JP2003509572A - Dishwashing detergent compositions containing color stabilized phosphonates - Google Patents

Abstract

  (57) [Summary] By hand, comprising an organic diamine, an olefin-derived amine oxide surfactant and a fragrance, by incorporating an alkylene aminomethylene phosphonic acid or a salt thereof to provide a detergent composition having excellent cleaning ability and long-term color stability, by hand. A detergent composition suitable for washing dishes.

Description

Detailed Description of the Invention

TECHNICAL FIELD The present invention relates to a liquid or gel dishwashing detergent composition suitable for use in hand dishwashing operations. These compositions include olefin-derived amine oxide surfactants, organic diamines, perfumes, trace amounts of transition metal ions (present as impurities), and solvents and other cleaning adjuncts. These ingredients, in the combinations disclosed herein, have stable color while having good cleaning, handling, and lathering properties of food soils, i.e. for dishwashing that does not change color over time. Work to provide you with detergent products.

BACKGROUND OF THE INVENTION Light-duty liquid (LDL) or gel detergent compositions useful for hand dishwashing are well known in the art. Such products are generally formulated to provide a number of widely diverse capabilities and aesthetic properties and attributes. First of all, a liquid or gel dishwashing product is sufficient to solubilize food stains, especially greasy stains, from dishes being cleaned with such products or in an aqueous solution formed from such products. Must be formulated with the type and amount of surfactant and other cleaning adjuncts to allow for subsequent removal. Accordingly, there is an ongoing effort by formulators of liquid dishwashing compositions to incorporate additional ingredients into hand-held liquid dishwashing detergents in order to provide consumers with improved cleaning benefits.

Diamines are a type of nitrogen compounds that can improve the cleaning ability of liquid dishwashing detergent compositions, especially against hydrophobic greasy stains on dishes and other kitchen utensils. Liquid handwashing dishwashing compositions containing a combination of diamines with amine oxides and fragrances will not only have excellent cleaning capabilities, but will also have a pleasant aroma that is well received by the consumer.

However, liquid hand-washing dishwashing compositions containing this combination of nitrogen-containing surfactants, diamines and perfumes tend to have an unstable color, ie the time elapsed between shipping and storage. It has been pointed out that the color changes unpredictably during the period. Color is a very important property of liquid dishwashing products for hand-washing, as color is the aesthetic property most easily noticed by consumers. In particular, consumers may at least to some extent identify their favorite dishwashing product by its color. Detergent manufacturers also use product colors to help consumers identify the different hand-washing liquid dishwashing products of their manufacturers, each of which provides special or enhanced features. Can be used. For example, manufacturers have added one color to their hand-washing liquid dishwashing products that are particularly good at cleaning fats and oils, and another color to hand-washing liquid dishwashing products that are particularly gentle on hands, antibacterial and hygiene. Additional colors can be added to products that provide the benefits of.
Furthermore, although many of the final liquid handwashing dishwashing products sold to consumers are dyed to a particular color, if the color inherent in the composition itself is unstable and changes over time, The color of the final dyed handwash liquid dishwashing product will also change unpredictably. Given the above, there continues to be a need for detergent products that not only provide excellent cleaning performance and cleaning benefits, but are also color stable.

One solution to the problem of color instability or fading in liquid detergent compositions is:
It is paste bleaching. In paste bleaching, certain components of the detergent composition (generally surfactants) that are responsible for the color instability or discoloration of the detergent composition are preferably oxidative bleaching in which hydrogen peroxide is used as the oxidant. Bleached in the process. The bleaching process is typically carried out at elevated temperature (> 100 ° C.) in a pressure reactor. Although this bleaching process is very effective, it has the disadvantages of being expensive and time consuming, and also presents serious industrial hygiene and safety issues. There is also the additional disadvantage that the bleached surfactant may react adversely with other detergent ingredients when added to a liquid detergent. If the color instability of the detergent formulation is caused by the presence of chemical impurities, another solution is to take measures to reduce or eliminate the impurity level in the formulation. However, like the paste bleaching process, any refining process is expensive and time consuming.

Given the above, without resorting to paste bleaching or process refining procedures,
There continues to be a need to formulate color stable liquid handwash dishwashing products containing diamines, nitrogen-containing surfactants such as olefin-derived amine oxides, and perfumes.

Accordingly, it is an advantage of the present invention to provide a light liquid dishwashing composition containing olefin-derived amine oxides, perfumes, and diamines that not only provides improved cleaning benefits, but is also color stable. Is.

Related Background Art Shehad et al., US Pat. No. 5,023,376, Blez.
ard) et al., No. 5,442,113, and Blazard et al., No. 5,498,
No. 791 discusses methods of making amine oxides and amine oxide compositions, all of which are discussed and differentiated from the present invention in the text below.

SUMMARY OF THE INVENTION A color stable liquid handwash dishwashing detergent composition containing an olefin-derived amine oxide, a perfume, and a diamine comprises adding alkyleneaminomethylenephosphonic acid or a salt thereof to the detergent composition. It is currently confirmed that can be manufactured by. According to the present invention, whenever a liquid handwashing and dishwashing detergent composition contains both transition metal ions present as impurities and amine oxides derived from olefins together with diamines and perfumes, the addition of the abovementioned acids or salts. Have been found to provide these color stability benefits.

Therefore, according to a first aspect of the present invention, the detergent composition of the present invention comprises an effective amount of an organic diamine, an olefin-derived amine oxide surfactant, a perfume, a transition metal cation and the following formula: And an alkyleneaminomethylenephosphonic acid or salt thereof selected from the group consisting of:

[Chemical 4] (Wherein, X is -CH ₂ -PO ₃ M _y group, R represents include 2 to 6 carbon atoms,
It is an aliphatic or cycloaliphatic diradical having 2 or 3 carbon atoms in length. M is H
Or a non-transition metal cation that enhances water solubility. y is 1 or 2, n is an integer of 1 to 4, and m is an integer of 4 to 6. In this first aspect of the invention, the detergent composition has a pH of less than about 12.5 (measured in a 10% aqueous solution). )

In a second aspect of the invention, a detergent composition of the invention comprises an effective amount of a low molecular weight organic diamine having pK1 and pK2, an olefin-derived amine oxide surfactant, a perfume, and a transition metal cation. Alkyleneaminomethylenephosphonic acid or a salt thereof selected from the group consisting of about 0.0001% to about 0.5% of the following formula, wherein the pK1 and pK2 of the diamine are both about 8.0 to about It is in the range of 11.5.

