CA2055045C - Light-duty dishwashing detergent composition containing an alkyl ethoxy carboxylate surfactant and calcium ions - Google Patents
Light-duty dishwashing detergent composition containing an alkyl ethoxy carboxylate surfactant and calcium ionsInfo
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- CA2055045C CA2055045C CA 2055045 CA2055045A CA2055045C CA 2055045 C CA2055045 C CA 2055045C CA 2055045 CA2055045 CA 2055045 CA 2055045 A CA2055045 A CA 2055045A CA 2055045 C CA2055045 C CA 2055045C
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Abstract
A light-duty liquid or gel dishwashing detergent composition containing an alkyl ethoxy carboxylate surfactant mixture and calcium ions. The composition may require a calcium chelating agent, particularly at pH levels above 9, to prevent the formation of CaCO3 precipitates during storage. The compositions exhibit good grease removal while manifesting mildness to the skin. The compositions also have good storage stability. A preferred type of dishwashing detergent composition is in the liquid form. High pH and calcium ions of the compositions increase grease removal properties while maintaining mildness.
Description
LIGHT-DUTY DISHWASHING DETERGENT COMPOSITION CONTAINING
AN ALKYL ETHOXY CARBOXYLATE SURFACTANT AND CALCIUM IONS
Kofi Ofosu-Asante Technical Field The present invention relates to light-duty liquid or gel dishwashing detergent compositions containing alkyl ethoxy carboxylate surfactants (alternatively labeled alkyl polyethoxy carboxy methylates, alkyl polyethoxy acetates, alkyl polyether carboxylates, etc.) of the type disclosed in U.S. Pat. Nos.
AN ALKYL ETHOXY CARBOXYLATE SURFACTANT AND CALCIUM IONS
Kofi Ofosu-Asante Technical Field The present invention relates to light-duty liquid or gel dishwashing detergent compositions containing alkyl ethoxy carboxylate surfactants (alternatively labeled alkyl polyethoxy carboxy methylates, alkyl polyethoxy acetates, alkyl polyether carboxylates, etc.) of the type disclosed in U.S. Pat. Nos.
2,183,853; 2,653,972; 3,003,954; 3,038,862; 3,741, 911; and 3,941,710; British Pat. Nos. 456,517 and 1,169,496; Canadian Pat.
No. 912,395: French Pat. Nos. 2,014,084 and 2,042,793.
Backqround Art There has been considerable demand for light-duty liquid or gel dishwashing detergents capable of providing good grease removal. These compositions are well known in the art and are described, for example, in U.S. Pat. Nos. 4,316,824 (Pancheri), 4,681,704 (Bernardino et al.), 4,133,779 (Hellyer et al.), and 4,615,819 (Leng et al). These compositions, although being good grease and soil cleaners, can be harsh to the skin under certain conditions, particularly when used during the dry winter months.
Likewise, the art is replete with detergent compositions that are mild to the skin. These mild compositions often contain sulfates of highly ethoxylated alcohols. See, for example, U.S.
Pat. No. 3,743,233. Rose and Thiele. Betaines have also been suggested for use in improving mildness of a liquid dishwashing composition. See, for example, U.S. Pat. No. 4,555,360 (Bissett et al). Alkyl ethoxy carboxylates are also known as mild surfactants for use in liquid detergent compositions. These alkyl ethoxy carboxylate surfactants, however, have been described as being poor in their grease cutting ability and require the use of other surfactants to achieve the desired cleaning.
r-~
- A -20~504~
Rarely have these two important features of mildness and grease cutting ability been incorporated in one product. It is generally thought that one must be sacrificed for the benefit of the other. It has been discovered that detergent compositions containing a particular alkyl ethoxy carboxylate surfactant mixture provide a detergent composition that exhibits good grease removal while manifesting mildness to the skin- This dual benefit is enhanced when the composition has a pH of from about 7 to 11 and contain a small amount of divalent ions, e.g. magnesium.
io These alkaline compositions containing magnesium ions may exhibit poor stability during storage though. In an alkaline environment, the precipitation of magnesium hydroxide can be a substantial problem. Therefore, it is an object of this invention to provide a detergent composition that exhibits good grease ~ 1~ removal and mildness to the skin while providing superior stability during storage of the composition.
Summarv of the Invention The present invention relates to a light-duty liquid or gel, preferably liquid, dishwashing detergent composition comprising:
(a) from about 5% to 70% of a surfactant mixture comprising:
(i) from about 80% to 100% of alkyl ethoxy carboxylates of the formula:
~5 RO(CH2CH20)xCH2COO-M+
wherein R is a C12 to C16 alkyl group, x ranges from 0 to about 10 and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than about 20% and the amount of material where x is greater than 7 is less than about 25%, the average x is from about 2 to 4 when the average R is C13 or less, and the average x is from about 3 to 6 when the average R is greater than C13, and M is a cation;
(ii) from 0% to about 10% of alcohol ethoxylates of the formula:
20S50~5 RO(CH2CH20)xH
wherein R is a C12 to C16 alkyl group and x ranges from 0 to about 10 and the average x is less than about 6; and (iii) from 0% to about 10% of soaps of the formula:
RCOO-M+
wherein R is a C11 to C1s alkyl group and M is a cation; and (b) from about 0.1% to 4_YO calcium ions; and (c) a calcium chelating agent which forms a soluble calcium complex, having a log of formation constant, log Kf, between about 0.5 and 5, in an amount sufficient to prevent the formation of calcium carbonate precipitates in the composition;
wherein a 10% by weight aqueous solution of said composition has a pH from about 7 to 11.
- 15 Detailed DescriPtion of the Invention The light-duty liquid or gel, preferably liquid, dishwashing detergent compositions of the present invention contain a surfactant mixture comprising a major amount of an alkyl ethoxy carboxylate surfactant and little or no alcohol ethoxylate and soap by-product contaminants, and a source of calcium ions. The compositions hereof may also require a calcium chelating agent.
These and other complementary optional ingredients typically found in liquid or gel dishwashing compositions are set forth below.
2s Alkvl Ethoxv Carboxvlate-Containinq Surfactant Mixture The liquid compositions of this invention contain from about 5% to 50% by weight, preferably from about 10% to 40%, most preferably from about 12% to 30%, of a surfactant mixture restricted in the levels of contaminants. Gel compositions of this invention contain from about 5% to about 70%, preferably from about 10% to about 45%, most preferably from about 12% to about 35%, of the surfactant mixture.
The surfactant mixture contains from about 80% to 100%, preferably from about 85% to 95%, most preferably from about 90%
to 95%, of alkyl ethoxy carboxylates of the generic formula RO(CH2CH20)xCHzCOO-M+ wherein R is a C12 to C16 alkyl group, x ranges from O to about 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is O is less than about 20%, preferably less than about 15%, most preferably less than about 10%, and the amount of material where x is greater than 7 is less than about 25%, preferably less than about 15%, most preferably less than about 10%, the average x is from about 2 to 4 when the average R is C13 or less, and the average x is from about 3 to 6 when the average R is greater than C13,- and M is a cation, preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanol-ammonium, most preferably from sodium, potassium, ammonium, and mixtures thereof with magnesium ions. The preferred alkyl ethoxy carboxylates are those where R is a C12 to C14 alkyl group.
Suitable alcohol precursors of the alkyl ethoxy carboxylates of this invention are primary aliphatic alcohols containing from about 12 to about 16 carbon atoms. Other suitable primary aliphatic alcohols are the linear primary alcohols obtained from the hydrogenation of vegetable or animal fatty acids such as coconut, palm kernel, and tallow fatty acids or by ethylene build up reactions and subsequent hydrolysis as in the Ziegler type processes. Preferred alcohols are n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, and n-hexadecyl. Other suitable alcohol precursors include primary alcohols having a proportion of branching on the beta or 2-carbon atoms wherein the alkyl branch contains from 1 to 4 carbon atoms.
In such alcohols at least 30% of the alcohol of each specific chain length is desirably linear and the branching preferably comprises about 50% of methyl groups with smaller amounts of ethyl, propyl and butyl groups. These alcohols are conveniently produced by reaction of linear olefins having from about 11 to 17 carbon atoms with carbon monoxide and hydrogen. Both linear and branched chain alcohols are formed by these processes and the mixtures can either be used as such or can be separated into individual components and then recombined to give the desired blend.
20~S045 Typical processes for producing "Oxo" halides which are then used to prepare alcohols are disclosed in U.S. Patent Nos.
2,564.456 and 2,587,858 and the direct hydroformylation of olefins to give alcohols is disclosed in U.S. Patent Nos. 2,504,682 and 1,581,988.
The equivalent secondary alcohols can also be used. It will be apparent that by using a single chain length olefin as starting material, a corresponding single chain length alcohol will result, but it is generally more economical to utilize mixtures of olefins having a spread of carbon chain length around the desired mean.
This will, of course, provide a mixture of alcohols having the same distribution of chain lengths around the mean.
Primary aliphatic alcohols derived from vegetable oils and fats and from other petroleum feed stocks having alkyl or alkylene groups as part of their structure will also contain a range of chain lengths. Since the range of chain lengths is Ca-C20 and beyond, it is therefore normal practice to separate the product from such feed stocks into different chain length ranges which are chosen with reference to their ultimate use.
The desired average ethoxy chain length on the alcohol ethoxylate can be obtained by using a catalyzed ethoxylation process, wherein the molar amount of ethylene oxide reacted with each equivalent of fatty alcohol will correspond to the average number of ethoxy groups on the alcohol ethoxylated. The addition of ethylene oxide to alkanols is known to be promoted by a catalyst, most conventionally a catalyst of either strongly acidic or strongly basic character. Suitable basic catalysts are the basic salts of the alkali metals of Group I of the Periodic Table, e.g., sodium, potassium, rubidium, and cesium, and the basic salts of certain of the alkaline earth metals of Group II of the Periodic Table, e.g., calcium, strontium, barium, and in some cases magnesium. Suitable acidic catalysts include, broadly, the Lewis acid of Friedel-Crafts catalysts. Specific examples of these catalysts are the fluorides, chlorides, and bromides of boron, antimony, tungsten. iron, nickel, zinc, tin, aluminum, r~
20~0~5 titanium, and molybdenum. The use of complexes of such halides with, for example, alcohols, ethers, carboxylic acids, and amines have also been reported. Still other examples of known acidic alkoxylation catalysts are sulfuric and phosphoric acids;
5 perchloric acid and the perchlorates of magnesium, calcium, manganese, nickel, and zinc; metals oxalates, sulfates, phosphates, carboxylates, and acetates; alkali metal fluoroborates, zinc titanate; and metal salts of benzene sulfonic acid. The type of catalyst used will determine the distribution of the range of ethoxy groups. Stronger catalysts will result in a very tight or narrow distribution of the ethoxy groups around the mean. Weaker catalysts will result in a wider distribution.
- The surfactant mixture also contains from 0% to about 10%, preferably less than about 8%, most preferably less than about 5%, is of alcohol ethoxylates of the formula RO(CH2CH20)xH wherein R is a C12 to C16 alkyl group and x ranges from O to about 10 and the average x is less than 6. The surfactant mixture also contains 0%
to about 10%, preferably less than about 8%, most preferably less than about 5%, of soaps of the formula RCOO-M+ wherein R is a C
to C1s alkyl group and M is a cation as described above.
