Hydroxyalkanoate ester aqueous composition

Abstract

This application concerns one or more compounds of formula (I): JPEG2026524860000027.jpg2439 (in the formula, R 1 , R 2 (i) an aqueous composition comprising (ii) a surfactant (e.g., a surfactant, an emulsifier, or a combination thereof), (ii) a surfactant, and (iii) a surfactant, as defined herein. The aqueous composition is useful as a cleaning formulation. Compounds of formula (I) in the aqueous composition improve viscosity, foaming properties, and functional properties, and are particularly advantageous for low-sulfate or sulfate-free formulations.

Description

[Technical Field]

[0001] The cleansing composition is used to cleanse hair and / or skin to remove dirt, sweat, sebum, and oil, and may also help promote the normal exfoliation and restoration of the skin. The components in the formulation are designed to help produce desirable viscosity, foam, and mildness. These desirable properties may be enhanced by using components that modulate the foaming and viscosity properties of the formulation.

[0002] One type of formulation that is becoming increasingly important is the "sulfate-free" formulation. These formulations contain only surfactants that do not contain a sulfate portion. In the absence of sulfate-containing surfactants, it can be very difficult to achieve desirable viscosity, abundant and persistent foaming, and beneficial functional properties such as a good feel. Furthermore, many of the main formulation accelerators (e.g., diethanolamide) are constrained due to toxicity issues, and alternative solutions are being explored in sulfate-free formulations. Additives that can improve sulfate-free formulations are of particular interest. One such additive is based on hydroxyalkanoate esters, which can be used to provide compositions, particularly low-sulfate or sulfate-free formulations, that exhibit desirable viscosity and / or foaming action, as well as improved functional properties. [Overview of the Initiative]

[0003] This application is, (i) A compound of formula I, [ka] During the ceremony: Each R 1 They are independent, non-branched or branched (C 6-12 ) is alkyl, Each R 2 These are independently hydrogen, or unbranched or branched (C 1-6 ) is alkyl, Each n is independently 1, 2, or 3, one or more compounds of formula I. (ii) A surfactant, emulsifier, or a surface-active substance which is a combination thereof, discloses an aqueous composition containing one or more of the compounds of formula I are present at 0.1 weight percent ("wt%") to 15 wt%, the surface-active substance is present at 5 wt% to 30 wt%, the weight percent is based on the total weight of the aqueous composition, one or more of the compounds of formula I and the surface-active substance are different.

[0004] The aqueous composition is useful in a cleaning preparation having a low sulfate content or no sulfate. The aqueous composition is useful as a shampoo, hair conditioner, shower gel, soap, or other cleaning composition.

Mode for Carrying Out the Invention

[0005] Definition Generally, cleaning formulations are complex chemical compositions consisting of surfactants, emulsifiers, and various other additives. Surfactants are mass-produced chemicals that constitute the main components of cleaning compositions, whether for household or commercial use. The incorporation of one or more surfactants into a cleaning composition serves the purpose of reducing the interfacial tension between oil and water by adsorption at liquid-liquid and / or liquid-solid interfaces. When dissolved in water, surfactants provide the cleaning composition with the ability to remove dirt from surfaces and further disperse the dirt in the cleaning solution. Chemically, each surfactant molecule is characterized by a hydrophilic head portion and a hydrophobic tail portion. The hydrophilic head portion is attracted to surrounding water molecules, while the hydrophobic tail portion repels surrounding water molecules and simultaneously binds itself to the oil and grease of the dirt. As a result, these opposing forces loosen the dirt and then suspend it in the aqueous environment. In other words, surfactants disperse dirt that would not normally dissolve in water on its own. Thus, surfactants constitute an important component of cleaning compositions by removing dirt and further preventing the dirt from reattaching to the removed surface by retaining the dirt in the surrounding aqueous environment. In this technical field, surfactants are generally of four types: anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.

