These tertiary diester amines are also contemplated. A and E are the same or different and are alkoxy groups that are preferably ethoxy, propoxy or butoxy groups. Longer groups up to C8 are also possible. When propoxy, butoxy or longer groups are used, they may be straight chain or branched.
The designations u and x may be the same or different and are at least 2 and at most about 80 with the proviso that the number of ethoxy groups for each of A and E will be about 80 or less and the number of propoxy and butoxy groups for A and E is about 30 or less. If A were a mixture of such alkoxy units, u could be 80 no.
It is preferred that at least u or x be at least 2 and more preferred that both u and x be at least 5. For example, where u and x are each 2 and A and E are both 1 unit of propoxy and 1 unit of ethoxy, because of the ethoxy groups bound directly to the nitrogen which are not part of A or E , the majority of all alkoxy groups in Formula I are ethoxy, 4 ethoxy groups to 2 propoxy groups.
In another preferred embodiment, u and x may be the same or different and are at least 2 and at most about 30 and even more preferably u and x may be the same or different and are at least 2 and at most about 20 units. Most preferably, u and x are 5 and are composed of two blocks, the first block composed of 2 branched propoxy groups - CH2CH CH3 0 - and the second block composed of 3 ethoxy groups - CH2CH20 -.
A "C36" group is a molecule that includes 36 carbons and this general style of nomenclature will be used throughout. R3 is H or [-L-CR6] where can be saturated or unsaturated, substituted or unsubstituted, straight or branched, alkyl, cyclic or aromatic and can be a Co-C36 group; and v and y may be the same or different and are 0 or 1. Artificially created mixtures including, without limitation gadoleic Cl , erucic Cl , arachadonic C and culpodonic C could be used as well.
Fatty substituents may be provided from fatty acid containing oils, triglycerides, which can be converted to produce mono and diglycerides of the Formula V, and as fatty acids, fatty alcohols, esters or salts.
Indeed, fatty acid materials useful in accordance with the present invention can come from natural or synthetic sources and include pure fatty acids, fatty mixtures, triglycerides, oils, and waxes such as, for example, jojoba oil fatty acids and fatty alcohols Often, the mixtures of fatty acids or fatty substituents useful for R3, R4 and Rs-R10 can be composed of not only different fatty acid chain lengths and saturation, but also fatty acids with structural differences like ante-iso and iso fatty acids as well.
One mixture that can be used is shown in Table I. TABLE I A more preferred fatty acid mixture useful to produce diester quats in accordance with the present invention has a fatty acid content distribution as shown in Table II below.
Of course, they can be mixtures of fatty alcohols of the same content and proportion depending again upon whether the amine ends in an acid or hydroxy group. Recall that in each instance, esters must be formed.
A typical distribution of the fatty acids contained in lanolin acids is shown in Table III below. This alkyl group may be substituted or unsubstituted. Hydroxy fatty acids include at least one -OH group attached to the fatty acid chain.
Iso fatty acids are similar to ante-iso fatty acids except that the attached alkyl group is located closer to the carbonyl group, usually on the next adjacent carbon. Hydroxy fatty alcohols are also contemplated. Fatty acids, alcohols and glycerides useful for R3, R4 and Rs-R10 are generally often derived from, or can be created from, naturally occurring and artificially created oils. Oils, in accordance with the present invention include, without limitation, HEAR oil, as well as cod liver oil, herring oil, menhaden oil, mustard seed oil, pilchard oil, HEAR oil, salmon oil, sardine oil, meadowfoam oil and shark liver oil.
Of course, variations in content can occur. Fatty acids, alcohols and mono and diglycerides can be derived from these or other triglycerides. UV protecting groups include a UV-active moiety.
A group of atoms or a portion of a molecule qualifies as a UV-active moiety if such group of atoms or portion of a molecule is capable of absorbing or blocking electromagnetic waves in ultraviolet region of electromagnetic spectra. For example, a UV protecting group may be any organic moiety that possesses quantized levels of molecular energy suitable for excitation in the UV spectral region.
Also, chemical compounds that contain such organic moieties, for example, may be observed in the dark upon irradiation of such compounds by UV radiation. UV protecting groups can end in an acid or alcohol. If they are to be attached as R3, R4 or R6 to an alkoxylated amine, then they will be in the form of an acid having a reactive carboxyl group for creating an ester.
If they are to be attached as R3, R4 or R6 to a diacid or triacid, which is itself bound to the alkoxylated amine, then it should have a reactive alcohol or hydroxy group. Of course, these acid forms could also be used to attach to the di-, triacid groups, however, a bridge such as a diol will be required.
