Formulations comprising biodegradable polyalkoxylated polyol polyesters

Abstract

The compounds included herein relate to biodegradable thickeners (e.g., polyalkoxylated polyol polyesters) having viscosities that allow the product to be pouched but still remain on the desired surface to which it is applied. Embodiments of the compounds may be exemplified by the formula: Q-[(OA) n-OR] m.

Description

[0001] Priority claim

[0002] This application claims priority to U.S. application No. 18 / 140,646, filed on April 28, 2023, which is a continuation-in-part application of 17 / 838,503, filed on June 13, 2022, which claims priority to U.S. application No. 16 / 369,544, filed on March 29, 2019, which claims priority to U.S. application No. 15 / 652,679, filed on July 18, 2017, which claims priority to U.S. application No. 62 / 499,642, filed on February 1, 2017, and U.S. application No. 62 / 495,444, filed on September 15, 2016, the contents of all applications are incorporated herein by reference in their entirety. Technical Field

[0003] The field of the present invention and embodiments thereof relates to thickeners which create a viscosity that allows a product to be poured yet remain on the desired surface to which it is applied. Background Art

[0004] Rheology, or the study of the flow of matter, is applied to consumer products such as shower gels, shampoos, liquid detergents, liquid dishwashing detergents, liquid hand soaps, skin lotions or creams, hair conditioners, hair styling products, etc., to develop a specific viscosity profile. This profile is critical to consumers' product preferences and ultimate purchasing decisions. Consumers would prefer products with a rheological profile that makes the product stable in the container, has a low enough viscosity to pour easily from the container, and is also viscous enough to be applied to the body, hair, or fabric without dripping from the consumer's hands or the surface to which it is applied. In addition, the product must be stable and maintain a consistent rheological profile during storage in warehouses, during transportation, and while potentially sitting on a shelf for years.

[0005] Consumers prefer environmentally friendly products, for example, products that are biodegradable in the environment, rather than harmless byproducts, so that it does not permanently accumulate in the environment. Therefore, the most preferred products by consumers must be able to both effectively thicken the composition and be biodegradable in the natural environment.

[0006] There are many commercial thickeners that use esters of polyalkoxylated polyols and fatty acids to thicken surfactant-containing formulations. Examples of commercial products include polyethylene glycol 6000 distearate, also known as the INCI name - PEG-150 distearate; PEG 120 methyl glucose dioleate and PEG 120 methyl glucose trioleate (Glucomate TM DOE 120 and Glucomate TMVLT); PEG-150 pentaerythritol tetrastearate (Crothix TM 、Crothix TM Liquids and Versathix TM ); PEG-150 polyglyceryl-2 tristearate (Genapol LT); PEG / PPG-120 / 10-trimethylolpropane trioleate (Arlypon TT). The number of hydrophilic polyalkoxylated arms of PEG-150 distearate is two, the number of hydrophilic polyalkoxylated arms of Arlypon TT is three, the number of hydrophilic polyalkoxylated arms of Genapol LT and Crothix, Crothix Liquid and Versathix is ​​four, and the number of hydrophilic polyalkoxylated arms of Glucomate DOE 120 is five.

[0007] US 5,192,462 (Gloor et al.) relates to thickeners comprising tetraesters made from fatty acids and polyoxyethylene pentaerythritol having four hydrophilic poly-(ethylene glycol) arms. Its preferred chemical structure is PEG-150 pentaerythritol tetrastearate, in which all four hydrophilic poly-(ethylene glycol) arms are terminated with stearic fatty acid, and is the base for Crothix, Crothix liquid, and Versathix liquid.

[0008] US Pat. No. 7,709,011 and US Pat. No. 7,553,495 (both Klug et al.) are directed to thickeners of alkoxylated polyglycerol esters with fatty acids for topical formulations containing surfactants, as shown below.

[0009]

[0010] Where A is formula -C 2 H 4 - or C 3 H 6 -, B is hydrogen or a group of the formula -COR, wherein at least one symbol B is a group of the formula -COR-, R is C 7 -C 21 -alkyl, C 7 -C 21 - hydroxyalkyl or alkenyl, n is a number from 1 to 30, and x, y, z are numbers from 0 to 100, wherein the sum of x, y and z is from 50 to 250. (See column 1, lines 43-48).

[0011] US20180072817 and US20180071198 owned by the applicant relate to compounds related to polyalkoxylated polyol polyesters having a viscosity that allows the product to be poured but still remain on the desired surface to which it is applied. Embodiments of these compounds can be illustrated by the following formula: Q-[(OA)n-OR]m.

[0012] For those skilled in the art, the number of hydrophilic poly-(ethylene glycol) arms is equal to n + 2. When n = 30 and x + y + z = 250, the average number of ethylene glycol units or (x + y + Z) / (n + 2) is [250 / (30 + 2)], and the maximum is about 7.81. Summary of the invention

[0013] Embodiments of the present invention teach and describe novel polyalkoxylated polyol polyesters (eg, thickeners) conforming to Formula-2, which are the reaction product of (a) a fatty acid and (b) a polyalkoxylated polyol.

