Formulations containing biodegradable polyalkoxylated polyol polyesters

Abstract

The compounds included herein relate to biodegradable thickeners (e.g., polyalkoxylated polyol polyesters) that have a viscosity that allows the product to flow while being retained on the desired surface to which it is applied. Embodiments of the compounds include those having the following formula: Q-[(OA) n -OR] m This can be exemplified by:

Description

[Technical Field]

[0001] This application claims priority to U.S. Patent Application No. 18 / 140,646, filed April 28, 2023, which is a continuation-in-part of U.S. Patent Application No. 17 / 838,503, filed June 13, 2022, which claims priority to U.S. Patent Application No. 16 / 369,544, filed March 29, 2019, which claims priority to U.S. Patent Application No. 15 / 652,679, filed July 18, 2017, which claims priority to U.S. Patent Application No. 62 / 499,642, filed February 1, 2017, and U.S. Patent Application No. 62 / 495,444, filed September 15, 2016, the contents of all of which are incorporated herein by reference in their entireties.

[0002] The field of the invention and its embodiments relate to thickeners that allow a product to flow while creating a viscosity that is held to the desired surface to which it is applied. [Background technology]

[0003] Rheology, the study of how materials flow, is applied to consumer products such as shower gels, shampoos, liquid detergents, liquid dish soaps, liquid hand soaps, skin care lotions or creams, hair conditioners, and hair styling products to create specific viscosity profiles that are crucial to consumer product preferences and ultimate purchasing decisions.

[0004] Consumers prefer products that have a low enough viscosity to stabilize the product in the container and flow easily from the container, yet have a high enough rheological profile to allow application to body, hair, or fabric without dripping off the consumer's hand or application surface. Additionally, products must maintain a stable and consistent rheological profile during warehouse storage, shipping, and potential storage periods of several years.

[0005] Consumers also prefer environmentally friendly products, for example, products that biodegrade in the environment and turn into harmless by-products so as not to permanently accumulate in the environment. Therefore, the most preferred products by consumers must be both effective in thickening compositions and biodegradable in the natural environment.

[0006] There are many commercially available thickeners that use polyalkoxylated polyols and esters of fatty acids to thicken surfactant-containing formulations. Commercially available examples include polyethylene glycol 6000 distearate, known by its INCI name PEG-150 distearate; PEG 120 methyl glucose dioleate and PEG 120 methyl glucose trioleate (Glucomate™ DOE 120 and Glucomate™ VLT); PEG-150 pentaerythrityl tetrastearate (Crothix™, Crothix™ Liquid, and Versathix™); PEG-150 polyglyceryl-2 tristearate (Genapol LT); and PEG / PPG-120 / 10 trimethylolpropane trioleate (Arlypon TT). The number of hydrophilic polyalkoxylated arms is 2 in PEG-150 distearate, 3 in Arlypon TT, 4 in Genapol LT and Crothix, liquid Crothix, Versathix, and 5 in Glucomate DOE 120.

[0007] US 5,192,462 (Gloor et al.) relates to a thickening agent comprising a tetraester made of fatty acids and polyoxyethylene pentaerythritol having four hydrophilic poly(ethylene glycol) arms, the preferred chemical structure of which is PEG-150 pentaerythrityl tetrastearate, all four hydrophilic poly(ethylene glycol) arms capped with stearic fatty acids, which is the base for Crothix, Liquid Crothix, and Liquid Versathix.

[0008] US Pat. No. 7,709,011 and US Pat. No. 7,553,495 (both to Klug et al.) relate to thickening agents of oxyalkylated polyglycerol esters with fatty acids for surfactant-containing topical products, as shown below. [ka]

[0009] wherein A is a group of formula -C2H4- or C3H6-, B is hydrogen or a group of formula -COR, and at least one symbol B is a group of formula -COR-, and R is a C7-C 21 Alkyl, C7-C 21 It is hydroxyalkyl or alkenyl, n is a number from 1 to 30, x, y, and z are numbers from 0 to 100, and the sum of x, y, and z is 50 to 250. (See lines 43 to 48 on page 1.)

[0010] Commonly owned US20180072817 and US20180071198 relate to compounds related to polyalkoxylated polyol polyesters that have a viscosity that allows the product to flow while being retained on the desired surface to which it is applied. Embodiments of the compounds can be illustrated by the formula: Q-[(OA)n-OR]m.

[0011] Those skilled in the art will appreciate that the number of hydrophilic poly(ethylene glycol) arms is equal to n+2. For n=30 and x+y+z=250, the average number of ethylene glycol units, i.e. (x+y+Z) / (n+2), is [250 / (30+2)], which is at most about 7.81. Summary of the Invention [Means for solving the problem]

[0012] Embodiments of the present application teach and describe novel polyalkoxylated polyol polyesters (e.g., thickeners) conforming to Formula-2, which are the reaction product of (a) a fatty acid and (b) a polyalkoxylated polyol. Q-[(OA) n-OR] m formula-2 wherein Q is a group of a natural or synthetic organic polyol compound having 6 to 50 carbon atoms forming a linear, branched, cyclic, saturated or unsaturated structure, each carbon atom being represented by a group of the formula -[(OA) n each of the 6 to 50 carbon atoms may be independently substituted with hydrogen, oxygen, or nitrogen; A is selected from -C2H4- or -C3H6-; R is independently selected from hydrogen or -COR1, and R1 is selected from C6 to C 22 Alkyl and C2-C 22 alkenyl, preferably stearic acid moieties, isostearic acid moieties, oleic acid moieties, or mixtures thereof, with oleic acid moieties being the most preferred moieties; the average total number of COR1 is ≧3, preferably ≧4, more preferably ≧5, and even more preferably 5 and 6; n is an integer selected from 1 to 125, and may be the same or different for each polyalkoxylated hydrophilic arm; (OA) n The average number of n per unit is 25 to 120, preferably 30 to 85, and most preferably 30 to 70; each (OA) n The total n, which is the sum of all n's from the arms, is 150 to 350, preferably 180 to 300; and m is an integer selected from 6 to 25, preferably 6 to 12.