In contrast to many known sunscreen agents, the diester quats of the invention have good adhesion to hair, and thus remain on the hair to performing its sunscreen function. At the same time, these compounds may still be used as active hair conditioning ingredients in products and formulations that are not intended for sun protection purposes. Preferred examples include aminobenzoate system where examples of R' and R" include hydrogen, methyl, methoxy, ethyl, and other groups known to as part of the aminobenzoate system in conventional UV-absorbing compounds, and -NR'R' is preferably in para position, and cinnamate system where examples of R' ' ' include hydrogen, methyl, methoxy, and other groups known to as part of the cinnamate system in conventional UV-absorbing compounds.
Particularly preferred examples include para-aminobenzoate system and cinnamate system These groups of atoms are arranged in a manner that provides conjugated multiple bonds and aromatic ring. Non-limiting examples of such compounds include para-aminobenzoic acid PABA , dimethyl PABA, benzophenone-1, benzophenone-2, benzophenone-3 , benzophenone-4, benzophenone-6, benzophenone-8, benzophenone, methoxycinnamate, ethyl dihydroxypropyl-PABA, glyceryl PABA, homosalate, methyl anthranilate, octocrylene, octyl dimethyl PABA, octyl methoxycinnamate, octyl salicylate, PABA, 2- phenylbenzimidazolesulphonic acid, triethanolamine salicylate, 3- 4-methylbenzylidene -camphor, avobenzone, and 2, 6-dicarboxynaphtalenic acid.
Poly fatty acids are preferably hydrophobic in nature and are often produced by reacting the acid groups of fatty acids with hydroxy group substitutions on their fatty substituents. These poly fatty acids can terminate in an alcohol or acid as may be needed for attachment to a diester quat of the present invention. Substituted or unsubstituted but at least substituted with a hydroxy group fatty alcohols and fatty acids having between 4 and 36 carbons including, for example, lactic acid, isostearic, hydroxy stearic and ricinoleic acids, and derivatives thereof may be used to produce poly fatty acids such as those having the structures : and: While both of these include a total of 5 units, the number of units can range from 2 to 15 units.
Moreover, it is possible to make hybrids that are combinations of, for example, different hydroxy fatty acids or different fatty acids and fatty alcohols, etc. Again, when these are used for R3, R4, or R6, if the alkoxylated amine ends in OH or 0-, the poly fatty acids will end in a reactive carboxylic group -- they will end in acids.
If the alkoxylated amine is reacted with di or triacids, the poly fatty acids will end in a reactive alcohol or hydroxy group.
Poly fatty acids can be reacted with acid groups by using a diol. R7, UV protecting groups and poly fatty acids are as previously defined. R8, R9 and ,10 are the same or different, branched or straight chain, substituted or unsubstituted, saturated or unsaturated alkyl, cyclic or aromatic groups Cx to C3G in total carbon atoms and were defined previously as were the UV protecting group and poly fatty acids.
R8, R9 and 10 are the same or different, branched or straight chain, substituted or unsubstituted, saturated or unsaturated alkyl, cyclic or aromatic groups C to C3e in total carbon atoms and were defined previously as were the UV protecting groups and poly fatty acids.
R8, R9 and R10 are the same or different, branched or straight chain, substituted or unsubstituted, saturated or unsaturated alkyl, cyclic or aromatic groups Cx to C36 in total carbon atoms and were defined previously as were the UV protecting groups and poly fatty acids. Of course, as to all of the foregoing, bridging molecules such as diols, can be used to connect Formula IV to amines where x or y is 1.
These include, without limitation, halogens, alkyl sulfates and anything else known to be useful as a counter ion for quats. This can include, for example, the use of additional fatty acid species such as lactates to form a cation ion salt. The at least one personal care ingredient can include, without limitation, any solvent, surfactant, conditioner, pigment, UV protector, color, fragrance, dye, excipient or additive useful in formulating personal care products such as, without limitation, cosmetics, sun-screens and sun-blocks, shampoos, conditioners, softeners and the like.
Particularly preferred are those personal care products having a pH which ranges from between about 4. A particularly preferred diester quat useful in accordance with the present invention has the Formula VII. In fact, u and x are each 5 with three of the A units being ethoxy groups and two being branched propoxy groups. The same is true for E. Both R1 and R2 are methyl groups and both v and y are zero so that there are no groups of B or F.