[0014] Q-[(OA) n -OR] m

[0015] Formula-2

[0016] Wherein Q is a radical 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 independently represented by a radical having the formula -[(OA) n -OR], wherein each of the 6 to 50 carbon atoms may be independently substituted by hydrogen, oxygen or nitrogen; A is selected from -C 2 H 4 -or-C 3 H 6 -; R is independently selected from hydrogen or -COR 1 , where R 1 Independently selected from C 6 -C 22 -alkyl and C 2 -C 22 -alkenyl, preferably a stearic acid moiety, an isostearic acid moiety, an oleic acid moiety or a mixture thereof, most preferably oleic acid; COR 1 The average total number of is ≥3, preferably ≥4, more preferably ≥5, even more preferably 5 to 6; n is an integer selected from 1 to 125 and may be the same or different for each polyalkoxylated hydrophilic arm; each (OA) n The average number of n units is from 25 to 120, preferably from 30 to 85, and most preferably from 30 to 70; the total number of n, i.e. each (OA) nThe sum of all n of the arms is from 150 to 350, preferably from 180 to 300; and m is an integer selected from 6 to 25, preferably from 6 to 12.

[0017] In another embodiment of the present invention, it relates to cosmetic, dermatological, pharmaceutical, personal cleaning, fabric cleaning, and household, industrial and institutional cleaning preparations containing the polyalkoxylated polyol polyester of Formula-2.

[0018] The polyesters of embodiments of the present invention are suitable as thickeners, rheology modifiers and solubilizers for aqueous, aqueous / alcoholic, and surfactant-containing formulations. Examples of these surfactant-containing formulations, emulsions and suspensions are shampoos, shower formulations, shower gels, bubble baths, facial cleansers, hand soaps, bar soaps, shaving creams, hair conditioners, deodorants, lotions, creams, ointments, wipes, antiperspirants, sunscreens, and the like. Embodiments of the present invention are also suitable as thickeners and rheology modifiers for fabric care products such as fabric conditioners and liquid laundry detergents; as thickeners and rheology modifiers for dishwashing liquids, liquid carpet washes and liquid floor cleaners, car wash liquid soaps / detergents, household and industrial liquid cleaning products, and the like.

[0019] The preparations, cleaning preparations, emulsions and suspensions according to the invention preferably contain 0.05 to 20 wt. %, particularly preferably 0.1 to 10 wt. %, especially preferably 0.5 to 5 wt. %, based on the final formulation, of the polyalkoxylated polyol polyester of formula 1.

[0020] The cleaning composition of an embodiment 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 active substances, such as cosmetic oils, petrolatum, vegetable oils, hydrogenated vegetable oils, UV filters, proteins, brighteners, anti-aging agents, amino acids, biologically active substances, wetting agents, conditioning polymers, silicones, cationic polymers, sucrose polyesters, anti-dandruff zinc salts, hydroxy acids, skin whitening agents; all commonly used stabilizers, such as silica, 12-hydroxystearic acid, hydrogenated castor oil, ethylene glycol distearate, bentonite and hectorite clays, fatty acids, fatty alcohols; all commonly used thickeners, such as hydroxyethylcellulose, xanthan gum, polyacrylates, modified or unmodified starches, etc.; all commonly used dyes, colorants, pearlescent agents, fragrances, chelating agents, solvents, humectants, salts, etc.

[0021] The total amount of surfactant used in the composition of the present invention may range from 5 to 70 wt%, preferably from 10 to 40 wt%, most preferably from 12 to 35 wt%, based on the final composition.

[0022] definition

[0023] As used above, and throughout this disclosure, unless otherwise indicated, the following terms shall be understood to have the following meanings. In the absence of a definition, conventional definitions known to those skilled in the art shall prevail.

[0024] As used herein, the terms "including," "containing," and "comprising" are used in their open, non-limiting sense.

[0025] As used herein, the singular form "a / an / the" includes plural referents unless the context clearly dictates otherwise.

[0026] In order to provide a more concise description, some quantitative expressions given herein are not suitable for the term "about". It should be understood that, whether or not the term "about" is explicitly used, each quantity given herein is meant to refer to the actual given value, and it is also meant to refer to the approximate value of such a given value that can be reasonably inferred based on the ordinary technology in the art, including equivalent values ​​and approximate values ​​generated due to the experimental and / or measurement conditions of such a given value. Whenever the yield or amount is given as a percentage, this yield or amount refers to the mass (weight percentage) of the entity, for which the yield is relative to the maximum amount of the same entity that can be obtained under specific stoichiometric conditions. Unless otherwise stated, the concentration given as a percentage refers to the mass ratio.

[0027] As used herein, "alkyl" means a straight chain or branched saturated chain having from 1 to 30 or more carbon atoms. Alkyl groups may be unsubstituted or substituted. Alkyl groups containing three or more carbon atoms may be straight chain, branched or cyclic.

[0028] 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 the alkenyl group may be unconjugated or conjugated with another unsaturated group. The alkenyl group may be unsubstituted or substituted.

[0029] The term "hydroxyl" means an OH group;

[0030] The term "hydroxyalkyl" refers to an alkyl group as defined above, wherein the alkyl group has an OH group disposed thereon.

[0031] As used herein, the term "alkoxy" or "alkoxylated" includes -O-(alkyl) wherein alkyl is as defined above.

[0032] As used herein, the term "composition" is intended to encompass a product comprising the specified ingredients in the specified amounts, as well as any product which results, directly or indirectly, from combination of the specified ingredients in the specified amounts.

[0033] The term "amino" as used herein refers to a substituent containing at least one nitrogen atom.

[0034] As used herein, the term "substituted" means that the specified group or moiety bears one or more suitable substituents, wherein the substituents may be attached to the specified group or moiety at one or more positions.

[0035] As used herein, the term "unsubstituted" means that the specified group bears no substituents.