[0013] In another embodiment of the present invention are cosmetic cleansers, dermatological cleansing formulations, medicinal cleansing formulations, personal cleansing products, fabric cleaners, and household, industrial, and institutional cleansing products containing the polyalkoxylated polyol polyesters of Formula-2.

[0014] Polyesters according to embodiments of the present invention are suitable as thickeners, rheology modifiers, and solubilizers for aqueous solutions, aqueous / alcohol solutions, and surfactant-containing formulations. Examples of these surfactant-containing formulations, emulsions, and suspensions include shampoos, shower products, shower gels, bubble baths, facial cleansers, hand soaps, bar soaps, shaving creams, hair conditioners, deodorants, toners, creams, ointments, wet wipes, antiperspirants, and sunscreens. Embodiments of the present invention are also suitable as thickeners and rheology modifiers for fabric care products such as fabric softeners and liquid laundry detergents; for dishwashing liquids; for liquid carpet shampoos and liquid floor cleaners; for liquid carwash soaps / detergents; and for household and industrial liquid cleaning products.

[0015] Based on the finished formulation, the preparations, cleansing products, emulsions and suspensions according to the invention preferably contain from 0.05% to 20% by weight, particularly preferably from 0.1% to 10% by weight, particularly preferably from 0.5% to 5% by weight of the polyalkoxylated polyol polyester of formula -1.

[0016] Cleansing compositions according to embodiments of the present invention may further comprise at least one of the following ingredients: all commonly used anionic, cationic, zwitterionic, nonionic, and amphoteric surfactants; all commonly used skin and hair benefit actives, such as cosmetic oils, petrolatum, vegetable oils, hydrogenated vegetable oils, UV filters, proteins, shine ingredients, anti-aging agents, amino acids, bioactive ingredients, moisturizers, conditioning polymers, silicones, cationic polymers, sucrose polyesters, anti-dandruff zinc salts, hydroxy acids, skin lightening agents; all commonly used stabilizers, such as silica, 12-hydroxystearic acid, hydrogenated castor oil, ethylene glycol distearate, bentonite, and hectorite clay, fatty acids, fatty alcohols; all commonly used thickeners, such as hydroxyethyl cellulose, xanthan gum, polyacrylates, modified or unmodified starches; and all commonly used dyes, colorants, pearlizing agents, fragrances, chelating agents, solvents, humectants, salts, and the like.

[0017] The total amount of surfactant used in the compositions of the present invention may be from 5% to 70%, preferably from 10% to 40%, and most preferably from 12% to 35% by weight of the finished composition.

[0018] definition As used above, and throughout this disclosure, the following terms, unless otherwise indicated, shall be understood to have the following meanings: In the absence of a definition, conventional definitions known to those of ordinary skill in the art shall prevail.

[0019] As used herein, the terms "including," "containing," and "comprising" are used in an open, non-limiting sense.

[0020] As used herein, the singular forms "a," "an," and "the" include the plural forms unless the context clearly dictates otherwise.

[0021] In order to provide a more concise explanation, some quantitative expressions in this specification omit the term "about." Regardless of whether the term "about" is explicitly used, all numerical quantities indicated in this specification refer to the actual given value and to approximate values for the given value that can be reasonably estimated based on ordinary skill in the art, including equivalents and approximate values based on experimental and / or measurement conditions for the given value. When a yield or amount is indicated as a percentage, the yield or amount refers to the mass (weight percent) of the entity for which the yield is indicated relative to the maximum amount of the mass of the entity that can be obtained under specific stoichiometric conditions. Concentrations indicated as percentages refer to mass ratios unless otherwise specified.

[0022] As used herein, "alkyl" means a straight or branched saturated chain having from 1 to 30 or more carbon atoms. Alkyl groups can be unsubstituted or substituted. Alkyl groups containing 3 or more carbon atoms can be straight, branched, or cyclized.

[0023] As used herein, "alkenyl" includes an unbranched or branched hydrocarbon chain having one or more double bonds therein and having from 1 to 30 or more carbon atoms. The double bond of an alkenyl group can be unconjugated or conjugated to another unsaturated group. An alkenyl group can be unsubstituted or substituted.

[0024] The term "hydroxyl" refers to an --OH group.

[0025] The term "hydroxyalkyl" means an alkyl group, as defined above, having an OH group disposed thereon.

[0026] As used herein, the term "alkoxy" or "alkoxylated" includes --O-(alkyl), where alkyl is defined above.

[0027] As used herein, the term "composition" is intended to encompass a product containing the specified ingredients in the specified amounts, as well as any product that results directly or indirectly from combining the specified ingredients in the specified amounts.

[0028] As used herein, the term "amino" refers to a substituent containing at least one nitrogen atom.

[0029] As used herein, the term "substituted" means that the specified group or moiety has one or more suitable substituents, and the substituents may be attached to the specified group or moiety at one or more positions.

[0030] As used herein, the term "unsubstituted" means that the particular group bears no substituents.

[0031] In formula 2, m is (OA) n The total number of arms is n, and n is the number of repeating units -OA in each arm. The total n refers to the sum of all n obtained from all m arms. Sorbeth-xxx, such as Sorbeth-300, is the INCI (International Cosmetic Ingredients) name, and xxx is the total n.

[0032] All patents or patent applications referenced herein are fully incorporated by reference in their entirety. DETAILED DESCRIPTION OF THE INVENTION

[0033] In one embodiment, Formula-2: Q-[(OA) n -OR] m formula-2 and polyalkoxylated polyol polyesters of the formula: Q is defined as a group of natural or synthetic organic polyol compounds having carbon, hydrogen, oxygen, and nitrogen atoms, which may be linear, branched, cyclic, saturated, or unsaturated, and Q has 6 to 50 carbon atoms and is independently substituted with 6 to 25 groups having the formula -[(OA)n-OR]. wherein A is selected from -C2H4- or -C3H6-; n is 1 to 125; R is independently selected from hydrogen or -COR1; and R1 is C6 to C 22 Alkyl and C2-C 22 alkenyl; R1 is preferably a stearic acid moiety, an isostearic acid moiety, an oleic acid moiety, or a mixture thereof, with oleic acid being the most preferred moiety; the average total number of COR1 is ≧3, preferably ≧4, more preferably ≧5, and even more preferably between 5 and 6; and m is an integer selected from 6 to 25, preferably 6 to 12. n per hydrophilic poly(alkylene glycol) arm can range from 1 to 125, with the average number of n being 25 to 120, preferably 30 to 85, and most preferably 30 to 70. The total n is selected from 150 to 350, preferably 180 to 300.