[0006] As used herein, the term “anionic surfactant” means having at least one negatively charged associated counterion (M +This refers to surfactants that do not have a positive charge other than M+. Anionic surfactants are known to those skilled in the art of detergent compositions. Non-limiting examples of M+ include lithium, sodium, potassium, magnesium, calcium, barium, ammonium, or alkylammonium counterions. Non-limiting examples of alkylammonium salts include monoethanolammonium salts, diethanolammonium salts, and triethanolammonium salts. Examples of such anionic surfactants include surfactants of the following classes.Alpha-olefin sulfonates prepared by sulfonation of long-chain alpha-olefins such as sodium C12-C14 olefin sulfonate; acyl isethionates such as sodium cocoil isethionate, sodium methyl lauroyl isethionate, and sodium lauroyl isethionate; alkyl sulfosuccinates such as disodium lauryl sulfosuccinate; dialkyl sulfosuccinates such as dioctyl sulfosuccinate; alpha-sulfo fatty acid esters such as sodium methyl 2-sulfolaurate; alpha-sulfo fatty acid salts such as disodium 2-sulfolaurate; alkyl sulfacetates such as sodium lauryl sulfacetate; alkyl sulfonates such as C13-C17 alkane sulfonates, alkyl aryl sulfonates or linear alkyl benzene sulfonates such as sodium decyl benzene sulfonate; alkyl ether carboxylates such as sodium laureth-13 carboxylate, alkyl ether sulfosuccinates such as disodium laureth sulfosuccinate; alkyl amide alkyl sulfosuccinates such as disodium cocamid MIPA sulfosuccinate; alkyl sulfosuccinamic acid salts such as disodium stearyl sulfosuccinamate, acyl glutamates such as disodium cocoyl glutamate; acyl aspartates such as disodium M-lauroyl aspartate, acyl taurates such as sodium cocoyl taurate and sodium cocoyl methyl taurate; acyl lactate esters such as sodium lauroyl lactate; acyl glycine esters such as sodium cocoyl glycine; acyl sarcosinates such as sodium lauroyl sarcosinate; anionic derivatives of alkyl polyglucosides such as sodium lauryl glucoside carboxylate and sodium decyl glucoside hydroxypropyl sulfonate; alkyl sulfates such as sodium lauryl sulfate; alkyl ether sulfates such as sodium laureth sulfate; alkyl monoglyceride sulfates such as sodium coco monoglyceride sulfate.

[0007] An anionic surfactant can be chemically synthesized using conventional methods known to those skilled in the art. An anionic surfactant can be commercially available from a variety of suppliers. The anionic surfactant may be sulfated, sulfonated, and / or carboxylated.

[0008] The "sulfated anionic surfactant" refers to an anionic surfactant containing a -SO4 - M + group (where M + is absent or is selected from H + , Na + , K + , or other monovalent or polyvalent cations). Examples of sulfated anionic surfactants include, but are not limited to, sodium lauryl sulfate and sodium laureth sulfate.

[0009] The "nonsulfate anionic surfactant" refers to an anionic surfactant containing a -SO4 - M +This refers to anionic surfactants that do not contain a group but are often sulfonates or carboxylates. Examples of non-sulfate anionic surfactants include alpha-olefin sulfonates prepared by sulfonating long-chain alpha-olefins such as sodium C12-C14 olefin sulfonate; acyl isethionates such as sodium cocoyl isethionate, sodium methyl lauroyl isethionate, and sodium lauroyl isethionate; alkyl sulfosuccinates such as disodium lauryl sulfosuccinate; dialkyl sulfosuccinates such as dioctyl sulfosuccinate; α-sulfo fatty acid esters such as sodium methyl 2-sulfolaurate; alpha-sulfo fatty acid salts such as disodium 2-sulfolaurate; alkyl sulfoacetates such as sodium lauryl sulfoacetate; alkyl sulfonates such as C13-C17 alkanesulfonates, alkylaryl sulfonates, or linear alkylbenzene sulfonates such as sodium decylbenzenesulfonate, sodium laureth-13 carboxylate Examples include, but are not limited to, alkyl ether carboxylates such as M, alkyl ether sulfosuccinates such as disodium laureth sulfosuccinate; alkylamide alkyl sulfosuccinates such as disodium cocamide MIPA sulfosuccinate; alkyl sulfosuccinates such as disodium stearyl sulfosuccinate; acyl glutamates such as disodium cocoyl glutamate; acyl aspartate such as disodium M-lauroyl aspartate; acyl taurates such as sodium cocoyl taurate and methyl sodium cocoyl taurate; acyl lactate such as sodium lauroyl lactate; acyl glycinate such as sodium cocoyl glycinate; acyl sarcosinate such as sodium lauroyl sarcosinate; and anionic derivatives of alkyl polyglucosides such as sodium lauryl glucoside carboxylate and sodium decyl glucoside hydroxypropyl sulfonate.