[Chemical 5] (Wherein, X is -CH ₂ -PO ₃ M _y group, R represents include 2 to 6 carbon atoms,
It is an aliphatic or cycloaliphatic diradical having 2 or 3 carbon atoms in length. M is either H or a non-transition metal cation and enhances water solubility. y is 1 or 2, n is an integer of 1 to 4, and m is an integer of 4 to 6. ) This first of the invention
In this aspect, the detergent composition has a pH of less than about 12.5 (measured in a 10% aqueous solution).

The present invention also improves the color stability of a liquid dishwashing detergent composition comprising the step of adding to the detergent composition an alkyleneaminomethylenephosphonic acid or salt thereof selected from the group consisting of: Also included are method embodiments for.

[Chemical 6] (Wherein, X is -CH ₂ -PO ₃ M _y group, R represents include 2 to 6 carbon atoms,
It is an aliphatic or cycloaliphatic diradical having 2 or 3 carbon atoms in length. M is either H or a non-transition metal cation that enhances water solubility. y is 1 or 2, n is an integer of 1 to 4, and m is an integer of 4 to 6. In the formula, the composition is
It contains amine oxides, diamines, and fragrances, and has a pH (10
% Aqueous solution). )

All percentages, percentages and ratios used herein are expressed as percent weight, unless otherwise specified. All documents cited are, in relevant part, incorporated herein by reference. Unless otherwise stated, all pH values reported for the compositions are as measured as a 10% aqueous solution.

Detailed Description of the Invention Definitions The detergent compositions of the present invention comprise an "effective amount" or a "fat removal improving amount" of the individual components as defined herein. Diamine in the text and auxiliary components in the text
By "effective amount" is meant an amount sufficient to directionally or significantly improve the cleaning composition's ability to target at least some of the stains and stains at a 90% level of confidence. Thus, for compositions whose goal is to include certain oil stains, the formulator will use sufficient diamine to at least directionally improve the cleaning ability against such stains.

By “color stability” is meant a property of a detergent composition that explains that the color of the detergent composition tends to change over time. Color change can be monitored by continuously measuring the Hunter b value of the detergent composition over a period of time. Therefore, "improvement of color stability" means that the absolute amount of change in the Hunter b value of the detergent composition over a certain period by the addition of a certain component is the Hunter b value of the detergent composition over the same period before the addition of a certain component. It means less than the absolute amount of change. By "light liquid (LDL) detergent composition" is meant a detergent composition used in hand (ie, by hand) dishwashing.

The liquid detergent composition of the present invention contains alkyleneaminomethylenephosphonic acid or a salt thereof selected from the group consisting of the following formulas.

[Chemical 7] (Wherein, X is -CH ₂ -PO ₃ M _y group, R represents include 2 to 6 carbon atoms,
It is an aliphatic or cycloaliphatic diradical having 2 or 3 carbon atoms in length. M is either H or a non-transition metal cation that enhances water solubility. y is 1 or 2, n is an integer of 1 to 4, and m is an integer of 4 to 6. ) Aminopolyphosphonates, especially ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylene-phosphonic acid are preferred.

As discussed above, the addition of alkyleneaminomethylenephosphonic acid results in color stabilization of detergent compositions containing diamines, olefin-derived amine oxides, perfumes, and transition metal ions present as impurities. Greatly enhances sex. Without being bound by theory, it is believed that the previously mentioned color instabilities are the result of complex color-forming reactions catalyzed by transition metals and other components. By including a sequestering agent such as the phosphonic acid and its salts described above, the metal ion is complexed, leaving only a very low concentration of metal ion that is free to react with other components in solution. .

Phosphonic acids have already been used in amine oxide production reactions. For example,
The presence of transition metal impurities has the effect of reducing the efficiency of the peroxide / amine reaction,
It is known that the inclusion of phosphonic acid can reduce this effect. 6 of 1991
See US Pat. No. 5,023,376 issued to Shehad et al. On Jan. 11. However, in the present invention, the phosphonic acid or salt thereof is not added during the peroxide / amine reaction, but rather directly to the detergent composition containing the olefin-derived amine oxide. Unlike the Shehad patent, the order of addition is not an important or essential part of the invention.

US Pat. No. 5,442,1 issued to Blazard et al. On Aug. 15, 1995
No. 13, as well as its resolving US Pat. No. 5,449,791, issued to Blazard et al. On March 12, 1996, also describes a method of making amine oxides in the presence of phosphonic acid or its salts. Discuss. However, the Blazard patent does not address the issue of color stability, nor does it discuss the issue of contamination with transition metal impurities.

Solvents The present invention can contain various water-miscible liquids such as lower alkanols, diols, other polyols, ethers, amines, etc. and can be used in the present invention. Particularly preferred are C1-4 alkanols. When present, the composition preferably comprises at least about 0.01% by weight of the composition.
, More preferably at least about 0.5% by weight, and even more preferably at least about 1% by weight solvent. The composition will also preferably include no more than about 20% by weight of the composition, more preferably no more than about 10%, and even more preferably no more than about 8% by weight solvent.

These solvents may be used with an aqueous liquid carrier such as water, or may be used in the absence of any aqueous liquid carrier. The solvent is 20 ° C to 2
It is widely defined as a compound that is liquid at a temperature of 5 ° C and is not considered a surfactant. One of the hallmarks is that solvents tend to exist as discrete entities rather than as a broad mixture of compounds. Examples of suitable solvents for the present invention include:
Mention may be made of ethanol, propanol, isopropanol, 2-methylpyrrolidinone, benzyl alcohol and morpholine n-oxide. Preferred among these solvents are ethanol and isopropanol.

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

The liquid detergent composition of the present invention can also include either a diol or a polymeric glycol, or a mixture of both a diol and a polymeric glycol. Suitable diols and polymeric glycols for use in the present invention are Clark (
Clarke et al., "Diols and Polymeric Glycols for Improved Dishwashing Deterge
nt Compositions) ”and has P & G Incident Number 7408, 19
Further details are disclosed in Provisional Application No. 60 / 119,044, filed February 8, 1999, the contents of which are incorporated herein by reference.

In addition to the propylene glycol, polypropylene glycol and diols of the above incorporated applications, other glycols according to the formula HO-CR1R2-OH are suitable and can be used herein. , R1 and R2 are independently H or a C2-C10 saturated or unsaturated aliphatic hydrocarbon chain and / or ring). One such suitable glycol is dodecane glycol.