The uncarboxylated alcohol ethoxylates noted above are a detriment to the alkyl ethoxy carboxylate surfactant mixture, especially with respect to the performance benefits provided therefrom. Therefore, it is critical that the alkyl ethoxy carboxylate-containing surfactant mixture used in this invention contain less than about 10% by weight of the alcohol ethoxylates they are derived from. Although commercially available alkyl ethoxy carboxylates contain 10% or more of alcohol ethoxylates, there are known routes to obtain the desired high purity alkyl ~o ethoxy carboxylates. For example, unreacted alcohol ethoxylates can be removed by steam distillation, U.S. Pat. No. 4,098,818 (Example I), or by recrystallization of the alkyl ethoxy carboxylate, British Pat. No. 1,027,481 (Example 1). Other routes to the desired carboxylates are the reaction of sodium hydroxide or sodium metal and monochloracetic acetic, or its salt, with alcohol ethoxylates under special pressure and temperature 7 205504~
combinations, as described in U.S. Pat. Nos. 3,992,443 and 4,098,818.
Alternatively, a hindered base, such as potassium tert-butoxide can replace the sodium hydroxide in the above cited patents, thus yielding high purity alkyl ethoxy carboxylates with less stringent temperature and pressure requirements. Specifically, a hindered base of the formula RO M+, constituting generally an alkyl group, a reactive oxygen center, and a cation is used. The structure of this hindered base is secondary or tertiary and contains a non-linear alkyl group with at least one site of branching within 3 carbon atoms of the reactive center, the oxygen atom, and an alkali metal or alkaline earth metal cation. The process comprises reacting the alcohol ethoxylates with the hindered base described above and either anhydrous chloroacetic acid, at a molar ratio of the hindered base to the anhydrous chloroacetic acid of 2:1, or an alkali metal salt or alkaline earth metal salt of anhydrous chloroacetic acid, at a molar ratio of the hindered base to the alkali metal salt or alkaline earth metal salt of chloroacetic acid of 1:1, wherein the molar ratio of the ethoxylated fatty alcohol to the anhydrous chloroacetic acid or the alkali metal salt or alkaline earth metal salt thereof is from about 1:0.7 to about 1:1.25, the temperature is from about 20 to 140C, and the pressure is from about 1 to 760 mmHg.
Other routes to high purity alkyl ethoxy carboxylates are the reaction of alcohol ethoxylate with oxygen in the presence of platinum, palladium, or other noble metals, as disclosed in U.S.
Pat. No. 4,223,460 (Example 1-7); U.S. Pat. No. 4,214,101 (Example 1); U.S. Pat. No. 4,348,509; and German Patent No. 3,446,561. One of the by-products of such reactions is soap, which should be limited, as described above, to avoid adversely affecting the cleaning and mildness advantages provided by the present compositions. This can be accomplished by using alcohol ethoxylate feedstock containing low levels of unethoxylated fatty alcohol and by r~
. f,~
selecting catalysts that preferentially oxidize the terminal methylene in the alcohol ethoxylate, at least about 90% of the time, preferably at least about 95% of the time. Oxidation of non-terminal methylene groups in the alcohol ethoxylate will generate soap from ethoxylated fatty alcohol components.
The cations for the alkyl ethoxy carboxylates herein can be alkali metals, alkaline earth metals, ammonium, and lower alkanol ammonium ions. The source of cations for the alkyl ethoxy carboxylates come from neutralization of the alkyl ethoxy io carboxylic acid and from additional ingredients, e.g., performance enhancing divalent ion-containing salts.
Preferred cations for compositions of the invention are - ammonium, sodium, and potassium. For compositions having a pH
between about 7 and 8, ammonium is most preferred, but at pH
levels above about 8, it is undesirable due to the release of small amounts of ammonia gas resulting from deprotonation of the ammonium ions in the composition.
For liquid compositions of the invention, potassium is preferred over sodium since it makes the compositions of the invention more resistant to precipitate formation at low temperatures and provides improved solubility to the composition.
On the other hand, for gel compositions of the invention, sodium is preferred over potassium since it makes it easier to gel a composition. Mixtures of the cations may be present in any of the compositions of the invention.
pH of the ComDosition Traditionally, liquid dishwashing compositions have a pH of about 7. It is known for detergent compositions containing the 3G alkyl ethoxy carboxylate surfactant that a more alkaline pH
greatly improves the grease cleaning as compared to a neutral pH, particularly in soft water conditions. This cleaning benefit appears to be unique to compositions containing the present alkyl _J .
2~5~04~
g ethoxy carboxylates ssurfactant. Surprisingly, the compositions of this invention are also more mild to hands at this alkaline pH
than at a pH of 7. The compositions of this invention have a pH
from about 7 to 11, preferably from 8 to 10, most preferably from s 8 to 9.5j determined as the pH of a 10% by weight aqueous solution with a pH meter. Across the entire pH range of the compositons of the invention thereof, i.e. from about 7 to 11, there is little or no formation of calcium hydroxide precipitates. Calcium hydroxide is much more soluble than magnesium hydroxide in water.
At pH levels between about 7 and 9 there is little or no chance of formation of calcium carbonate precipitates since at these pH levels there is little or no source of carbonate ions available to interact with free calcium ions to form CaC03 precipitates because the carbonate species are in the form of - 15 bicarbonate or carbonic acid which do not form insoluble calcium complexes.
At pH levels between about 9 and 11 the bicarbonate and carbonic acid species are deprotonated to form carbonate which readily interact with calcium to form calcium carbonate precipitates. Therefore, at these high pH levels a calcium chelating agent is required to prevent the formation of these undesirable species.
If a composition with a pH greater than about 7 is to be most effective in improving performance, it should contain a buffering agent capable of maintaining the alkaline pH in the composition and in dilute solutions, i.e., about 0.1% to 0.2% by weight aqueous solution, of the composition. The pKa value of this buffering agent should be about 0.5 to 1.0 pH units below the desired pH value of the composition (determined as described above).
Dishwashing compositions of the invention will be subjected to acidic stresses created by food soils when put to use, i.e., diluted and applied to soiled dishes. To maintain the performance 20a5~5 benefits of the compositions in use, a buffering agent having a pKa value about 0.5 to 1.0 pH units below the desired pH value should be present therein. Under these conditions the buffering agent most effectively controls the pH while using the least amount thereof.
The buffering agent may be an active detergent in its own right, or it may be a low molecular weight, organic or inorganic material that is used in this composition solely for maintaining an alkaline pH. Suitable buffering agents for compositions of io this invention are nitrogen-containing materials. Some examples are glycine or other amino acids or lower alcohol amines like mono-, di-, and tri-ethanolamine. The preferred nitrogen-con-taining buffering agents are 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol, and tris-(methanol) aminomethane, (a.k.a. tris) N-methyldiethanolamine, 1,3-diamino-2-propanol, N,N-tetramethyl -1,3-diamino-2-propanol, bis(2-ethanol)glycine (a.k.a. bicine) imidazole, N-tris-(methanol)methylglycine (a.k.a. tricine) are also preferred.
These buffering agents are typically present at a level of from about 0.1% to 10% by weight, preferably from about 1% to 7%, most preferably from about 1.5% to 5%.
Calcium Ions It has been found for composition containing the present alkyl ethoxy carboxylates that the presence of divalent cations greatly improves the cleaning of greasy soils. This is especially true when the compositions are used in softened water that contains few divalent ions. Dishwashing liquid compositions that contain alkyl ethoxy carboxylates that do not conform to the narrow definition of this invention will be less benefited by the addition of divalent ions and, in many cases, will actually exhibit reduced cleaning performance upon the addition of divalent cations. ~t is bélieved that divalent ions increase the packing of the present alkyl ethoxy carboxylates at the oil/water interface, thereby reducing interfacial tension and improving grease cleaning.
205~4~
Furthermore, it has been found that formulating such divalent ion-containing compositions in alkaline pH matrices is difficult due to the incompatability of the divalent ions with hydroxide ions. When both divalent ions and alkaline pH are combined with the surfactant mixture of this invention, grease cleaning is achieved that is superior to that obtained by either alkaline pH
or divalent ions alone. Yet, during storage, the stability of these compositions becomes poor due to the formation of hydroxide precipitates. This is particularly evident in compositions containing magnesium ions.
It has now been discovered that compositions of the invention hereof containing calcium ions exhibit good grease removal, manifest mildness to the skin, and provide good storage stability.
Calcium ions are present in the compositions hereof at a level of from about 0.1% to 4% preferably from about 0.5% to 3.5% by weight.
Preferably, the calcium ions are added as a chloride, acetate, or nitrate salt to compositions containing an alkali metal or ammonium salt of the alkyl ethoxy carboxylate, most preferably the sodium salt, after the composition has been neutralized with a strong base.
Previously it was believed that compositions hereof containing magnesium ions were preferred due to the improved cleaning provided over similar compositions without divalent ions.
Subsequently, it was discovered that the incompatability between magnesium and hydroxide ions in these alkaline compositions resulted in unacceptable levels of precipitates formed during storage of the compositions.
Now it has been discovered that alkaline compositions of the invention hereof containing calcium ions provide improved grease cleaning while manifesting mildness to the skin.
At pH levels between about 7 and 9 compositions containing calcium ions exhibit superior grease cleaning benefits over compositions containing other divalent ions, e.g.magnesium.
Without being held to theory, it is beleived that calcium binds the alkyl ethoxy carboxylate molecules tighter allowing for _J ~
20S~04S
tighter packing at the water/oil interface. This is eYident from the lower inter-facial tension (IFT) measurements exhibited by composition containing calcium ions as compared to composiitons containing other divalent ions. Furthermore, at these pH leYels, compositions of the invention hereof provide better storage stability over other compositions as described above.
At pH leYels between about 9 and 11, although both calcium-containing and magnesium containing compositions require chelating agents to prevent precipitate formation, the amount of such chelating agent required for calcium containing compositions is lower than that required for magnesium-containing compositons.
Futhermore, at the upper pH range, i.e. between about 10 and 11, compositions containing magnesium ions readily form hydroxide precipitates. Although the incorporation of a strong chelating agent would avoid such precipitate formation, the grease cleaning benefit provided therefrom would be compromised. On the other hand, compositions containing calcium ions can be formulated at these higher pH levels without compromising the grease cleaning benefit by incorporating a chelating agent.
Formulating compositions containing calcium ions is easier than that for compositions containing magnesium ions since the pH
level of such compositions can be readily adjusted without - inducing precipitate formation, whereas in formulating the magnesium compositions once hydroxide precipitates are formed they cannot be readily dissolved.
Alkaline compositions hereof can tolerate a higher level of calcium ions at higher pH levels without forming undesirable precipitates, provided some amount of a chelating agent is used.
The amount of calcium ions present in compositions of the invention will be dependent upon the amount of total anionic surfactant present therein, including the amount of alkyl ethoxy carboxylates. When calcium ions are present in the compositions of this invention, the molar ratio of calcium ions to total anionic surfactant is from about 0.25:1 to about 2:1 for compositions of the invention.
- 13 - 205S0~
Calcium Chelatinq Agent The composition of the invention hereof may contain a calcium chelating agent to sequester calcium ions present in the liquid phase of the composition thereby inhibiting the interaction between the calcium and hydroxide ions which would result in the formation of CaC03 precipitates, particularly at pH levels between about 9 and 11.
The calcium complex the chelating agent forms with calcium ions must be soluble. If an insoluble calcium-chelant complex is o formed, it will cause unsightly product turbidity, and if the complex settles to the bottom of the product there may be insufficient levels of calcium ion delivered to the wash solution upon normal dispensing of the product.
- The chelating agent must associate with the calcium ions only 1~ moderately, i.e. only strong enough to prevent interaction between the calcium and carbonate ions, but not too much so as to significantly reduce the amount of calcium ions available in dilute solution. Therefore, the log of formation constant, log Kf, for the chelating agent is between about 0.5 and 5.