[0010] As used herein, the term “nonionic surfactant” refers to a surfactant molecule that does not carry an electrostatic charge. Any of the various nonionic surfactants are suitable for use in the present invention. Examples of suitable nonionic surfactants include, but are not limited to, aliphatic alcohol ethoxylates, sorbitan ester ethoxylates, alkyl polyglucosides, polyglycerol esters, and fatty acid alkanolamides, such as coconut fatty acid monoethylamide or coconut fatty acid monoisopropylamide.

[0011] Zwitterionic or amphoteric surfactants refer to amphiphilic molecules containing a hydrophobic group and one or more hydrophilic groups, which contain two opposite formal charges (often as a function of solution pH) and are therefore net neutral in charge. Examples of zwitterionic surfactants include alkyl betaines, e.g., cocobetaine, lauryl betaine, myristyl betaine; alkylamide alkyl betaines, e.g., cocamidopropyl betaine, lauramidopropyl betaine, myristoamidopropyl betaine, and oleamidopropyl betaine; cocamidopropyl hydroxysultaine, lauramidopropyl hydroxysultaine, myristoamidopropyl hydroxysultaine, and oleamidopropyl hydroxysultaine, cocamidopropyl sultaine, lauramidopropyl sultaine, myristoamidopropyl sultaine, and oleamidopropyl sultaine. Examples include alkylamide alkylsultaines containing; amphoacetates such as sodium lauroamphoacetate and sodium cocoamphoacetate; amphodiacetates such as disodium lauroamphodiacetate and disodium cocoamphoacetate; amphopropionates such as disodium lauroamphodipropionate and disodium cocanhodipropionate; amphohydroxypropyl sulfonates such as sodium lauroamphohydroxypropylsulfonate and sodium cocoamphohydroxypropylsulfonate; and amino acid-based amphoteric surfactants described in U.S. Patent Application No. US20170081277, which are exemplified by the following formula: [ka] In the formula, R represents branched-chain and linear, saturated, unsaturated, and polyunsaturated C3-C 24 Hydrocarbyl, or selected from substituted and unsubstituted C3-C8 cycloalkyl groups, R 1 This is a C2-C8 divalent hydrocarbyl group, and R 2 and R 3 Each of these is independently a C1-C6 alkyl or alkenyl group, and at least two of R1, R2, or R3 are N + They may be linked together to form a complex ring, R 4 is a C1-C8 hydrocarbyl group, where X is O or NH, and Y- is CO2-, SO3-, SO4-, PO3-, or PO4-.

[0012] As used herein, the term “cationic surfactant” means having at least one positively charged associated counterion (X - This refers to surfactants that do not have a negative charge other than quaternary alkyl, quaternary benzyl, quaternary ester, ethoxylated quaternary compound, and mixtures thereof, where alkyl groups have about 6 to about 30 carbon atoms, preferably about 8 to about 22. In certain embodiments, the composition includes cationic conditioning polymers, including those derived from cationic cellulose and its derivatives (e.g., polyquaternium-10), cationic guar and its derivatives, and monomeric diallyldimethylammonium chloride (polyquaternium-6 and polyquaternium-7).

[0013] The term "emulsifying agent" or "emulsifier" refers to a compound that is soluble in both oil or hydrophobic molecules and water. Emulsifiers can uniformly disperse oil and hydrophobic molecules in water as an emulsion.

[0014] The term "alkyl" refers to hydrocarbons that are unbranched or may be branched. Alkyl groups are defined by the number of carbon atoms, for example, (C 6-12 ) can be further defined in C.6-12 This means that alkyl hydrocarbons can have 6 to 12 carbon atoms. Non-limiting examples of alkyl groups include methyl, ethyl, isopropyl, hexyl, and dodecyl.