Suitable alkoxylated glycols that can be used herein have the formula R- (A) _n
According to —R ¹ —OH, where R is H, OH, straight-chain saturated or unsaturated alkyl having 1 to 20, preferably 2 to 15 and more preferably 2 to 10 carbon atoms. R ¹ is H or straight-chain saturated or unsaturated alkyl having 1 to 20, preferably 2 to 15 and more preferably 2 to 10 carbon atoms, A is an alkoxy group, preferably Ethoxy, methoxy, and / or propoxy.
n is 1-5, preferably 1-2). Suitable alkoxylated glycols to be used herein are methoxyoctadecanol and / or ethoxyethoxyethanol.

Suitable aromatic alcohols that can be used herein are according to the formula R-OH, where R is 1-20, preferably 1-15, more preferably 1-10 carbons. Alkyl-substituted or non-alkyl-substituted aryl groups having atoms). For example,
A suitable aromatic alcohol to be used herein is benzyl alcohol. Suitable aliphatic branched alcohols that can be used herein follow the formula R-OH (
In the formula, R is a branched saturated or unsaturated alkyl group having 1 to 20, preferably 2 to 15, more preferably 5 to 12 carbon atoms). Particularly suitable aliphatic branched alcohols to be used herein include 2-ethylbutanol and / or 2-methylbutanol.

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

Suitable straight chain C1-C5 alcohols that can be used herein are according to the formula R-OH, where R is a straight chain having 1 to 5, preferably 2 to 4 carbon atoms. Is a saturated or unsaturated alkyl group). Suitable straight chain C ₁ -C ₅ alcohol is methanol, ethanol, propanol or mixtures thereof. Other suitable solvents include, but are not limited to, butyl diglycol ether (BDGE), butyl triglycol ether, t-amyl alcohol, and the like. Particularly preferred solvents that can be used herein are
Butoxypropoxypropanol, butyl diglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol,
And mixtures thereof.

Other solvents suitable for use herein include propylene glycol derivatives such as n-butoxypropanol or n-butoxypropoxypropanol, the water-soluble CARBITOL® solvent, or water-soluble CELLOSOLVE. ) R
Solvents may be mentioned. The water-soluble carbitol R solvent is a compound of 2- (2-alkoxyethoxy) ethanols, wherein the alkoxy group is derived from ethyl, propyl or butyl, the preferred water-soluble carbitol is also known as butyl carbitol. It is 2- (2-butoxyethoxy) ethanol. The water-soluble cellosolve R solvent is a compound of 2-alkoxyethoxyethanols, and 2-butoxyethoxyethanol is preferable. Other suitable solvents include benzyl alcohol and
2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3
-Diols such as pentanediol, as well as mixtures thereof. Some preferred solvents for use herein are n-butoxypropoxypropanol, butyl carbitol (trade name), and mixtures thereof.

The solvent may also be selected from the group of compounds including mono-, di- and tri-ethylene glycol ether derivatives, butylene glycol ethers, and mixtures thereof. The molecular weight of these solvents is preferably less than 350,
It is more preferably 100 to 300, and even more preferably 115 to 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 ether are commercially available from Dow Chemical Company under the trade name "Dowano".
l) ”and under the trade name“ Arcosolv ”from Arco Chemical Company. Other preferred solvents, including mono- and di-ethylene glycol n-hexyl ethers, are available from Union Carbide.

Diamines As noted above, diamines are used herein in detergent compositions with detersive surfactants at levels effective to at least directionally improve cleaning performance. In the context of hand-washing dishwashing compositions, such "use levels" not only depend on the type and severity of the stains and stains, but also on the temperature of the wash water, the volume of wash water, and the amount of contact of the dishes with wash water. It can also change depending on the length of time that you are in

Since the habits and habits of detergent composition users vary considerably, the composition is preferably at least about 0.1% by weight of the composition, more preferably at least about 0.2.
%, Even more preferably at least about 0.25% by weight, and even more preferably at least about 0.5% by weight diamine. Also, the composition is preferably no more than about 15%, more preferably no more than about 10%, even more preferably no more than about 6%, even more preferably no more than about 5%, even more preferably no more than about 15% by weight of the composition. Will contain up to about 1.5% by weight diamine. In one of its several aspects, the present invention provides a means for enhancing the removal of greasy / greasy soils by combining certain diamines of the present invention with a surfactant. Greasy / oily "everyday" soils are mixtures of triglycerides, lipids, complex polysaccharides, fatty acids, inorganic salts and protein substances.

Accordingly, the diamines provide the benefit of improving the cleaning of fats and stubborn foods in combination with amphoteric and anionic surfactants in the specific ratios discussed below, thereby improving the invention. In the preferred embodiment of the method of (1), it is possible to eliminate or reduce the amount of divalent ions. This improved cleaning is a result of the properties of the diamine as a buffer to increase the alkalinity of dishwashing compositions. The excellent dissolution rate achieved by the removal of divalent ions is further enhanced by the formulator at significantly higher viscosities (eg, 1,000 centipoise or more) than conventional formulations while maintaining excellent dissolution and cleaning capabilities. To be able to produce hand dishwashing detergents, especially compact formulations. This has important potential advantages for producing higher viscosity compact products while maintaining acceptable dissolution. By "compact" or "ultra" is meant a detergent formulation with reduced moisture levels compared to conventional liquid detergents. In "compact" or "ultra" formulations, the moisture level is less than 70% by weight of the liquid dishwashing detergent composition, preferably less than 40%. The concentrated product described above offers advantages to consumers who obtain products that can be used in smaller quantities and to producers who obtain lower shipping costs. For compositions that are not intended to be concentrated, a suitable moisture level is less than about 85%, more preferably less than about 70% by weight of the liquid dishwashing detergent composition.

The diamine used in the present invention is preferably substantially free of impurities.
That is, "substantially free" means that the diamine has a purity of more than 95%, that is, preferably 97%, more preferably 99%, and even more preferably 9%.
9.5%, which means that it contains no impurities. Examples of impurities that may be present in commercially available diamines include 2-methyl-1,3-diaminobutane and alkylhydropyrimidines. Further, it is believed that the diamine should not contain oxidation reactants to avoid decomposition of the diamine and formation of ammonia.

