Background Information Surfactants are generally recognized as being amphiphillic molecules that comprise a hydrophobic and a hydrophilic portion within the same molecule, and may be either synthetic or naturally-occurring. Early synthetic surfactants were typically based on fatty acids obtained from natural glyceride oils or fats for a source of the hydrophobic part of the molecule which provided, exclusively, straight chain alkyl or alkenyl groups with an even number of carbon atoms. More recently, branched chain oxo alcohols, polypropylene oxide, and/or alkylbenzene groups of petrochemical origin have also been used as materials from which surfactants may be derived. Some naturally-occurring surfactants include saponins in which the hydrophobic portion is a tri-terpenoid, such as a steroid, and the hydrophilic portion is a polyglycoside. However, owing to limited quantities of available natural sources, the amount of surfactants which are procurable therefrom are correspondingly limited.

In contrast to the very restricted choice of feedstock for the hydrophobic part of surfactant molecules, the methods used to generate the hydrophilic portion of synthetic surfactants have been numerous and very diverse. They have included, alone or in various combinations: saponification of glycerides to give soaps; hydrogenation of fatty acids to give fatty alcohols; amination or amidation to give amines, alkanolamides, amido amines or imidazolines; ethoxylation of alcohols, acids, amines or hydroxy esters, to give polyethoxylates; sulphation, sulphonation or phosphorylation of alcohols, ethoxylates, esters or hydrocarbons to give anionic surfactants; neutralisation or quaternisation of amines, amido amines or imidazolines to give cationic surfactants; carboxymethylation or carboxyethylation of amines, amido amines or imidazolines to give amphoteric or zwitterionic surfactants; oxidation of amines to give amine oxides; esterificaton of carboxylic acids with sucrose or sorbitan; and glycosylation of carboxylic acids to give polyglycosides.

Despite the very large number of different surfactants which are commercially available there is a constant demand for new products with properties, which often differ only slightly from those already accessible, but which are better suited to particular, niche applications. This demand has been largely met by seeking yet more variations on the hydrophilic group. The hydrophobic group has remained essentially unchanged, as it is often regarded as little more than an inert source of hydrophobicity.

One object of the present invention is to provide alternatives to the limited range of conventional hydrophobic feedstocks, which have chemical and biological activity capable of conferring, on the surfactants derived therefrom, enhanced surface activity, mildness, anti-microbial properties, self-preservation and favorable biodegradability and/or other functionalities in addition to their surface activity, in addition to being produced from renewable natural sources.

We have discovered that certain derivatives of terpenes satisfy the above requirements. Terpenes, may be notionally constructed from two or more isoprene units. The hydrophobes of the present invention exhibit a range of biological activity, typically biocidal or biostatic, and often have characteristic aromas capable of attracting or repelling pests or enhancing the fragrance or flavour of a product.

Certain terpenes are known to possess conjugated double bonds, and therefore to be capable of undergoing Diels Alder addition reactions with dienophiles. We have discovered that the resulting adducts, when formed from a hydrophobic terpene and a dienophile, having a hydrophilic or hydrophilisable substituent, may be used as, or as intermediates in the preparation of, a new class of multifunctional surfactants.

Desalted amphoteric and zwitterionic surfactants generally form La-phase at higher concentrations, e. g. up to 80% or even higher, and are particularly preferred, where the objective is to supply the product in a pourable form at the highest convenient concentration. However, in the presence of added electrolyte less concentrated and more mobile expanded La-phases can be obtained that are capable of indefinitely suspending particulate material.

Expanded La-phases, typically with repeat-spacing between 8 and 20, e. g.

10 to 15 nanometers, form when electrolyte is added to aqueous surfactants at concentrations just below those required to form a normal La-phase, particularly to surfactants in the H-phase. The H-phase, also referred to as the M-phase, comprises surfactant molecules arranged to form cylindrical rods of indefinite length. It exhibits hexagonal symmetry and a distinctive texture under the polarising microscope.

Typical H-phases have so high a viscosity that they appear to be curdy solids. H-phases near the lower concentration limit (the LJH-phase boundary) may be pourable but have a very high viscosity and often a mucous-like appearance. Such systems tend to form expanded La-phases particularly readily on addition of sufficient electrolyte.

Expanded La-phases are described in more detail in EP O 530 708. In the absence of suspended matter they are translucent, unlike dispersed

lamellar or spherulitic phases, which are usually opaque. They are optically anisotropic and have shear dependent viscosity.