[0015] The term "alkenyl" refers to an alkyl group having one or more unsaturated bonds formed by the removal of two or more hydrogen atoms from a carbon atom. Non-restrictive examples of alkenyls include ethenyl, allyl, 2-butenyl, 1-butenyl, and 1-hexene.

[0016] This application relates to (i) a compound of formula I, [ka] In the formula, each R 1 They are independent, non-branched or branched (C 6-12 ) is alkyl, and each R 2 These are independently hydrogen, or unbranched or branched (C 1-6 The disclosure provides an aqueous composition comprising (ii) one or more compounds of formula I, wherein each n is alkyl, and each n is independently 1, 2, or 3; and (ii) a surfactant, emulsifier, or combination thereof, wherein the one or more compounds of formula I are present in an amount of 0.1 wt% to 15 wt%, and the surfactant is present in an amount of 5 wt% to 30 wt%, the wt% being based on the total weight of the aqueous composition, and the one or more compounds of formula I and the surfactant are different.

[0017] The aqueous compositions disclosed in this application exhibit improved viscosity-building properties, similar or better foaming action, and better functional properties compared to formulations that do not contain one or more compounds of Formula I.

[0018] In one embodiment, or in combination with any other embodiment, the aqueous composition may be less than 20 wt%, less than 15 wt%, or less than 10 wt%, or less than 9 wt%, or less than 8 wt%, or less than 7 wt%, or less than 6 wt%, or less than 5 wt%, or less than 4 wt%, or less than 3 wt%, or less than 2 wt%, or less than 1 wt%, or less than 0.5 wt%, or less than 0.1 wt%, or 0 wt%, or 0 It contains 0.1-15 wt%, or 0.1-10 wt%, or 0.1-5 wt%, or 0.1-2 wt%, or 1-20 wt%, or 1-15 wt%, or 1-10 wt%, or 1-5 wt%, or 2-20 wt%, or 2-15 wt%, or 2-10 wt%, or 2-5 wt%, or 5-20 wt%, or 5-15 wt%, or 5-10 wt%, or 10-20 wt%, or 10-15 wt% of sulfated anionic surfactant. In one class of this embodiment, the aqueous composition does not contain sulfated anionic surfactant.

[0019] In one embodiment, or in combination with any other disclosed embodiment, the sulfated anionic surfactant is (C 6-30 ) Alkyl-SO4 - M + or (C 6-30 ) Alkenil-SO4 - M + And in the formula, M+ is H + kaNa + , K + NH4 + , (C 1-4 ) Alkyl H3N + , ((C 1-4 )Alkyl)2H2N + , ((C 1-4 )Alkyl)3HN + , or ((C 1-4 )Alkyl)3N + In one embodiment, or in combination with any other disclosed embodiment, the sulfated anionic surfactant is (C 6-30 ) Alkyl-SO4 - M + or (C 6-30) Alkenil-SO4 - M + And in the formula, M+ is H + kaNa + , or K + In one embodiment, or in combination with any other disclosed embodiment, the sulfated anionic surfactant is sodium lauryl sulfate, sodium laureth sulfate, sodium myreth sulfate, sodium pareth sulfate, or ammonium laureth sulfate.

[0020] In one embodiment, or in combination with any other embodiment disclosed herein, the aqueous composition further comprises one or more of the following: (3) conditioning agents, (4) emollients, (5) humectants, (6) humectants, (7) thickeners, (8) lubricants, (9) chelating agents, (10) fillers, (11) binders, (12) antioxidants, (13) preservatives, (14) ultraviolet light absorbers, (15) fragrances, (16) pigments, (17) buffers, (18) exfoliants, (19) pH adjusters, (20) solvents, (21) viscosity modifiers, or (22) active ingredients including vitamins.

[0021] Examples of UV absorbers include organic and inorganic sunscreen activators.

