MXPA98008789A - Compositions of ultrasua detergents - Google Patents

Abstract

The present invention relates to a mild detergent formulation comprising ED3A of N-acyl, preferably as the sodium or potassium salt. The acyl group is not particularly limited, and may include linear or branched aliphatic or aromatic groups containing from 1 to 40 carbon atoms, preferably from 8 to 18 carbon atoms. Applications include shampoos and cleansers of the pi

Description

COMPOSITIONS OF ULTRASOUND DETERGENTS FIELD AND BACKGROUND OF THE INVENTION Ethylenediaminetriacetic acid (ED3A) and its salts (such as ED3ANa3) have applications in the field of chelation chemistry, and can be used as a starting material in the preparation of strong chelating polymers, oil-soluble chelants, surfactants and others. Conventional pathways for the synthesis of ethylenediamintriacetic acid are achieved via its N-benzyl derivative, which is subsequently hydrolyzed in alkaline solutions for ED3ANa3, then cyclization is avoided for its 2-oxo-l, 4-piperazindiacetic acid derivative ( 3KP). An example of the synthesis of ethylene diamine N, N, N'-triacetic acid is described in Chemical Abstracts 78, Vol. 71, page 451, no. 18369c, 1969. It is established that ethylenediamine reacts with C1H2CC02H in a molar ratio of 1: 3 in basic solution at 10 ° C for 24 hours to form a mixture from which ethylene diamine-N can be separated, N, N "-triacetic complexing itself with Co (III). The resulting cobalt complexes can be isolated through ion exchange.

REF .: 28500 The North American Patent No. 5,250,728, the description of which is incorporated herein by reference, describes a simple process for the synthesis of ED3A or its salts in high yield. Specifically, a salt of N, N'-ethylenediadiacetic acid (ED2AH2) is condensed with stoichiometric amounts, preferably light molar excesses of formaldehyde, at the temperature between 0 ° C and 110 ° C, preferably 0 ° C to 65 ° C and the pH greater than 7.0 to form a ring intermediate with 5 stable elements. The addition of a source of cyanide, such as gaseous or liquid hydrocyanic acid, aqueous solutions of hydrocyanic acid or alkali metal cyanide, in stoichiometric amounts or in a slight molar excess, through this cyclic material at temperatures between 0 ° C and 110 ° C, preferably between 0 ° C and 65 ° C, forms the ethylene diamine N, N'-diacetic acid-N'-cyanomethyl or salts thereof (mononitrile-diacid). The nitrile in aqueous solutions can be cyclized spontaneously in the presence of less than 3.0 moles of base: mol of ED2AH2, the base includes hydroxides of alkali metals or alkaline earth metals, to form 2-oxo-l, 4-piperazindiacetic acid (3KP) ) or salts thereof, this is the desired cyclic intermediate. In the presence of excess base, ED3A salts are formed with excellent yield and purity. This patent also describes an alternative embodiment in which the starting material is ED2AHaXb, wherein X is a base cation, for example, an alkaline or alkaline earth metal, a is 1 to 2, and b is 0 to 1 in aqueous solutions. The reaction mixture is also acidified to ensure the complete formation of carboxymethyl-2-oxopiperazine (the lactam) prior to the reaction. Formaldehyde is added, essentially resulting in the hydroxymethyl derivative. With the addition of a cyanide source, l-cyanomethyl-4-carboxymethyl-3-ketopiperazine (mononitrile monoacid) or a salt thereof is formed. Instead of CH20 and a source of cyanide, HOCH2CN, which is the product of formaldehyde and cyanide reaction, can also be used in this method. With the addition of any suitable base or acid, this material can be hydrolyzed to 3KP. The addition of a base will open this ring structure to form the ED3A salt. U.S. Patent No. 5,284,972, the disclosure of which is incorporated herein by reference, discloses ED3A derivatives of N-acyl and a process for producing the same. The production of N-acyl derivatives of ethylenediamine triacetic acid can be carried out or completed in accordance with the following general reaction scheme: NaOH ED3ANa3 + Acyl chloride > N-acyl ED3ANa3 + NaCl (I) The starting ED3A derivative may be the acid itself, or suitable salts thereof, such as salts of alkaline metals and alkaline earth metals, preferably sodium or potassium salts. The saturated N-acyl ED3A derivatives which are the product of the preceding reaction can be represented by the following chemical formula: O CH2COOH L C "H? T ^ -C-N - CH2CH2 - N C IH, \ CECOOH I COOH where n is from 1 to 40. Where unsaturation occurs, the structure can be shown as follows: CH2COOH CH GOOH t COOH where n is from 2 to 40. When the unsaturation increases, the formulas are: CHXOOH CH, COOH where n is 3 to 40. where n is 4 to 40; Y OR C? UiB.t-C-COOH1.5 desirable, especially for use in the hair of infants and children. The "No More Tears" baby shampoo from Johnson & Johnson, is an example of a commercially available mild shampoo. However, such shampoos tend to be relatively ineffective in terms of foaming, and are much more intolerable to water hardness. The present inventors have found that N-acyl ED3A, when produced in the pure form with impurities such as free fatty acids of less than about 1%, surprisingly work as well as chelating surfactants, which combine the properties of a chelating agent and a surfactant in a molecule. Detergent compositions containing N-acyl ED3A exhibit abundant foam and cleaning properties and lower ocular irritability. Accordingly, these chelating surfactants can be advantageously used in detergent formulations including shampoos and skin cleansers.

