additional, see McCutcheon's EMULSIFIERS AND DETERGENTS, North American Edition, 1997, McCutcheon Division, MC Publishing Company Kirk, and WO 95/07971.

Other ingredients

Detergent compositions will comprise preferably and additionally one or more detersive adjuvants selected from the following: polymers for the release of the dirt, polymer dispersants, polysaccharides, abrasives, bactericides and other antimicrobials, tarnish inhibitors, detergent booster additives, enzymes, dyes, buffers, antifungal or mold control agents, insect repellents, perfumes, hydrotropes, thickeners, processing aids, enhancers foaming, brighteners, anticorrosive aids, antioxidant stabilizers and chelators. It can be included in the compositions in the present invention a wide variety of others useful ingredients in detergent compositions, including others active ingredients, carriers, hydrotropes, antioxidants, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc. If high foaming is desired, in the compositions can be incorporated forming enhancers of foam such as alkanolamides C 10 -C 16, typically at levels of 1% -10%. Monoethanolamides and diethanolamides C_ {10} -C_ {14} represent a typical class of said foaming enhancers. It also turns out advantageous the use of said foaming enhancers with high foam adjuvant surfactants such as oxides of amine, betaines and sultains.

To the detergent compositions herein invention can optionally be added an antioxidant. Can be any conventional antioxidant used in compositions detergents, such as 2,6-di-tert-butyl-4-methylphenol (BHT), carbamate, ascorbate, thiosulfate, monoethanolamine (MEA), diethanolamine, triethanolamine. Be prefer that the antioxidant, when present, is present in the composition from about 0.001% to about 5% in weight.

Optionally, various detersive ingredients used in the present compositions may also be stabilized causing a porous hydrophobic substrate to absorb said ingredients and then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient It is mixed with a surfactant before being absorbed into the substrate porous. During use, the detersive ingredient is released from the substrate in the aqueous wash liquid, where it performs its function detersive

To illustrate this technique in greater detail, a porous hydrophobic silica (registered trademark SIPERNAT D10, Degussa) is mixed with a proteolytic enzyme solution containing 3% -5% of non-ionic ethoxylated alcohol surfactant C_ {13-15} (EO 7). Typically, the solution of Enzyme / surfactant is 2.5 times the weight of silica. Dust resulting is dispersed by stirring in silicone oil (se they can use various viscosities of silicone oil in the 500-12,500 range). The oil dispersion of resulting silicone is emulsified or added to the detergent matrix final. By these means, ingredients such as enzymes before mentioned, bleach, bleach activators, catalysts bleaching, photoactivators, dyes, fluorescents, tissue conditioners and hydrolysable surfactants can "protect" for use in detergents, including liquid detergent compositions for laundry.

In addition, these detergent embodiments for the handwashing the dishes preferably comprises additional a hydrotrope. Suitable hydrotropes include salts of sodium, potassium, ammonium or substituted ammonium, soluble in water, of toluenesulfonic acid, naphthalenesulfonic acid, acid cumenesulfonic acid, xylenesulfonic acid.

Non-aqueous liquid detergents

The manufacture of detergent compositions liquids comprising a non-aqueous carrier medium can be prepared according to the descriptions of US patents. UU. 4,753,570; 4,767,558; 4,772,413; 4,889,652; 4,892,673; GB-A-2,158,838; GB-A-2,195,125; GB-A-2,195,649; U.S. 4,988,462; U.S. 5,266,233; EP-A-225,654 (6/16/87); EP-A-510,762 (10/28/92); EP-A-540,089 (5/5/93); EP-A-540,090 (5/5/93); U.S. 4,615,820; EP-A-565,017 (10/13/93); EP-A-030,096 (10/6/81). Such compositions may contain several particulate ingredients detersives suspended stably in them. Non-aqueous compositions of this type therefore comprise a PHASE LIQUID and, optionally but preferably, a SOLID PHASE, all of this as described in greater detail below and in the references cited.

The compositions of this invention may be used to form aqueous wash solutions for use in the manual dishwashing Generally, an effective amount is added of such compositions to water to form said cleaning or water immersion solutions. The aqueous solution as well formed then contact the cutlery, the crockery and kitchen utensils.

An effective amount of the compositions detergents of this invention added to the water to form aqueous cleaning solutions may comprise amounts sufficient to form approximately 500 to 20,000 ppm of aqueous solution composition. More preferably, it will provide approximately 800 to 5,000 ppm of the detergent compositions of this invention in a cleaning liquor aqueous.

The following examples are illustrative of the present invention, but are not intended to limit or define otherwise mode its scope. All parts, percentages and relationships used herein are expressed as percentage by weight, at unless otherwise specified.