[0022] In one embodiment, or in combination with any other embodiment, the thickener may be xanthan gum, dehydroxyxanthan gum, guar gum, cassia gum, carrageenan gum, alginic acid and alginic acid gum, gellan gum, pectin, microcrystalline cellulose, cellulose derivatives (e.g., sodium carboxymethylcellulose and hydroxypropyl methylcellulose), hydroxypropyl guar, synthetic alkali-swelling acrylate polymers (e.g., acrylates copolymer (trade name: Carbopol® AQAU SF-1, Lubrizol Corp., Brecksville, OH)), hydrophobic-modified acrylate copolymers (e.g., acrylates C10-30 alkyl acrylates crosspolymer (Lubrizol Carbopol® 1382) manufactured by Corp., Brecksville, OH; low molecular weight thickeners (e.g., cocamide MIPA, lauryl lactate, or sorbitan sesquicaprylate); inorganic salts, such as sodium chloride, potassium chloride, sodium bromide, potassium bromide, ammonium chloride, ammonium bromide, and combinations thereof.

[0023] In one embodiment, or in combination with any other embodiment, the aqueous composition may be, based on the total weight of the aqueous composition, 0.1wt% to 5wt%, or 1wt% to 5wt%, or 2wt% to 5wt%, or 3wt% to 5wt%, or 4wt% to 5wt%, or 0.1wt% to 10wt%, 1wt% to 10wt%, or 2wt% to 10wt%, or 3wt% to 10wt%, or 4wt% to 10wt%, or 5wt% to 10wt%, or 6wt% to 10wt%, or 7wt% to 10wt%, or 8wt% to 10wt%, or 9wt% to 10wt%, or 0.1wt% to 15wt%, 1wt% to 15wt%, or 2wt% to 15wt%, or 2wt% to 15wt%. The present invention further comprises inorganic salts in amounts of wt% to 15 wt%, or 3 wt% to 15 wt%, or 4 wt% to 15 wt%, or 5 wt% to 15 wt%, or 6 wt% to 15 wt%, or 7 wt% to 15 wt%, or 8 wt% to 15 wt%, or 9 wt% to 15 wt%, or 10 wt% to 15 wt%, or 0.1 wt% to 20 wt%. In one class of these embodiments, the inorganic salts are sodium chloride, potassium chloride, sodium bromide, potassium bromide, ammonium chloride, and ammonium bromide.

[0024] In one embodiment, or in combination with any other embodiment, the preservative is benzoic acid, lactic acid, salicylic acid, benzyl alcohol, caprylyl glycol, decylene glycol, ethylhexylglycerin, gluconolactone, methylisosazolinone, phenoxyethanol, or a combination thereof.

[0025] Compositions containing hydroxyalkanoate esters exhibit improved viscosity and foaming behavior in low-sulfate or sulfate-free systems containing amphoteric auxiliary surfactants. Furthermore, the formulations are stable and exhibit excellent mildness.

[0026] In one embodiment, or in combination with any other embodiment, the active ingredient is one or more of the following: (i) an anti-aging ingredient, (ii) an anti-inflammatory agent, (iii) an antibacterial agent, (iv) an antifungal agent, (v) a plant extract, or (vi) one or more vitamins.

[0027] In one class of this embodiment, one or more vitamins are vitamin E, vitamin C, vitamin B3, vitamin B5, vitamin B9, vitamin K, vitamin D, or a combination thereof.

[0028] In one embodiment, or in combination with any other embodiment, one or more compounds of formula I are present in an amount based on the total weight of the aqueous composition of 0.1 wt% to 14 wt%, or 0.1 wt% to 12 wt%, or 0.1 wt% to 10 wt%, or 0.1 wt% to 8 wt%, or 0.1 wt% to 7 wt%, or 0.1 wt% to 6 wt%, or 0.1 wt% to 4 wt%, or 0.1 wt% to 3 wt%, or 0.1 wt% or 2 wt%, or 0.1 wt% or 1 wt%, or 0.1 wt% to 0.5 wt%, or 0.5 It exists in the range of wt%~1wt%, or 0.5wt%~2wt%, or 0.5wt%~4wt%, or 0.5wt%~5wt%, or 0.5wt%~6wt%, or 0.5wt%~8wt%, or 0.5wt%~10wt%, or 1wt%~2wt%, or 1wt%~4wt%, or 1wt%~6wt%, or 1wt%~8wt%, or 1wt%~10wt%, or 2wt%~3wt%, or 2wt%~4wt%, or 2wt%~6wt%, or 2wt%~8wt%, or 2wt%~10wt%.