[0034] The polyalkoxylated polyol polyester (Formula-2) of the present invention can be prepared by a single-stage or multi-stage reaction. The polyalkoxylated polyol is prepared by drying a mixture of a polyol compound and a base catalyst such as KOH, NaOH, or calcium metal at 100°C to 200°C under vacuum, followed by alkoxylation of a polyol compound having 6 to 20 hydroxyl groups with ethylene oxide or propylene oxide at 130°C to 200°C. The alkylene oxide is metered into the reactor under pressure over a period of 10 to 20 hours. The use of ethylene oxide, propylene oxide, or a mixture of ethylene oxide and propylene oxide can result in primary -OH groups, secondary -OH groups, or a mixture thereof.

[0035] The organic polyol compound (Q) of embodiments of the present invention may be a natural or synthetic polyol having at least six hydroxyl groups, examples of which are shown (but not limited to) from the following classes of compounds: 1. Sugar alcohols, also called polyhydric alcohols or polyalcohols, have at least six hydroxyl groups and have the general formula HOCH2(CHOH) x Examples include, but are not limited to, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, maltotritol, maltotetritoitol, and polyglycitol. 2. Disaccharides are formed from two monosaccharides by dehydration through a glycosidic bond. Examples include, but are not limited to, trehalose, sucrose, lactose, maltose, etc. Disaccharides contain six or more hydroxyl groups. 3. The chemical structure is (CH 10 O5) n and n is 2 to 20. 4. Dipentaerythritol 5. Dendrimer polyols, such as Bolton® H2004, H2003, and H20, have 6, 12, and 16 terminal hydroxyls, respectively. 6. Polyglyceryls having 3 to 10 glycerin units and 6 or more hydroxyl groups.

[0036] After reaction, the hydroxyl groups of the starting polyol compound each grow into a hydrophilic poly-(alkylene glycol) arm, all of which may be the same or different in length depending on the reaction conditions.

[0037] The next reaction is an esterification reaction between the polyalkoxylated polyol compound and the fatty acid, resulting in some or all of the hydrophilic poly-(alkylene glycol) arms being capped with fatty acid esters. The reaction is carried out at temperatures between 120°C and 250°C, with or without a catalyst, until the desired acid value or degree of esterification is reached. A preferred method is to use an esterification catalyst, such as alkylbenzene sulfonic acid, methanesulfonic acid, organotin catalyst, or organotitanate catalyst. The preferred molar ratio of fatty acid to alkoxylated polyol compound is one that forms 50% to 130% ester with respect to the hydrophilic poly-(alkylene glycol) arms.

[0038] For example, when the starting polyol compound is sorbitol, six poly(alkylene glycol) arms are formed per sorbitol molecule, resulting in a molar ratio of 3 to 7.8. When the starting polyol compound is trehalose, eight poly(alkylene glycol) arms are formed, resulting in a molar ratio of 4 to 10.4. Most preferred are those that form at least four or more fatty ester-capped arms. In one such embodiment, the present thickener has six arms, in contrast to more common thickener compositions that may exhibit four arms developed for thickening surfactant-based formulations. In at least one embodiment, it is derived from natural sorbitol with ethylene oxide to provide six hydrophilic arms. Subsequent reaction with natural oleic acid produces an oleic group with four hydrophobic interactions at each end of the arm. The present thickener thickens surfactant formulations by crosslinking surfactant micelles with hydrophobic fatty groups, resulting in a crosslinked micellar structure that is significantly larger than the original micelles. The two "uncapped" arms are hydrophilic and serve to increase water solubility, while the four "capped" hydrophobic arms bind to the surfactant (micelle) based on a given formulation.

[0039] In another embodiment, Q is the organic radical portion of sorbitol having six carbons, and Formula-3 is the chemical structure of a polyol ester from a sorbitol starting compound. [ka]

[0040] Another embodiment of the present invention is a cosmetic, dermatological, and pharmaceutical formulation containing the polyalkoxylated polyol polyester (Formula 1) of the present invention. The polyalkoxylated polyol polyester of the present invention is suitable as a thickener, rheology modifier, solubilizer, regulator, or dispersant for aqueous solutions, aqueous / alcoholic solutions, and surfactant-containing formulations; and as an emulsifier and suspending agent for thickening and thickening emulsions and suspensions. These surfactant-containing formulations, emulsions, and suspensions include, for example, shampoos, shower products, shower gels, bubble baths, facial cleansers, hand soaps, bar soaps, shaving creams, hair conditioners, deodorants, lotions, creams, ointments, wet wipes, antiperspirants, sunscreens, liquid fabric softeners, liquid laundry detergents, liquid dish soaps / detergents, and all-purpose liquid cleaners.

[0041] Based on the finished formulation, cleansing products and emulsion and suspension products according to embodiments of the invention preferably contain 0.05% to 20% by weight, particularly preferably 0.1% to 10% by weight, and especially preferably 0.5% to 5% by weight of polyalkoxylated polyol polyesters of formula-2 or formula-3.

[0042] Cleansing compositions according to embodiments of the present invention may further include the following components: all commonly used anionic, cationic, zwitterionic, nonionic, and amphoteric surfactants; active ingredients beneficial to skin and hair, such as cosmetic oils, petrolatum, vegetable oils, hydrogenated vegetable oils, UV filters, proteins, shine ingredients, anti-aging agents, amino acids, bioactive ingredients, moisturizers, conditioning polymers, silicones, cationic polymers, sucrose polyesters, anti-dandruff zinc salts, hydroxy acids, skin lightening agents; stabilizers, such as silica, 12-hydroxystearic acid, hydrogenated castor oil, ethylene glycol distearate, bentonite, and hectorite clay, fatty acids, fatty alcohols, and the like; other thickeners, such as hydroxyethyl cellulose, xanthan gum, polyacrylates, modified or unmodified starch, and polyethylene glycol. The cleansing compositions may be in liquid, paste, gel, or solid form.