As discussed in more detail below, when the composition contains an enzyme, it is important that the composition be free of hydrogen peroxide. Even small amounts of hydrogen peroxide can cause problems with enzyme-containing formulations. However, the diamine can react with any peroxide present and acts as an enzyme stabilizer, preventing hydrogen peroxide from reacting with the enzyme. The only drawback of this enzyme stabilization with diamines is that the nitrogen compounds formed are believed to generate a malodor that may be present in the diamine-containing composition. By acting the diamine as an enzyme stabilizer,
The diamine may interfere with providing the composition with the benefits that it should be added to the composition initially to accomplish, namely, grease cleaning, foaming, dissolution, and low temperature stability. Thus, even though the diamines may form malodorous compounds, reducing the amount of available diamines present to perform their initial role,
Present as an impurity in the compositions of the present invention by using components that are substantially free of hydrogen peroxide or other bleaching species and / or by using non-diamine antioxidants. It is preferred to minimize the amount of hydrogen peroxide.

Preferred organic diamines have pK1 and pK2 in the range of about 8.0 to about 11.5, preferably about 8.4 to about 11, and even more preferably about 8.6 to about 10.
It is in the range of 75. A preferable substance in consideration of capacity and supply is 1,3-
Bis (methylamine) -cyclohexane (pKa = 10-10.5), 1,3 propanediamine (pK1 = 10.5, pK2 = 8.8), 1,6 hexanediamine (pK1 = 11, pK2 = 10) , 1,3-pentanediamine (Dietec EP
) (PK1 = 10.5, pK2 = 8.9) and 2-methyl 1,5 pentanediamine (Dietec A) (pK1 = 11.2, pK2 = 10.0). Other preferred materials are primary / primary diamines with alkylene spacers in the C4 to C8 range. It is generally believed that primary diamines are preferred over secondary and tertiary diamines.

Definitions of pK1 and pK2 As used herein, “pKa1” and “pKa2” are quantities of the type collectively known to those skilled in the art as “pKa”. pKa is used in the text as it is commonly known to those skilled in the chemical arts. The values referred to in this text are "Critical Stability Constants, Volume 2,
Amine ”(Smith and Martell, Plenham Press, New York and London, 1975) and the like. Further information on pKa can be obtained from the prints of the relevant companies, such as the information provided by DuPont, the supplier of diamines.

As a basic definition in the text, all pKas of diamines are 0.
It is specified for ionic strength between 1 and 0.5M. pKa is an equilibrium constant that can change with temperature and ionic strength, so the values reported in the literature may not match depending on the measurement method and conditions. To disambiguate, suitable conditions and / or references used for the pKa of the present invention are as defined herein or as defined in "Critical Stability Constant, Volume 2, Amine". On the street. One typical measurement method is potentiometric titration of acid with sodium hydroxide, which is described in "The Chemist's Ready Reference Handbook".
) ”(Sugar and Dean, McGraw-Hill, New York, 1990)
PKa by the appropriate method as described and referenced in

It has been determined that substituents and structural modifications that reduce pK1 and pK2 to less than about 8.0 are undesirable and result in loss of performance. This includes ethoxylated diamines, hydroxyethyl substituted diamines, diamines having oxygen in the beta (and less gamma) position relative to the nitrogen of the spacer group (eg Jeffamine EDR14.
Substitutions leading to 8) can be included. Furthermore, ethylenediamine-based materials are unsuitable.

[0040]   The diamines useful herein can be defined by the structure:

[Chemical 8] _Where R _2-5 is independently selected from H, methyl, —CH ₃ CH ₂ , and ethylene oxide. C _x and C _v are independently selected from a methylene group or a branched alkyl group. , X + y is about 3 to about 6. A is optionally present and p of the diamine.
It is selected from electron donating or attracting moieties selected to adjust Ka to the desired range. ) If A is present, then x and y must both be 1 or greater.

Examples of preferred diamines are Phillip Kyle Vinson
Son) et al., "Dishwashing Detergent Compositions C Containing Organic Diamines to Improve Oil Cleaning, Foaming, Low Temperature Stability and Dissolution.
ontaining Organic Diamines for Improved Grease Cleaning, Sudsing, Low Te
P & G case number 7 under the heading "Mperature Stability and Dissolution"
167P, serial number 60 / 087,693, serial number 1998, 6
It can be found in the pending provisional patent application filed on March 2, which is hereby incorporated by reference.

Anionic Surfactants Anionic surfactants useful in the present invention are preferably linear alkylbenzene sulfonates, alpha olefin sulfonates, paraffin sulfonates, alkyl ester sulfonates, alkyl sulfates, alkyls. It is selected from the group consisting of alkoxysulfates, alkylsulfonates, alkylalkoxycarboxylates, alkylalkoxylated sulfates, sarcosinates, taurates, and mixtures thereof. Typically, an effective amount of about 0.5% to about 90%, preferably about 5% to about 50%, more preferably about 10% to about 30% by weight of the anionic detersive surfactant is present. Can be used in inventions.

Suitable examples of anionic surfactants are Chandrika Kast.
uri) et al. “Liquid Detergent Composit containing a polymeric foam enhancer
"Ions Comprising Polymeric Suds Enhancers)" with P & G Incident Number 6938P, Serial Number 60 / 066,344, 1997 1
It can be found in the pending provisional patent application filed January 21, which is incorporated herein by reference. Further examples of suitable anionic surfactants are "
Surface Active Agents and Detergents "(Volumes I and II by Schwarz, Perry and Berch). Also, various such surfactants are described generally in U.S. Pat. No. 3,929,678 issued Dec. 30, 1975 to Laughlin et al. At column 23, line 58 to column 29, line 23. Disclosed in. Suitable anionic surfactants are further described in US Pat. No. 5,415,15 issued to Ofosu-Asante et al. On May 16, 1995.
No. 814, all of which are incorporated herein by reference.

Amphoteric Surfactants Amphoteric surfactants useful in the present invention are preferably selected from amine oxide surfactants. Amine oxides are semi-polar nonionic surfactants that contain one alkyl moiety having from about 10 to about 18 carbon atoms, as well as from about 1 to about 3 carbon atoms.
Water-soluble amine oxide having two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups, one alkyl moiety having from about 10 to about 18 carbon atoms, and from about 1 to about 1 carbon atoms. A water-soluble phosphine oxide having two moieties selected from the group consisting of about 3 alkyl groups and hydroxyalkyl groups, one alkyl moiety having about 10 to about 18 carbon atoms, and about 1 carbon atom. Water soluble sulfoxide having a moiety selected from the group consisting of 1 to about 3 alkyl and hydroxyalkyl moieties.