[0036] In formula 2, m is (OA) n The total number of arms, n is the number of repeating units -OA in each arm. The total number n means the sum of all n's for all m arms. Sorbiteth-xxx, such as Sorbiteth-300, is an INCI (International Cosmetic Ingredient) name, where xxx is the total number n.

[0037] All patents or patent applications cited herein are fully incorporated by reference in their entirety. DETAILED DESCRIPTION

[0038] In one embodiment, the polyalkoxylated polyol polyester of Formula-2,

[0039] Q-[(OA)n-OR]m

[0040] Formula-2

[0041] Wherein Q is defined as a radical of a natural or synthetic organic polyol compound having carbon, hydrogen, oxygen and nitrogen elements and being linear, branched, cyclic, saturated or unsaturated, and wherein Q has 6 to 50 carbon atoms and is independently represented by a radical having the formula -[(OA) n -OR] is substituted with 6 to 25 groups;

[0042] Where A is selected from -C 2 H 4 -or-C 3 H 6 -; n is 1 to 125; R is independently selected from hydrogen or -COR 1 ; and R 1 Independently selected from C 6 -C 22 -alkyl and C 2 -C 22 -alkenyl, where R 1 Preferably, it is a stearic acid moiety, an isostearic acid moiety, an oleic acid moiety or a mixture thereof, and most preferably, it is oleic acid; COR1 The average total number of is ≥3, preferably ≥4, more preferably ≥5, even more preferably 5 to 6; and m is an integer selected from 6 to 25, preferably 6 to 12. n of each hydrophilic poly-(alkylene glycol)-arm may be from 1 to 125, with an average number of n from 25 to 120, preferably from 30 to 85, most preferably from 30 to 70. The total number of n is selected from 150 to 350, preferably from 180 to 300.

[0043] The polyalkoxylated polyol polyester (Formula-2) of the present invention is prepared by one or more reaction stages. The polyalkoxylated polyol is prepared by the following method: after a mixture of a polyol compound and a base catalyst (such as KOH, NaOH or calcium metal) is dried under vacuum at 100° C. to 200° C., a polyol compound having 6 to 20 hydroxyl groups is alkoxylated with ethylene oxide or propylene oxide at 130° C. to 200° C. The alkylene oxide is metered into the reactor under pressure for 10 to 20 hours. Ethylene oxide, propylene oxide, or a mixture of ethylene oxide and propylene oxide can be used to obtain primary-OH groups, secondary-OH groups or mixtures thereof.

[0044] The organic polyol compound (Q) of the embodiment of the present invention may be a natural polyol or a synthetic polyol having at least six hydroxyl groups, and examples thereof are shown by the following classes of compounds (but are not limited thereto):

[0045] 1. Sugar alcohols, also known as polyhydric alcohols (polyalcohols) with at least six hydroxyl groups, have the general formula HOCH 2 (CHOH) x CH 2 Examples include, but are not limited to, mannitol, sorbitol, dulcitol, fucitol, iditol, inositol, heptanoic acid, isomalt, maltitol, lactitol, maltotriitol, maltotetraitol, and polyglycitol.

[0046] 2. Disaccharides, which are formed by dehydration of two monosaccharides via a glycosidic bond. Examples include, but are not limited to, trehalose, sucrose, lactose, maltose, etc. They contain six or more hydroxyl groups.

[0047] 3. Dextrin, which has a chemical structure (C 6 H 10 O 5 ) n , where n is 2 to 20.

[0048] 4. Dipentaerythritol.

[0049] 5. Dendrimer polyols. For example, H2003 and H20 have 6, 12, and 16 terminal hydroxyl groups, respectively.

[0050] 6. Polyglycerols having 3 to 10 glycerol units with 6 or more hydroxyl groups.

[0051] After the reaction, each hydroxyl group of the starting polyol compound will grow into a hydrophilic poly-(alkylene glycol) arm. Depending on the reaction conditions, the length of all arms can be the same or different.

[0052] The next step is an esterification reaction between the polyalkoxylated polyol compound and the fatty acid so that some or all of the hydrophilic poly-(alkylene glycol) arms are capped with fatty acid esters. The reaction is carried out at 120°C to 250°C with or without a catalyst until the desired acid value or degree of esterification is achieved. A preferred method is to use an esterification catalyst such as alkylbenzene sulfonic acid, methanesulfonic acid, an organotin catalyst, an organotitanate catalyst, and the like. The preferred molar ratio of fatty acid to alkoxylated polyol compound is to form 50% to 130% of the hydrophilic poly-(alkylene glycol) arms.

[0053] For example, when the starting polyol compound is sorbitol, this will result in six poly-(alkylene glycol) arms per sorbitol molecule, and the molar ratio will be 3 to 7.8. When the starting polyol compound is trehalose, this will result in eight poly-(alkylene glycol) arms, and the molar ratio is 4 to 10.4. It is most preferred to form more than at least four fatty acid ester-terminated arms. In one such embodiment, the thickener of the present invention has six arms, which is contrary to the more common thickener composition that may have four arms developed for thickening surfactant-based formulations. In at least one embodiment, it is derived from natural sorbitol and ethylene oxide to provide six hydrophilic arms. Subsequent reaction with natural oleic acid forms four hydrophobically interacting oleic acid groups at the end of each arm. The thickener of the present invention thickens the surfactant formulation by bridging the surfactant micelles with hydrophobic fatty groups, resulting in a much larger bridged micelle structure than the original micelles. The two "uncapped" arms are hydrophilic and serve to enhance water solubility, while the four "capped" hydrophobic arms are attached to the surfactant (micelle) of a given formulation.