[0043] The total amount of surfactant used in compositions of the present invention may be between 5% and 70% by weight of the finished composition, preferably between 10% and 40% by weight, and most preferably between 12% and 35% by weight.

[0044] Each of these ingredients, as well as preferred and optional components in the cleansing composition, are described below.

[0045] A. Detersive surfactants Commonly used detersive surfactants can be selected from anionic, cationic, nonionic, amphoteric / zwitterionic surfactants, or mixtures thereof. Details of these commonly used detersive surfactants are known, for example, US 7,659,235 (B2); US 8,361,450 (B2); US 8,802,607 (B2); US 3,929,678; US 2,528,378; and "McCutcheon's Emulsifiers and Detergents," 1989 Annual, MC Publishing Co., Ltd. Examples of anionic surfactants include alkyl sulfates or alkyl ether sulfates (including alkyl glycerol ether sulfates). Anionic surfactants can also include sulfate-free anionic surfactants, as exemplified below:

[0046] Aliphatic sulfonates, such as primary alkanes (e.g., C8-C 22 ) Sulfonates, primary alkane disulfonates, C8-C 22 Alkenesulfonates, alkyl glyceryl ether sulfonates, aromatic alkyl sulfonates, or C8-C 22 Hydroxyalkanesulfonates.

[0047] Alkyl sulfosuccinates (monoalkyl and dialkyl, e.g., C6-C 22 (including sulfosuccinates), alkyl and acyl taurates, alkyl and acyl glycinates, alkyl sulfoacetates, alkyl phosphates, alkyl and alkyloxyalkyl phosphates, and acyl lactates, C8-C 22Monoalkyl succinates and maleates. Fatty acyl isethionates are generally prepared by the reaction of an isethionate, such as an alkali metal isethionate, with an aliphatic fatty acid having 8 to 20 carbon atoms. Commercially available fatty acyl isethionates include, for example, DEFI, Hostapon SCI-78C, Jordapon CI prill, YA-SCI-85, and Iselux LQ-CLR-SB. The formula R-(CH2CHO) n Anionic carboxylate surfactants with COM [wherein R is C8-C 20

[0023] alkyl; n is 1 to 20; and M is a positive ion or ions, such as sodium, potassium, etc. Another class of anionic surfactants is soap or fatty acid salts. Examples of sulfonate derivatives of alkyl polyglucosides include hydroxypropyl lauryl glucoside sulfonate and sodium hydroxypropyl decyl glucoside sulfonate.

[0048] Another class of mild, sulfate-free surfactants is the alkanoyl surfactant class, which are prepared from amino acids. The alkyl groups range from C8 to C 20 Alkyl groups, preferably C 12 ~C 16 The alkyl group is an alkyl group. Examples of surfactants in this class include alkanoyl sarcosinates, alkanoyl glycinates, and alkanoyl glutamates. Commercially available products include Amisoft (registered trademark) and Amirite (registered trademark) from Ajinomoto Co., Inc., and Eversoft from Sino Lion Co., Ltd.

[0049] Preferred anionic surfactants are sulfate-free, mild surfactants and mixtures thereof. The weight ratio of the anionic surfactant in the composition according to the present invention is within the range of 5% to 35% by weight, preferably 10% to 25% by weight.

[0050] Amphoteric or zwitterionic surfactants are surfactants that have both positive and negative charges. They can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, where the aliphatic groups can be straight or branched chains, and one of the aliphatic groups contains C8 to C6. 18 C, one of which contains an anionic group, such as a carboxyl group, a sulfonate group, a sulfate group, a phosphate group, or a phosphonate group. Examples include commonly used betaines, such as N-alkyl-N,N-dimethylammonium glycinates, coco-amidopropyl betaine; C 12 ~C 18 -alkyldimethyl-sulfopropylbetaine, and amine oxide. The proportion of the amphoteric surfactant in the composition according to the embodiment of the present invention is 0.5% by weight to 30% by weight, preferably 1% by weight to 15% by weight.

[0051] Examples of nonionic surfactants include alkoxylated fatty alcohols, acids, amides, or alkylphenols; long-chain tertiary amine oxides; long-chain tertiary phosphine oxides; dialkyl sulfoxides; sugar amides, such as those described in U.S. Pat. Nos. 5,389,279 and 5,009,814; and alkyl polyglucosides, such as those described in U.S. Pat. Nos. 4,565,647 and 3,723,325. Preferred nonionic surfactants are alkyl polyglucosides and alkyl polyglucamides. Commercially available examples include the Plantaren® series from BASF, the Ecosense® series from Dow Chemicals, Gluco Tain® from Clariant, and Poly Suga Mulse from Colonial Chemicals. The proportion of the nonionic surfactant according to an embodiment of the present invention is in the range of 1% to 20% by weight, preferably 1% to 15% by weight.

[0052] Cationic surfactants are surfactants that have a positively charged group. Suitable cationic surfactants include quaternary ammonium salts, such as di-(C 10 ~C 24)-Alkyldimethylammonium hydrochloride, (C 10 ~C 24 )-alkyltrimethylammonium hydrochloride or sulfate, and N-acylaminoethyl-N,N-diethyl-N-methylammonium hydrochloride. Other commonly used cationic surfactants are described by reference in US Pat. No. 8,470,305 (B2) and US Pat. The weight proportion of the cationic surfactant in the composition according to the present invention is in the range of 1% to 10% by weight, preferably 1% to 7% by weight.