Spherulitic phases comprise well-defined spheroidal bodies, usually referred to in the art as spherulites, in which surfactant bilayers are arranged as concentric shells. The spherulites usually have a diameter in the range 0.1 to 15 microns and are dispersed in an aqueous phase in the manner of a classical emulsion, but interacting to form a structured system. Spherulitic systems are described in more detail in EP O 151 884. Fatty acid based amphoteric or zwitterionic surfactants do not readily form structured suspending systems, which has restricted their usefulness in liquid laundry detergents, despite their superior soil- removing power.

It has been found that amphoteric or zwitterionic surfactants readily form La-phases, at concentrations, typically above about 60% and below about 80%, by weight active concentration. La-phases are lyotropic mesophases, in which bilayers of surfactant are arranged with the hydrophobic part of the molecule on the interior and the hydrophilic part on the exterior of the bilayer (or vice versa). The bilayers lie side by side, e. g. in a parallel or concentric configuration, sometimes separated by aqueous layers. La-phases (also known as G-phases) can usually be identified by their characteristic textures under the polarising microscope

and/or by x-ray diffraction, which is often able to detect evidence of lamellar symmetry. Such evidence may comprise first, second and sometimes third order peaks with repeat spacing (27r/Q, where Q is the momentum transfer vector) in a simple integral ratio 1 : 2: 3. Other types of symmetry give different ratios, usually non-integral.

Fatty acid-derived amphoteric and zwitterionic surfactants do not normally form La-phases. The ability to form such phases is an important advantage, because it enables the products to be supplied in a pourable form at much higher concentrations than would otherwise be possible.

Hitherto it has not been possible to prepare these surfactants, in pourable form, at concentrations above about 39%, by weight, and most are not available commercially at concentrations above about 34%.

A number of surfactant blends are available as La-phases at about 60 or 70% concentration. They are usually referred to as"high active"products and are described in GB 2 021 141. Relatively few single surfactants can be obtained as high active products because most single surfactants either do not form an La-phase at normal room temperature, or do so over a concentration range, which is too narrow to permit commercial manufacture.

Summary of the Invention The present invention provides Diels Alder adducts, which are either surfactants having a hydrophobic portion and a hydrophilic portion, or intermediates in the preparation thereof, wherein the hydrophobic portion is derived from a hydrophobic terpene, which comprises two conjugated double bonds, or an isolated double conjugated with an allylic hydrogen atom, and which has from 10 to 30 carbon atoms per molecule, and wherein the hydrophilic portion: a) is derived from a dienophile, which comprises a double-bonded pair of carbon atoms and at least one adjacent activating group; and b) has at least one hydrophilic group, present in said dienophile prior to, or introduced during or after, the formation of the adduct.

Provided herein are surfactant material that is derived from a terpene- derived acid having a structure selected from the group consisting of: and

, wherein R is selected from the group consisting of: hydrogen or methyl, and wherein said surfactant material is selected from the group consisting of: amphoacetates, betaines, amine oxides, alkoxylates, esters, amides, sugar esters, and simple metallic soaps such as the alkali metal, alkaline earth metal, and ammonium (alkyl-substituted or un-substituted) soaps.

Brief Description of the Drawings In the annexed drawings: FIG. 1 shows a comparison between surface tensions of conventional surfactants and those of the present invention; and FIG. 2 shows surface tension profiles of AAPB based on myrcene versus those of the prior art.

Detailed Description In this specification, unless otherwise stated, the disclosure of alternative values for the upper or lower limit of the permitted range of a parameter, coupled with an indication that one of said values is more highly preferred than the other, is to be construed as an implied statement that each intermediate value of said parameter, lying between the more preferred and the less preferred of said alternatives, is itself preferred to said less preferred value and also to each value lying between said less preferred value and said intermediate value.

Definitions As used in the present specification, the following terms have the following meanings: "Diels Alder adduct"includes products of variations on the classical Diels Alder addition, such as the hetero variant, in which the dienophile is reacted with a compound, which comprises an ethylenic double bond conjugated with a non-ethylenic bond, such as a carbonyl group, or the ene reaction, in which the dienophile reacts with an isolated double bond, conjugated with an allylic hydrogen atom.

"Terpene"refers to the naturally occurring oligomers of isoprene and their derivatives, or their nature-identical synthetic counterparts. The terpene is preferably a mono-, sesque-, or diterpene, and is desirably a hydrocarbon. However the term"terpene"as used herein includes hydrophobic terpenoids having one or more carbonyl groups and monohydroxy terpenols. A preferred terpene for use as the diene is myrcene. Other examples include a-terpinene, citral (hetero variant of a diene), ocimene, p-ionone and (3-ironie, or p-pinene (ene reagent).