The amount of chelating agent present in the composition of the invention hereof is that amount sufficient to prevent the formation of CaC03 precipitates in the composition. This amount is dependent upon three factors: the desired pH of the composition, the level of calcium ions in the composition and the strength of the chelating agent, i.e. its log Kf.
At pH levels between about 7 and 9 it is unlikely that calcium precipitates formation will form (see above). Therefore, it is unlikely that a chelating agent will be required in compositions having such pH levels.
3~ At pH levels between about 9 and 11 the tendency of calcium carbonate precipitates increases (see above) and therefore some amount of a calcium chelating agent may be required.
More importantly, the log of formation constant, log Kf, must be considered in determining the amount of chelating agent to use in a composition. The log Kf of the chelating agent is between - 14 - 2055 0 ~ ~
about 0.5 and 5, preferably between 1 and 3.5. The higher the log Kf, the tighter the hold on calcium ions, and the less required for the prevention of CaC03 precipitate formation in the composition. The amount of chelating agent in the compositions hereof is set forth in Table I, below. In determining the amount of chelating agent to use in compositions of the invention hereof, the formulator must determine the log Kf of the chelating agent. A
method for determining the formation constants of these chelating agents is described in Determination and Use of StabilitY
Constants; A.E. Martell and K.J. Motekaitis; V.C. Publishers Inc.
(1988, N.Y., N.Y.). Critical StabilitY Constants; R.M. Smith and A.E. Martell; Plenum Publishers (1974-81, N.Y., N.Y.) lists formation constants for various common inorganic compounds. Based upon the level of calcium ions and the pH level desired for the composition, the formulator can determine a range for the amount of a chelating agent required in the composition.
Table I
loq Kf % (bY weiqht) 0.5 to 1.5 '10 1.5 to 3 <8 3 to 5 '3 Examples of suitable chelating agents, bicine (bis(2-ethanol)glycine), N-(2-hydroxyethyl)iminodiacetic acid (HIDA), N-(2,3-dihydroxypropyl)iminodiacetic acid (GIDA), and their alkali metal salts. Mixtures of the above are acceptable.
The preferred chelating agent is bicine.
Co-Surfactants The compositions of this invention preferably contain certain co-surfactants to aid in the foaming, detergency, and/or mildness.
Included in this category are several anionic surfactants commonly used in liquid or gel dishwashing detergents. The cations associated with these anionic surfactants can be the same as the cations described previously for the alkyl ethoxy carboxylates. Examples of anionic co-surfactants that are useful in the present invention are the following classes:
(1) Alkyl benzene sulfonates in which the alkyl group contains from 9 to 15 carbon atoms, preferably 11 to 14 carbon atoms in straight chain or branched chain configuration. An especially preferred linear alkyl benzene sulfonate contains about 12 carbon atoms. U.S. Pat. Nos. 2,220,099 and 2,477,383 describe these surfactants in detail.
lo (2) Alkyl sulfates obtained by sulfating an alcohol having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms. The alkyl sulfates have the formula ROS03-M+ where R is the Cg 22 alkyl group and M is a mono- and/or divalant cation.
(3) Paraffin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, in the alkyl moiety. These surfactants are commercially available as Hostapur SAS from Hoechst Celanese.
(4) Olefin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms. U.S. Pat. No. 3,332,880 contains a description of suitable olefin sulfonates.
(5) Alkyl ether sulfates derived from ethoxylating an alcohol having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, less than 30, preferably less than 12, moles of ethylene oxide. The alkyl ether sulfates having the formula:
Ro(c2H4o)xso3-M+
where R is the Cg 22 alkyl group, x is 1-30, and M is a mono- or divalent cation.
No. 912,395: French Pat. Nos. 2,014,084 and 2,042,793.
Backqround Art There has been considerable demand for light-duty liquid or gel dishwashing detergents capable of providing good grease removal. These compositions are well known in the art and are described, for example, in U.S. Pat. Nos. 4,316,824 (Pancheri), 4,681,704 (Bernardino et al.), 4,133,779 (Hellyer et al.), and 4,615,819 (Leng et al). These compositions, although being good grease and soil cleaners, can be harsh to the skin under certain conditions, particularly when used during the dry winter months.
Likewise, the art is replete with detergent compositions that are mild to the skin. These mild compositions often contain sulfates of highly ethoxylated alcohols. See, for example, U.S.
Pat. No. 3,743,233. Rose and Thiele. Betaines have also been suggested for use in improving mildness of a liquid dishwashing composition. See, for example, U.S. Pat. No. 4,555,360 (Bissett et al). Alkyl ethoxy carboxylates are also known as mild surfactants for use in liquid detergent compositions. These alkyl ethoxy carboxylate surfactants, however, have been described as being poor in their grease cutting ability and require the use of other surfactants to achieve the desired cleaning.
r-~
- A -20~504~
Rarely have these two important features of mildness and grease cutting ability been incorporated in one product. It is generally thought that one must be sacrificed for the benefit of the other. It has been discovered that detergent compositions containing a particular alkyl ethoxy carboxylate surfactant mixture provide a detergent composition that exhibits good grease removal while manifesting mildness to the skin- This dual benefit is enhanced when the composition has a pH of from about 7 to 11 and contain a small amount of divalent ions, e.g. magnesium.
io These alkaline compositions containing magnesium ions may exhibit poor stability during storage though. In an alkaline environment, the precipitation of magnesium hydroxide can be a substantial problem. Therefore, it is an object of this invention to provide a detergent composition that exhibits good grease ~ 1~ removal and mildness to the skin while providing superior stability during storage of the composition.
Summarv of the Invention The present invention relates to a light-duty liquid or gel, preferably liquid, dishwashing detergent composition comprising:
(a) from about 5% to 70% of a surfactant mixture comprising:
(i) from about 80% to 100% of alkyl ethoxy carboxylates of the formula:
~5 RO(CH2CH20)xCH2COO-M+
wherein R is a C12 to C16 alkyl group, x ranges from 0 to about 10 and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than about 20% and the amount of material where x is greater than 7 is less than about 25%, the average x is from about 2 to 4 when the average R is C13 or less, and the average x is from about 3 to 6 when the average R is greater than C13, and M is a cation;
(ii) from 0% to about 10% of alcohol ethoxylates of the formula:
20S50~5 RO(CH2CH20)xH
wherein R is a C12 to C16 alkyl group and x ranges from 0 to about 10 and the average x is less than about 6; and (iii) from 0% to about 10% of soaps of the formula:
RCOO-M+
wherein R is a C11 to C1s alkyl group and M is a cation; and (b) from about 0.1% to 4_YO calcium ions; and (c) a calcium chelating agent which forms a soluble calcium complex, having a log of formation constant, log Kf, between about 0.5 and 5, in an amount sufficient to prevent the formation of calcium carbonate precipitates in the composition;
wherein a 10% by weight aqueous solution of said composition has a pH from about 7 to 11.
- 15 Detailed DescriPtion of the Invention The light-duty liquid or gel, preferably liquid, dishwashing detergent compositions of the present invention contain a surfactant mixture comprising a major amount of an alkyl ethoxy carboxylate surfactant and little or no alcohol ethoxylate and soap by-product contaminants, and a source of calcium ions. The compositions hereof may also require a calcium chelating agent.
These and other complementary optional ingredients typically found in liquid or gel dishwashing compositions are set forth below.
2s Alkvl Ethoxv Carboxvlate-Containinq Surfactant Mixture The liquid compositions of this invention contain from about 5% to 50% by weight, preferably from about 10% to 40%, most preferably from about 12% to 30%, of a surfactant mixture restricted in the levels of contaminants. Gel compositions of this invention contain from about 5% to about 70%, preferably from about 10% to about 45%, most preferably from about 12% to about 35%, of the surfactant mixture.
The surfactant mixture contains from about 80% to 100%, preferably from about 85% to 95%, most preferably from about 90%
to 95%, of alkyl ethoxy carboxylates of the generic formula RO(CH2CH20)xCHzCOO-M+ wherein R is a C12 to C16 alkyl group, x ranges from O to about 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is O is less than about 20%, preferably less than about 15%, most preferably less than about 10%, and the amount of material where x is greater than 7 is less than about 25%, preferably less than about 15%, most preferably less than about 10%, the average x is from about 2 to 4 when the average R is C13 or less, and the average x is from about 3 to 6 when the average R is greater than C13,- and M is a cation, preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanol-ammonium, most preferably from sodium, potassium, ammonium, and mixtures thereof with magnesium ions. The preferred alkyl ethoxy carboxylates are those where R is a C12 to C14 alkyl group.
Suitable alcohol precursors of the alkyl ethoxy carboxylates of this invention are primary aliphatic alcohols containing from about 12 to about 16 carbon atoms. Other suitable primary aliphatic alcohols are the linear primary alcohols obtained from the hydrogenation of vegetable or animal fatty acids such as coconut, palm kernel, and tallow fatty acids or by ethylene build up reactions and subsequent hydrolysis as in the Ziegler type processes. Preferred alcohols are n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, and n-hexadecyl. Other suitable alcohol precursors include primary alcohols having a proportion of branching on the beta or 2-carbon atoms wherein the alkyl branch contains from 1 to 4 carbon atoms.
In such alcohols at least 30% of the alcohol of each specific chain length is desirably linear and the branching preferably comprises about 50% of methyl groups with smaller amounts of ethyl, propyl and butyl groups. These alcohols are conveniently produced by reaction of linear olefins having from about 11 to 17 carbon atoms with carbon monoxide and hydrogen. Both linear and branched chain alcohols are formed by these processes and the mixtures can either be used as such or can be separated into individual components and then recombined to give the desired blend.
20~S045 Typical processes for producing "Oxo" halides which are then used to prepare alcohols are disclosed in U.S. Patent Nos.
2,564.456 and 2,587,858 and the direct hydroformylation of olefins to give alcohols is disclosed in U.S. Patent Nos. 2,504,682 and 1,581,988.
The equivalent secondary alcohols can also be used. It will be apparent that by using a single chain length olefin as starting material, a corresponding single chain length alcohol will result, but it is generally more economical to utilize mixtures of olefins having a spread of carbon chain length around the desired mean.
This will, of course, provide a mixture of alcohols having the same distribution of chain lengths around the mean.
Primary aliphatic alcohols derived from vegetable oils and fats and from other petroleum feed stocks having alkyl or alkylene groups as part of their structure will also contain a range of chain lengths. Since the range of chain lengths is Ca-C20 and beyond, it is therefore normal practice to separate the product from such feed stocks into different chain length ranges which are chosen with reference to their ultimate use.
The desired average ethoxy chain length on the alcohol ethoxylate can be obtained by using a catalyzed ethoxylation process, wherein the molar amount of ethylene oxide reacted with each equivalent of fatty alcohol will correspond to the average number of ethoxy groups on the alcohol ethoxylated. The addition of ethylene oxide to alkanols is known to be promoted by a catalyst, most conventionally a catalyst of either strongly acidic or strongly basic character. Suitable basic catalysts are the basic salts of the alkali metals of Group I of the Periodic Table, e.g., sodium, potassium, rubidium, and cesium, and the basic salts of certain of the alkaline earth metals of Group II of the Periodic Table, e.g., calcium, strontium, barium, and in some cases magnesium. Suitable acidic catalysts include, broadly, the Lewis acid of Friedel-Crafts catalysts. Specific examples of these catalysts are the fluorides, chlorides, and bromides of boron, antimony, tungsten. iron, nickel, zinc, tin, aluminum, r~
20~0~5 titanium, and molybdenum. The use of complexes of such halides with, for example, alcohols, ethers, carboxylic acids, and amines have also been reported. Still other examples of known acidic alkoxylation catalysts are sulfuric and phosphoric acids;
5 perchloric acid and the perchlorates of magnesium, calcium, manganese, nickel, and zinc; metals oxalates, sulfates, phosphates, carboxylates, and acetates; alkali metal fluoroborates, zinc titanate; and metal salts of benzene sulfonic acid. The type of catalyst used will determine the distribution of the range of ethoxy groups. Stronger catalysts will result in a very tight or narrow distribution of the ethoxy groups around the mean. Weaker catalysts will result in a wider distribution.