R7 is a mixture of fatty groups or fatty substituents of various length and proportion produced by using lanolin fatty acids. A includes one propoxy group and 48 ethoxy groups, u is 49 and v is zero. E is composed entirely of ethoxy units and x is 5. F has the structure of Formula II, G is C0, and y is 1 The preparation of diester quats of the invention may be carried out by well known methods.
Condensation reactions are predominant. Schematically, however, an alkyl diethanol amine can be reacted with various proportions of alkoxylating compounds to produce alkoxylated amine species. The amount and order of addition of these alkoxylating species will determine their relative arrangement and proportion. For example, if in Step 1AA, M moles is 10, then the resulting compound will be symmetrical and with u and x both being 5 and A and E being five consecutive ethoxy groups each.
If the next reactant added is N Moles, which is 2, then the sixth alkoxy group for each side will be propoxy. It will be appreciated that variations can occur and therefore it is possible that the result will be a mixture that is neither symmetric nor in the desired order. However, generally, the predominant fraction of all of the alkoxylated amines produced will be the desired structure. These can be separated to isolate the amine of the desired structure. The reaction can proceed as illustrated in 1AA.
If an acid is used, the resulting intermediate is then reacted with one of the other groups discussed herein for R3, R4 and possibly R6. Alternatively, it may be desirable to produce various chains of alkoxy groups separately and then react them either with a fatty acid, fatty alcohol, glyceride or an alkyl diethanol amine.
This allows one to tailor the specific chain length and order of the alkoxy groups more precisely. Indeed, separations can be performed to eliminate mixtures as the chain length grows. Alternatively, a fatty acid or fatty alcohol can be alkoxylated in the case of a fatty alcohol, a bridging diacid or triacid may be necessary and the resulting molecule then reacted with the alkyl diethanol amine to produce compounds like those found in Formula I.
However, obviously, these compounds are tertiary amines until they have been quaternized. Lastly, quats are formed. This is preferably done after the diester tertiary amines are completely formed. After the fatty acids, for example, are reacted with the alkoxylated amine, the resulting diester tertiary amines are then quaternized using known techniques with any suitable alkylating agent that can provide the appropriate R1 or R2 group.
These can include methyl chloride, ethyl chloride, benzyl chloride, behyneal halide, dimethyl sulfate, diethyl sulfate, etc.
The viscosity of the personal care products in accordance with the present invention ranges from about , cps, more preferably about , cps, most preferably from about 1,, cps. The amount of the diester quats in accordance with the invention found in the resulting personal care product generally range from about 0. More preferably, the amount is between about 0. Cationic activity may be measured by several methods readily understood by those skilled in the art.
One such method utilizes a standardized solution of an anionic material, such as sodium lauryl sulfate. Cationic activity may be measured by several methods readily understood by those skilled in the art. One such method utilizes a standardized solution of an anionic material, such as sodium lauryl sulfate.
This material is added to the solution containing the quat until full complexation of the quat ' s cations the end point has been reached. The end point can be measured potentiometrically or by the use of color indicators.
Typical tests involve titrating a sample of the quat, usually dissolved in a solvent, with the standardized solution of sodium lauryl sulfate until the endpoint is reached. As described in the co-pending and co-assigned U. Patent Application No. Schempp and H. Trau, Wochenblatt fur Papierfabrikation 19, , pp.
Fischer and K. April , both incorporated herein by reference in their entirety. It is also generally appropriate to describe the amount of claimed materials using other terminology.
It is unusual for diesters to be produced or sold in a completely pure form. Whether singular compounds or as parts of mixtures, they generally are present as liquids or solids, which are including a solvent which, preferably, acts as a carrier. Because it is possible, to drive off all, or substantially all, of the solvent, the upper limit on the proportion of diesters is generally less critical. However, when mixed in a solvent, the diester quats and the diester tertiary amines if not formed into quats should be present in the resulting solutions in an amount of at least about 0.
If solvent or carrier is present, the diesters, quats or amines may be present in as much as about An effective amount of the solvent or carrier in this context is an amount sufficient to solubilize the diesters, tertiary amines or quats, understanding that they can be in the form of solid solutions or other forms which can be flakable which may provide for more convenient handling.
Solvents for flakable quats would often include free fatty alcohols as a cosolvent. Most preferably, the amount of solvent is, however, minimized. When diester quat additives with or without solvent or carriers are used to formulate personal care products, the amount used will vary depending upon a number of factors none the least of which is the overall diester quat molecule, the end product and the role that the diester quat will play.