According to the present invention, the dienophile selected preferably has from 2 to 10 carbon atoms per molecule. The activating group (s) may comprise a hydrophilic group, such as a carboxyl, carboxylic anhydride, hydroxymethyl, sulphonyl or phosphonyl group. Alternatively, the activating group may comprise, for example, a carbonyl, carboxylic ester, halogen, aryl, aminomethyl, cyano or nitro group. Typical examples include acrylic acid, methyl acrylate, polyethyleneglycol acrylate, glyceryl monoacrylate, methacrylic acid, methyl methacrylate, maleic acid, maleic anhydride, fumaric acid, citraconic acid, mesaconic acid, crotonic acid, isocrotonic acid, aconitic acid, itaconic acid, angelic acid, tiglic acid, vinylphosphonic acid, vinyl sulphonic acid, vinyl chloride, styrene, styrene sulphonic acid, allyl alcohol, allyl amine and acrolein.

The reaction may be carried out in the conventional manner for Diels Alder additions by heating the reaction mixture, in substantially stoichiometric proportions, optionally in a suitable organic solvent, e. g. petroleum, limonene, or an aromatic solvent such as benzene or toluene, if required for fluidity. If required, a Diels Alder catalyst, e. g. a Lewis acid such as aluminium chloride may be employed, however we have found that un-catalysed reactions may give better coloured end products, especially in processes, which involve the subsequent amidation of the adduct.

The reaction temperature is preferably greater than 50°C, more preferably greater than 70°C, even more preferably greater than 90°C, more preferably still, greater than 100°C, most preferably greater than 120°C, provided that it does not exceed the decomposition temperature of the product. Depending on stability of the product and reactivity of the reaction mixture, higher temperatures, greater than 130°C may sometimes be preferred. Temperatures will preferably be less than 250 ° C more preferably less than 200°C, even more preferably less than 180°C, most preferably less than 160°C.

The elevated temperature is maintained for a sufficient time to obtain an acceptable yield of the adduct. The time required depends on the reactivity of the particular reagents, the temperature, the stability of the

product and commercial considerations (e. g. the value of the product against the cost of prolonging the heating step), however, typically, it is greater than 30 minutes, preferably greater than one hour, more preferably greater than two hours, but is preferably less than twenty four hours, more preferably less than fifteen hours, and more preferably still less than ten hours.

The adducts of the invention are typically ring compounds, which comprise a mixture of para and meta isomers, with the activating group either in, or perpendicular to the plane of the ring, respectively. The mixture may be used as such, but we do not exclude separating the isomers.

Where the dienophile comprises one or more hydrophilic groups, the product may be used as a surfactant in its own right. Where these groups are anionic groups, such as carboxyl, sulphonyl or phosphonyl, the product may require neutralisation with a suitable base to form a salt, such as the sodium, potassium, ammonium, ethanolamine or isopropylamine salt. Alternatively the adduct may be used as an intermediate in the preparation of the surfactant product, by treating it with any of the conventional processes used for generating the hydrophilic portion of a surfactant, such as those listed above. For example a carboxylate group may be esterified with sorbitan or sucrose,

glycosylated or ethoxylated to provide a non-ionic surfactant. It may be amidated, e. g. with an alkanolamine to form an alkanolamide, with a diamine, to form an amido amine, or with diethylenetriamine to form an imidazoline, which may in turn be quaternised, e. g. with hydrochloric acid or dimethyl sulphate to form a cationic surfactant, or carboxymethylated with chloracetic acid to form an amphoacetate. It may be hydrogenated to form an alcohol, which may be ethoxylated to form a non-ionic surfactant, and either the alcohol, or its ethoxylate may be sulphated to form an anionic surfactant. By these and other means well known to those skilled in the art, adducts of this invention may be converted into novel members of any of the surfactant groups currently available commercially, and the invention includes all such derivatives.

For example according to one particularly preferred derivatisation, carboxylic acid intermediates of the invention, especially those obtained by the reaction of an unsaturated carboxylic acid, such as acrylic acid, with, e. g. myrcene, or a-terpinene, are ethoxylated with at least one, preferably at least 2, more preferably at least 4, even more preferably at least 6, most preferably at least 7, but preferably less than 70, more preferably less than 50, even more preferably less than 30, more preferably still, less than 20, most preferably less than 15 ethyleneoxy groups. Alternatively the same products may be obtained by reacting the terpene with a pre-ethoxylated acrylic, or other unsaturated, acid. These products exhibit particularly good biocidal properties.