- The surfactant mixture also contains from 0% to about 10%, preferably less than about 8%, most preferably less than about 5%, is of alcohol ethoxylates of the formula RO(CH2CH20)xH wherein R is a C12 to C16 alkyl group and x ranges from O to about 10 and the average x is less than 6. The surfactant mixture also contains 0%
to about 10%, preferably less than about 8%, most preferably less than about 5%, of soaps of the formula RCOO-M+ wherein R is a C
to C1s alkyl group and M is a cation as described above.
The uncarboxylated alcohol ethoxylates noted above are a detriment to the alkyl ethoxy carboxylate surfactant mixture, especially with respect to the performance benefits provided therefrom. Therefore, it is critical that the alkyl ethoxy carboxylate-containing surfactant mixture used in this invention contain less than about 10% by weight of the alcohol ethoxylates they are derived from. Although commercially available alkyl ethoxy carboxylates contain 10% or more of alcohol ethoxylates, there are known routes to obtain the desired high purity alkyl ~o ethoxy carboxylates. For example, unreacted alcohol ethoxylates can be removed by steam distillation, U.S. Pat. No. 4,098,818 (Example I), or by recrystallization of the alkyl ethoxy carboxylate, British Pat. No. 1,027,481 (Example 1). Other routes to the desired carboxylates are the reaction of sodium hydroxide or sodium metal and monochloracetic acetic, or its salt, with alcohol ethoxylates under special pressure and temperature 7 205504~
combinations, as described in U.S. Pat. Nos. 3,992,443 and 4,098,818.
Alternatively, a hindered base, such as potassium tert-butoxide can replace the sodium hydroxide in the above cited patents, thus yielding high purity alkyl ethoxy carboxylates with less stringent temperature and pressure requirements. Specifically, a hindered base of the formula RO M+, constituting generally an alkyl group, a reactive oxygen center, and a cation is used. The structure of this hindered base is secondary or tertiary and contains a non-linear alkyl group with at least one site of branching within 3 carbon atoms of the reactive center, the oxygen atom, and an alkali metal or alkaline earth metal cation. The process comprises reacting the alcohol ethoxylates with the hindered base described above and either anhydrous chloroacetic acid, at a molar ratio of the hindered base to the anhydrous chloroacetic acid of 2:1, or an alkali metal salt or alkaline earth metal salt of anhydrous chloroacetic acid, at a molar ratio of the hindered base to the alkali metal salt or alkaline earth metal salt of chloroacetic acid of 1:1, wherein the molar ratio of the ethoxylated fatty alcohol to the anhydrous chloroacetic acid or the alkali metal salt or alkaline earth metal salt thereof is from about 1:0.7 to about 1:1.25, the temperature is from about 20 to 140C, and the pressure is from about 1 to 760 mmHg.
Other routes to high purity alkyl ethoxy carboxylates are the reaction of alcohol ethoxylate with oxygen in the presence of platinum, palladium, or other noble metals, as disclosed in U.S.
Pat. No. 4,223,460 (Example 1-7); U.S. Pat. No. 4,214,101 (Example 1); U.S. Pat. No. 4,348,509; and German Patent No. 3,446,561. One of the by-products of such reactions is soap, which should be limited, as described above, to avoid adversely affecting the cleaning and mildness advantages provided by the present compositions. This can be accomplished by using alcohol ethoxylate feedstock containing low levels of unethoxylated fatty alcohol and by r~
. f,~
selecting catalysts that preferentially oxidize the terminal methylene in the alcohol ethoxylate, at least about 90% of the time, preferably at least about 95% of the time. Oxidation of non-terminal methylene groups in the alcohol ethoxylate will generate soap from ethoxylated fatty alcohol components.
The cations for the alkyl ethoxy carboxylates herein can be alkali metals, alkaline earth metals, ammonium, and lower alkanol ammonium ions. The source of cations for the alkyl ethoxy carboxylates come from neutralization of the alkyl ethoxy io carboxylic acid and from additional ingredients, e.g., performance enhancing divalent ion-containing salts.
Preferred cations for compositions of the invention are - ammonium, sodium, and potassium. For compositions having a pH
between about 7 and 8, ammonium is most preferred, but at pH
levels above about 8, it is undesirable due to the release of small amounts of ammonia gas resulting from deprotonation of the ammonium ions in the composition.
For liquid compositions of the invention, potassium is preferred over sodium since it makes the compositions of the invention more resistant to precipitate formation at low temperatures and provides improved solubility to the composition.
On the other hand, for gel compositions of the invention, sodium is preferred over potassium since it makes it easier to gel a composition. Mixtures of the cations may be present in any of the compositions of the invention.
pH of the ComDosition Traditionally, liquid dishwashing compositions have a pH of about 7. It is known for detergent compositions containing the 3G alkyl ethoxy carboxylate surfactant that a more alkaline pH
greatly improves the grease cleaning as compared to a neutral pH, particularly in soft water conditions. This cleaning benefit appears to be unique to compositions containing the present alkyl _J .
2~5~04~
g ethoxy carboxylates ssurfactant. Surprisingly, the compositions of this invention are also more mild to hands at this alkaline pH
than at a pH of 7. The compositions of this invention have a pH
from about 7 to 11, preferably from 8 to 10, most preferably from s 8 to 9.5j determined as the pH of a 10% by weight aqueous solution with a pH meter. Across the entire pH range of the compositons of the invention thereof, i.e. from about 7 to 11, there is little or no formation of calcium hydroxide precipitates. Calcium hydroxide is much more soluble than magnesium hydroxide in water.
At pH levels between about 7 and 9 there is little or no chance of formation of calcium carbonate precipitates since at these pH levels there is little or no source of carbonate ions available to interact with free calcium ions to form CaC03 precipitates because the carbonate species are in the form of - 15 bicarbonate or carbonic acid which do not form insoluble calcium complexes.
At pH levels between about 9 and 11 the bicarbonate and carbonic acid species are deprotonated to form carbonate which readily interact with calcium to form calcium carbonate precipitates. Therefore, at these high pH levels a calcium chelating agent is required to prevent the formation of these undesirable species.
If a composition with a pH greater than about 7 is to be most effective in improving performance, it should contain a buffering agent capable of maintaining the alkaline pH in the composition and in dilute solutions, i.e., about 0.1% to 0.2% by weight aqueous solution, of the composition. The pKa value of this buffering agent should be about 0.5 to 1.0 pH units below the desired pH value of the composition (determined as described above).
Dishwashing compositions of the invention will be subjected to acidic stresses created by food soils when put to use, i.e., diluted and applied to soiled dishes. To maintain the performance 20a5~5 benefits of the compositions in use, a buffering agent having a pKa value about 0.5 to 1.0 pH units below the desired pH value should be present therein. Under these conditions the buffering agent most effectively controls the pH while using the least amount thereof.
The buffering agent may be an active detergent in its own right, or it may be a low molecular weight, organic or inorganic material that is used in this composition solely for maintaining an alkaline pH. Suitable buffering agents for compositions of io this invention are nitrogen-containing materials. Some examples are glycine or other amino acids or lower alcohol amines like mono-, di-, and tri-ethanolamine. The preferred nitrogen-con-taining buffering agents are 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol, and tris-(methanol) aminomethane, (a.k.a. tris) N-methyldiethanolamine, 1,3-diamino-2-propanol, N,N-tetramethyl -1,3-diamino-2-propanol, bis(2-ethanol)glycine (a.k.a. bicine) imidazole, N-tris-(methanol)methylglycine (a.k.a. tricine) are also preferred.
These buffering agents are typically present at a level of from about 0.1% to 10% by weight, preferably from about 1% to 7%, most preferably from about 1.5% to 5%.
Calcium Ions It has been found for composition containing the present alkyl ethoxy carboxylates that the presence of divalent cations greatly improves the cleaning of greasy soils. This is especially true when the compositions are used in softened water that contains few divalent ions. Dishwashing liquid compositions that contain alkyl ethoxy carboxylates that do not conform to the narrow definition of this invention will be less benefited by the addition of divalent ions and, in many cases, will actually exhibit reduced cleaning performance upon the addition of divalent cations. ~t is bélieved that divalent ions increase the packing of the present alkyl ethoxy carboxylates at the oil/water interface, thereby reducing interfacial tension and improving grease cleaning.
205~4~
Furthermore, it has been found that formulating such divalent ion-containing compositions in alkaline pH matrices is difficult due to the incompatability of the divalent ions with hydroxide ions. When both divalent ions and alkaline pH are combined with the surfactant mixture of this invention, grease cleaning is achieved that is superior to that obtained by either alkaline pH
or divalent ions alone. Yet, during storage, the stability of these compositions becomes poor due to the formation of hydroxide precipitates. This is particularly evident in compositions containing magnesium ions.
It has now been discovered that compositions of the invention hereof containing calcium ions exhibit good grease removal, manifest mildness to the skin, and provide good storage stability.
Calcium ions are present in the compositions hereof at a level of from about 0.1% to 4% preferably from about 0.5% to 3.5% by weight.
Preferably, the calcium ions are added as a chloride, acetate, or nitrate salt to compositions containing an alkali metal or ammonium salt of the alkyl ethoxy carboxylate, most preferably the sodium salt, after the composition has been neutralized with a strong base.
Previously it was believed that compositions hereof containing magnesium ions were preferred due to the improved cleaning provided over similar compositions without divalent ions.
Subsequently, it was discovered that the incompatability between magnesium and hydroxide ions in these alkaline compositions resulted in unacceptable levels of precipitates formed during storage of the compositions.
Now it has been discovered that alkaline compositions of the invention hereof containing calcium ions provide improved grease cleaning while manifesting mildness to the skin.
At pH levels between about 7 and 9 compositions containing calcium ions exhibit superior grease cleaning benefits over compositions containing other divalent ions, e.g.magnesium.
Without being held to theory, it is beleived that calcium binds the alkyl ethoxy carboxylate molecules tighter allowing for _J ~
20S~04S
tighter packing at the water/oil interface. This is eYident from the lower inter-facial tension (IFT) measurements exhibited by composition containing calcium ions as compared to composiitons containing other divalent ions. Furthermore, at these pH leYels, compositions of the invention hereof provide better storage stability over other compositions as described above.
At pH leYels between about 9 and 11, although both calcium-containing and magnesium containing compositions require chelating agents to prevent precipitate formation, the amount of such chelating agent required for calcium containing compositions is lower than that required for magnesium-containing compositons.
Futhermore, at the upper pH range, i.e. between about 10 and 11, compositions containing magnesium ions readily form hydroxide precipitates. Although the incorporation of a strong chelating agent would avoid such precipitate formation, the grease cleaning benefit provided therefrom would be compromised. On the other hand, compositions containing calcium ions can be formulated at these higher pH levels without compromising the grease cleaning benefit by incorporating a chelating agent.
Formulating compositions containing calcium ions is easier than that for compositions containing magnesium ions since the pH
level of such compositions can be readily adjusted without - inducing precipitate formation, whereas in formulating the magnesium compositions once hydroxide precipitates are formed they cannot be readily dissolved.
Alkaline compositions hereof can tolerate a higher level of calcium ions at higher pH levels without forming undesirable precipitates, provided some amount of a chelating agent is used.