If the diester quat is merely being used for conditioning, one amount may be necessary. If the diester quat is also being used to provide UV protection, some other amount may be indicated. Moreover, depending upon the concentration of the diester quat in the additive to be used, the overall amount of additive may need to be adjusted. This is why the amount is often expressed in terms of cationic activity. The amount of quat containing additive used in each case may be dramatically different although the intended amount of diester quat used may be the same.
Furthermore, there is generally no upper limit on the amount of diester quat used. Usually cost is the only limiting factor. Of course, at some point the amount of diester quat used may produce a diminishing return.
The lower limit is often more critical. Generally, at least about 0. More preferably at least about 0. It is desirable to provide diester quats in a concentrated form with high cationic activity, as a solid or semi-solid solution or dispersion. Without wishing to be bound by any specific theory, it is believed that a desired amount of a given quat or mixture of quats to be placed in a formulation may be measured by the cationic activity of the quat raw material.
Diester quat raw materials with high cationic activity permit better transportation efficiency since they occupy smaller space while providing the same desired quat amounts.
It is also desirable to produce raw quats that, in addition to having high cationic activity, provide for ease in commercial handling and storage.
For example, the raw quat that melt at lower temperatures minimize quat decomposition and improve energy efficiency. For this purpose, it is preferred for the raw quats to be flakable or pastillatable. Thus, the invention also provides compositions containing diester quats and mixtures of diester quats, as well as mixtures of diester quats with other conventional active materials and additives.
It is possible to mix diester quat diesters and diester quats and conventional esters and or quats, in the form of concentrated, often solid, solutions or suspensions in a suitable carrier.
This is more likely, however for mixtures of diester quats and non-diester quats, with or without solvents or carriers. The preferred carrier or solvent is one that is or cosmetically acceptable and used or recognized to have such uses. Preferred solvents include isopropyl alcohol, SDA, propylene glycol, butylene glycol, various fatty alcohols, and mixtures thereof. In such instances, the combination of the carrier and the diester quats may be referred to as an additive and the diester quats may be present in an amount of from about 0.
In accordance with another aspect, the invention also provides compositions in the form of various, personal care products which include one or more of the diester quats of the present invention. The preferred final product compositions of the invention are compositions for treating human hair, such as shampoos or conditioners.
The nature of final products in accordance with the invention dictates a number of parameters including, amongst others, the type of diester quat to be used, whether a single type of diester quat is used or whether it is mixed with other diester quats of the present invention or other quats of other types, the amount of diester quats in accordance with the present invention which will be used, and the type and amount of additional ingredients.
For example, in a topical skin conditioner, it may be desirable to omit coloring agents. However, in a hair dye, a nail polish or a blush, for example, pigments, dyes or colors, or materials which will develop color at some point in time during or after application may be specifically contemplated.
The type and amount of pigment in a hair dye may be very different than the type and amount of pigment in a blush. Personal care products in accordance with the present invention generally include a diester quat of the present invention, often in an acceptable solvent; said diester quat being present in the amount of from about 0. Of course, the solvent may be omitted. Those of ordinary skill in the art can readily substitute the diester quats of the present invention into existing formulations in an amount that approximates the use of functionally analogous compounds in existing formulations of the same type and function.
For example, in a conditioning shampoo, diester quat formulations of the present invention may be substituted for some or all of the conditioning agents previously included.
However, the personal care ingredient in this instance is the surfactants used for shampooing hair. Therefore, an amount of surfactants must be provided to meet that "intended use" in this case.
If, in a given formulation, insufficient conditioning is obtained by a one to one substitution of the diester quats of the invention for conventional conditioners, then it is a relatively easy and conventional to determine the amount of diester quats necessary to provide sufficient additional conditioning using conventional techniques. Similarly, if one of the objects or "intended uses" of the formulation is to act as a sunscreen product for skin or hair, and a diester quat produced using a derivative of a UV-active compound as one of the groups bound is used as a UV absorbing agent, then the amount to be used will be that amount which imparts the desired skin protection factor or "SPF".
If UV protection were to provided by a mixture of such diester quats with or without conventional UV absorbing quats, then the amount of each component will be such that in total, they provide the formulation with the desired SPF.
How much of each used to provide the desired level of SPF will be dictated not only by the resulting SPF but also by the relative cost of each, their relative availability, ease of formulation, other advantageous properties they may impart i. In this instance, the personal care ingredient might be a conventional UV absorbing material or a cream,, lotion or gel base and the effective amount would either be that which is required to provide some SPF factor or to form a cream, gel or lotion useful as a personal care product that successfully and stably supports the diester quats of the invention.