[0054] In another embodiment, Q is an organic radical moiety of sorbitol having 6 carbons and Formula-3 is the chemical structure of a polyol ester derived from a sorbitol starting compound.

[0055]

[0056] Another embodiment of the present invention is a cosmetic, dermatological and pharmaceutical preparation 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, conditioner and dispersant for aqueous, aqueous / alcoholic, and surfactant-containing preparations; as an emulsifier and suspending agent with thickening and thickening effects for emulsions and suspensions. These surfactant-containing preparations, emulsions and suspensions are, for example, shampoos, bath preparations, shower gels, foam baths, facial cleansers, hand soaps, bar soaps, shaving creams, hair conditioners, deodorants, lotions, creams, ointments, wet wipes, antiperspirants, sunscreens, liquid fabric conditioners, liquid laundry detergents, liquid dishwashing soaps / detergents, multi-purpose liquid cleaners, etc.

[0057] The cleaning formulations, emulsions and suspensions of the embodiments of the present invention preferably contain 0.05 to 20 wt %, particularly preferably 0.1 to 10 wt %, and especially preferably 0.5 to 5 wt %, of the polyalkoxylated polyol polyester of Formula-2 or Formula-3, based on the final formulation.

[0058] The cleaning composition of the embodiment of the present invention may further comprise the following components: all commonly used anionic, cationic, zwitterionic, nonionic and amphoteric surfactants; skin and hair beneficial active substances, such as cosmetic oils, petrolatum, vegetable oils, hydrogenated vegetable oils, UV filters, proteins, brighteners, anti-aging agents, amino acids, biologically active substances, wetting agents, conditioning polymers, silicones, cationic polymers, sucrose polyesters, anti-dandruff zinc salts, hydroxy acids, skin whitening agents; stabilizers, such as silicon dioxide, 12-hydroxystearic acid, hydrogenated castor oil, ethylene glycol distearate, bentonite and hectorite clay, fatty acids, fatty alcohols, etc.; other thickeners, such as hydroxyethylcellulose, xanthan gum, polyacrylates, modified or non-modified starches, etc.; and polyethylene glycol. The cleaning composition may be in the form of a liquid, paste, gel or solid.

[0059] The total amount of surfactant used in the composition of embodiments of the present invention may range from 5 to 70 wt%, preferably from 10 to 40 wt%, most preferably from 12 to 35 wt%, based on the final composition.

[0060] Each of these components, as well as preferred and optional components of the cleaning compositions, are described below.

[0061] A. Detergent surfactant

[0062] Commonly used detergent surfactants can be selected from anionic, cationic, nonionic, amphoteric / zwitterionic surfactants or mixtures thereof. The details of these commonly used detergent surfactants are known, such as US 7,659,235B2, US8,361,450B2, US 8,802,607B2, US 3,929,678, US2,528,378 and McCutcheon's, Emulsifiers and Detergents, 1989, published by MC Publishing Co. Anionic surfactants can include alkyl sulfates or alkyl ether sulfates (including alkyl glyceryl ether sulfates). Anionic surfactants can also include sulfate-free anionic surfactants as described below.

[0063] Aliphatic sulfonates, such as primary alkanes (e.g. C 8 -C 22 ) sulfonates, primary alkane disulfonates, C 8 -C 22 Olefin sulfonates, alkyl glyceryl ether sulfonates, aromatic alkyl sulfonates or C 8 -C 22 Hydroxyalkane sulfonates.

[0064] Alkyl sulfosuccinates (including monoalkyl and dialkyl, such as C 6 -C 22 sulfosuccinates). Alkyl and acyl taurates, alkyl and acyl glycinates, alkyl sulfoacetates, alkyl phosphates, alkyl phosphate esters, alkoxyalkyl phosphate esters and acyl lactylates, C 8 -C 22 Monoalkyl succinates and maleates. Fatty acyl isethionates, which are usually prepared by the reaction of isethionates (such as alkali metal isethionates) and aliphatic fatty acids of 8 to 20 carbon atoms. For example, commercial products of fatty acyl isethionates are DEFI, Hostapon SCI-78C, Jordapon CIprill, YA-SCI-85, Iselux LQ-CLR-SB, etc. 2 CH 2 O) n CO 2 M anionic carboxylate surfactant, wherein R is C 8 -C 20 Alkyl; n is 1 to 20; and M is a positive ion, such as sodium, potassium, etc. Another type of anionic surfactant is soap or fatty acid salt. Sulfonate derivatives of alkyl polyglucosides include, for example, sodium lauryl glucoside hydroxypropyl sulfonate and sodium decyl glucoside hydroxypropyl sulfonate.

[0065] Another mild sulfate-free surfactant is a class of alkanoyl surfactants prepared from amino acids. 8 To C 20 , preferably C 12 To C 16 Such surfactants may include, for example, alkanoyl sarcosinates, alkanoyl glycinates, and alkanoyl glutamates. For example, commercial products are Ajinamoto's and Eversoft from Sino Lion Chemical, etc.

[0066] Preferred anionic surfactants are mild sulfate-free surfactants and mixtures thereof. The weight ratio of anionic surfactants in the composition of the embodiment of the present invention is 5 wt% to 35 wt%, preferably 10 wt% to 25 wt%.