The amount of calcium ions present in compositions of the invention will be dependent upon the amount of total anionic surfactant present therein, including the amount of alkyl ethoxy carboxylates. When calcium ions are present in the compositions of this invention, the molar ratio of calcium ions to total anionic surfactant is from about 0.25:1 to about 2:1 for compositions of the invention.
- 13 - 205S0~
Calcium Chelatinq Agent The composition of the invention hereof may contain a calcium chelating agent to sequester calcium ions present in the liquid phase of the composition thereby inhibiting the interaction between the calcium and hydroxide ions which would result in the formation of CaC03 precipitates, particularly at pH levels between about 9 and 11.
The calcium complex the chelating agent forms with calcium ions must be soluble. If an insoluble calcium-chelant complex is o formed, it will cause unsightly product turbidity, and if the complex settles to the bottom of the product there may be insufficient levels of calcium ion delivered to the wash solution upon normal dispensing of the product.
- The chelating agent must associate with the calcium ions only 1~ moderately, i.e. only strong enough to prevent interaction between the calcium and carbonate ions, but not too much so as to significantly reduce the amount of calcium ions available in dilute solution. Therefore, the log of formation constant, log Kf, for the chelating agent is between about 0.5 and 5.
The amount of chelating agent present in the composition of the invention hereof is that amount sufficient to prevent the formation of CaC03 precipitates in the composition. This amount is dependent upon three factors: the desired pH of the composition, the level of calcium ions in the composition and the strength of the chelating agent, i.e. its log Kf.
At pH levels between about 7 and 9 it is unlikely that calcium precipitates formation will form (see above). Therefore, it is unlikely that a chelating agent will be required in compositions having such pH levels.
3~ At pH levels between about 9 and 11 the tendency of calcium carbonate precipitates increases (see above) and therefore some amount of a calcium chelating agent may be required.
More importantly, the log of formation constant, log Kf, must be considered in determining the amount of chelating agent to use in a composition. The log Kf of the chelating agent is between - 14 - 2055 0 ~ ~
about 0.5 and 5, preferably between 1 and 3.5. The higher the log Kf, the tighter the hold on calcium ions, and the less required for the prevention of CaC03 precipitate formation in the composition. The amount of chelating agent in the compositions hereof is set forth in Table I, below. In determining the amount of chelating agent to use in compositions of the invention hereof, the formulator must determine the log Kf of the chelating agent. A
method for determining the formation constants of these chelating agents is described in Determination and Use of StabilitY
Constants; A.E. Martell and K.J. Motekaitis; V.C. Publishers Inc.
(1988, N.Y., N.Y.). Critical StabilitY Constants; R.M. Smith and A.E. Martell; Plenum Publishers (1974-81, N.Y., N.Y.) lists formation constants for various common inorganic compounds. Based upon the level of calcium ions and the pH level desired for the composition, the formulator can determine a range for the amount of a chelating agent required in the composition.
Table I
loq Kf % (bY weiqht) 0.5 to 1.5 '10 1.5 to 3 <8 3 to 5 '3 Examples of suitable chelating agents, bicine (bis(2-ethanol)glycine), N-(2-hydroxyethyl)iminodiacetic acid (HIDA), N-(2,3-dihydroxypropyl)iminodiacetic acid (GIDA), and their alkali metal salts. Mixtures of the above are acceptable.
The preferred chelating agent is bicine.
Co-Surfactants The compositions of this invention preferably contain certain co-surfactants to aid in the foaming, detergency, and/or mildness.
Included in this category are several anionic surfactants commonly used in liquid or gel dishwashing detergents. The cations associated with these anionic surfactants can be the same as the cations described previously for the alkyl ethoxy carboxylates. Examples of anionic co-surfactants that are useful in the present invention are the following classes:
(1) Alkyl benzene sulfonates in which the alkyl group contains from 9 to 15 carbon atoms, preferably 11 to 14 carbon atoms in straight chain or branched chain configuration. An especially preferred linear alkyl benzene sulfonate contains about 12 carbon atoms. U.S. Pat. Nos. 2,220,099 and 2,477,383 describe these surfactants in detail.
lo (2) Alkyl sulfates obtained by sulfating an alcohol having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms. The alkyl sulfates have the formula ROS03-M+ where R is the Cg 22 alkyl group and M is a mono- and/or divalant cation.
(3) Paraffin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, in the alkyl moiety. These surfactants are commercially available as Hostapur SAS from Hoechst Celanese.
(4) Olefin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms. U.S. Pat. No. 3,332,880 contains a description of suitable olefin sulfonates.
(5) Alkyl ether sulfates derived from ethoxylating an alcohol having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, less than 30, preferably less than 12, moles of ethylene oxide. The alkyl ether sulfates having the formula:
Ro(c2H4o)xso3-M+
where R is the Cg 22 alkyl group, x is 1-30, and M is a mono- or divalent cation.
(6) Alkyl glyceryl ether sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, in the alkyl moiety.
(7) Fatty acid ester sulfonates of the formula:
Rl - CH(S03-M+)C02R2 wherein Rl is straight or branched alkyl from about Cg to Clg, preferably C12 to C16, and R2 is straight or branched alkyl from about Cl to C6, preferably primarily Cl, and M+ represents a mono-or divalent cation.
Rl - CH(S03-M+)C02R2 wherein Rl is straight or branched alkyl from about Cg to Clg, preferably C12 to C16, and R2 is straight or branched alkyl from about Cl to C6, preferably primarily Cl, and M+ represents a mono-or divalent cation.
(8) Mixtures thereof.
` - 16 - 2 0 5 5 045 The above described anionic surfactants are all available commercially. It should be noted that although both dialkyl sulfosuccinates and fatty acid ester sulfonates will function well at neutral to slightly alkaline pH, they will not be chemically stable in a composition with pH much greater than about 8.5.
Other useful co-surfactants for use in the compositions are the nonionic fatty alkylpolyglucosides. These surfactants contain straight chain or branched chain C8to C1s, preferably from about Clz to C14, alkyl groups and have an average of from about 1 to 5 glucose units, with an average of 1 to 2 glucose units being most preferred. U.S. Pat. Nos. 4,393,203 and 4,732.704 describe these surfactants.
The compositions hereof may also contain a polyhydroxy fatty acid amide surfactant of the structural formula:
(I) R2 ¦ - N - Z
wherein: R1is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxy-propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl):
and R2is a Cs-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C17 alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction;
more preferably Z is a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
.
2055û~5 Z preferably will be selected from the group consisting of-CH2-(CHOH) n -CH2OH, -CH(CH2OH)-(CHOH) n- 1 ~ CH20H, -CH2-(CHOH)2(CHOR')(CHOH)-CH2OH, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH) 4- CH20H .
In Formula (I), Rlcan be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl, or N-2-hydroxy-propyl.
R2-CO-N' can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymalto-triotityl, etc.
Methods for making polyhydroxy fatty acid amides are knownin the art. In general, they can be made by reacting an alkyl amine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product. Processes for making compositions containing polyhydroxy fatty acid amides are disclosed, for example, in G.B. Patent Specification 809,060, published February 18, 1959, by Thomas Hedley & Co., Ltd., U.S.
Patent 2,965,576, issued December 20, 1960 to E. R. Wilson, and U.S. Patent 2,703,798, Anthony M. Schwartz, issued March 8, 1955, and U.S. Patent 1,985,424, issued December 25, 1934 to Piggott.
In a preferred process for producing N-alkyl or N-hydroxyalkyl, N-deoxyglycityl fatty acid amides wherein the glycityl component is derived from glucose and the N-alkyl or N-hydroxyalkyl functionality is N-methyl, N-ethyl, N-propyl, N-butyl, N-hydroxyethyl, or N-hydroxypropyl, the product is made by reacting N-alkyl- or N-hydroxyalkyl-glucamine with a fatty ~t , ~ .
2 0 5 ~ 0 9 5 ester selected from fatty methyl esters, fatty ethyl esters, and fatty triglycerides in the presence of a catalyst selected from the group consisting of trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, pentapotassium 5 tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, disodium tartrate, dipotassium tartrate, sodium potassium tartrate, trisodium citrate, tripotassium citrate, sodium basic silicates, potassium basic silicates, sodium o basic aluminosilicates, and potassium basic aluminosilicates, and mixtures thereof. The amount of catalyst is preferably from about 0.5 mole % to about 50 mole %, more preferably from about 2.0 mole % to about 10 mole %, on an N-alkyl or N-hydroxyalkyl-glucamine molar basis. The reaction is preferably carried out at from about - 15 138-C to about 170-C for typically from about 20 to about 90 minutes. When triglycerides are utilized in the reaction mixture as the fatty ester source, the reaction is also preferably carried out using from about 1 to about 10 weight % of a phase transfer agent, calculated on a weight percent basis of total reaction mixture, selected from saturated fatty alcohol polyethoxylates, alkylpolyglycosides, linear glycamide surfactant, and mixtures thereof.
Preferably, this process is carried out as follows:
(a) preheating the fatty ester to about 138-C to about 170-C;
(b) adding the N-alkyl or N-hydroxyalkyl glucamine to the heated fatty acid ester and mixing to the extent needed to form a two-phase liquid/liquid mixture;
(c) mixing the catalyst into the reaction mixture; and (d) stirring for the specified reaction time.
Also preferably, from about 2% to about 20% of preformed linear N-alkyl/N-hydroxyalkyl, N-linear glucosyl fatty acid amide - product is added to the reaction mixture, by weight of the reactants, as the phase transfer agent if the fatty ester is a 3, triglyceride. This seeds the reaction, thereby increasing reaction rate.
These polyhydroxy "fatty acid" amide materials also offer the advantages to the detergent formulator that they can be prepared wholly or primarily from natural, renewable, non-petrochemical feedstocks and are degradable. They also exhibit low toxicity to aquatic life.
It should be recognized that along with the polyhydroxy fatty acid amides of Formula (I), the processes used to produce them will also typically produce quantities of nonvolatile by-product such as esteramides and cyclic polyhydroxy fatty acid amide. The level of these by-products will vary depending upon the particular reactants and process conditions. Preferably, the polyhydroxy fatty acid amide incorporated into the detergent compositions - hereof will be provided in a form such that the polyhydroxy fatty acid amide-containing composition added to the detergent contains less than about 10%, preferably less than about 4%, of cyclic polyhydroxy fatty acid amide. The preferred processes described above are advantageous in that they can yield rather low levels of by-products, including such cyclic amide by-product.
The co-surfactants for the compositions of this invention can also contain mixtures of anionic surfactants with alkyl polyglucosides or polyhdroxy fatty acid amides. The co-surfactants are present in the composition at a level of from 0% to about 3-5%
by weight, preferably from about 5% to 25%, and most preferably from about 7% to 20%.
Suds Booster Another component which may be included in the composition of this invention is a suds stabilizing surfactant (suds booster) at a level of less than about 15%, preferably from about 0.5% to 12%, more preferably from about 1% to 10%. Optional suds stabilizing surfactants operable in the instant composition are of five basic types -- betaines, ethylene oxide condensates, fatty acid amides, amine oxide semi-polar nonionics, and cationic surfactants.
20~S04S
The composition of this invention can contain betaine detergent surfactants having the general formula:
( ) ( ) R - N(Rl)2 - R2COO
wherein R is a hydrophobic group selected from the group consisting of alkyl groups containing from about 10 to about 22 carbon atoms, preferably from about 12 to about 18 carbon atoms, alkyl aryl and aryl alkyl groups containing a similar number of carbon atoms with a benzene ring being treated as equivalent to about 2 carbon atoms, and similar structures interrupted by amido or ether linkages; each R1is an alkyl group containing from 1 to about 3 carbon atoms; and R2is an alkylene group containing from 1 to about 6 carbon atoms.