[0029] In one embodiment, or in combination with any other embodiment, the compound of formula I is 2-ethylhexyl 3-hydroxybutyrate or 1-octyl 3-hydroxybutyrate. In one class of these embodiments, the compound of formula I is 2-ethylhexyl 3-hydroxybutyrate. In one class of these embodiments, the compound of formula I is 1-octyl 3-hydroxybutyrate.

[0030] In one embodiment, or in combination with any other embodiment, the pH of the aqueous composition is 3-8, or 4-7, or 3-7, or 3-6, or 3-5, or 4-8, or 4-6, or 4-5, or 5-8, or 5-7, or 5-6, or 5-7, or 5-6.5, or 6-8, or 6-7. The pH of the composition can be adjusted to a desired level using organic or inorganic acids or bases that are acceptable as cosmetics, such as citric acid, acetic acid, glycolic acid, lactic acid, malic acid, tartaric acid, hydrochloric acid, sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate, or similar materials or combinations thereof. pH adjusters can be added in aqueous or non-aqueous form.

[0031] Experiment Section Abbreviation AFC is amfotaine FC (cocobutylamide hydroxysultaine), AOS is alpha-olefin sulfonate, atm is atmosphere, °C is degrees Celsius, CAPB is cocamidopropyl betaine, CFEx is comparative formulation example(s), DecylGluc is decyl glucoside, DFA is dynamic foam analyzer, dH2O is deionized water, DSLSS is disodium laureth sulfosuccinate, eq. is equivalent, Ex is example(s), FEx is formulation example(s), g is grams, h is time, L is liters, mi n is minutes, mL is milliliters, mmHg is millimeters of mercury, mol is moles, qs is appropriate amount, rt is room temperature, s is seconds, SCI is sodium cocoyl isethionate, SLSarc is sodium lauroyl sarcosinate, SLES is sodium laureth sulfate, SLS is sodium lauryl sulfate, SMCT is sodium methyl cocoyl taurate, SLMI is sodium lauroyl methyl isethionate, sorn is solution, TEA is triethylamine, temp is temperature, v is rate, and η is viscosity;

[0032] Preparation process of the compound of formula I Scheme 1 provides a process for producing compounds of formula I (i.e., hydroxyalkanoate esters), the process comprising (a) lower alcohol ketoesters of formula 2 (wherein R 2 (is methyl or ethyl) the desired alcohol (R 1 (b) Contacting the intermediate of formula 3 with (-OH) under transesterification conditions to form a ketoester of formula 3, and (b) contacting the intermediate of formula 3 with hydrogen and a catalyst to hydrogenate the ketone and form a hydroxyalkanoate ester 1.

[0033] [ka]

[0034] Scheme 2 provides an alternative process for synthesizing the compound of formula I (i.e., a hydroxyalkanoate ester), where n is equal to 1, and the process involves (a) optionally, in the presence of a catalyst, the diketene derivative of formula 4 being converted into a desired alcohol (R 1 (b) Contacting with (a) an OH group to form a ketoester of formula 3 (wherein n=1), and (b) contacting the intermediate of formula 3 with hydrogen and a catalyst to hydrogenate the ketone and form a hydroxyalkanoate ester 1 (wherein n=1). [ka]

[0035] Example 1: 2-Ethylhexylacetoacetate 2-Ethylhexylacetoacetate (derived from diketene) 2-ethylhexane-1-ol (1740 g; 13.36 mol; 1.05 equivalents) and TEA (64.4 g; 0.636 mol; 0.05 equivalents) were added to a 5 L jacketed flask. The reaction mixture was heated to 50 °C in a recirculating bath set to 60 °C, and diketene (1073 g; 1.28 mol) was added continuously at a rate of 5.5 mL / min. The bath temperature was lowered to 35 °C, and the reaction temperature was maintained between 55 and 60 °C during the addition. After the addition was complete, the mixture was distilled at 138 °C / 16 mmHg to obtain the title compound.