Therefore, it is an object of the present invention to provide new detergent compositions comprising N-acyl ED3A. where n is 5 to 40, etc. Derivatives of poly-N-acyl ethylenediamine triacetic acid, such as dicarboxylic acid derivatives having the following general formula, can also be produced: HOOCCHi O N - CH2CHi -NC - (CHj), - COOH HOOCCH- CH2 COOH wherein x is 1 to 40. Specific examples include mono and di ED3A derivatives such as oxalyldi ED3A. oxalilmono ED3A, maleilmono ED3A, maleildi ED3A, succinoilmono ED3A, succinoildi ED3A, etc. Hair shampoos that are mild in terms of irritation of the skin and eyes are an object of the present invention to provide a mild shampoo having acceptable foaming, even in the presence of highly hard water. It is still a further object of the present invention to provide a mild shampoo that causes minimal eye irritation and low toxicity. It is a further object of the present invention to provide a mild skin cleanser having acceptable foam formulation, minimal eye irritation and low toxicity.

BRIEF DESCRIPTION OF THE INVENTION The problems of the prior art have been overcome by the present invention, which provides a mild detergent formulation comprising N-acyl ED3A, preferably as the sodium or potassium salt. The acyl group is not particularly limited, and may include aromatic or aliphatic, straight or branched groups, containing from 1 to 40 carbon atoms, preferably from 8 to 18 carbon atoms.

BRIEF DESCRIPTION OF THE DRAWINGS Figures 1 to 11 are graphs comparing the stability of the foam of various compositions.