Examples of preferred betaines are dodecyl dimethyl betaine, cetyl dimethyl betaine, dodecyl amidopropyldimethyl betaine, tetradecyldimethyl betaine, tetradecylamidopropyldimethyl betaine, and dodecyldimethylammonium hexanoate.
Other suitable amidoalkylbetaines are disclosed in U.S. Pat.
Nos. 3,950,417; 4,137,191; and 4,375,421; and British Patent GB
No. 2.103,236.
It will be recognized that the alkyl (and acyl) groups for the above betaine surfactants can be derived from either natural or synthetic sources, e,g., they can be derived from naturally occurring fatty acids; olefins such as those prepared by Ziegler, or Oxo processes; or from olefins separated from petroleum either with or without "cracking".
The ethylene oxide condensates are broadly defined as compounds produced by the condensation of ethylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which can be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired balance between hydrophilic and hydrophobic elements.
Examples of such ethylene oxide condensates suitable as suds stabilizers are the condensation products of aliphatic alcohols ~,~'''.d ~A~
with ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched and generally contains from about 8 to about 18, preferably from about 8 to about 14, carbon atoms for best performance as suds stabilizers, the ethylene oxide being present in amounts of from about 8 moles to about 30, preferably from about 8 to about 14 moles of ethylene oxide per mole of alcohol.
Examples of the amide surfactants useful herein include the ammonia, monoethanol, and diethanol amides of fatty acids having lo an acyl moiety containing from about 8 to about 18 carbon atoms and represented by the general formula:
R1 - C0 - N(H)m - 1(R2oH)3 - m wherein R is a saturated or unsaturated, aliphatic hydrocarbon radical having from about 7 to 21, preferably from about 11 to 17 is carbon atoms; R2 represents a methylene or ethylene group; and m is 1, 2, or 3, preferably 1. Specific examples of said amides are mono-ethanol amine coconut fatty acid amide and diethanol amine dodecyl fatty acid amide. These acyl moieties may be derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil, and tallow, but can be derived synthetically, e.g., by the oxidation of petroleum or by hydrogenation of carbon monoxide by the Fischer-Tropsch process. The monoethanol amides and diethanolamides of C12 14 fatty acids are preferred.
Amine oxide semi-polar nonionic surfactants comprise compounds and mixtures of compounds having the formula Rl (c2H4o) nN ~
wherein R1 is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from about 8 to about 18 carbon atoms, R2 and R3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl, and n is from 0 to about 10.
- 22 - 2055 o 4 ~
Particularly preferred are amine oxides of the formula:
I
R1 - N ~ O
wherein R1 is a C1216 alkyl and R2 and R3 are methyl or ethyl. The above ethylene oxide condensates, amides, and amine oxides are more fully described in U.S. Pat. No. 4,316,824 (Pancheri).
The composition of this invention can also contain certain cationic quaternary ammonium surfactants of the formula:
[Rl(oR2)y][R3(0R2)y]2R4N X-or amine surfactants of the formula:
[R1(oR2)y][R3(0R2)y]R4N
wherein R1is an alkyl or alkyl benzyl group having from about 6 to about 16 carbon atoms in the alkyl chain; each R2is selected from the group consisting of -CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH2-, and mixtures thereof: each R3is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl, and hydrogen when y is not O; R4is the same as R3 or is an alkyl chain wherein the total number of carbon atoms of R1plus R4is from about 8 to about 16; each y is from 0 to about 10, and the sum of the y values is from 0 to about 15; and X is any compatible anion.
Preferred of the above are the alkyl quaternary ammonium surfactants, especially the mono-long chain alkyl surfactants described in the above formula when R4is selected from the same groups as R3. The most preferred quaternary ammonium surfactants are the chloride, bromide, and methyl sulfate C816 alkyl trimethylammonium salts, C816 alkyl di(hydroxyethyl)methylammonium salts, the C816 alkyl hydroxyethyldimethylammonium salts, C816 alkyloxypropyl trimethylammonium salts, and the C816 alkyloxypropyl dihydroxyethylmethylammonium salts. Of the above, the C1014 alkyl trimethylammonium salts are preferred, e.g., decyl trimethylammonium methyl sulfate, lauryl trimethylammonium chloride, myristyl trimethylammonium bromide and coconut trimethylammonium chloride, and methyl sulfate.
~5 F~
~--`- A
- 23 - 2 OSS O ~S
The suds boosters used in the compositions of this invention can contain any one or mixture of the suds boosters listed above.
Additional Optional Inqredients In addition to the ingredients described hereinbefore. the compositions can contain other conventional ingredients suitable - for use in liquid or gel dishwashing compositions.
Optional ingredients include drainage promoting ethoxylated ~ nonionic surfactants of the type disclosed in U.S. Pat.
No. 4.316.824. Pancheri (February 23. 1982).
Alcohols. such as ethyl alcohol and propylene glycol. can be utilized in the interests of achieving a desired product phase stability and viscosity. Alcohols such as ethyl alcohol and propylene glycol at a level of from 0% to about 15%. are particularly useful in the liquid compositions of the invention.
Gel compositions of the invention normally would not contain alcohols. These gel compositions may contain higher levels of potassium or sodium toluene. xylene or cumene sulfonate. and urea at higher levels. i.e. from about 10% to about 30%. as gelling agents (see U.S. Pat. No. 4.615 819 and GB 2.179 054A).
Other desirable ingredients include diluents and solvents.
Diluents can be inorganic salts. such as ammonium chloride. sodium chloride. potassium chloride. etc.. and the solvents include water lower molecular weight alcohols. such as ethyl alcohol.
isopropyl alcohol. etc. Compositions herein will typically contain up to about 80% preferably from about 30% to about 70%.
most preferably from about 40% to about 65% of water.
As used herein. all percentages. parts. and ratios are by weight unless otherwise stated.
The following Examples illustrate the invention and facilitate its understanding.
~"~
20~S04~
ExamDle I
The following liquid composition of the present invention is prepared according to the descriptions set forth below. The alkyl ethoxy carboxylate and the appropriate co-surfactant the booster, ethanol, sodium chloride, and the buffer are blended. The pH of the mixture is adjusted with ammonium hydorixed to about 8. Then, the calcium ions (added as calcium chloride dihydrate) are added and the final pH adjusted, if necessary, to about 7.2. Final viscosity and minor pH adjustments can be made at this time, followed by the 0 addition of perfume and dye. The balance is water.
/0 Bv Weiqht Components i5 Sodium C1z 13 alkyl ethoxy 20 (3.5 ave.) carboxylate*
C12 13 alkyl ethoxy 1.23 (3.5 ave.) alcohol*
Sodium C12 13 alkyl ethoxy (1.0 ave.) sulfate 8 C12 14 alkyl amidopropyl dimethyl betaine 3 C12 14 16 alkyl dimethyl amine oxide 3 Calcium ions (added as CaCl2.2H2O) Triethanol amine 6 Sodium chloride 0.5 Ethanol 7.5 ,o Water and minor ~ -------Balance-------------pH (10% aqueous solution) 9.4 9.4 8.5 9.4 * The surfactant mixture contains about 94.2% alkyl ethoxy carboxylates of the formula RO(CH2CH2O)xCHzCOO~Na+ where R is a C12 13 alkyl averaging 12.5; x ranges from 0 to about 10, and the 205~045 ethoxylate distribution is such that the amount of material where x is 0 is about 1.0 and the amount of material where x is greater than 7 is less than about 2% by weight of the alkyl ethoxy carboxylates. The average x in the distribution is 3.5. The surfactant mixture also contains about 5.8% of alcohol ethoxylates of the formula RO(CH2CH20)xH with R being a C12 13 alkyl averaging 12.5 and the average x = 3.5. The surfactant mixture contains 0%
soap materials.
The above formulation give excellent combinations of grease ld cleaning and mildness and are stable to storage at elevated temperatures (up to 120-F). The cleaning provided by this composition at pH of about 7.2-7.5 is better than that provided by a similar composition containing an equivalent (molar basis) amount of magnesium ions. These formulations also provide superior stability during storage especially when compared to similar compositions containing magnesium ions.
ExamDle II
The following liquid composition is prepared according to the method set forth in Example I, except sodium hydroxide is used to adjust the pH of the compositions to about 8.5 % Bv Weiqht Com w nents Sodium C12 13 alkyl ethoxy 22 (3.5 ave.) carboxylate*
C12 13 alkyl ethoxy 1.35 (3.5 ave.) alcohol*
Sodium C12 13 alkyl sulfate ` 5 C12 14 alkyl amidopropyl 3 dimethyl betaine C12.14 16 alkyl dimethyl 2 amine oxide 2n~50~5 C12 13 alkyl ethoxy (8.0 ave.)alcohol 3 Calcium ions 1.2 (added as CaCl2.2H20) Bicine 1.5 Ethanol 7.S
Sodium chloride 0.5 Balance water and minors ---------------Balance---------------pH (10% aqueous solution) 8.5 This formulation of the present invention provides both good o dilute solution grease cleaning and formulation storage stability at elevated temperatures of 120-F.
ExamDle III
The following liquid composition is prepared according to the - 1, method set forth in Example I, except sodium hydroxide is used to adjust the pH of the compositions to about 9.5 % BY Weight Comwnents Sodium C12 13 alkyl ethoxy 22 (3.5 ave.) carboxylate*
C12 13 alkyl ethoxy 1.35 (3.5 ave.~ alcohol*
zs Sodium C12 13 alkyl sulfate ` 6 C12 14 alkyl amidopropyl 3 dimethyl betaine C12 14 16 alkyl dimethyl 2.5 amine oxide 30 Calcium ions 1.5 (added as CaCl2.2H20) Bicine 2 Ethanol 7.5 Balance water and minors ---------------Balance---------------35 pH (10% aqueous solution) 9.S
This formulation of the present invention provides both good dilute solution grease cleaning and formulation storage stability at elevated temperatures of 120-F especially, when compared to equivalent magnesium ion-containing compositons.
s ExamPle IV
The following liquid composition, having a relatively low surfactant level and high calcium ion level is prepared according to the method set forth in Example I.
YO Bv Weiqht -ComDonents -Sodium C12 13 alkyl ethoxy 16 (3.5 ave.) carboxylate*
C12-13 alkyl ethoxy 0.98 (3.5 ave.) alcohol*
Sodium C12 13 alkyl ethoxy (3.0 ave.) sulfate 4 12-14 alkyl amidopropyl 2 dimethyl betaine C12-14-16 alkyl dimethyl 2 amine oxide 25 Calcium ions 3.2 (added as Cacl2~2H2o) Bicine Triethamolamine Ethanol 8 30 Balance water and minors ---------------Balance---------------pH (10% aqueous solution) 8.5 3, The above formulation of the present invention provides both good dilute solution grease cleaning and formulation storage stability at elevated temperatures of 120-F especially, when compared to equivalent magnesium ion-containing compositons. This formulation is particularly useful for dishwashing habits where high product contration in solution is used.
` - 16 - 2 0 5 5 045 The above described anionic surfactants are all available commercially. It should be noted that although both dialkyl sulfosuccinates and fatty acid ester sulfonates will function well at neutral to slightly alkaline pH, they will not be chemically stable in a composition with pH much greater than about 8.5.
Other useful co-surfactants for use in the compositions are the nonionic fatty alkylpolyglucosides. These surfactants contain straight chain or branched chain C8to C1s, preferably from about Clz to C14, alkyl groups and have an average of from about 1 to 5 glucose units, with an average of 1 to 2 glucose units being most preferred. U.S. Pat. Nos. 4,393,203 and 4,732.704 describe these surfactants.