Examples TABLE I

Liquid dishwashing detergents of Non intensive use are as follows. Composition II contains a phosphonate and is prepared according to the present invention. The composition I It is identical except that it does not contain phosphonate.

9

one:  \ begin {minipage} [t] {120mm} C12-13 alkylethoxysulfonate containing an average of 0.6 ethoxy groups. \ end {minipage} 2: oxide of amine C_ {12} -C_ {14}. 3:  \ begin {minipage} [t] {120mm} on polymer is the homopolymer of (N, N-dimethylamino) ethyl methacrylate \ end {minipage} 4:  \ begin {minipage} [t] {120mm} The nonionic surfactant can be an ethoxylated alkyl surfactant C10 containing 8 ethoxy groups or an alkyl ethoxylated surfactant C10 containing 8 ethoxy groups. \ end {minipage} 5: 1.3 bis (methylamine) -cyclohexane 6: diethylenetriaminepenta (methylene phosphonic acid)

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

Color can be measured analytically by a Hunter color measurement test where the color of a solution by reflection spectrometry. For the purposes of the present test, only "value b" is indicated from Hunter.

Test results:% phosphonate by weight

10

The change in Hunter's b value after the aging of compositions containing phosphonates was significantly less than for compositions that did not contain phosphonates, which indicates that the compositions containing phosphonates had greater color stability than the compositions without phosphonates. This result is confirmed by appearance visual of the products before and after aging.

Claims (8)

1. A liquid or gel dishwashing detergent composition suitable for use in manual dishwashing, said composition characterized by:

to)

 a effective amount of an organic diamine;

b)

 a amine oxide surfactant derived from olefin;

C)

 a fragrance;

d)

transition metal cations, present as impurities; Y

and)

 a alkylene aminomethylene phosphonic acid or salt thereof selected from the group consisting of:

X ---

 \ delm {N} {\ delm {\ para} {X}} 

--- (R ---

 \ delm {N} {\ delm {\ para} {X}} 

) n --- X

where X is the remainder -CH_ {2} -PO_ {3} M_ {y}; R contains 2 to 6 carbon atoms and is an aliphatic or alicyclic diradical of 2 or 3 carbon atoms in length; M is H or a cation of a metal not of transition that improves water solubility; and is 1 or 2, n is a integer between 1 and 4, inclusive and m is an integer between 4 and 6, inclusive; f) an anionic surfactant, and wherein the detergent composition has a pH (measured as aqueous solution at 10%) less than 12.5.

2. A washing detergent composition of liquid or gel dishes according to claim 1, wherein the Transition metal cations are iron cations. 3. A liquid or gel dishwashing detergent composition according to any one of claims 1-2, wherein the composition is characterized by 0.0001% to 0.5% alkylene-aminomethylene phosphonic acid or salt thereof. 4. A washing detergent composition of liquid or gel dishes according to any of the claims 1-3, where transition metal cations they are Fe 3+ cations. 5. A washing detergent composition of liquid or gel dishes according to any of the claims 1-4, wherein said organic diamine is selected of the group consisting of: eleven

where R_ {2-5} are independently selected from of H, methyl, ethyl, and ethylene oxides; C_ {x} and C_ {v} are independently selected from methylene groups or groups branched alkyl where x + v is 3 to 6; and A is optionally present and selected from donor or acceptor moieties of electrons chosen to adjust the pKa of the diamine to the interval from 8.0 to 11.5; where A is present, both x and y must be 1 or greater

6. A method to improve the color stability of a liquid detergent composition characterized :

to)

transition metal cations, present in trace amounts in the form of impurities;

b)

a olefin-derived amine oxide surfactant;

C)

a organic diamine;

d)

 a fragrance; wherein the detergent composition has a pH (measured as 10% aqueous solution) less than about 12.5;

characterized by the step of: preferably adding from 0.0001% to 0.5%, an alkylene-aminomethylene phosphonic acid or salt thereof selected from the group consisting of:

         \ newpage
      

X ---

 \ delm {N} {\ delm {\ para} {X}} 

--- (R ---

 \ delm {N} {\ delm {\ para} {X}} 

) n --- X

where X is the remainder -CH_ {2} -PO_ {3} M_ {y}; R contains 2 to 6 carbon atoms and is an aliphatic or alicyclic diradical of 2 or 3 carbon atoms in length; M is H or a cation of a metal not of transition that improves water solubility; and is 1 or 2, n is a integer between 1 and 4, inclusive and m is an integer between 4 and 6, inclusive.

7. A method according to claim 6, wherein Transition metal cations are iron cations. 8. A method according to any of claims 6-7, wherein the liquid detergent composition is characterized by anionic surfactants and solvents and is suitable for use in a manual washing operation.