Semi-polar nonionic detersive surfactants include amine oxide surfactants having the formula:

[Chemical 9] (Wherein R ³ is an alkyl, hydroxyalkyl, or alkylphenyl group having about 8 to about 22 carbon atoms, or a mixture thereof. R ⁴ is about 2 to about 3 carbon atoms. Alkylene or hydroxyalkylene group or a mixture thereof, x is 0 to about 3, and each R ⁵ is an alkyl or hydroxyalkyl group having about 1 to about 3 carbon atoms, or about 1 to about 3 R ⁵ groups can be joined together, for example by oxygen or nitrogen atoms, to form a cyclic structure.

These amine oxide surfactants include, in particular, C ₁₀ -C ₁₈ alkyldimethylamine oxides and C ₈ -C ₁₂ alkoxyethyldihydroxyethylamine oxides. Further, amine oxides such as propylamine oxide represented by the following formula are also suitable.

[Chemical 10] Wherein R ₁ is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical, each alkyl and alkoxy having about 8 to about 18 carbon atoms. R ₂ and R ₃ are methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl,, n is 0 to about 10.)

Further suitable classes of amine oxide semipolar surfactants include compounds having the formula: and mixtures of compounds.

[Chemical 11] Wherein R ₁ is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical, each alkyl and alkoxy having about 8 to about 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 about 10.) The amine oxide of the formula Particularly preferred.

[Chemical 12] (Wherein R ₁ is C _10-14 alkyl and R ₂ and R ₃ are methyl or ethyl.) Because of their low foaming properties, it is also desirable to use long chain amine oxide surfactants, These are US Pat. No. 4,316,824 (Puncheri),
Further details are provided in US Pat. Nos. 5,075,501, and 5,071,594, which are incorporated herein by reference.

Other suitable non-limiting examples of amphoteric detersive surfactants useful in the present invention include amidopropyl betaine and derivatives of aliphatic or heterocyclic secondary and tertiary amines, where Wherein the aliphatic moiety is straight or branched, one of the aliphatic substituents has about 8 to about 24 carbon atoms, and at least one aliphatic substituent is anionic water-solubilized. Including a group. Further examples of suitable amphoteric surfactants are given in "Surfactants and Detergents" (Volumes I and II by Schwarz, Perry and Berch), incorporated herein by reference. The amphoteric surfactant is preferably present in the composition in an effective amount, more preferably from about 0.1% to about 20%, even more preferably from about 0.1% to about 15%, and even more preferably. Preferably about 0.5% to about 10% is present.

Second Surfactant The second detersive surfactant can be selected from the group consisting of nonionic, cationic, amphoteric, zwitterionic, and mixtures thereof. By selecting the type and amount of detergent surfactant, along with other adjunct ingredients disclosed herein,
The detergent compositions of the present invention can be formulated for use in the context of laundry cleaning and other different cleaning applications, especially including dishwashing. The particular surfactant used can, therefore, vary widely depending on the particular end use application envisioned. Suitable second surfactants have P & G Case No. 6938P, Application Serial No. 60 / 066,344, entitled "Liquid Detergent Compositions Containing a Polymeric Foam Enhancing Agent," incorporated above. It is described in detail in the pending provisional patent application of Chandrika Kasuturi et al.

Anionic Surfactant to Amphoteric Surfactant to Diamine Ratio In the compositions of the present invention, the anionic surfactant: amphoteric surfactant: diamine ratio is about 100: 40: 1 to about 9 in molar ratio. : 0.5: 1. Preferably, the anionic surfactant: amphoteric surfactant: diamine ratio is about 27: 8: 1 in molar ratio.
Is about 11: 3: 1. 11. Detergent compositions containing anionic surfactants, amphoteric surfactants and diamines in specific ratio ranges provide improved low temperature stability.
It has been found that a pH below 5 provides improved fat removal and stubborn food cleaning benefits, improving hard water cleaning. In another aspect of the invention, a molar ratio of anionic surfactant to diamine of greater than 9: 1, preferably greater than 20: 1 provides improved low temperature stability and provides better oil removal and It has been found that the advantages of stubborn food cleaning are brought about and that hard water cleaning is improved.

Optional Detergent Component Polymeric Foam Stabilizer The compositions of the present invention can optionally include a polymeric suds stabilizer. These polymeric suds stabilizers provide expansion of suds volume and suds duration without sacrificing the oil-cutting ability of the liquid detergent composition. These polymeric suds stabilizers are i) homopolymers of (N, N-dialkylamino) alkyl acrylates having the formula:

[Chemical 13] Where 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, and n is 2 About 6) and ii) (i) and copolymers of the formula:

[Chemical 14] Where R ¹ is hydrogen, C1-C6 alkyl, and mixtures thereof, and (ii
) To (i) is from about 2: 1 to about 1: 2. ) The molecular weight of the polymeric foam booster determined by conventional gel permeation chromatography is about 1.0.
00 to about 2,000,000, preferably about 5,000 to about 1,000,
000, more preferably about 10,000 to about 750,000, even more preferably about 20,000 to about 500,000, even more preferably about 35,000 to about 20.
It is 10,000. The polymeric suds stabilizer is optionally of a salt, either inorganic or organic, such as, for example, citrate, sulphate, acetate or nitrate of (N, N-dimethylamino) alkyl acrylate. Can exist in a form.

One preferred polymeric suds stabilizer is a (N, N-dimethylamino) alkyl acrylate ester, ie:

[Chemical 15] When present in the composition, the polymeric suds enhancer is present in the composition at about 0.01% by weight.
Can be present from about 15% to about 15%, preferably from about 0.05% to about 10%, more preferably from about 0.1% to about 5%.

Builders The composition according to the invention may further comprise a builder system. Builders such as citric acid and citrate impair the stability of enzymes in LDL compositions, thus reducing or completely eliminating the amount of builder salt normally utilized in LDL compositions incorporating propylene glycol as a builder. It is desirable to do. When the detergent composition comprises propylene glycol solvent as part or all of the detergent carrier, the enzyme is more stable and less or no builder salt is needed. When it is desired to use builders, any conventional builder system is used herein, including materials such as aluminosilicate materials, silicates, polycarboxylates and fatty acids, ethylenediaminetetraacetate salts and the like. Suitable for. Although less preferred for obvious environmental reasons, phosphate builders can also be used herein.