[0053] B. Liquid Crystal Inducers and Liquid Crystal Modifiers Liquid crystal inducers are small, nonionic molecules that, when solubilized in a surfactant mixture, are believed to alter the packing of surfactant micelles into lamellar liquid structures or aggregates of larger structures of different shapes and sizes, such as vesicles, rods, and cubic liquid crystals. Another name for liquid crystal inducers is hydrophobic thickeners. These include the alkanoamide, alkylamine oxide, or mixtures thereof. Examples of this class include monoethanolamides and diethanolamides, isopropanolamides of fatty acids with 10 to 20 carbon atoms, PPG-hydroxyethyl cocamide, and alkylamine oxides with 10 to 20 carbon atoms. Another class of chemicals in liquid crystal inducers is alkoxylated alkyl alcohols with 8 to 18 carbon atoms, preferably 8 to 12 carbon atoms, and 1 to 4 ethylene oxide units.

[0054] Liquid crystal modifiers include fatty acids and fatty alcohols having 8 to 20 carbon atoms and aliphatic hydrocarbons with a molecular weight of less than 400 g per mole. These are believed to control the size and shape of liquid crystals. References for ranges and examples of liquid crystal inducers and modifiers are found in US Pat. No. 7,655,607 (B2).

[0055] C. Active ingredients beneficial to skin and hair These beneficial active ingredients can be water-soluble, water-insoluble, or water-dispersible. Water-soluble active ingredients include, but are not limited to, polyols such as glycerin, diglycerin, sorbitol, propylene glycol, propanediol, panthenol, and sugars; alpha-hydroxyl acids and their salts; and low molecular weight polyethylene glycols. Water-insoluble and water-dispersible skin and hair beneficial active ingredients include, but are not limited to, petrolatum, silicones, vegetable oils, essential oils, emollients, hydrocarbon oils, fatty esters, cationic polymers, high refractive index oils for shine, anti-dandruff agents, proteins / protein derivatives, and the like. These water-insoluble beneficial active ingredients are usually present in the composition as emulsions or bands. Non-limiting examples in U.S. Pat. No. 7,262,158 are incorporated herein by reference. A wide variety of other skin and hair benefit actives may include vitamins, lipids (such as sucrose esters, lanolin, cholesterol), liposomes, essential fatty acids, butters, minerals, antibacterial agents, anti-acne agents, oil control agents, astringents, oil control agents, scrubs and exfoliating particles, essential oils, sunscreens, styling aids, dyes, fragrances, cyclodextrin / fragrance complexes, anti-wrinkle actives (amino acids and their derivatives, e.g., N-acetyl-L-cysteine), thiols, anti-cellulite agents (such as caffeine and theophylline), skin tone adjusting actives, skin lightening actives, emollients (such as bisabolol, aloe vera, dipotassium glycyrrhizinate, etc.).

[0056] Cationic water-soluble and / or dispersible polymers are highly useful in compositions according to the present invention as conditioning actives or deposition enhancers. Suitable cationic polymers for compositions according to the present invention have a cationic charge density in the range of 0.2 to 8 meq / g and a molecular weight in the range of 1,000 to 3,000,000. The cationic group is a nitrogen-containing moiety, such as a quaternary ammonium or a cationic protonated amino moiety, which can be a primary, secondary, or tertiary amine. Non-limiting examples of cationic polymers are described in the "CTFA Cosmetic Ingredient Dictionary," 3rd Edition, edited by Estrin, Crosley, and Haynes, and in US Pat. No. 8,470,305 (B2) and US Pat. No. 8,105,994 (B2). Non-limiting examples include copolymers of vinyl monomers having cationic protonated amine or quaternary ammonium functional groups with water-soluble spacer monomers, such as acrylamide, methacrylamide, alkyl and dialkyl acrylamides, vinylpyrrolidone, and vinylcaprolactone. Specific, non-limiting examples include polyquaternium-11, -16, -7, -6, -22, -47, and -39. Other suitable cationic polymers include polysaccharide polymers, such as cationic cellulose derivatives, cationic starch derivatives, and cationic guar gum derivatives. Non-limiting examples include products under the following trade names: Jaguar® from Rhone Poulenc, Aqua® and N-Hance polymers from Aqualon, UCARE polymers from Dow Chemical, MerQuat from Nalco, and Galactasol from Henkel.

[0057] D. Stabilizers and further thickeners Stabilizers (or structuring systems) are used to form a stabilizing network of crystals in the composition, preventing droplets of lipophilic beneficial active ingredients from coalescing and phase separating in the product. Non-limiting examples include hydroxyl-containing fatty acids, fatty esters, or fatty soap-containing water-insoluble wax-like substances, such as 12-hydroxystearic acid, 9,10-dihydroxystearic acid, tri-9,10-dihydroxystearin, and tri-12-hydroxystearin. Another class of stabilizers is C 10 ~C 22 Examples of stabilizers commonly used include ethylene glycol fatty acid esters, fumed silica, precipitated silica, smectite clay, etc. Examples of other commonly used stabilizers are disclosed in US 6,194,363 and US 9,138,428. Another class of stabilizers is a gel network of stearic acid and a fatty amphiphile such as behenyltrimethylammonium chloride, as disclosed in US 8,470,305. Another class of stabilizers is a blend of unmodified starch, modified starch, and fatty acids, as disclosed in US 6,906,016.

[0058] Further thickening agents for stabilizing the composition and improving its viscosity according to the present invention are polymers. Non-limiting examples include carbohydrate gums such as cellulose gum, microcrystalline cellulose, cellulose gel, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethylcellulose, methyl / propyl cellulose, guar gum, karaya gum, tragacanth gum, gum arabic, acacia gum, agar gum, xanthan gum, and mixtures thereof; modified and unmodified starch granules with a gelatinization temperature between 30°C and 85°C, and pregelatinized cold water-soluble starch. Further non-limiting examples include the class of hydrophobic associative crosslinked alkali-swellable acrylate polymers comprising an acidic monomer and an associative monomer with a hydrophobic end group, as disclosed in US Pat. No. 9,161,899. Non-limiting commercial examples include Carbopol Aqua SF-1 from Lubrizol, Stabylen 30 from 3V Sigma SPA, and the Aqupec series from Sumitomo Seika Chemicals Co., Ltd. of Japan.