[0067] Amphoteric surfactants or zwitterionic surfactants are surfactants having both a positive charge and a negative charge. They can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds, in which the aliphatic group can be straight chain or branched, and in which one of the aliphatic groups is C 8 To C 18 carbon atoms, and one contains an anionic group such as carboxyl, sulfonate, sulfate, phosphate or phosphonate. Examples may include commonly used betaines such as N-alkyl-N,N-dimethyl ammonium glycinate, cocamidopropyl betaine; C 12 -C 18 Alkyldimethyl-sulfopropyl betaine and amine oxide. The proportion of the amphoteric surfactant in the composition of the embodiment of the present invention is 0.5 to 30% by weight, preferably 1 to 15% by weight.

[0068] Nonionic surfactants may 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 US 5,389,279 and US 5,009,814; alkyl polyglucosides, such as those described in US 4,565,647 and US 3,723,325. Preferred nonionic surfactants are alkyl polyglucosides and alkyl polyglucosamides. Examples of commercial products may include BASF's Series, Dow Chemicals series, Clariant's Gluco and Poly Suga Mulse from Colonial Chemicals. The proportion of the nonionic surfactant of the embodiment of the present invention is 1% to 20% by weight, preferably 1% to 15%.

[0069] Cationic surfactants are surfactants having positively charged groups. Suitable cationic surfactants may include quaternary ammonium salts, such as di-(C 10 -C 24 )-alkyl dimethyl ammonium chloride, (C 10 -C 24 )-alkyltrimethylammonium chloride or (C 10 -C 24 )-alkyltrimethylammonium sulfate and N-acylaminoethyl-N,N-diethyl-N-methylammonium chloride. Other commonly used cationic surfactants are described in references US8,470,305B2 and 8,470,305B2. The weight proportion of the cationic surfactant in the composition of the embodiment of the present invention is 1 weight % to 10 weight %, preferably 1 weight % to 7 weight %.

[0070] B. Liquid crystal inducers and modifiers

[0071] Liquid crystal inducers are small nonionic molecules and are believed to dissolve in a mixture of surfactants, thereby changing the packing of surfactant micelles to form larger structural aggregates of different shapes and sizes, such as lamellar liquid structures or vesicles, rod-shaped and cubic liquid crystals. An alternative name for liquid crystal inducers is hydrophobic thickeners. Liquid crystal inducers include alkanolamides, alkylamine oxides or mixtures thereof. Examples of this class include monoethanolamide and diethanolamide, isopropanolamide of fatty acids of 10 to 20 carbon atoms, PPG-hydroxyethyl cocamide and alkylamine oxides of 10 to 20 carbon atoms. Another class of chemicals in liquid crystal inducers are alkoxylated alkyl alcohols of 8 to 18 carbon atoms, preferably 8 to 12 carbon atoms and 1 to 4 ethylene oxide units.

[0072] Liquid crystal modifiers include fatty acids and alcohols of 8 to 20 carbon atoms, and aliphatic hydrocarbons with a molecular weight of less than 400 g / mol. They are believed to change the size and shape of liquid crystals. US 7,655,607 B2 is a reference for the scope and examples of liquid crystal inducing agents and liquid crystal modifiers.

[0073] C. Active substances beneficial to skin and hair

[0074] These beneficial actives may be water soluble, water insoluble or water dispersible. Water soluble actives may include, but are not limited to, polyols such as glycerol, diglycerol, sorbitol, propylene glycol, propanediol, panthenol and sugars; alpha-hydroxy acids and their salts; low molecular weight polyethylene glycols. Water insoluble and water dispersible skin and hair beneficial actives 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 agents are typically present in the composition as emulsions or strips. The non-limiting examples in US 7,262,158 are incorporated herein by reference. Other various skin and hair beneficial active substances can include vitamins, lipids (sucrose esters, lanolin, cholesterol, etc.), liposomes, essential fatty acids, butters, minerals, antimicrobial 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 active substances (amino acids and their derivatives, such as N-acetyl-L-cysteine), thiols, anti-cellulite agents (caffeine, theophylline, etc.), tanning active substances, skin whitening active substances, skin soothing agents (such as bisabolol, aloe vera, dipotassium glycyrrhizinate, etc.).

[0075] Cationic water-soluble / or dispersible polymers are very useful as conditioning actives or deposition aids for the composition of the present invention. The cationic charge density of suitable cationic polymers for the composition of the present invention is 0.2meq / g to 8meq / g, and the molecular weight is 1,000 to 3,000,000. Their cationic groups are nitrogen-containing moieties, such as quaternary ammonium or cationic protonated amino moieties, which can be primary amines, secondary amines and tertiary amines. Non-limiting examples of cationic polymers are described in the CTFA Cosmetic Ingredient Dictionary, edited by Estrin, Crosley and Haynes, 3rd edition, and US 8470,305B2 and US 8,105,994B2. Non-limiting examples may include copolymers of vinyl monomers with cationic protonated amine or quaternary ammonium functional groups and water-soluble spacer monomers (such as acrylamide, methacrylamide, alkyl and dialkyl acrylamide, vinyl pyrrolidone, vinyl caprolactone, etc.). Non-limiting specific examples are polyquaternium-11, polyquaternium-16, polyquaternium-7, polyquaternium-6, polyquaternium-22, polyquaternium-47, polyquaternium-39. Other suitable cationic polymers include polysaccharide polymers, such as cationic cellulose derivatives, cationic starch derivatives, cationic guar gum derivatives, etc. Non-limiting examples include the following trade name products: From Aqualon and N-Hance polymers, UCARE polymers from Dow Chemical, MerQuat from Nalco, Galactasol from Henkel, and others.