Personal care products in accordance with the present invention, which include one or more of the diester quats of the present invention, will generally include between about 0. More preferably, the amount of diester quats will range from between about 0. However, it will be appreciated that different amounts of the diester quats may be preferred given a particular product type.
Personal care products including the diester quats or mixtures thereof in accordance with the present invention may be in the form of liquids, ointments, lotions, sprays, gels, creams, emulsions, foams, pastes and solids; may be clear or opaque; and may be formulated as aqueous and non-aqueous preparations, including but not limited to topical preparations. Preferably, such final products are dispersions or solutions in water, or in a mixture of water with a suitable secondary solvent.
Suitable solvents include various lower alkanols and glycols. Lower alkanols having from one to four carbon atoms are suitable for use with the present invention, and lower alkanols having from two to three carbon atoms are preferred. Glycols having from three to eight carbon atoms are suitable for use with the present invention, while glycols having from three to six carbon atoms are preferred. Examples of suitable lower alkanols and glycols include methanol, ethanol, isopropanol, butanol, hexylene glycol, 1,3-butylene glycol, 1,2- and 1,3 -propane diol, 2-methyl 1,3 -propane diol, propylene glycol, diethylene glycol, and the like.
Again, however, different amounts of solvent may be preferred depending on the nature of the product. In addition to diester quats, the formulations of the invention may include various personal care ingredients, both conventional and otherwise. Of course, a decision to include an ingredient and the choice of specific ingredients depends on the specific application and product formulation.
Such personal care ingredients may include one or more substances such as cleaning agents, hair conditioning agents, skin conditioning agents, hair styling agents, antidandruff agents, hair growth promoters, perfumes, sunscreen compounds, pigments, moisturizers, film formers, humectants, alpha-hydroxy acids, hair colors, make-up agents, detergents, thickening agents, emulsifiers, antiseptic agents, deodorant actives and surfactants. They may include agents which enhance permeation into or through the skin, or topical pharmaceuticals such as, without limitation, corticosteriods, analgesics, anti- inflammatory agents, antibiotics, anesthetics, etc.
Personal care ingredients generally can be included in various forms. They may be included in a liquid or solid form. Solids can be crystalline or amorphous, granular, powder, particulate and the like. However, it is also possible for such additives to be microencapsulated or in the form of micro particles. One of the personal care ingredients which may be used in products along with the diester quats of the present invention are surfactants including one or more nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.
Surfactants in cleansers or shampoos could be an active agent. In other formulations, it can be an emulsifier and is, therefore, an additional agent. For some of surfactants that may be used in combination with the compositions of the invention, see McCutcheon' s, Detergents and Emulsifiers, , as well as U. Patents 5,,, 5,,, 5,,, 5,,, 4,,, 4,,, 4,,, 4,,, 4,,, and 3,,; all incorporated herein by reference in their entirety. Additional quaternary ammonium salts include those wherein the Ci2-C22 alkyl is derived from a tallow fatty acid or from a coconut fatty acid.
Examples of quaternary ammonium salts derived from these tallow and coconut sources include ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, di hydrogenated tallow dimethyl ammonium chloride, di hydrogenated tallow dimethyl ammonium acetate, ditallow dipropyl ammonium phosphate, ditallow dimethyl ammonium nitrate, di coconut alkyl dimethyl ammonium chloride, di coconut alkyl dimethyl ammonium bromide, tallow ammonium chloride, coconut ammonium chloride, stearamidopropyl PG- dimonium chloride phosphate, stearamidopropyl ethyldimonium ethosulfate, stearamidopropyl dimethyl myristyl acetate ammonium chloride, stearamidopropyl dimethyl cetearyl ammonium tosylate, stearamidopropyl dimethyl ammonium chloride, stearamidopropyl dimethyl ammonium lactate, and mixtures thereof.
More preferred quaternary ammonium surfactants are dilauryl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dimyristyl dimethyl ammonium chloride, dipalmityl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, stearamidopropyl PG-dimonium chloride phosphate, stearamidopropyl ethyldimonium ethosulfate, stearamidopropyl dimethyl myristyl acetate ammonium chloride, stearamidopropyl dimethyl cetearyl ammonium tosylate, stearamidopropyl dimethyl ammonium chloride, stearamidopropyl dimethyl ammonium lactate, and mixtures thereof.