Polycarboxylate builders suitable for use herein include citric acid, preferably in the form of water-soluble salts, succinic acid derivatives of the formula R—CH (COOH) CH ₂ (COOH). _Where R is C _10-20 alkyl or alkenyl, preferably C _12-16 . Alternatively, R may be substituted with hydroxyl, sulfosulfoxyl, or sulfone substituents. Specific examples include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate, 2 succinate.
-Tetradecenyl. The succinate builder is preferably used in the form of water soluble salts including sodium, potassium, ammonium and alkanol ammonium salts. Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acids, as described in US Pat. No. 4,663,071. Is. Suitable fatty acid builders for use herein are saturated or unsaturated _C10-18 fatty acids, as well as the corresponding soaps, especially for liquid implementations herein.
Preferred saturated species have 12 to 16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acid is oleic acid. Other preferred builder systems for liquid compositions are based on dodecenyl succinic acid and citric acid. If a detersive builder salt is included, it is included in an amount of 0.5% to 50% by weight of the composition, preferably 5% to 30%, most commonly 5% to 25%.

Enzymes The detergent compositions of the present invention can further include one or more enzymes that provide the benefit of detergency. Such enzymes include cellulase, hemicellulase, peroxidase, protease, glucoamylase, amylase, lipase, cutinase, pectinase, xylanase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, β-glucanase, Enzymes selected from arabinosidase, or mixtures thereof. A preferred combination is a detergent composition with a mixture of conventional applicable enzymes such as proteases, amylases, lipases, cutinases and / or cellulases. The enzyme, when present in the composition, is about 0.0001% to about 5% active enzyme by weight of the detergent composition. A preferred proteolytic enzyme then consists of Alcalase® (Novo Industri A / S), BPN ′, Protease A and Protease B (Genencor), and mixtures thereof. Selected from the group. Protease B is most preferred. Preferred amylase enzymes include TERMAMYL, registered trademark, DURAMYL, and the amylase enzymes described in International Patent Nos. 9418314 (Zennencor International) and 9402597 (Novo). To be

Further, non-limiting examples of suitable and preferred enzymes include pending application “grease cleansing, foaming, low temperature stability and lysis” having P & G Case No. 7167P and Application Serial No. 60 / 087,693. To improve dishwashing detergent compositions containing organic diamines "and is incorporated herein by reference. Hydrogen peroxide and builders such as citric acid and citrate impair the stability of enzymes in LDL compositions, so it is desirable to reduce or eliminate the level of these compounds in compositions containing enzymes. Hydrogen peroxide is often found as an impurity in surfactants and surfactant pastes. Thus, the preferred level of hydrogen peroxide in the amine oxide or amine oxide surfactant paste is 0-40 ppm, more preferably 0-15 ppm. Amine impurities in amine oxides and betaines, if present, should be minimized to the levels listed above for hydrogen peroxide.

Magnesium Ions Divalent ions are preferably omitted from LDL compositions prepared according to the present invention, although alternative embodiments of the present invention may include magnesium ions. It is desirable to exclude all divalent ions from the LDL compositions of the present invention as they may slow dissolution, compromise rinsability, and degrade low temperature stability properties. Furthermore, formulating such divalent ion-containing compositions in an alkaline pH matrix may be difficult due to the incompatibility of divalent ions, especially magnesium, and hydroxide ions.

Nevertheless, the presence of magnesium ions offers several benefits. Notably, the inclusion of such divalent ions improves the cleaning of greasy soils for various LDL compositions, especially those containing alkyl ethoxycarboxylates and / or polyhydroxy fatty acid amides. This is especially true when the composition is used in soft water containing few divalent ions. However, the present invention allows these benefits to be obtained without the inclusion of divalent ions. In particular, by containing the organic diamine in combination with the amphoteric and anionic surfactants in the specific ratios discussed above, improved oil cleaning can be achieved without divalent ions, while the enzyme is present Has been shown to improve the skin-friendly performance of the LDL composition.

If included in an alternative embodiment of the LDL composition of the present invention, the magnesium ion is present in an amount of about 0.01% to 1% by weight, preferably about 0.015% by weight.
It is present at an activity level of 0.5% by weight, more preferably about 0.025% to 0.1% by weight. The amount of magnesium ions present in the composition of the present invention will also depend on the total amount of surfactant present in the composition, including the amount of alkyl ethoxycarboxylate and polyhydroxy fatty acid amide. Let's do it. Preferably, magnesium ions are added to the compositions of the invention as hydroxides, chlorides, acetates, sulphates, formates, oxides, nitrates and the like. During storage, in the presence of compositions containing moderate concentrations of hydroxide ions, the stability of these compositions deteriorates due to the formation of hydroxide precipitates, thus leading to the formation of certain chelates. It may be necessary to add an agent. Suitable chelating agents are discussed further below and in US Pat. No. 5,739,092 (issued to Ofos-Asante on April 14, 1998, incorporated herein by reference).

Fragrances Fragrances and fragrance ingredients useful in the compositions and processes of the invention include aldehydes,
Includes a wide variety of natural and synthetic chemical moieties including, but not limited to, ketones, esters, and the like. It also contains various natural extracts and essences that can include a complex mixture of ingredients such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, and cedar. Is also included. The finished perfume can include highly complex mixtures of such ingredients. The finished perfume typically comprises from about 0.01% to about 2% by weight of the detergent composition herein, with the individual perfume ingredients being about 0.0001% of the finished perfume composition. ~ 90% can be made up. A non-limiting example of perfume ingredients useful herein is the pending provisional patent application "Fat cleansing," having P & G Case No. 7167P, Application Serial No. 60 / 087,693, incorporated above. Dishwashing Detergent Compositions Containing Organic Diamines to Improve Foaming, Low Temperature Stability and Dissolution ".

Chelating Agents The detergent compositions herein also optionally include one or more iron and / or
Or it may contain a manganese chelating agent. Such chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctional substituted aromatic chelating agents, and mixtures thereof, all of which are defined below. It Without wishing to be bound by theory, it is believed that the benefit of these materials is due in part to their special ability to remove iron and manganese ions from the wash solution by the formation of soluble chelates.

Aminocarboxylic acid salts useful as optional chelating agents include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraaminehexaacetate. , Diethylenetriaminepentaacetic acid salt, and ethanol di-glycine, alkali metal, ammonium, and substituted ammonium salts therein, and mixtures thereof. Also, at least when total phosphorus is allowed at low levels in detergent compositions,
Aminophosphonic acids are also suitable for use as chelating agents in the compositions of the present invention and include ethylenediaminetetrakis (methylenephosphonate) such as DEQUEST. These aminophosphonates preferably contain no alkyl or alkenyl groups with more than about 6 carbon atoms. Polyfunctionally substituted aromatic chelating agents are also useful in the compositions herein.
U.S. Pat. No. 3,812 issued May 21, 1974 to Connor et al.
, 044. Preferred compounds of this type are 1,2 in the acid form
A dihydroxydisulfobenzene such as dihydroxy-3,5-disulfobenzene.