DETAILED DESCRIPTION OF THE PRESENT INVENTION Those skilled in the art will recognize that N-acyl ED3A suitable for use in the present invention can be prepared in accordance with reaction (I) above from any acyl chloride, including pentanoyl, hexanoyl, heptanoyl, octanoyl. , nananoyl, decanoyl, lauroyl, myristoyl, palmitoyl, oleoyl, stearoyl and nonanoyl. Also suitable are branched acyl chlorides, such as neopentanoyl, neoheptanoyl, neodecanopyl, iso-octanoyl, iso-nananoyl and iso-tridecanoyl, as well as aromatic acyl groups, such as benzoyl and naptoyl. The fatty acid chains can be substituted, such as by one or more halogen and / or hydroxyl groups. Examples of hydroxy-substituted fatty acids including ipurolic (3, ll-dihydroxytetradecanoic), ustylic (2,15, 16-trihydroxyhexadecanoic), ambretolic (16-hydroxy-7-hexadecanoic), ricinoleic (12-hydroxy-cis-9-octadeceneic), ricinelalylic (12-hydroxy-trans-9) -octadeceneic), 9, 10-dihydroxioctadecanoic, 12-hydroxyoctadecanoic, kalmollenic (18-hydroxy-8, 11, 13-octadecatrienoic), ximeninolic (8-hydroxy-trans-11-octadecen-9-inoic), isanolic (8- hydroxy-17-octadecen-9, 11, diinoic) and lequeroic (14-hydroxy-cis-11-eicosenoic), as well as acyl chlorides of the above (the derivatives named above where the "olic" suffix is replaced by "oyl chloride"). Suitable halogen-substituted fatty acids include trifluoromethylbenzoyl chloride, pentadecafluoro-octanoyl chloride, pentafluoropropionoyl chloride, pentafluorobenzoyl chloride, perfluorostearoyl chloride, perfluorononamoyl chloride, perfluoro-trimathoyl chloride and trifluoromethylacetyl chloride. Preferably, the N-acyl group contains from 8 to 18 carbon atoms. It is preferred to use the N-acyl ED3A in the form of its salts, in view of its solubility. Where the N-acyl ED3A is produced first, it can easily be converted into salts by partial or complete neutralization of the acid with the appropriate base. The acid can also be produced from ED3A salts of N-acyl by neutralization of the base with a quantitative amount of acid. Preferred chelating surfactants for use in the detergent compositions of the present invention are lauroyl-ED3A sodium and potassium. Other suitable counterions or counter ions include triethanolamine, diethanolamine, monoethanolamine, ammonium, isopropyl amine, N-propylamine and amino alcohols such as 2-amino-1-butanol, 2-amino-2-methyl-1,3-propane diol, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-l, 3-propane diol and Tris (hydroxylmethyl) aminomethane. The ED3A salts of N-acyl can be used in the detergent compositions of the present invention, alone or in combination with other surfactants. The total amount of surfactant in the composition is generally between about 3 to about 30%, preferably between about 10 and about 15%. The N-acyl ED3A may be a minor or major portion of the active surfactant, depending on the desired smoothness and other characteristics of the formulation. Conventional surfactants which can be used in combination with the N-acyl ED3A include sarcosinates (including oleoyl, lauroyl and myristoyl), N-acyl glutamates, imidazoline amphoteric derivatives, fatty amides and sulfosuccinate esters, soluble linear alkylbenzene sulphonate , alkyl sulfate and alkyl ethoxy sulfates, sodium lauryl ether sulfate; alcohol ethoxylates and alkyl polyglycosides; trimethyl ammonium chloride of C? 2-C? , di-tallow di-methyl ammonium chloride; and di-tallow methylamine, etc. Many of the preceding compounds are frequently used in combination. The imidazolines are usually combined with ethanol-containing mannitol or sorbitan esters. The pH of the detergent composition should be within the range of about 6 to about 8. A pH of about 7 is especially preferred to minimize eye irritability. Other ingredients conventionally added to detergent compositions may be included, such as dyes, perfumes, thickeners (such as electrolytes, natural gums, alginates, cellulose derivatives and carboxyvinyl polymers), diluents, conditioning agents (such as lanolin, mineral oil , polypeptides, herbal additives, for example synthetic derivatives and resins), humectants, buffers, opacifiers (such as high fatty acid alkanolamides, glycol mono and distearate, propylene glycol monostearate and glycerol, fatty alcohols, vinyl polymer emulsions and latexes, insoluble salts, finely dispersed zinc oxide or titanium dioxide and magnesium aluminum silicate), preservatives (such as formaldehyde, phenyl mercuric salts and p-hydroxybenzoic acid esters), antioxidants, etc. A typical baby shampoo formulation is as follows: Sodium lauroyl ED3A 17.1% Tridecylether sulfate salt 4.4 EtO 65% 8.3% Polyoxyethylene monolaurate (100) sorbitan 7.5% Condoms, perfume, dye q.s. 100% water The ability of many surfactants to produce good foam is inhibited by the presence of excess electrolyte, such as sodium chloride, and hard multivalent ions, such as Ca ++ and Mg ++. Surprisingly, the present inventors have found that electrolytes and hard ions actually significantly improve the stability of the alkaline metal N-acyl ED3A foam.

EXAMPLE 1 The stability of the foam of a surfactant solution, expressed as foam drainage time, can be determined by the method of Hart and DeGeorge, J. Soc. Cos et. Chem., 31, 223-226 (1980). In this method, a 200 ml portion of the test solution is stirred in a mixer for one minute. The produced foam is immediately poured into a Nalge PF150 funnel, which has been modified for easy detection of the end point by incorporating a fine strand of a Nicrome wire through the funnel, where the diameter is 9 cm. The funnel is supported by a 20 mesh or mesh screen. The time elapsed between the pouring of the contents of the mixer into the funnel and the reappearance of the wire through the sinking foam, determined using a stopwatch, is reported as the foam drainage time in seconds. A stable, high foaming surfactant will be expected to exhibit a draining time of 60-100 seconds for a 1% solution, while an unstable foam should be expected to produce a value of less than 10 seconds. The effect of sodium chloride on the drainage time of the foam of a 1% solution of NA lauroyl ED3A, at pH 7, was compared with the effect of sodium lauryl sulfate, a common surfactant used in detergent formulations. The results are shown in Figure 1. The time for draining the foam by sodium lauryl sulfate is reduced by 30 seconds during the addition of 4% electrolyte, while the time for LED3A of Na is increased by more than 70 seconds for the same increase in salinity.