[0059] Further suitable thickening agents may include salts such as sodium chloride and sodium sulfate; cellulose derivatives such as hydroethylcellulose; xanthan gum, guar gum; starch and starch derivatives; carboxyvinyl polymers such as Carbopol® 940; polyacrylate emulsions such as Carbopol® Aqua SF-1 polymer; polyethylene glycol; and polyvinyl alcohol.

[0060] The emulsions and suspensions according to the present invention comprise water, oil, an emulsifier, a polyester of Formula-1, preferably 0.05% to 20% by weight, particularly preferably 0.1% to 10% by weight, and particularly preferably 0.5% to 5% by weight, and other commonly used ingredients for skin care, hair care, and body care. The non-aqueous content of the emulsion is typically in the range of 2% to 85%, preferably 5% to 45%. The oils include, but are not limited to, cosmetic oils such as refined vegetable oils, refined synthetic or fermented hydrocarbon oils, silicone oils, and synthetic ester oils.

[0061] The following non-limiting examples demonstrate the compositions and superior performance of the present invention. [Example]

[0062] (Example 1) Synthesis of polyalkoxylated polyol polyesters of formula-3 with different molecular structures. Table 1 lists the preparation of polyesters of formula-3 with a range of molecular weights of alkoxylated sorbitol and fatty acids. The reaction flask used was a four-necked, 1-liter resin kettle. Sorbitol was mixed with a KOH or NaOH base catalyst and dried under vacuum at 90-110°C. X moles of ethylene oxide or a blend of ethylene oxide and propylene oxide per mole of sorbitol was added under pressure and reacted at 140-180°C for 10-20 hours. After the reaction, the resulting product was cooled, degassed, and filtered to obtain Sorbeth-xxx (see Table 1 below). The Sorbeth-xxx, oleic acid or stearic acid components, and catalyst methanesulfonic acid were added to a flask and then purged with nitrogen gas. The mixture was heated to between 120-220°C while mixing under nitrogen and collecting water. The reaction was maintained until the total R1 (or acid number) reached the target value or remained nearly constant. After the flask was cooled to room temperature, the product was recovered. The resulting polyester was a waxy solid. [Table 1]

[0063] (Example 2) Polyesters #1-6 of the present invention and PEG-150 pentaerythrityl tetrastearate were formulated into a non-sulfate personal cleansing composition containing 6% potassium cocoyl glycinate (Amyrite GCK-11F, manufactured by Ajinomoto Co., Inc.), 15% cocamidopropyl betaine (35% active ingredient by weight, trade name: Monteric LMAB), 0.3% EDTA, 78.7% water, and citric acid adjusted to pH 6. Potassium cocoyl glycinate surfactants are derived from glycine amino acids and are known to be very mild to the skin. The trade name for PEG-150 pentaerythrityl tetrastearate is CROTHIX, manufactured by Croda Inc., and is based on U.S. Pat. No. 5,192,462.

[0064] At 2 wt. % thickener, Polyester-6 of the present invention achieved a viscosity of 72,900 cP, while Crothic achieved a viscosity of 45,840 cP, demonstrating the superior performance of the polyesters of the present invention over the prior art.

[0065] (Example 3) This personal cleansing formulation is based on another amino acid-derived surfactant, sodium cocoyl sarcosinate. Its composition is 29.89% sodium cocoyl sarcosinate (Protelan LS 9011, Zschimmer & Schwarz, 29% active by weight), 12.38% cocamidopropyl betaine (Monateric LMAB, 35% active by weight), 1.8% thickener, 1% cocamide MEA, 0.1% EDTA, 1% NaCl, 53.83% water, and citric acid adjusted to pH 6. At 1.8% by weight in the formulation, Polyester #1-7 of the present invention achieved a viscosity of 6960 cP, compared to 3640 cP for Crothix.

[0066] (Example 4) This personal cleansing formulation is based on two mild, nonionic surfactants well known in the personal cleansing market: a nonionic alkyl polyglucoside surfactant and an anionic sodium cocoyl isethionate. The formulation contains 13% decyl glucoside (BASF's Plantaren 2000 N UP), 7% sodium cocoyl isethionate (Pureact I-78C), 7% cocamidopropyl betaine (Montaric LMAB), 1% PEG-7 glyceryl cocoate (Protachem GC-7), 0.35% EDTA, citric acid adjusted to pH 5.5, and water. At the same 1.2% by weight, the inventive polyesters #1-4 and CROTHIX thickened the surfactant formulation to 26,340 cP and 22,200 cP, respectively. The inventive polyester 4 again outperformed the prior art CROTHIX.

[0067] (Example 5) This formulation is a classic sulfate surfactant cleansing product: 10.7% aqueous sodium lauryl ether sulfate (70% active by weight), 8.58% cocamidopropyl betaine (35% active by weight), 0.25% cocamide MEA, 0.2% EDTA, 0.5% NaCl, x% thickener, and 79.57% water. The pH is 5.5. In this sulfate cleansing formulation, polyesters #1-5 of the present invention from Table 1 were compared with three commercially available thickeners. 1) Trade name: CROTHIX, solid, supplied by Croda, INCI name: PEG-150 pentaerythrityl tetrastearate; 2) Trade name: Glucamate DOE-120, supplied by Lubizol Inc., INCI name: PEG-120 methylglucose dioleate; 3) Trade name: Rewopal PEG 6000 DS, supplied by Evonik Inc., INCI name: PEG-150 distearate [Table 2]

[0068] The results demonstrate that thickeners of embodiments of the present invention outperform many commercially available thickeners of the prior art in classic sulfate surfactant personal cleansing products. This and other examples demonstrate that a wide range of polyesters of embodiments of the present invention were more effective and versatile thickeners than current commercial products of the prior art in a wide range of personal cleansing products using different types of surfactants.

[0069] (Example 6) A comparative analysis was conducted by synthesizing four polyesters (polyesters A, B, C, and D) following the example of Chen et al. in US 2013 / 0079536(A1). A control polyester, polyester #4-4, was incorporated to determine the thickening properties of the four polyesters.