Examples of such suitable amines include stearamido propyl dimethyl amine, diethyl amino ethyl stearamide, dimethyl stearamine, dimethyl soyamine, soyamine, tri decyl amine, ethyl stearylamine, ethoxylated stearylamine, dihydroxyethyl stearylamine, and arachidylbehenylamine. Suitable amine salts include the halogen, acetate, phosphate, nitrate, citrate, lactate and alkyl sulfate salts.
The alkoxylated oligoesters may then be derivatized if desired. The inventors have discovered that oligoesters having alkoxylated backbone can be formulated and maintained at a generally neutral pH, as well as at a mildly basic and mildly acidic pHs.
Such oligoesters may be formulated and maintained at pHs greater than 4 and less than 9. Prior art ester compositions and particularly esterquats are generally unstable at a pH above four and this dramatically inhibits the ability to use such products, particularly in shampoos and cosmetics.
Oligoesters with alkoxy groups in their backbone can be used in place of conventional ester quats in formulations at neutral pH, mildly acidic pH, or mildly basic pH, for example at pHs from 4 to 9. Preferably, the backbones of oligoesters in accordance with the present invention terminate in a hydroxy group -OH or similar functionality, a carboxy-containing group, such as -C O OH , ester group -C 0 OR, an ether group and the like.
Whether the backbone is hydroxy-terminated, carboxy-terminated or both, the terminal functional group s may also be derivatized. Thus, the terminal hydroxy group s , carboxy group s , or both may be "end-capped. Likewise, the carboxy-terminated oligoesters may be end-capped via esterification with a desired compound s bearing a hydroxy group or other suitable reactive functionality. Ether groups may also be formed. End caps can be simple such as hydrogen or methyl group or they can be large and complex such as a group derived from polyricinoleate.
Therefore, the compounds of this aspect of the invention can be used to make oligoesters which are particularly useful as hair and skin conditioners. Because of their high hydrophobicity believed to be related to the size of their alkyl chains , such compounds will often remain on the hair or skin without washing off for longer periods of time. These advantageous features can also be readily combined, providing an end-capped oligoester comprised of repeating units containing diol fragments, diacid fragments, and alkoxy groups, for example, providing an end-capped oligoester, which is both stable at generally neutral, mild basic and mild acidic pH, and able to provide effective conditioning.
This would allow the creation of conditioners which can be used in conjunction with shampoos, products which can generally not be formulated at the more acid pHs necessary to maintain the stability of esterquats. A particularly preferred aspect of the present invention is oligoester quats. The quaternary groups of oligoesters of the present invention can be constructed from backbones that include amine nitrogen s that are reacted with a fourth group so as to form a positively charged quaternary nitrogen or "quat.
However, they may also include, for example, groups which can act as UV radiation absorbers or UV-protecting group. Again, these features can be combined in the single molecule.
So, for example, an oligoester quat end-capped with groups which provide effective conditioning, quaternized with groups providing UV absorption characteristics and alkoxylated within the oligoester backbone to impart neutral pH stability is contemplated.
The oligoesters of the present invention can be used as a part of the formulation of pharmaceutical products, personal care products and cosmetics by being mixed, blended, or reacted, in a convention manner, with traditional ingredients for such products.
The present invention also relates to methods of treating patients including mammals and in particular, humans, by applying, topically, various pharmaceutical, cosmetic or personal care products produced in accordance with the present invention containing the oligoesters of the present invention.
These would be applied in the conventional manner with regard to pharmaceutical products, topical application includes not only transdermal patches, creams, gels and other traditional topical applications, but also application to the nasal and sinus cavities, the windpipe and esophagus, and even the lungs as well as other mucosal membranes including those found in the mouth, rectum or vagina using suppositories, nasal sprays, inhalers, enemas and the like.
For the purposes of the present invention, various terms used herein are defined as follows. A "compound" is a distinct substance, e. A "compound" is not a mixture of molecules having different chemical structures. A mixture of oligoesters is a mixture of two or more different oligoester molecules. The mixture is generally identified by the oligoester that exists in the mixture in the highest proportion relative to any other single oligoester in that mixture.
The substitution patterns described as Cx-Cy define substituents having carbon chains that may range from x carbon atoms to y carbon atoms, and are referred to as Cx-Cy groups.
In this regard, a description of the range encompasses carbon chains of every length inside the described range, as well as the upper and lower ends of the range. For example, the substitution pattern described as "Ci- Cs" encompasses all carbon chains having from 1 to 8 carbon atoms, inclusive. The oligoesters in accordance with the present invention preferably have structural units that have the structural formulas I and II.