According to a further particularly preferred derivatisation, the aforesaid carboxylic acid intermediates of the invention may be amidated, e. g. with 3- (dimethylamino) propylamine, using any of the conventional amidation methods to make, e. g. , an alkylamidopropyl amine. The amidation product may be carboxymethylated with sodium chloroacetate to provide a novel betaine, which combines a mildness characteristic of betaines with a microbicidal activity, contrasting with the usual behaviour of fatty acid derived betaines. The latter are microbial growth promoters. Alternatively the amidation product may be oxidised, e. g. by reaction with hydrogen peroxide, to form a novel amine oxide.

We have found that in general the terpene adduct analogues of those fatty acid-derived surfactants, which are most prone to microbial spoilage, are particularly effective as biocides.

Amphoteric or zwitterionic surfactants of the invention, which have been prepared by carboxymethylation, normally contain about 20%, by weight based on the total weight of surfactant, of sodium chloride, formed as a by-product of the reaction between the amine or amidoamine precursor, and chloroacetic acid. If desired, the salt can be removed or substantially reduced, either during or after preparation, for example by electrodialysis, e. g. as described in GB 1 525 692 or in EP 0 736 521, by

membrane filtration, for example as described is EP 0 626 881, or, less preferably, by displacing metal ion e. g. using ion exchange or by solvent precipitation. Alternatively, it is possible to prepare zwitterionic surfactants with low salt levels by carboxyethylating the precursor amine or amidoamine with acrylic acid.

Amphoteric or zwitterionic surfactants of the invention have also been observed to form spherulitic suspending systems, in the presence of sufficient electrolyte. The exact concentration ranges, within which the surfactants of this invention form La-phases, vary according to the particular surfactant and the salt concentration. We have found that, generally, the terpene derived surfactants of this invention form La- phases more readily than their fatty acid analogues, and may be supplied as high active products.

Surfactants of the present invention have been found to exhibit useful secondary properties in addition to surface activity. These include biocidal or biostatic activity, or the ability to enhance or modify fragrances and flavours. They have also been found to exhibit improved surfactancy, and higher critical micelle concentrations, compared with their fatty acid-derived analogues.

The invention will be illustrated by the following examples, in which all proportions are by weight, based on the total weight of the composition, and all temperatures are in degrees centigrade, unless stated to the contrary. The following examples shall be construed as exemplary of various embodiments of the present invention, and shall not be construed as being delimitive thereof in any way.

EXAMPLE I 20. 1g myrcene (0.14 moles) and 50. Og of 7-mole polyethoxy acrylate (0.14 moles), with l. Og aluminium chloride catalyst were heated under nitrogen to 125°C. A small exotherm raised the temperature to 132°. The temperature was allowed to return to 125°C, and was then maintained at that level for a further three hours. The product had a pleasant resinous odour and formed a clear solution in water at 20°C, with a cloud point between 25 and 30°C. The surface tension of solutions of the product in deionised water over a range of concentrations was measured, using a bubble tensiometer. The results indicated an effective surfactant, with a critical micellar concentration between 0.05 and 0. 1%.

EXAMPLE II Example I was repeated, replacing the myrcene with a-terpinene in the same molar proportions. The reaction temperature was raised to

150°C, and maintained for five hours. The product had a sweet spicy aroma and a cloud point below 20°C.

EXAMPLE III Example I was repeated, replacing the acrylate with acrylic acid in the same molar proportions. The temperature was maintained at 130°C for three hours. The product was insoluble in deionised water, but is a valuable intermediate for the preparation of surfactants. It dissolves in dilute alkali, e. g. sodium hydroxide, to form a soap. It may be substituted for fatty acid in any of the known processes for converting the latter into surfactants.

EXAMPLE IV The carboxylic acid of example III was amidated with 3- (dimethylamino) propylamine, to form the corresponding alkyl amido propylamine. The adduct was refluxed at atmospheric pressure with a small stoichiomteric excess of the amine, and the product stripped, with further additions of amine to help remove water. The amido propylamine was then carboxymethylated in aqueous solution by heating with an equimolar proportion of sodium chloracetate for 8 hours at 80°C, while maintaining the pH at 10. The pH was then raised to 11.5, and heating continued for a further 4 hours. The pH was finally adjusted to 5.