[0076] D. Stabilizers and other thickeners

[0077] Stabilizers (or structuring systems) are used to form a crystalline stable network structure in the composition to prevent the droplets of lipophilic benefit agents from coalescing and phase separation in the product. Non-limiting examples include hydroxyl-containing fatty acids, fatty esters or fatty soaps, water-insoluble waxy substances such as 12-hydroxystearic acid, 9,10-dihydroxystearic acid, tri-9,10-dihydroxystearin and tri-12 hydroxystearin. Other types of stabilizers are C 10 -C 22Ethylene glycol fatty acid esters, fumed silica, precipitated silica, montmorillonite clay, etc. US 6,194,363 and US 9,138,428 disclose other conventional stabilizer examples. Another class of stabilizers is a gel network structure of fatty amphiphiles (e.g., stearic acid and behenyltrimethylammonium chloride) as disclosed in US 8,470,305. Another class of stabilizers is a blend of unmodified and modified starch and fatty acids as disclosed in US 6,906,016.

[0078] According to the present invention, other thickeners for stabilizing the composition and changing the viscosity of the composition are polymers. Non-limiting examples include carbohydrate gums, such as cellulose gum, microcrystalline cellulose, cellulose gel, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethyl cellulose, 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 of 30°C to 85°C and pre-gelatinized cold water soluble starch. Other non-limiting examples include hydrophobically associating, cross-linked, alkali-swellable acrylate polymers, including acidic monomers and associative monomers with hydrophobic end groups as disclosed in US9,161,899. Non-limiting commercial examples are CarbopolAquaSF-1 from Lubrizol, Stabylen 30 from 3VSigma SPA, and Aqupec series from Sumitomo Seika.

[0079] Suitable other thickeners may include salts, such as sodium chloride and sodium sulfate; cellulose derivatives, such as hydroxyethyl cellulose; xanthan gum, guar gum; starch and starch derivatives; carboxyvinyl polymers, such as 940; polyacrylate emulsions, e.g. Aqua SF-1 polymer; polyethylene glycol; and polyvinyl alcohol.

[0080] According to the present invention, the preparation of emulsions and suspensions comprises water, oil, emulsifier, preferably 0.05 wt % to 20 wt %, particularly preferably 0.1 wt % to 10 wt %, especially preferably 0.5 wt % to 5 wt % of the polyester of formula-1; and other conventional ingredients for skin care, hair care and body care. The non-aqueous part of the emulsion is usually 2 % to 85 %, preferably 5 % to 45 %. The oil includes, but is not limited to, cosmetic oils of refined vegetable oils, refined synthetic or fermented hydrocarbon oils, silicone oils and synthetic ester oils.

[0081] The following non-limiting examples illustrate the compositions and outstanding properties of the present invention.

[0082] Example

[0083] Example 1. Synthesis of polyalkoxylated polyol polyesters of formula-3 with different molecular structures. Table 1 lists the preparation of formula-3 polyesters of alkoxylated sorbitol and fatty acids with a range of molecular weights. The reaction flask used is a one-liter resin kettle with four necks. Sorbitol is mixed with a KOH or NaOH base catalyst and dried at 90°C to 110°C in a vacuum. X moles of ethylene oxide or a blend of ethylene oxide and propylene oxide per mole of sorbitol are added under pressure and reacted at 140°C to 180°C for a reaction time of 10h to 20h. After the reaction, the resulting product is cooled, degassed and filtered to obtain sorbitol polyether-xxx (see Table 1 below). The ingredients of sorbitol polyether-xxx, oleic acid or stearic acid and the catalyst-methanesulfonic acid are added to a flask and then purged with nitrogen. The mixture is heated to 120°C to 220°C while mixing and collecting water under nitrogen. The reaction is continued until R 1 The sum of (or acid value) reaches the target or is nearly constant. The product is collected after the flask is cooled to room temperature. The obtained polyester is a waxy solid.

[0084]

[0085]

[0086] Example 2. Polyesters #1-6 of Table 1 of the present invention and PEG-150 pentaerythritol tetrastearate were formulated into a non-sulfate personal cleansing composition having 6% potassium cocoyl glycinate (Amilite GCK-11F from Ajinomoto), 15% cocamidopropyl betaine (35% active by weight, trade name - Monteric LMAB), 0.3% EDTA, 78.7% water, and adjusted to pH 6 with citric acid. The potassium cocoyl glycinate surfactant is derived from glycine amino acid and is known to be very mild to the skin. PEG-150 pentaerythritol tetrastearate is tradenamed CROTHIX from Croda and is based on US 5,192,462.

[0087] At 2 wt% thickener, the viscosity of the polyester-6 of the present invention is 72,900 cP, while the viscosity of CROTHIC is 45,840 cP. This shows that the polyester of the present invention performs better than the prior art.

[0088] 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 (Zschimmer & Schwarz trade name - Protelan LS9011, 29% by weight of active substances), 12.38% cocamidopropyl betaine (trade name - Monateric LMAB, 35% by weight of active substances), 1.8% thickener, 1% cocamide MEA, 0.1% EDTA, 1% NaCl, 53.83% water, and adjusted to pH 6 with citric acid. At 1.8% by weight in the formulation, the viscosity of the polyester #1-7 of the present invention is 6960 cP viscosity, while the viscosity of CROTHIX is 3640 cP.