S is a whole number of 2 or greater, more preferably between 2 and , even more preferably between 3 and 50, and most preferably between 3 and 25, and is the number of structural units in the oligoester backbone. This number does not include an additional diol or diacid fragment that may be used so that each end of the oligoester terminates in the same type of fragment. OB-D-EO is a diol fragment. D may be an alkyl group or radical or an alkylene group, saturated or unsaturated, straight chain or branched, substituted or unsubstituted, having 1 to 50 carbon atoms, preferably, 1 to 40 carbon atoms and even more preferably 1 to 18 carbon atoms.
Thus, D may be an aliphatic group, saturated or unsaturated, straight chain or branched, substituted or unsubstituted, having 1 to 50 carbon atoms, preferably, 1 to 40 carbon atoms and even more preferably 1 to 18 carbon atoms. D may also be an aromatic group such as aryl-, phenylaryl-, alkylaryl-, or naphthalene group, having 6 to 40 carbon atoms, preferably, 6 to 35 carbon atoms.
If D is an aromatic group, D may include an aromatic nucleus, preferably having 6 to 18 carbon atoms, more preferably 6, 10 or 14 carbon atoms. D may also be a cyclic alkane such as cyclohexane having 4 to 35 carbons. D may, instead of or in addition to internal substitutions, have one or more external substitutions wherein one or more of the atoms in the backbone are substituted with one or more halogen, carbon, oxygen, nitrogen, sulfur or Si containing groups.
F is part of the diacid fragment, and is at least one atom, preferably an alkyl or radical or alkylene group, saturated or unsaturated, straight chain or branched, substituted or unsubstituted, having 1 to 60 carbon atoms, preferably, 1 to 40 carbon atoms most preferably carbon atoms.
Thus, F may be an aliphatic group, saturated or unsaturated, straight chain or branched, substituted or unsubstituted, having 1 to 60 carbon atoms, preferably, 1 to 40 carbon atoms and even more preferably 2 to 18 carbon atoms. F may also be an aromatic group such as aryl-, phenylaryl-, alkylaryl-, or naphthalene group, having 6 to 60 carbon atoms, preferably, 6 to 35 carbon atoms.
If F is an aromatic group, F may include an aromatic nucleus, preferably having 6 to 18 carbon atoms, more preferably 6, 10 or 14 carbon atoms. F may also be a cyclic alkane such as cyclohexane or derivative thereof having 4 to 35 carbons. The diacid may also be, or may be derived from, for example, an anhydride. Particularly preferred diacids in accordance with the present invention include Azeliec acid; Malonic acid; Pimelic acid; Sebacic acid; Suberic acid; Succinic acid; Phthalic acid; and C36 dimer acid cast Most preferably, at least one of D or F in at least one of a diol fragment s and diacid fragment s of the oligoesters of formulas I and II include an amine group within their backbone.
Most preferably, at least one of the D's and F's in each structural unit of diol and diacid of Formulae I and II includes and amine nitrogen. In this example, m, which is more preferably , is 2. When more than one alkoxy group is present in a chain, any structural order may be used. Thus, they may be randomly ordered, ordered in blocks, or ordered in alternating patterns with each other.
Preferably in is 1 to 6 and more preferably 2 to 3 and nn is 0 to and more preferably 1 to 40 and most preferably 1 to In the prior example, m was 2 and nn was also 2. The following formulae A and B relate to a particularly preferred group of the oligoesters of the present invention. Note that the various groups are denoted by superscripted numbers as well as the letters p, v, f, and g and not subscripted numbers as used above and elsewhere in this - document in connection with formulas I and II.
The oligoesters of formulae A and B are to be considered preferred embodiments of the oligoesters identified previously with regard to formulas I and II. To the extent that any group or substituent is identified in connection with formulas A and B , which falls outside the scope of the corresponding group noted above using subscripted radicals and the accompanying letters in Formula I and II, such groups are to be considered supplementary.
For these preferred embodiments, a, denotes the positive charge of the structural unit A , ranges from 0 to 10; p, may be same or different for D, E, B, and F, independently ranges from 1 to 40; v, may be same or different for E, B, and F, independently ranges from 1 to 40; f, may be same or different for E, B, and D, independently ranges from 1 to 10; g, may be same or different for E, B, and D, independently ranges from 1 to 10; and k is 0 or 1.
Similarly, the formula B shows alkoxylated oligoesters which are preferred embodiments of those in formula II B where all of the groups are as defined in connection with formula A except that -OK and J0-, which may be same or different, are alkoxy spacers having m units of the structure n is ranging from 1 to 6; m is ranging from 1 to Both of these may be quaternized and associated with an appropriate number of counter ions.