EXAMPLE 2 The drainage or dissipation time test of the foam was used to determine the effect of water hardness ions on the stability of the lauroyl ED3A sodium foam. Figure 2 shows that the addition of approximately 3,000 ppm water hardness (CaCO3) results in a fivefold increase in foam stability of a 1% solution of NaLED3A. In contrast, an equivalent addition for sodium lauryl sulfate results in a fivefold reduction in drainage time or foam dissipation.

EXAMPLE 3 A baby shampoo, commercial, (Johnsons Baby Shampoo) which has the composition listed below, is dried to constant weight in an oven at 100 ° C. The product is found to contain approximately 16% solids.

COMPOSITION Water, Laurato de Sorbitan PEG-80, Cocamido Propil Betaine, Trideceth Sodium Sulfate, Glycerin, Lauroanfoglycinate, PEG 150 Distearate, Laureth-13 Sodium Carboxylate, Fragrance, Polyquaternium-10, Tetrasodium EDTA, Quaternium 15, Citric acid, Color.

The high purity lauroyl ED3A is neutralized to about pH 7 with about 2 moles of sodium hydroxide and diluted to a concentration of about 16%. The solutions of 1) the above-mentioned commercial baby shampoo, 2) Na2LED3A, and 3) a 3: 1 ratio ratio or mixture of baby shampoo and Na2LED3A were subjected to the foam stability test using the method described in Example 1. The results are shown in Figure 10. The addition of Na2LED3A, as one third of the product, improves the foam stability of the product approximately 7 times in both hard and soft water. The system with Na2LED3A in the presence of 200 ppm hardness was the most effective foaming agent with a dissipation or drainage time of more than 200 seconds.EXAMPLE 4 Samples of 1) the commercial baby shampoo mentioned above, 2) Na2LED3A, 3) a 3: 1 ratio mixture of baby shampoo and Na2LED3A, and 4) a 16% solution of laureth 3 sodium sulfate (an agent surfactant commonly used in ordinary shampoo) were subjected to the skin irritation test in vitro. A sample of the tissue was immersed for 24 hours in a solution of the substrate to be evaluated and subsequently tested by viable mitochondria by an MTT assay. The MTT assay is a colorimetric method for determining the viability of cells based on the reduction of a tetrazolium salt (MTT) in a formazan dye colored by mitochondrial enzymes of the electron transport chain. The prolongation at which the number of viable mitochondria has been reduced, compared to a control, is taken as a measure of the toxicity of the test substance to human skin cells. The in vitro labeling classification used was as follows: Marking of MTT-50 in vitro (micro g / ml) Classification 0-200 Severe 201-1,000 Moderate 1,001-10,000 Soft > 10,000 Non-irritating Results are shown in table 2: TABLE 2 Product Marking MTT-50 in vitro Classification (micro g / ml) Baby Shampoo 1,900 Soft Baby Shampoo + Na2LED3A 2,149 Soft Na2LED3A > 10,000 Non-irritating Laureth (3) sulfate 522 Moderate Na These results indicate that Na2LED3A is compatible with the ingredients in mild shampoos and can improve performance while reducing irritation. The surfactant by itself can function as a shampoo in 16% concentration and is extremely mild. The potential for incorporation into formulations containing additives such as thickening agents, conditioners, color, fragrance and other ingredients is clear.

EXAMPLE 5 The high purity lauroyl ED3A was neutralized to about pH 7 with about 2 moles of sodium hydroxide and diluted to a concentration of about 16%. The solutions of 1) Johnsons Baby 2 in 1 shampoo, and 2) a 3: 1 ratio of Johnsons Baby 2 in 1 shampoo and Na2LED3A were tested for foam stability using the method described in Example 1. The results are shown in Figure 3. The addition of Na2LED3A, as a third part of the product, improves the foam stability of the product approximately 6 times in soft water and 5 times in hard water.

EXAMPLE 6 The high purity lauroyl ED3A is neutralized to about pH 7 with about 2 moles of sodium hydroxide and diluted to a concentration of about 16%. The solutions of 1) Johnsons Baby Bath, and 2) a 3: 1 ratio or ratio of Johnsons Baby Bath and Na2LED3A were subjected to the foam stability test using the method described in Example 1. The results are shown in FIG. Figure 4. The addition of Na2LED3A, as a third of the product, improved the foam stability of the product more than 4 times in soft water and more than 12 times in hard water.