Preferred biodegradable chelating agents for use herein are US Pat. No. 4,704,233 (Hartman and Perkins, November 3, 1987).
Ethylenediaminedisuccinate (“EDDS”), especially
S, S] isomer. The compositions herein can also include a water soluble methylglycine diacetate (MGDA) salt (or acid form) as a chelating agent or cobuilder. Similarly, so-called "weak" builders such as citrate can be used as chelating agents. If utilized, these chelating agents will generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agent will comprise from about 0.1% to about 3.0% by weight of such composition.
It will make up the weight percent.

Composition pH The pH of the composition of the present invention (measured as a 10% aqueous solution) is less than about 12.5,
Preferably less than about 10.5. The dishwashing composition of the present invention, when used,
That is, if a composition having a pH higher than 7 is more effective, it is generally preferred in the composition as it is exposed to the acid forces generated by food stains when applied diluted to soiled dishes. And a buffer that can provide a higher alkaline pH in the dilute solution. The dishwashing composition of the present invention therefore has about 0.1% by weight.
~ 15 wt%, preferably about 1 wt% to 10 wt%, most preferably about 2 wt%
Will contain ~ 8 wt% buffer. The pKa value of this buffer should be about 0.5-1.0 pH units lower than the desired pH value of the composition (determined as above). Preferably, the buffer's pKa should be from about 7 to about 12. Under these conditions, the buffer most effectively controls pH while using its minimum amount. Preferred inorganic buffer / alkalinity sources include alkali metal carbonates, alkali metal hydroxides, and alkali metal phosphates, such as sodium carbonate, sodium hydroxide, sodium polyphosphate, and the like.

The optional buffer (used in compositions having a pH greater than 7) may be the active detergent itself, or it may be used alone in this composition to maintain an alkaline pH. It may be the low molecular weight organic or inorganic material used. The preferred buffering agent for the compositions of the present invention is a nitrogen-containing material. Some examples are amino acids such as lysine, and lower alcohol amines such as mono-, di-, and tri-ethanolamine. The diamines described in detail above also serve as buffering agents and are preferred buffering agents. A preferred buffer system for use in the detergent composition of the present invention is a combination of 0.5% diamine and 2.5% citric acid, and 0.
A combination of 5% diamine, 0.75% potassium carbonate and 1.75% sodium carbonate is included. Other preferred nitrogen containing buffers are tri (hydroxymethyl) aminomethane (HOCH2) 3CNH3 (TRIS), 2-amino-2-ethyl-.
1,3-propanediol, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanol, disodium glutamate, N-methyldiethanolamide, 1,3-diamino-propanol N, N'-tetra-methyl-1,3-diamino-2-propanol, N, N-bis (2-hydroxyethyl) glycine (baicine), and N-tris (hydroxymethyl) methylglycine (tricine). Mixtures of any of the above are also acceptable. For additional buffers, see McCutcheon's "Emulsifiers and Detergents (EMUL
SIFIERS AND DETERGENTS) "(North American version, 1997, McCutcheon Division, MC Publisher Kirk), and International Patent Application No. 95/07971. Both of which are incorporated herein by reference.

Other Ingredients The detergent composition will more preferably comprise one or more cleaning adjuncts selected from: soil release polymers, polymeric dispersants, polysaccharides, abrasives,
Bactericides and other antibacterial substances, tarnish inhibitors, builders, enzymes, dyes, buffers, fungicides or mold control agents, anthelmintics, fragrances, hydrotropes, thickeners, processing aids, foam enhancers, gloss Agents, corrosion inhibitors, stabilizers, antioxidants, and chelating agents. A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein and other active ingredients, carriers, hydrotropes, antioxidants, processing aids, dyes or pigments. , Solvents for liquid formulations, solid fillers for rod-like compositions, and the like. If high foaming properties are desired, the foam enhancing agent, such as C ₁₀ -C ₁₆ alkanolamides can typically be incorporated in the composition at from 1% to 10% level. C ₁₀ -C ₁₄ monoethanol and diethanol amides illustrate a typical class of such suds enhancers. It is also advantageous to use such suds boosters with high sudsing co-surfactants such as the amine oxides, betaines and sultaines described above.

Antioxidants can optionally be added to the detergent compositions of the present invention. These are detergent compositions such as 2,6-di-t-butyl-4-methylphenol (BHT), carbamate, ascorbate, thiosulfate, monoethanolamine (MEA), diethanolamine and triethanolamine. Any of the conventional antioxidants used in. Antioxidants, when present, are present in the composition at about 0.00
It is preferably present from 1% to about 5% by weight. The various cleaning ingredients used in the compositions of the invention are optionally further stabilized by imbibing the ingredients on a porous hydrophobic substrate and then coating the substrate with a hydrophobic coating. be able to. Preferably, the cleaning component is mixed with the surfactant before being absorbed on the porous substrate. In use, the wash components are released from the substrate into the aqueous wash solution to perform its intended wash function.

To describe this technique in more detail, porous hydrophobic silica (trade name SIP
ERNAT D10, Degussa) is admixed with a proteolytic enzyme solution containing 3% -5% of C _13-15 ethoxylated alcohol (EO 7) nonionic surfactant.
Typically, the enzyme / surfactant solution is 2.5 times the weight of silica. The resulting powder is dispersed in silicone oil (various silicone oil viscosities in the range 500-12,500 can be used) with stirring. The silicone oil dispersion obtained is emulsified or else added to the final detergent matrix. By this means, the components such as enzymes, bleaching agents, bleaching activators, bleaching catalysts, photoactivators, dyes, fluorescent agents, fabric conditioners and hydrolyzable surfactants described above are used in liquid laundry detergent compositions. Can be "protected" for use in detergents containing. Further, these hand dishwashing detergent embodiments preferably further comprise a hydrotrope. Suitable hydrotropes include sodium, potassium, ammonium, or water soluble substituted ammonium salts of toluene sulfonic acid, naphthalene sulfonic acid, cumene sulfonic acid, xylene sulfonic acid.