[0089] Example 4. This personal cleansing formulation is based on nonionic alkyl polyglucoside surfactants and anionic sodium cocoyl isethionate, both of which are well known mild non-sulfate surfactants in the personal cleansing market. The composition is 13% decyl glucoside (trade name of BASF - Plantaren 2000N UP), 7% sodium cocoyl isethionate (trade name - Pureact I-78C), 7% cocamidopropyl betaine (trade name - Montaric LMAB), 1% PEG-7 cocoglyceride (trade name of Protameen - Protachem GC-7), 0.35% EDTA, citric acid to pH 5.5 and water. At the same 1.2 wt%, the polyesters #1-4 of the present invention and CROTHIX thickened the above surfactant formulation to 26340 cP and 22200 cP respectively. Polyester 4 of the present invention again shows superior performance to the prior art CROTHIX.

[0090] Example 5. The formulation is a typical sulfate surfactant cleaning product: 10.7% sodium laureth sulfate solution (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 of the formulation is 5.5. The polyesters #1-5 of the present invention in Table 1 were compared with three commercially available thickeners in the sulfate cleaning formulation: 1) Trade name: CROTHIX, solid form, provided by Croda, INCI: PEG-150 Pentaerythritol Tetrastearate; 2) Trade name: Glucamate DOE-120, provided by Lubizol, INCI name: PEG-120 Methyl Glucose Dioleate; 3) Trade name: Rewopal PEG 6000DS, provided by Evoni), INCI name: PEG-150 Distearate.

[0091]

[0092] This result shows that in conventional sulfate surfactant personal cleansing products, the thickeners of embodiments of the present invention outperform many commercial thickeners of the prior art. This example and other examples show that in a wide variety of personal cleansing products with different types of surfactants, a wide variety of polyesters of embodiments of the present invention are more effective and versatile thickeners than existing commercial products of the prior art.

[0093] Example 6. According to the example of US2013 / 0079536 A1 of Chen et al., four polyesters (polyester A, polyester B, polyester C and polyester D) were synthesized for comparative analysis. A control polyester, polyester #4-4, was included to determine the thickening performance of the four polyesters.

[0094] Polyester A

[0095] Sorbitol polyether-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 charged into a glass reactor. They were mixed at 190° C. to 200° C. for 24 hours under nitrogen pressure. After cooling to below 100° C., polyester A was discharged with an HLB of about 13.5.

[0096] Polyester B

[0097] Same conditions as Polyester A, but using sorbitan polyether-50 (PEG-50 sorbitol) (78.25 g, 31.3 wt%), hydroxystearic acid (171.50 g, 68.6%) and tin oxalate (0.25%, 0.1%). Its HLB is about 6.3.

[0098] Polyester C

[0099] It was prepared under similar conditions - 200°C for 24 hours using sorbitol polyether-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%). About half of it was discharged as polyester C. It was in R 3 There is one hydroxystearic acid unit in it.

[0100] Polyester D

[0101] An additional 28.60 g of hydroxystearic acid was added to the 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. It was discharged as polyester D. The polyester D was 3 There are two hydroxystearic acid units in it.

[0102] These four comparative polyesters and one control polyester (preferred polyester of the present invention) are used as thickeners for standard shampoo formulations under standard processing conditions for shampoos in the beauty industry. They are dissolved into the shampoo formulation while mixing at 70°C to 90°C. Their viscosity is measured and the average viscosity of three measurements at 24.5°C is shown below. The weight composition of the shampoo is: water, 57.06%; cocamidopropyl betaine (30% strength), 11.5%; C 14-16 Sodium olefin sulfonate, 30%; and polyester, 1.44%.

[0103] Table 3

[0104]

[0105] As can be seen from the average viscosity (cP), no useful thickening was found in Chen's polyesters A to D, which are made from hydroxystearic acid (HSA) and polyhydroxystearate. Chen et al. claimed that R 3 are independently the residues of polyhydroxyalkyl or polyhydroxyalkenyl carboxylic acids, the residues of hydroxyalkyl or hydroxyalkenyl carboxylic acids, and / or the residues of oligomers of hydroxyalkyl or hydroxyalkenyl carboxylic acids.

[0106] Example 8. Preparation of polyesters 4-1 to 4-11 and polyester C and polyester D. In addition to the properties of each polyester of Formula 2 of the present invention, the viscosity is also recorded below. The results are shown in Table 5 below.

[0107] Table 4

[0108]

[0109]

[0110] Polyesters with viscosities above about 2500 cP showed good or excellent thickening results, while polyesters with viscosities below about 2500 cP showed poor thickening and / or unsatisfactory results (0-220 = no thickening, 1220-1240 = little thickening, 2000-2980 = some thickening, 3400-7300 = good thickening, 12600-15000 = strong thickening, 21000 and greater = strong thickening). Table 4 shows a number of unexpected results that are very surprising from the perspective of one skilled in the art. 1) As R 1 With the increase of medium carbon # (12-18), polyester 1 to polyester 5 continue to increase thickening viscosity. 1 Polyester-6, which is 22 carbons, shows a sharp drop in thickening viscosity; a skilled person would expect the opposite. 2) Chen's prior art polyesters C and D have R derived from hydroxystearic acid. 1 , showing no significant thickening at all. 3) Polyester-7, Polyester-8, Polyester-4, Polyester-9 and Polyester-10, with total values ​​of n of 135, 170, 230, 200 and 400 respectively, showed an optimum thickening viscosity of 14900 cp when the total number of n = 230. In other words, higher molecular weight does not lead to higher thickening effect. These results are not linear and are surprising and novel to those skilled in the art.

[0111] Example 7. The Organization for Economic Co-operation and Development (OECD) has developed a number of methods for assessing the environmental impact of man-made chemicals. The OECD 301B series of tests utilize inocula from wastewater treatment plants to provide a reasonable bacterial profile, and these tests have become the standard method for measuring the biodegradation of chemicals and their impact on the environment.