[0070] Polyester A Sorbeth-50 (PEG-50 sorbitol) (169.25 g, 67.7 wt%), polyhydroxystearic acid (AC#41) (80.50 g, 32.2%), and tin oxalate catalyst (0.25 g, 0.1%) were added to a glass reactor and mixed under nitrogen pressure at 190-200°C for 24 hours. After cooling to below 100°C, the mixture was processed to give Polyester A with an HLB of approximately 13.5.

[0071] Polyester B The same conditions as for Polyester A were used, but with Sorbeth-50 (PEG-50 sorbitol) (78.25 g, 31.3 wt%), hydroxystearic acid (171.50 g, 68.6%), and stannous oxalate (0.25%, 0.1%), and its HLB was approximately 6.3.

[0072] Polyester C Under similar conditions at 200°C for 24 hours, Sorbeth-230 (PEG-230 sorbitol) (258.82 g, 86.27 wt%), hydroxystearic acid (HAS) (40.48 g, 13.53%), and tin oxalate (0.25%, 0.1%) were used. Approximately half of the polyester was treated to obtain Polyester C. Polyester C was prepared using the R 3 It contains one hydroxystearic acid unit.

[0073] Polyester D An additional 28.60 g of hydroxystearic acid was treated with Polyester C (211.38 g) in the reactor and mixed for an additional 20 hours at 200° C. under nitrogen pressure until the AC# was 4.4, which was then processed to Polyester D. Polyester D was prepared using the R 3 It has two hydroxystearic acid units in it.

[0074] These four comparative polyesters, as well as a control polyester (the preferred polyester of the present application), were used as thickeners in the preparation of standard shampoo formulations under standard processing conditions for shampoos in the cosmetics industry. They were dissolved in the shampoo formulations with mixing at 70-90°C. Their viscosities were measured, and the average viscosity values measured three times at 24.5°C are reported below. The shampoo composition by weight consisted of 57.06% water; 11.5% cocamidopropyl betaine (at a concentration of 30%); 11.5% olefin (C 14~16 ) 30% sodium sulfonate; and 1.44% polyester. [Table 3]

[0075] No useful thickening was found in Chen's polyesters A-D, which were made from hydroxystearic acid (HSA) and polyhydroxystearic acid, as indicated by the average viscosity (cP). 3are independently claimed to be the residue of a polyhydroxyalkyl carboxylic acid or a polyhydroxyalkenyl carboxylic acid, the residue of a hydroxyalkyl carboxylic acid or a hydroxyalkenyl carboxylic acid, and / or the residue of an oligomer of a hydroxyalkyl carboxylic acid or a hydroxyalkenyl carboxylic acid.

[0076] (Example 8) Polyesters 4-1 through 4-11, Polyesters C and D were prepared and the viscosity, along with the characteristics of each polyester according to Formula 2 of the present application, were recorded below. Table 5 below shows the results. [Table 4]

[0077] Polyesters with viscosities above about 2500 cP exhibited good or excellent thickening results, while polyesters with viscosities below about 2500 cP exhibited poorer and / or unsatisfactory thickening results (0-220 = no thickening, 1220-1240 = little thickening, 2000-2980 = slight thickening, 3400-7300 = good thickening, 12600-15000 = strong thickening, and 21000 or greater = strong thickening). Table 4 reveals some very surprising and unexpected results from the perspective of those skilled in the art: 1) Polyesters 1-5, with increasing carbon number in R1 (from 12 to 18), continued to show an increase in viscosity. Furthermore, polyester-6, with R1 being 22 carbons, showed a sharp decrease in viscosity; those skilled in the art would have expected the opposite result. 2) Chen's prior art polyesters C and D, which have R1 derived from hydroxystearic acid, did not exhibit any significant thickening. 3) Polyesters 7, 8, 4, 9, and 10 had total n values of 135, 170, 230, 200, and 400, respectively, with the best viscosity increase of 14,900 cp at total n=230. In other words, the thickening effect did not increase with increasing molecular weight. These results are not linear and would be unexpected and novel from the prior art to one skilled in the art.

[0078] (Example 7) The Organization for Economic Cooperation and Development (OECD) has developed several methods to assess the environmental impact of manufactured chemicals. The OECD 301B series of tests, which use inocula sourced from wastewater treatment plants to provide a valid bacterial profile, have become the standard method for measuring the biodegradation of chemicals and their impact on the environment.

[0079] The OECD 301B test was used, which measures the carbon dioxide produced by the complete decomposition of a chemical's carbon content, as described above. To disperse the polyester of the present invention in the inoculum for this test, it was mixed with a non-biodegradable surfactant (Pluronic P123) in a 2 / 1 (surfactant / polyester) ratio, and the blend was dispersed in water using an ultrasonic probe. The resulting dispersion was mixed with the inoculum, and carbon dioxide release was measured periodically. After 28 days, the measured biodegradation data are shown in Table 5 below. These data demonstrated at least the following results: 1) Polyesters 5-2, 5-3, and 5-4 of the present invention showed the best and superior biodegradability results of 41.8±2.1%, 42.2±3.2%, and 42.2±3.2%, respectively. 2) Polyester 5-7, with a total n of 400, showed an unexpected drop in biodegradability of 17.3±4.9%. [Table 5]

[0080] Thus, in one embodiment of the invention, the viscosity amount is greater than about 2000 cP, or greater than about 3400 cP, or greater than about 12000 cP, or greater than about 20000 cP. In one embodiment of the invention, the % biodegradation as measured by the OECD 301B test is greater than about 19%, or greater than about 23%, or greater than about 26%, or greater than about 30%.

[0081] In one variant of the invention, the number of carbon atoms in R1 is 18. In one embodiment of the invention, the fatty acid from which R1 is derived is oleic acid, stearic acid, isostearic acid, or a mixture thereof. In one variant of the invention, the fatty acid from which R1 is derived is not hydroxystearic acid.

[0082] In one variation, the polyesters of the present invention have at least good or very good or excellent thickening properties and good biodegradability properties.