EXAMPLE V The amido propylamine of example IV was reacted with an equimolar amount of hydrogen peroxide in aqueous solution to form the corresponding amine oxide.

EXAMPLE VI Broad spectrum biocidal activity of the products of examples IV and V were assessed using cultures of E. coli (NCIMB 8545), S. aureus (NCTC 10788) and C. albicans (NCPF3179). Cultures were exposed to 3% by weight active ingredient solutions of surfactant for 60 minutes and recultured. The product of Example IV was compared with a commercial coconut amidopropyl betaine, sold under the registered trademark "EMPIGEN'BS/FA, which contained 0.5% sodium benzoate as a preservative. The product of Example V was compared with commercial coconut amidopropyl amine oxide sold under the registered trademark "EMPIGEN"OS/A. In each case an untreated control was included.

Critical micellar concentrations and surface tensions (y, measured at 9x 103 mg dm-3) of the surfactants were measured using a bubble tensiometer.

The results are set out in table I below: Substance C. M. C./Cell viability counts 103 mg.dm-3 γ /mN.m-1 E. coli S. aureas C. albicans EMPIGEN 1.0 35.1 + 81. 8% + 70.7%-27. 3 % BS/FA Example 1.6 25.6-88. 8%-58. 0%-72. 3 % IV Control N/A N/A-18. 1%-28. 1%-16. 7% EMPIGEN 1.0 35.0-15. 2%-18. 0% + 7. 2 % OS/A Example V 2. 6 30. 3-10. 7%-11. 1% + 3.0% Control N/A N/A-11. 1%-14. 3%-12.1%

Table I The examples of the invention show greater reductions in surface tension (greater surface activity) than the corresponding commercial fatty acid- derived products. Example IV shows strong broad spectrum biocidal activity, whereas the fatty acid equivalent, even with added preservative, is a promoter of microbial growth.

EXAMPLE VII The product of Example IV was concentrated to 60% by weight active, at which it formed a viscous, yellow oil. A drop of the latter on the slide of polarising microscope was observed. Initially a batonette texture, indicative of H-phase, was seen to develop rapidly, but after being allowed to dry by evaporation overnight, a typical texture indicative of La-phase was obtained.

EXAMPLE VIII The product of Example I was evaluated for activity against E. coli, following the procedure of Example VI. The ethoxylate gave a 61% reduction in the viability of E coli, compared to only 4% by a Cl2 l4 fatty alcohol ethoxylate.

EXAMPLE The product of Example II was evaluated for activity against E. coli, following the procedure of Example VII. The product gave an 82% reduction in the viability of E coli.

EXAMPLE X Example III was repeated without catalyst. On heating tol05° C, the mixture exothermed to 178° C. After cooling to 140° C, the product was aged for 1 hour.. The adduct was obtained in good yield. The isomer ratio was 50/50.

EXAMPLE XI Example IV was repeated using the adduct of Example X in place of that of Example III. A cream coloured product of substantially improved colour was obtained.

Thus, according to the present invention, a terpene, which is preferably selected from the group consisting of: myrcene and alpha terpinene, is reacted with acrylic acid to form an adduct acid material according to the following formula: 0 + I I-oH myrcene acrylic acid (I) _____ _ _ _C \OH adduct acid

using aluminum chloride (AlCl3), optionally, as a catalyst. The adduct acid product from the reaction in (I) may be subsequently employed in place of a conventional carboxylic acid (having hydrocarbon chain lengths (Cl0 to Czo) and branched or linear character recognized by those skilled in the detergent arts as being useful for producing detersive materials including soaps and the like) in forming various types of detergents known to those skilled in the art which include without limitation: betaines, amine oxides, amphoacetates, alkoxylates, amides and esters.

For example, reaction of the adduct acid from reaction (I) with dimethylaminopropylamine ("DMAPA") yields an amide having a dimethylamino end cap which can be subsequently quaternized with chloroacetic acid or its sodium salt, using means well known in the art, to

provide alkylamidopropylbetaines which are heretofore unknown, and which possess the properties descried in this specification, which make these materials high value added multi-functional detersive agents. The alkylamidopropylbetaines produced according to the foregoing has the structure in formula (II):

Another embodiment of the present invention involves the reaction of alpha-terpinene with acrylic acid to yield an adduct acid, according to the reaction:

Subsequent reaction of the acid produced in reaction (III) above with an amine such as DMAPA, followed by treatment with chloroacetate yields betaines having the structure: which betaines are mild, anti-microbial, self-preserving, and biodegradable.