Di may be same as D as defined above, or different so that Di may be converted to D via derivatization of the reaction products above.
Fi may be same as F that is defined above, or different so that Fi may be converted to F via derivatization of the reaction products. EO JOQj x Note that it may be desirable to have oligoesters that terminate only in diol fragments, both diol fragments and diacid fragments or only diacid fragments.
These protecting groups can also be groups that prevent further chain propagation such as end caps. Assuming for illustration, that an oligoester was composed of diacid fragments and diol or alkoxylated diol fragments, and referring to formulae I and II , if the oligoester terminates in two diacid fragments, the end caps used could both be G and if both were alcohols, the end caps could both be A. Amongst these factors are the desired properties of the finished composition of matter, such as polarity, viscosity and the like, the degree and type of substitution s , the type of end caps used, whether the composition will include quat groups and how may quat groups are desired, the end use will the backbone be used in a conditioner , etc.
In general, however, there will be at least two diol fragments and two diacid fragments, although there could be as many as 50 of one and 51 of the other.
The preferred carrier or solvent is one that is or cosmetically acceptable and used or recognized to have such uses. The examples of suitable isethionates include ammonium cocoyl isethionate, sodium cocoyl isethionate, sodium lauroyl isethionate, sodium stearoyl isethionate, and mixtures thereof.
The present invention also relates to methods of making these products and to the diester tertiary amines and diester quats useful in these personal care products. Because they have reactive nitrogen species, they can have previously unrecognized activity. Recall that in each instance, esters must be formed. Solids can be crystalline or amorphous, granular, powder, particulate and the like. Patents 2,,, 2,,, and 1,,, which are incorporated herein by reference.
A group of atoms or a portion of a molecule qualifies as a UV-active moiety if such group of atoms or portion of a molecule is capable of absorbing or blocking electromagnetic waves in ultraviolet region of electromagnetic spectra. However, it will be appreciated that different amounts of the diester quats may be preferred given a particular product type. Certainly, compounds with improved environmental properties, improved stability in a higher pH and improved substantivity would therefore be highly desirable.
More preferred quaternary ammonium surfactants are dilauryl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dimyristyl dimethyl ammonium chloride, dipalmityl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, stearamidopropyl PG-dimonium chloride phosphate, stearamidopropyl ethyldimonium ethosulfate, stearamidopropyl dimethyl myristyl acetate ammonium chloride, stearamidopropyl dimethyl cetearyl ammonium tosylate, stearamidopropyl dimethyl ammonium chloride, stearamidopropyl dimethyl ammonium lactate, and mixtures thereof. It is believed that under the reaction conditions described herein, the di- hydroxy-terminated Backbone oligoester 3 has an average S3 of 5. The amounts and the nature of cationic surfactants present in the compositions of the invention, if at all, depend on the nature of the composition. If non-ionic surfactants are used, their amounts will vary based on the formulation, the remaining ingredients and the types, if any, of any surfactants which are being used. A particularly preferred aspect of the present invention is oligoester quats.
However, it is also contemplated that the amine group may be part of only some of the structural units. Oils, in accordance with the present invention include, without limitation, HEAR oil, as well as cod liver oil, herring oil, menhaden oil, mustard seed oil, pilchard oil, HEAR oil, salmon oil, sardine oil, meadowfoam oil and shark liver oil. UV protecting groups can end in an acid or alcohol. Ra is H or [-L-COO-R6] where L can be saturated or unsaturated, substituted or unsubstituted, straight or branched, alkyl, cyclic or aromatic and can be a C0-C12 group; and v and y may be the same or different and are 0 or 1; when v equals 0, R3 may be Formula IV Formula IV, a UV protecting group ending in a reactive carboxyl group or a poly fatty acid ending in a reactive carboxyl group.
When propoxy, butoxy or longer groups are used, they may be straight chain or branched. Preferably, the nitrogen atom s is one part of an amine group. Ester quats are generally formed as mono, di, or tri esters, or a mixture of mono, di, or tri ester. F may also be a cyclic alkane such as cyclohexane or derivative thereof having 4 to 35 carbons. Personal care ingredients generally can be included in various forms.
In general, the amount of ionic surfactants which are useful in accordance with the present invention may vary from 0. Particularly preferred diacids in accordance with the present invention include Azeliec acid; Malonic acid; Pimelic acid; Sebacic acid; Suberic acid; Succinic acid; Phthalic acid; and C36 dimer acid cast