Claims

1. formula: Q-[(OA) ｎ -OR] ｍ Formula-2 wherein Q is a group of natural or synthetic organic polyol compounds having from 6 to 50 carbon atoms forming a linear, branched, cyclic, saturated or unsaturated structure; Q is a group of the formula -[(OA) ｎ -OR], each of the 6 to 50 carbon atoms may be independently substituted with hydrogen, oxygen, or nitrogen; A is -C ２ H ４ -or-C ３ H ６ - selected from; R is hydrogen or —COR １ are independently selected from R １ is C ６ ~C ２２ Alkyl or C ６ ~C ２２ alkenyl; n is an integer selected from 1 to 125, which may be the same or different for each polyalkoxylated hydrophilic arm, with the total n ranging from 150 to 350, preferably 200 to 300; COR １ the average total number of is less than or equal to m; m is an integer selected from 6 to 25. A thickener comprising: the thickener exhibits at least six polyalkoxylated hydrophilic arms emanating from a central core, at least four of the six arms being capped with hydrophobic groups; The thickened viscosity is greater than about 2000 cP. The thickener described above.

2. R １ 10. The thickener of claim 1, wherein is derived from an oleic acid moiety or a stearic acid moiety or a mixture thereof.

3. R １ 10. The thickener of claim 1, wherein is derived from a stearic acid moiety, an isostearic acid moiety, an oleic acid moiety, or a mixture thereof.

4. Average COR １ 10. The thickener of claim 1, wherein the number is from about 5 to about 6.

5. Q is, a. General formula HOCH ２ (CHOH) ｘ CH ２ sugar alcohols with OH; b. a disaccharide or disaccharides having a glycosidic bond; c. (C ６ H １０ O ５ ) ｎ [wherein n is 2 to 20]; d. dipentaerythritol; e. dendrimer polyols, and mixtures thereof is one or more polyols selected from the group consisting of The thickener according to claim 1 .

6. 2. The thickener of claim 1, wherein Q is sorbitol.

7. A cosmetic, dermatological or pharmaceutical composition comprising a thickener according to claim 1 or a mixture thereof.

8. A cosmetic, dermatological or pharmaceutical composition comprising a thickener according to claim 2 or a mixture thereof.

9. A cosmetic, dermatological or pharmaceutical composition comprising a thickener or mixtures thereof according to claim 3.

10. 10. Household, industrial, and institutional compositions comprising the thickener of claim 3 or mixtures thereof.

11. A cosmetic, dermatological or pharmaceutical composition comprising a thickener or mixtures thereof according to claim 4.

12. Q is a compound of formula 3: 【Chemical 1】 wherein A is independently -C ２ H ４ -or-C ３ H ６ - and; R is hydrogen or a group of formula -COR １ is a group; R １ is derived from a stearic acid moiety, an isostearic acid moiety, or an oleic acid moiety, or a mixture thereof; -COR １ the average total number of groups is 3 to 6; n １ ~n ６ are independently integers from 1 to 125; the total n is from 180 to 300. is the radical of sorbitol, 10. The cosmetic, dermatological or pharmaceutical composition of claim 1.

13. water; 1% to 50% by weight of a surfactant selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof; 0.1% to 10% by weight of a polyol polyester of formula-2; and 0.1% to 50% by weight of other ingredients selected from the group consisting of skin and hair benefit actives, stabilizers, additional thickeners, colorants, preservatives, and pearlizing agents 8. The cosmetic, dermatological, and pharmaceutical composition of claim 7, further comprising:

14. water; 2% to 50% by weight of a surfactant selected from the group consisting of sulfate-free anionic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof; 0.1% to 10% by weight of a polyalkoxylated polyol polyester of formula-2; and 0.1% to 50% by weight of other ingredients selected from the group consisting of skin and hair benefit actives, stabilizers, additional thickeners, colorants, and preservatives 9. The cosmetic, dermatological, and pharmaceutical composition of claim 8, further comprising:

15. Water; and 1% to 50% by weight of a surfactant selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof; 0.1% to 10% by weight of a polyol polyester of formula-2; and 0.1% to 50% by weight of other ingredients selected from the group consisting of skin and hair benefit actives, stabilizers, additional thickeners, colorants, preservatives, and pearlizing agents 10. The cosmetic, dermatological, and pharmaceutical composition of claim 9, further comprising:

16. Water; and 1% to 50% by weight of a surfactant selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof; 0.1% to 10% by weight of a polyol polyester of formula-2; and 0.1% to 50% by weight of other ingredients selected from the group consisting of skin and hair benefit actives, stabilizers, additional thickeners, colorants, preservatives, and pearlizing agents 11. The cosmetic, dermatological, and pharmaceutical composition of claim 10, further comprising:

17. Water; and 1% to 50% by weight of a surfactant selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof; 0.1% to 10% by weight of a polyalkoxylated polyol polyester of formula-3; and 0.1% to 50% by weight of other ingredients selected from the group consisting of skin and hair benefit actives, stabilizers, additional thickeners, colorants, preservatives, and pearlizing agents 12. The cosmetic, dermatological, and pharmaceutical composition of claim 11, further comprising:

18. Water; and about 1% to 30% by weight of skin and hair active ingredients selected from the group consisting of UV filters, moisturizers, conditioners, preservatives, deodorizing actives, reducing agents for permanent wave products, colorants for hair dyes, anti-aging actives, proteins / protein derivatives, fragrances, petrolatum, vegetable oils, cationic conditioning polymers, and mixtures thereof; and about 1% to 10% by weight of a polyalkoxylated polyol polyester of formula-1 8. The cosmetic, dermatological, and pharmaceutical composition of claim 7, further comprising:

19. 10. The thickener of claim 1, which exhibits at least 20% biodegradability after 28 days.

20. 2. The thickener of claim 1, wherein the total n is about 230.

21. R １ C containing an alkyl, alkenyl, or alkynyl moiety １８ 10. The thickener of claim 1 which is a fatty acid.

22. 8. The cosmetic, dermatological or pharmaceutical composition according to claim 7, exhibiting a viscosity of at least 12000 cP.

23. R １ 4. The thickener of claim 3, wherein is derived from oleic acid.

24. 10. The thickener of claim 1, having a percent biodegradation of about 19% or greater as measured by OECD 301B.

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