Non-Aqueous Liquid Detergents The manufacture of liquid detergent compositions containing non-aqueous carrier media is described in US Pat. No. 4,753,
No. 570, No. 4,767,558, No. 4,772,413, No. 4,8
89,652, 4,892,673, British Patent Publication No. A-2,158,
838, British Patent Publication No. A-2,195,125, British Patent Publication No. A-2,
195,649, US Pat. No. 4,988,462, US Pat. No. 5,266.
233, European Patent Publication No. A-225,654 (June 16, 1987), European Patent Publication No. A-510,762 (October 28, 1992), European Patent Publication No. A-54.
0,089 (May 5, 1993), European Patent Publication No. A-540,090 (93).
May 5, 2013), U.S. Pat. No. 4,615,820, European Patent Publication No. A-565.
017 (October 13, 1993), European Patent Publication No. A-030,096 (81
June 10, 2002), which are incorporated herein by reference. Such compositions can include various particulate cleaning components stably suspended therein. Such a non-aqueous composition therefore has a liquid phase (LIQUID P
HASE) and optionally but preferably solid phase (SOLID PHASE), all of which are described in more detail below and in the references.

The composition of the present invention can be used to form an aqueous cleaning solution for hand dishwashing. Generally, an effective amount of such a composition is added to water to form such an aqueous cleaning or soaking solution. The aqueous solution so formed is then contacted with the dishes, dishes and cooking utensils. An effective amount of a detergent composition herein, added to water to form an aqueous cleaning solution, comprises an amount sufficient to form about 500 to 20,000 ppm of the composition in aqueous solution. You can More preferably, about 800-5,000 ppm of the detergent composition herein will be provided in an aqueous cleaning solution. The following examples are illustrative of the invention but are not intended to limit the scope or otherwise define it. All percentages, percentages and ratios used herein are expressed as percent weight, unless otherwise specified.

Examples Table I Light liquid dishwashing detergents are as follows. Composition II comprises phosphonate and is prepared according to the present invention. Composition I is the same except that it contains no phosphonate.

[0072]

[Table 1]

1: C12-13 alkylethoxy sulfonate containing an average of 0.6 ethoxy groups. 2: C ₁₂ ~C ₁₄ amine oxides. 3: The polymer is (N, N-dimethylamino) ethyl methacrylic acid ester homopolymer. 4: The nonionic surfactant is a C10 alkyl ethoxylated surfactant having 8 ethoxy groups or a C10 alkyl ethoxylated surfactant having 8 ethoxy groups. 5: 1,3 bis (methylamine) -cyclohexane. 6: Diethylenetriamine penta (methylenephosphonic acid).

A color stability test to evaluate the relative color stability of Compositions I and II measured the visually perceived and analytically measured colors for each of the above compositions. Color can be measured analytically by the Hunter color measurement test, and solution color is determined by reflectance spectroscopy. For this test, Hunter "
Only the "b value" is displayed.

[0075]

[Table 2]

The change in Hunter b value after aging for compositions containing phosphonates was significantly less than that for compositions without phosphonates, with compositions containing phosphonates producing more color than compositions without phosphonates. It was shown that the stability was high. This result is confirmed by the visual appearance of the product before and after aging.

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, K E, LS, MW, SD, SL, SZ, TZ, UG, ZW ), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, C R, CU, CZ, DE, DK, DM, EE, ES, FI , GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, K Z, LC, LK, LR, LS, LT, LU, LV, MA , MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, S K, SL, TJ, TM, TR, TT, TZ, UA, UG , US, UZ, VN, YU, ZA, ZW (72) Inventor Embleton, Garry Kenneth             Belgium, 1853 Grimbergen, Str.             Rhombaek-Befère, Left 68             - (72) Inventor Clark, Joanna Margaret             Belgium, 1000 Brussels, Ryu             ー, Van, Kampenwoo 12 (72) Inventor Castro, Artemio             West, Chi, Ohio, United States             Esther, Comanche, Drive 6330 F-term (reference) 4H003 AC08 AC14 BA12 BA15 DA17                       EA16 EA25 EB04 EB06 EB13                       EB22 EB24 EB30 FA14 FA18                       FA26

Claims (10)

[Claims] 1. A liquid dishwashing detergent composition suitable for use in hand dishwashing, comprising: a) an effective amount of an organic diamine, b) an olefin-derived amine oxide surfactant, and c) a perfume. D) a transition metal cation present as an impurity, and e) (Wherein, X is -CH ₂ -PO ₃ M _y radical, R having from 2 to 6 carbon atoms, and is an aliphatic or alicyclic diradical of 2 or 3 carbon atoms in length. M is either H or a non-transition metal cation that enhances water solubility, y is 1 or 2, n is an integer from 1 to 4 and m is an integer from 4 to 6. Detergent compositions Is 12.5
It has a lower pH (measured in 10% aqueous solution). ) An alkyleneaminomethylenephosphonic acid or salt thereof selected from the group consisting of: 2. The liquid dishwashing detergent composition according to claim 1, wherein the transition metal cation is an iron cation. 3. A liquid dishwashing detergent composition according to claim 1, characterized in that the composition is characterized by 0.0001% to 0.5% of alkyleneaminomethylenephosphonic acid or salts thereof. object. 4. The liquid dishwashing detergent composition according to claim 1, wherein the transition metal cation is an Fe ³⁺ cation. 5. The method according to claim 1, wherein the liquid dishwashing detergent composition contains an organic diamine, an olefin-derived amine oxide, and a fragrance. 6. The organic diamine is represented by: _Where R _2-5 is independently selected from H, methyl, ethyl, and ethylene oxide. C _x and C _v are independently selected from a methylene group or a branched alkyl group and x + v is 3 To 6. A is optionally present and is selected from electron donating or withdrawing groups selected to adjust the pKa of the diamine to the desired range, when A is present both x and y are 2 The liquid dishwashing detergent composition according to any one of claims 1 to 5, which is selected from the group consisting of: 7. A p less than 12.5 characterized by a) a transition metal cation present in trace amounts as impurities, and b) an olefin-derived amine oxide surfactant.
A method for enhancing the color stability of a liquid detergent composition having H (measured in a 10% aqueous solution), comprising: (Wherein, X is -CH ₂ -PO ₃ M _y radical, R having from 2 to 6 carbon atoms, and is an aliphatic or alicyclic diradical of 2 or 3 carbon atoms in length. M is either H or a non-transition metal cation that enhances water solubility, y is 1 or 2, n is an integer from 1 to 4, and m is an integer from 4 to 6.) A method characterized by the step of adding an alkyleneaminomethylenephosphonic acid or salt thereof selected from the group, preferably 0.0001% to 0.5%. 8. The method according to claim 1, wherein the liquid detergent composition is further characterized by an organic diamine. 9. The method according to claim 1, wherein the transition metal cation is an iron cation. 10. The method according to claim 1, wherein the liquid detergent composition is characterized by an anionic surfactant and a solvent and is suitable for use in a manual dishwashing operation.