[0112] As mentioned above, the OCED 301B test was used, which measures the carbon dioxide produced by the complete decomposition of the carbon content of a chemical. In order to disperse the polyester of the present invention into the inoculum of the test, it was mixed with a non-biodegradable surfactant (Pluronic P123) in a ratio of 2 / 1 (surfactant / polyester) and the blend was dispersed in water using an ultrasonic probe. The resulting dispersion was mixed with the inoculum and the carbon dioxide released was measured regularly. After 28 days, the measured biodegradation data are listed in Table 5 below. These data show at least the following results: 1) Polyester 5-2, Polyester 5-3 and Polyester 5-4 of the present invention showed the best and excellent biodegradation results, which were 41.8±2.1%, 42.2±3.2% and 42.2±3.2%, respectively. 2) Polyester 5-7, with a total number of n of 400, showed an unexpected drop in biodegradation to 17.3±4.9%.

[0113] Table 5

[0114]

[0115] Thus, in embodiments of the invention, the viscosity amount is an amount greater than about 2000 cP, or greater than about 3400 cP, or greater than about 12000 cP, or greater than about 20000 cP. In embodiments of the invention, the % biodegradation measured by the OCED 301B test is greater than about 19%, or greater than about 23%, or greater than about 26%, or greater than about 30%.

[0116] In a variant of the invention, R 1 The number of carbon atoms in is 18. In an embodiment of the present invention, the derivative R 1 The fatty acid is oleic acid, stearic acid, isostearic acid or a mixture thereof. In a variant of the present invention, wherein R 1 The derivatized fatty acid is not hydroxystearic acid.

[0117] In a variant, the polyesters of the invention have at least good or very good, or excellent, thickening properties and good biodegradability.

Claims

1. A thickener comprising the formula: Q-[(OA) n -OR] m Formula-2 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, Wherein Q is 6 to 25 having the formula -[(OA) n -OR] group substitution, wherein each of the 6 to 50 carbon atoms may be independently substituted by hydrogen, oxygen or nitrogen; A is selected from -C2H4- or -C3H6-; R is independently selected from hydrogen or -COR1, R 1 Independently selected from C6-C 22 -alkyl or C6-C 22 -alkenyl, n is an integer selected from 1 to 125, and may be the same or different for each polyalkoxylated hydrophilic arm; the total number of n is 150 to 350, and preferably 200 to 300. The average total number of COR1 is less than or equal to m; m is an integer selected from 6 to 25; wherein the thickener exhibits at least six polyalkoxylated hydrophilic arms arising from a central core, at least four of the six arms being terminated by a hydrophobic group; and wherein the thickening viscosity is greater than about 2000 cP.

2. The thickener according to claim 1, wherein R1 is derived from an oleic acid moiety or a stearic acid moiety or a mixture thereof.

3. The thickener of claim 1, wherein R1 is derived from a stearic acid moiety, an isostearic acid moiety, an oleic acid moiety, or a mixture thereof.

4. The thickener according to claim 1, wherein the average COR1 is in the range of about 5 to about 6.

5. The thickener according to claim 1, wherein Q is one or more polyols selected from the group consisting of: a. Sugar alcohol, the sugar alcohol having the general formula HOCH2(CHOH) x CH2OH; b. a disaccharide having a glycosidic bond; c.(C6H 10 O5) n , wherein n is 2 to 20; d. dipentaerythritol; e. Dendritic polymer polyols, and mixtures thereof. The thickener according to claim 1 , wherein Q is sorbitol.

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

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

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

10. A composition for household, industrial and institutional use, or mixtures thereof, comprising the thickener of claim 3.

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

12. The cosmetic, dermatological or pharmaceutical composition according to claim 1, wherein Q is a sorbitol radical of formula-3: A is independently -C2H4- or -C3H6-; R is hydrogen or a group of formula -COR1, wherein R1 is derived from a stearic acid moiety, an isostearic acid moiety, or an oleic acid moiety or a mixture thereof; The average total number of COR1 groups is 3 to 6; n1 to n6 are independently integers from 1 to 125; and the total number of n is from 180 to 300.

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

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

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

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

17. The cosmetic, dermatological and pharmaceutical composition according to claim 11, further comprising: water; and 1 wt % to 50 wt % of a surfactant selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof; 0.1 wt% to 10 wt% of a polyol polyester of Formula-3; and 0.1 to 50 wt. % of other ingredients selected from the group consisting of skin and hair benefit actives, stabilizers, other thickeners, colorants, preservatives and pearlescent agents.

18. The cosmetic, dermatological and pharmaceutical composition according to claim 7, further comprising: water; about 1 wt. % to 30 wt. % skin and hair active ingredients selected from the group consisting of: UV filters, moisturizers, conditioning agents, antimicrobial agents, deodorant actives, reducing agents for hair waving products, colorants for hair dyeing, anti-aging actives, proteins / protein derivatives, fragrances, petrolatum, vegetable oils, cationic conditioning polymers, and mixtures thereof; and About 1 wt% to 10 wt% of the polyalkoxylated polyol polyester of Formula-1.

19. The thickener of claim 1, wherein the thickener exhibits at least 20% biodegradation after 28 days.

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

21. The thickener according to claim 1, wherein R1 is a C containing alkyl, alkenyl or alkynyl moiety. 18 fatty acid.

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

23. The thickener of claim 3, wherein R1 is derived from oleic acid.

24. The thickener of claim 1, wherein the percent biodegradation as measured by OECD 301B is greater than about 19%.

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