EXAMPLE 7 The high purity lauroyl ED3A was neutralized to about pH 7 with about 2 moles of sodium hydroxide and diluted to a concentration of about 16%. The solutions of 1) Soft Baby Care, and 2) a 3: 1 ratio or ratio of Soft Baby Care and Na2LED3A were subjected to the foam stability test using the method described in Example 1. The results are shown in the Figure 5. The addition of Na2LED3A, as a third of the product, only doubled the foam stability of the product in soft or light water. The addition of Na2LED3A improved the foam stability of the product more than 5 times in hard or cloudy water.

EXAMPLE 8 Example 3 was repeated except that the potassium LED3A was replaced by sodium LED3A. The results are shown in Figure 6. The addition of K2LED3A, as one third of the product, improved the foam stability of the product to approximately 8 times in soft or light water, more than 14 times in hard water (200 ppm CaCO3). ), and more than 24 times in even harder or heavier water (400 ppm CaCO3).

EXAMPLE 9 Example 5 was repeated except that the potassium LED3A was replaced by sodium LED3A. The results are shown in Figure 7. The addition of K2LED3A, as a third part of the product, improved the foam stability of the product more than 2 times in soft or light water, and approximately 7 times in hard water (200 ppm CaCO3). ).

EXAMPLE 10 Example 6 was repeated except that the potassium LED3A was replaced by sodium LED3A. The results are shown in Figure 8. The addition of K2LED3A, as a third part of the product, improved the foam stability of the product to approximately 5 times in soft or light water, and approximately 12 times in hard water (200 ppm CaCO3). ).

EXAMPLE 11 Example 7 was repeated except that the potassium LED3A was replaced by sodium LED3A. The results are shown in Figure 9. The addition of K2LED3A, as a third part of the product, improved the foam stability of the product to approximately 2 times in soft or light water, and 5 times in hard water (200 ppm CaC03) .

EXAMPLE 12 Example 3 was repeated except that the sodium myristoyl LED3A was replaced by sodium LED3A, and the Johnsons Baby 2 in 1 shampoo was replaced by Johnsons Baby Shampoo. The results are shown in Figure 11. The addition of Na2MED3A, as a third part of the product, improved the foam stability of the product more than 9 times in soft or light water, and 9 times in hard water (200 ppm CaCO3) . The pure sodium sodium myristil ED3A more than 100 times more effective in heavy or hard water than baby shampoo alone.

EXAMPLE 13 The LED3A was neutralized to approximately pH 7 with approximately 2 moles of tris amino. The concentration was adjusted to 16% active. The solution was maintained at 80 ° C for 20 minutes to ensure sterility. The solution was diluted 10 to 1 with distilled water. Two drops of this 1.6% solution were poured into an eye of 2 human subjects and allowed to moisten the entire surface. The second eye of each subject was instilled or applied with 2 drops of 1.6% of a Johnsons Baby Shampoo solution and allowed to moisten the entire surface. No subject was aware of the identity of the samples. Both subjects identified the sample of tris amino LED3A as producing significantly less irritation or sting to the eye, consequently the Baby Shampoo a shampoo of low irritant, commercial character.

It is noted that in relation to this date, the best method described by the applicant to carry out the aforementioned invention, is that which refers to the manufacture of the objects to which it refers. Having described the invention as above, the content of the following is claimed as property

Claims (9)

1. A mild detergent composition, characterized in that it comprises an effective amount of a salt of ethylenediaminetriacetic acid of N-acyl, while the acyl group is an aliphatic or aromatic group, linear or branched, containing from 1 to 40 carbon atoms.

2. The detergent composition according to claim 1, characterized in that the salt is present in an amount of about 3 to about 30% by weight of the composition.

3. The detergent composition according to claim 1, characterized in that the acyl group contains from 8 to 18 carbon atoms.

4. The detergent composition according to claim 1, characterized in that the N-acyl ethylenediaminetriacetic acid salt is an alkali metal salt.

5. The detergent composition according to claim 1, characterized in that the salt of ethylenediaminetriacetic acid of N-acyl is a salt of alkanol amine.

6. The detergent composition according to claim 1, characterized in that the N-acyl ethylenediaminetriacetic acid salt is an amino alcohol salt.

7. The detergent composition according to claim 1, characterized in that the acyl group is selected from the group consisting of lauroyl, oleoyl and myristoyl.

8. The detergent composition according to claim 8, characterized in that the acyl group is lauroyl.

9. The detergent composition according to claim 1, characterized in that it also comprises a co-surfactant agent.