Another embodiment of the present invention relates to alkylamidopropyl amine oxides which are prepared by first treating the acid produced in reaction (III) with a diamine such as DMAPA, and then subsequently oxidizing the amine so formed with a peroxide, such as hydrogen peroxide, under conditions known to those skilled in the art as being useful for producing amine oxides, which yields:

which is useful in one regard, as an ingredient in finished detergent formulations in place of amine oxides of the prior art. Additionally, the adduct acid from (II) can similarly be employed to produce amine oxides according to the same reaction scheme and having the general formula:

In addition, the acid adducts produced in reactions (I) and (III) may be used as starting materials for the preparation of the sucrose and sorbitan esters shown in (VII), (VIII), (IX), and (X) below.

Additionally, the adduct acids from reactions (I) and (III) can be used as the basis of alkoxylates having the general structures: and

(XD) in which RO is an alkylene oxide selected from the group consisting of: ethylene oxide, propylene oxide, and butylene oxide, including mixtures of any two or more of the foregoing, in random and block co-polymer fashion, wherein n may be any integral value between 1 and 50, preferably between 3 and 30, and more preferably still between about 3 and 20, and including mixtures of materials having different values of n.

The acid adducts from structures (I) and (III) above may also be employed to produce amphoacetates according to the following methods. To make

an imidazoline base intermediate, 300 grams (1.44 moles) of the adduct acid from reaction (I) above is combined with 151.5g (1.46 moles) of aminoethylethanolamine (AEEA). The temperature is slowly ramped up to 185°C and vacuum slowly increased from 240 mbar absolute to 20 mbar absolute over the course of about five hours. The reactor contents are cooled and a second charge of 37.5g (0.36 moles) AEEA is added.

The reactor is re-heated to 185°C at 90 mbar absolute and maintained at this temperature for a further 6 hours, after which time the vacuum is increased over 5 hours to 10 mbar absolute. At this stage, the contents of the reactor are cooled and offloaded.

220.8 grams of the imidazoline base prepared in accordance with the foregoing is charged into a three-necked 1 L flask equipped with a reflux condensor, mechanical stirrer, and addition funnel, along with 380 grams of water and 10.2 grams of a 47 % (wt. ) aqueous NaOH solution, and heated at 80°C for 2 hours. The flask contents are cooled to 60°C and sodium 135.1 grams of sodium monochloroacetate and 90 grams of water is added. A second quantity of 98.7 grams of 47 % (wt. ) aqueous NaOH is charged into the addition funnel and slowly added to the flask so as to maintain the pH of the flask in the range of 9.5 to 11.2 over the course of about 24 hours. The flask contents are cooled and sampled for analysis.

Analysis showed 53 ppm monochloroacetate remaining. The pH is

adjusted to 8.6 with concentrated aqueous HC1. The total solids content was determined to be 41. 85%, and the NaCl content was 9.4%.

The amphoacetates exist in two forms, as mono and di-carboxylated products, as shown in the following two structures: 0 C-NHNOH I CH2C02-Na+ Mono CH2CO2-Na+

Owing to the presence of the terpene-derived portion in the adduct acids of structures (I) and (III), the various surfactant materials of commerce which are derived from such adduct acids possess beneficial properties which are not present in conventional surfactant materials derived from conventional fatty acids. As mentioned, such surfactant materials include: amphoacetates, betaines, amine oxides, alkoxylates, esters, amides, sugar esters, and simple metallic soaps such as the alkali metal, alkaline earth metal, and ammonium (alkyl-substituted or un-substituted) soaps.

Consideration must be given to the fact that although this invention has been described and disclosed in relation to certain preferred embodiments, obvious equivalent modifications and alterations thereof will become apparent to one of ordinary skill in this art upon reading and understanding this specification and the claims appended hereto. This includes the subject matter defined by any combination of any one of the various claims appended hereto with any one or more of the remaining claims, including the incorporation of the features and/or limitations of any dependent claim, singly or in combination with features and/or limitations of any one or more of the other dependent claims, with features and/or limitations of any one or more of the independent claims, with the remaining dependent claims in their original text being read and applied to any independent claim so modified. This also includes combination of the features and/or limitations of one or more of the independent claims with the features and/or limitations of another independent claim to arrive at a modified independent claim, with the remaining dependent claims in their original text being read and applied to any independent claim so modified. Accordingly, the presently disclosed invention is intended to cover all such modifications and alterations, and is limited only by the scope of the claims which follow, in view of the foregoing and other contents of this specification.