The compositions hereof may also contain a polyhydroxy fatty acid amide surfactant of the structural formula:
(I) R2 ¦ - N - Z
wherein: R1is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxy-propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl):
and R2is a Cs-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C17 alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction;
more preferably Z is a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
.
2055û~5 Z preferably will be selected from the group consisting of-CH2-(CHOH) n -CH2OH, -CH(CH2OH)-(CHOH) n- 1 ~ CH20H, -CH2-(CHOH)2(CHOR')(CHOH)-CH2OH, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH) 4- CH20H .
In Formula (I), Rlcan be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl, or N-2-hydroxy-propyl.
R2-CO-N' can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymalto-triotityl, etc.
Methods for making polyhydroxy fatty acid amides are knownin the art. In general, they can be made by reacting an alkyl amine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product. Processes for making compositions containing polyhydroxy fatty acid amides are disclosed, for example, in G.B. Patent Specification 809,060, published February 18, 1959, by Thomas Hedley & Co., Ltd., U.S.
Patent 2,965,576, issued December 20, 1960 to E. R. Wilson, and U.S. Patent 2,703,798, Anthony M. Schwartz, issued March 8, 1955, and U.S. Patent 1,985,424, issued December 25, 1934 to Piggott.
In a preferred process for producing N-alkyl or N-hydroxyalkyl, N-deoxyglycityl fatty acid amides wherein the glycityl component is derived from glucose and the N-alkyl or N-hydroxyalkyl functionality is N-methyl, N-ethyl, N-propyl, N-butyl, N-hydroxyethyl, or N-hydroxypropyl, the product is made by reacting N-alkyl- or N-hydroxyalkyl-glucamine with a fatty ~t , ~ .
2 0 5 ~ 0 9 5 ester selected from fatty methyl esters, fatty ethyl esters, and fatty triglycerides in the presence of a catalyst selected from the group consisting of trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, pentapotassium 5 tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, disodium tartrate, dipotassium tartrate, sodium potassium tartrate, trisodium citrate, tripotassium citrate, sodium basic silicates, potassium basic silicates, sodium o basic aluminosilicates, and potassium basic aluminosilicates, and mixtures thereof. The amount of catalyst is preferably from about 0.5 mole % to about 50 mole %, more preferably from about 2.0 mole % to about 10 mole %, on an N-alkyl or N-hydroxyalkyl-glucamine molar basis. The reaction is preferably carried out at from about - 15 138-C to about 170-C for typically from about 20 to about 90 minutes. When triglycerides are utilized in the reaction mixture as the fatty ester source, the reaction is also preferably carried out using from about 1 to about 10 weight % of a phase transfer agent, calculated on a weight percent basis of total reaction mixture, selected from saturated fatty alcohol polyethoxylates, alkylpolyglycosides, linear glycamide surfactant, and mixtures thereof.
Preferably, this process is carried out as follows:
(a) preheating the fatty ester to about 138-C to about 170-C;
(b) adding the N-alkyl or N-hydroxyalkyl glucamine to the heated fatty acid ester and mixing to the extent needed to form a two-phase liquid/liquid mixture;
(c) mixing the catalyst into the reaction mixture; and (d) stirring for the specified reaction time.
Also preferably, from about 2% to about 20% of preformed linear N-alkyl/N-hydroxyalkyl, N-linear glucosyl fatty acid amide - product is added to the reaction mixture, by weight of the reactants, as the phase transfer agent if the fatty ester is a 3, triglyceride. This seeds the reaction, thereby increasing reaction rate.
These polyhydroxy "fatty acid" amide materials also offer the advantages to the detergent formulator that they can be prepared wholly or primarily from natural, renewable, non-petrochemical feedstocks and are degradable. They also exhibit low toxicity to aquatic life.
It should be recognized that along with the polyhydroxy fatty acid amides of Formula (I), the processes used to produce them will also typically produce quantities of nonvolatile by-product such as esteramides and cyclic polyhydroxy fatty acid amide. The level of these by-products will vary depending upon the particular reactants and process conditions. Preferably, the polyhydroxy fatty acid amide incorporated into the detergent compositions - hereof will be provided in a form such that the polyhydroxy fatty acid amide-containing composition added to the detergent contains less than about 10%, preferably less than about 4%, of cyclic polyhydroxy fatty acid amide. The preferred processes described above are advantageous in that they can yield rather low levels of by-products, including such cyclic amide by-product.
The co-surfactants for the compositions of this invention can also contain mixtures of anionic surfactants with alkyl polyglucosides or polyhdroxy fatty acid amides. The co-surfactants are present in the composition at a level of from 0% to about 3-5%
by weight, preferably from about 5% to 25%, and most preferably from about 7% to 20%.
Suds Booster Another component which may be included in the composition of this invention is a suds stabilizing surfactant (suds booster) at a level of less than about 15%, preferably from about 0.5% to 12%, more preferably from about 1% to 10%. Optional suds stabilizing surfactants operable in the instant composition are of five basic types -- betaines, ethylene oxide condensates, fatty acid amides, amine oxide semi-polar nonionics, and cationic surfactants.
20~S04S
The composition of this invention can contain betaine detergent surfactants having the general formula:
( ) ( ) R - N(Rl)2 - R2COO
wherein R is a hydrophobic group selected from the group consisting of alkyl groups containing from about 10 to about 22 carbon atoms, preferably from about 12 to about 18 carbon atoms, alkyl aryl and aryl alkyl groups containing a similar number of carbon atoms with a benzene ring being treated as equivalent to about 2 carbon atoms, and similar structures interrupted by amido or ether linkages; each R1is an alkyl group containing from 1 to about 3 carbon atoms; and R2is an alkylene group containing from 1 to about 6 carbon atoms.
Examples of preferred betaines are dodecyl dimethyl betaine, cetyl dimethyl betaine, dodecyl amidopropyldimethyl betaine, tetradecyldimethyl betaine, tetradecylamidopropyldimethyl betaine, and dodecyldimethylammonium hexanoate.
Other suitable amidoalkylbetaines are disclosed in U.S. Pat.
Nos. 3,950,417; 4,137,191; and 4,375,421; and British Patent GB
No. 2.103,236.
It will be recognized that the alkyl (and acyl) groups for the above betaine surfactants can be derived from either natural or synthetic sources, e,g., they can be derived from naturally occurring fatty acids; olefins such as those prepared by Ziegler, or Oxo processes; or from olefins separated from petroleum either with or without "cracking".
The ethylene oxide condensates are broadly defined as compounds produced by the condensation of ethylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which can be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired balance between hydrophilic and hydrophobic elements.
Examples of such ethylene oxide condensates suitable as suds stabilizers are the condensation products of aliphatic alcohols ~,~'''.d ~A~
with ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched and generally contains from about 8 to about 18, preferably from about 8 to about 14, carbon atoms for best performance as suds stabilizers, the ethylene oxide being present in amounts of from about 8 moles to about 30, preferably from about 8 to about 14 moles of ethylene oxide per mole of alcohol.
Examples of the amide surfactants useful herein include the ammonia, monoethanol, and diethanol amides of fatty acids having lo an acyl moiety containing from about 8 to about 18 carbon atoms and represented by the general formula:
R1 - C0 - N(H)m - 1(R2oH)3 - m wherein R is a saturated or unsaturated, aliphatic hydrocarbon radical having from about 7 to 21, preferably from about 11 to 17 is carbon atoms; R2 represents a methylene or ethylene group; and m is 1, 2, or 3, preferably 1. Specific examples of said amides are mono-ethanol amine coconut fatty acid amide and diethanol amine dodecyl fatty acid amide. These acyl moieties may be derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil, and tallow, but can be derived synthetically, e.g., by the oxidation of petroleum or by hydrogenation of carbon monoxide by the Fischer-Tropsch process. The monoethanol amides and diethanolamides of C12 14 fatty acids are preferred.
Amine oxide semi-polar nonionic surfactants comprise compounds and mixtures of compounds having the formula Rl (c2H4o) nN ~
wherein R1 is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from about 8 to about 18 carbon atoms, R2 and R3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl, and n is from 0 to about 10.
- 22 - 2055 o 4 ~
Particularly preferred are amine oxides of the formula:
I
R1 - N ~ O
wherein R1 is a C1216 alkyl and R2 and R3 are methyl or ethyl. The above ethylene oxide condensates, amides, and amine oxides are more fully described in U.S. Pat. No. 4,316,824 (Pancheri).
The composition of this invention can also contain certain cationic quaternary ammonium surfactants of the formula:
[Rl(oR2)y][R3(0R2)y]2R4N X-or amine surfactants of the formula:
[R1(oR2)y][R3(0R2)y]R4N
wherein R1is an alkyl or alkyl benzyl group having from about 6 to about 16 carbon atoms in the alkyl chain; each R2is selected from the group consisting of -CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH2-, and mixtures thereof: each R3is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl, and hydrogen when y is not O; R4is the same as R3 or is an alkyl chain wherein the total number of carbon atoms of R1plus R4is from about 8 to about 16; each y is from 0 to about 10, and the sum of the y values is from 0 to about 15; and X is any compatible anion.
Preferred of the above are the alkyl quaternary ammonium surfactants, especially the mono-long chain alkyl surfactants described in the above formula when R4is selected from the same groups as R3. The most preferred quaternary ammonium surfactants are the chloride, bromide, and methyl sulfate C816 alkyl trimethylammonium salts, C816 alkyl di(hydroxyethyl)methylammonium salts, the C816 alkyl hydroxyethyldimethylammonium salts, C816 alkyloxypropyl trimethylammonium salts, and the C816 alkyloxypropyl dihydroxyethylmethylammonium salts. Of the above, the C1014 alkyl trimethylammonium salts are preferred, e.g., decyl trimethylammonium methyl sulfate, lauryl trimethylammonium chloride, myristyl trimethylammonium bromide and coconut trimethylammonium chloride, and methyl sulfate.
~5 F~
~--`- A
- 23 - 2 OSS O ~S
The suds boosters used in the compositions of this invention can contain any one or mixture of the suds boosters listed above.
Additional Optional Inqredients In addition to the ingredients described hereinbefore. the compositions can contain other conventional ingredients suitable - for use in liquid or gel dishwashing compositions.
Optional ingredients include drainage promoting ethoxylated ~ nonionic surfactants of the type disclosed in U.S. Pat.
No. 4.316.824. Pancheri (February 23. 1982).
Alcohols. such as ethyl alcohol and propylene glycol. can be utilized in the interests of achieving a desired product phase stability and viscosity. Alcohols such as ethyl alcohol and propylene glycol at a level of from 0% to about 15%. are particularly useful in the liquid compositions of the invention.
Gel compositions of the invention normally would not contain alcohols. These gel compositions may contain higher levels of potassium or sodium toluene. xylene or cumene sulfonate. and urea at higher levels. i.e. from about 10% to about 30%. as gelling agents (see U.S. Pat. No. 4.615 819 and GB 2.179 054A).
Other desirable ingredients include diluents and solvents.
Diluents can be inorganic salts. such as ammonium chloride. sodium chloride. potassium chloride. etc.. and the solvents include water lower molecular weight alcohols. such as ethyl alcohol.
isopropyl alcohol. etc. Compositions herein will typically contain up to about 80% preferably from about 30% to about 70%.
most preferably from about 40% to about 65% of water.
As used herein. all percentages. parts. and ratios are by weight unless otherwise stated.
The following Examples illustrate the invention and facilitate its understanding.
~"~
20~S04~
ExamDle I
The following liquid composition of the present invention is prepared according to the descriptions set forth below. The alkyl ethoxy carboxylate and the appropriate co-surfactant the booster, ethanol, sodium chloride, and the buffer are blended. The pH of the mixture is adjusted with ammonium hydorixed to about 8. Then, the calcium ions (added as calcium chloride dihydrate) are added and the final pH adjusted, if necessary, to about 7.2. Final viscosity and minor pH adjustments can be made at this time, followed by the 0 addition of perfume and dye. The balance is water.
/0 Bv Weiqht Components i5 Sodium C1z 13 alkyl ethoxy 20 (3.5 ave.) carboxylate*
C12 13 alkyl ethoxy 1.23 (3.5 ave.) alcohol*
Sodium C12 13 alkyl ethoxy (1.0 ave.) sulfate 8 C12 14 alkyl amidopropyl dimethyl betaine 3 C12 14 16 alkyl dimethyl amine oxide 3 Calcium ions (added as CaCl2.2H2O) Triethanol amine 6 Sodium chloride 0.5 Ethanol 7.5 ,o Water and minor ~ -------Balance-------------pH (10% aqueous solution) 9.4 9.4 8.5 9.4 * The surfactant mixture contains about 94.2% alkyl ethoxy carboxylates of the formula RO(CH2CH2O)xCHzCOO~Na+ where R is a C12 13 alkyl averaging 12.5; x ranges from 0 to about 10, and the 205~045 ethoxylate distribution is such that the amount of material where x is 0 is about 1.0 and the amount of material where x is greater than 7 is less than about 2% by weight of the alkyl ethoxy carboxylates. The average x in the distribution is 3.5. The surfactant mixture also contains about 5.8% of alcohol ethoxylates of the formula RO(CH2CH20)xH with R being a C12 13 alkyl averaging 12.5 and the average x = 3.5. The surfactant mixture contains 0%
soap materials.
The above formulation give excellent combinations of grease ld cleaning and mildness and are stable to storage at elevated temperatures (up to 120-F). The cleaning provided by this composition at pH of about 7.2-7.5 is better than that provided by a similar composition containing an equivalent (molar basis) amount of magnesium ions. These formulations also provide superior stability during storage especially when compared to similar compositions containing magnesium ions.
ExamDle II
The following liquid composition is prepared according to the method set forth in Example I, except sodium hydroxide is used to adjust the pH of the compositions to about 8.5 % Bv Weiqht Com w nents Sodium C12 13 alkyl ethoxy 22 (3.5 ave.) carboxylate*
C12 13 alkyl ethoxy 1.35 (3.5 ave.) alcohol*
Sodium C12 13 alkyl sulfate ` 5 C12 14 alkyl amidopropyl 3 dimethyl betaine C12.14 16 alkyl dimethyl 2 amine oxide 2n~50~5 C12 13 alkyl ethoxy (8.0 ave.)alcohol 3 Calcium ions 1.2 (added as CaCl2.2H20) Bicine 1.5 Ethanol 7.S
Sodium chloride 0.5 Balance water and minors ---------------Balance---------------pH (10% aqueous solution) 8.5 This formulation of the present invention provides both good o dilute solution grease cleaning and formulation storage stability at elevated temperatures of 120-F.
ExamDle III
The following liquid composition is prepared according to the - 1, method set forth in Example I, except sodium hydroxide is used to adjust the pH of the compositions to about 9.5 % BY Weight Comwnents Sodium C12 13 alkyl ethoxy 22 (3.5 ave.) carboxylate*
C12 13 alkyl ethoxy 1.35 (3.5 ave.~ alcohol*
zs Sodium C12 13 alkyl sulfate ` 6 C12 14 alkyl amidopropyl 3 dimethyl betaine C12 14 16 alkyl dimethyl 2.5 amine oxide 30 Calcium ions 1.5 (added as CaCl2.2H20) Bicine 2 Ethanol 7.5 Balance water and minors ---------------Balance---------------35 pH (10% aqueous solution) 9.S
This formulation of the present invention provides both good dilute solution grease cleaning and formulation storage stability at elevated temperatures of 120-F especially, when compared to equivalent magnesium ion-containing compositons.
s ExamPle IV
The following liquid composition, having a relatively low surfactant level and high calcium ion level is prepared according to the method set forth in Example I.
YO Bv Weiqht -ComDonents -Sodium C12 13 alkyl ethoxy 16 (3.5 ave.) carboxylate*
C12-13 alkyl ethoxy 0.98 (3.5 ave.) alcohol*
Sodium C12 13 alkyl ethoxy (3.0 ave.) sulfate 4 12-14 alkyl amidopropyl 2 dimethyl betaine C12-14-16 alkyl dimethyl 2 amine oxide 25 Calcium ions 3.2 (added as Cacl2~2H2o) Bicine Triethamolamine Ethanol 8 30 Balance water and minors ---------------Balance---------------pH (10% aqueous solution) 8.5 3, The above formulation of the present invention provides both good dilute solution grease cleaning and formulation storage stability at elevated temperatures of 120-F especially, when compared to equivalent magnesium ion-containing compositons. This formulation is particularly useful for dishwashing habits where high product contration in solution is used.
Claims (27)
1. A light-duty liquid or gel dishwashing detergent composition comprising, by weight:
(a) from about 5% to 70% of a surfactant mixture comprising, by weight:
(i) from about 80% to 100% of alkyl ethoxy carboxylates of the formula:
RO(CH2CH2O)xCH2COO-M+
wherein R is a C12 to C16 alkyl group, x ranges from 0 to about 10 and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than about 20% and the amount of material where x is greater than 7 is less than about 25%, the average x is from about 2 to 4 when the average R is C13 or less, and the average x is from about 3 to 6 when the average R is greater than C13, and M is a cation:
(ii) from 0% to about 10% of alcohol ethoxylates of the formula:
RO(CH2CH2O)xH
wherein R is a C12 to C16 alkyl group and x ranges from 0 to about 10 and the average x is less than about 6; and (iii) from 0% to about 10% of soaps of the formula:
RCOO-M+
wherein R is a C11 to C15 alkyl group and M is a cation;
(b) from about 0.1% to 4% of calcium ions;
(c) a calcium chelating agent which forms a soluble calcium complex, having a log of formation constant, log Kf.
between about 0.5 and 5, in an amount sufficient to prevent the formation of calcium carbonate precipitates in the composition;
wherein a 10% by weight aqueous solution of said composition has a pH from about 7 to 11.
(a) from about 5% to 70% of a surfactant mixture comprising, by weight:
(i) from about 80% to 100% of alkyl ethoxy carboxylates of the formula:
RO(CH2CH2O)xCH2COO-M+
wherein R is a C12 to C16 alkyl group, x ranges from 0 to about 10 and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than about 20% and the amount of material where x is greater than 7 is less than about 25%, the average x is from about 2 to 4 when the average R is C13 or less, and the average x is from about 3 to 6 when the average R is greater than C13, and M is a cation:
(ii) from 0% to about 10% of alcohol ethoxylates of the formula:
RO(CH2CH2O)xH
wherein R is a C12 to C16 alkyl group and x ranges from 0 to about 10 and the average x is less than about 6; and (iii) from 0% to about 10% of soaps of the formula:
RCOO-M+
wherein R is a C11 to C15 alkyl group and M is a cation;
(b) from about 0.1% to 4% of calcium ions;
(c) a calcium chelating agent which forms a soluble calcium complex, having a log of formation constant, log Kf.
between about 0.5 and 5, in an amount sufficient to prevent the formation of calcium carbonate precipitates in the composition;
wherein a 10% by weight aqueous solution of said composition has a pH from about 7 to 11.
2. The composition of Claim 1 wherein the pH if from about 8 to 10.
3. The composition of Claim 2 wherein the pH is from about 8 to 9.5.
4. The composition of Claim 1 comprising from about 0.5% to 3% of calcium ions.
5. The composition of Claim 3 comprising from about 0.5% to 3% of calcium ions.
6. The composition of Claim 1 further comprising a co-surfactant selected from the group consisting of alkyl benzene sulfonates, alkyl sulfates, paraffin sulfonates, olefin sulfonates, alkyl ether sulfates, fatty acid ester sulfonates, alkyl polyglucosides, and polyhydroxy fatty acide amides, mixtures thereof.
7. The composition of Claim 1 further comprising a suds booster selected from the group consisting of betaines, ethylene oxide condensates, fatty acid amides, amine oxide semi-polar nonionics, cationic surfactants, and mixtures thereof.
8. The composition of Claim 6 further comprising a suds booster selected from betaines, ethylene oxide condensates, fatty acid amides, amine oxide semi-polar nonionics, cationic surfactants, and mixtures thereof.
9. The composition of Claim 8 wherein the pH is from about 8 to 9.5
10. The composition of Claim 8 comprising from about 0.5% to 3% of calcium ions.
11. The composition of Claim 8 wherein the pH is from about 8 to 9.5
12. The composition of Claim 1 wherein R in (a) is a C12 to C14 alkyl group.
13. A liquid composition of Claim 1 comprising from about 12% to 30% of the surfactant mixture.
14. The composition of Claim 1 wherein the surfactant mixture comprises from about 85% to 95% of the alkyl ethoxy carboxylates.
15. The composition of Claim 14 wherein the surfactant mixture comprises from about 90% to 95% of the alkyl ethoxy carboxylates.
16. The composition of Claim 12 wherein the surfactant mixture comprises from about 85% to 95% of the alkyl ethoxy carboxylates.
17. The composition of Claim 16 wherein the surfactant mixture comprises from about 90% to 95% of the alkyl ethoxy carboxylates.
18. The composition of Claim 1 wherein the surfactant mixture comprises less than about 8% of the alcohol ethoxylates.
19. The composition of Claim 18 wherein the surfactant mixture comprises less than about 5% of the alcohol ethoxylates.
20. The composition of Claim 1 wherein the surfactant mixture comprises less than about 5% of the soaps.
21. The composition of Claim 12 wherein the surfactant mixture comprises from about 90% to 95% alkyl ethoxy carboxylates, less than about 5% alcohol ethoxylates, and less than 5% soaps.
22. The composition of Claim 21 comprising from about 0.5%
to 3% calcium ions whereein the pH is from about 7 to 11.
to 3% calcium ions whereein the pH is from about 7 to 11.
23. The composition of Claim 22 comprising from about 0.5%
to 3% calcium ions wherein the pH if from about 8 to 9..5.
to 3% calcium ions wherein the pH if from about 8 to 9..5.
24. The composition of Claim 21 further comprising a co-surfactant selected from the group consisting of alkyl ether sulfates, fatty acid ester sulfonates, alkyl sulfates, alkyl polyglucosides, polyhydroxy fatty acid amides, and mixtures thereof.
25. The composition of Claim 21 further comprising a suds booster selected from the group consisting of betaines, amine oxide semi-polar nonionics, fatty acid amides, and mixtures thereof.
26. The composition of Claim 25 further comprising a co-surfactant selected from the group consisting of aklyl ether sulfates, fatty acid ester sulfonates, alkyl polyglucosides, polyhydroxy fatty acid amides, and mixtures thereof, and from 0.5% to about 3% of calcium ions are present and the pH is from about 8 to 9.5.
27. A gel compositon of Claim 1 comprising from about 10% to 45% of the surfactant mixtue.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US61453190A | 1990-11-16 | 1990-11-16 | |
| US614,531 | 1990-11-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2055045A1 CA2055045A1 (en) | 1992-05-17 |
| CA2055045C true CA2055045C (en) | 1996-11-12 |
Family
ID=24461656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2055045 Expired - Fee Related CA2055045C (en) | 1990-11-16 | 1991-11-06 | Light-duty dishwashing detergent composition containing an alkyl ethoxy carboxylate surfactant and calcium ions |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2055045C (en) |
-
1991
- 1991-11-06 CA CA 2055045 patent/CA2055045C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2055045A1 (en) | 1992-05-17 |
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