[0036] 2-Ethylhexylacetate (by enzymatic transesterification of methylacetate) 2-ethylhexanol (1000 g, 7.68 mol), methyl acetoacetate (891.7 g, 7.68 mol, 1.0 equivalent), and Novozym 435 (100 g) were added to a reactor equipped with an overhead stirrer, thermocouple, and N2 sparge tube. The mixture was heated under an N2 atmosphere (70°C) for 90 hours. The mixture was cooled to ambient temperature, and the enzyme was removed by filtration. The filtrate was concentrated under vacuum to obtain the residue.

[0037] 2-Ethylhexyl acetate (from tert-butyl acetate) In a 1 L jacketed reactor, tert-butyl acetoacetate (1 equivalent, 2.35 mol, 372 g) and 2-EH alcohol (1 equivalent, 2.35 mol, 306 g) were added. The reactor was fitted with a head equipped with an overhead stirrer (250 RPM), a vacuum pump with controller, a thermocouple, a distillation arm and condenser, and a rubber septum. The reactants were stirred under a vacuum pressure of 500 torr, and the mixture was heated to 130°C with N2 ablation at approximately 100 SCCM. The reaction progress was monitored by taking a sample and analyzing it by NMR. After 2 hours, the reaction was considered complete and was cooled to below 60°C before being released from the reactor. The crude product was used in the next step without further purification.

[0038] Example 2: 2-Ethylhexyl 3-Hydroxybutyrate 1350 g of 2-ethylhexyl acetoacetate and 38 g of catalyst (ES Cat440 50% w / w base) were placed in a 2 L autoclave. The container was purged with N2 (1000 psig) and aeration was performed. The container was then purged with hydrogen (2 x 300 psig) and stirring was started at 300 rpm. The container was then pressurized with hydrogen (900 psig) and heated (80°C), and maintained at that temperature until hydrogen uptake stopped (approximately 2 hours). The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain the crude product. The crude product was purified by distillation at 145°C and 16 torr to obtain the title compound.

[0039] Example 3: 1-Octylacetate (by enzymatic transesterification of methylacetate) In a reactor equipped with an overhead stirrer, thermocouple, and N2 sparge tube, 1-octanol (1000 g, 7.68 mol), methyl acetoacetate (891.7 g, 7.68 mol, 1.0 equivalent), and Novozym 435 (100 g) were added. The mixture was heated (70°C) and aeration with N2. Additional methyl acetoacetate (89 g; 0.77 mol; 0.1 equivalent) was added, and the reaction mixture was stirred until the reaction was complete. The reaction mixture was cooled to ambient temperature and filtered. The filtrate was concentrated under vacuum to obtain the title compound.

[0040] Example 4: 1-Octyl-3-hydroxybutyrate Octyl acetoacetate (1300 g) and ruthenium carbon (39 g) were placed in a 2 L autoclave. The container was flushed with N2 (3 x approximately 200 psig). The container was then purged with H2 (3 x 200 psig), and subsequently pressurized with hydrogen (900 psig). The reaction mixture was stirred at 80°C for 6 hours (1000 rpm). The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure (80-130°C, 13 mmHg) to obtain the title product.

[0041] Zein test The purpose of the zein test is to investigate the potential harshness of surfactant-based products. In this test, zein, a yellow corn protein similar to keratin found in skin and hair, is denatured (solubilized) by a irritating product (e.g., a surfactant product diluted with a specific amount of water). The more zein dissolved by the surfactant-based product, the higher the predicted potential for harshness.

[0042] 5 grams of the test sample and 45 g of dH2O were added to a test tube and mixed for 10-15 minutes, or until a homogeneous dispersion was formed. Positive and negative controls were prepared in the same manner, using CAPB (10% solution) for the positive control and dH2O for the negative control.

[0043] The pH of the test sample and the control solution was measured and recorded.

[0044] One gram of zein was added to the test sample and the control solution. The solutions were mixed for 60 minutes. The weight of each filter paper was measured before filtration. The solutions were filtered under vacuum. The filtrate and filter paper were placed in aluminum dishes and dried overnight at 45°C.

[0045] The day after the experiment, the weight of zein on the filter paper was measured for each test and control. The final weight of zein was calculated by subtracting the weight of the filter paper.

[0046] The percentage of solid zein after dissolution was calculated using the following formula:

number

[0047] The test results show no significant difference compared to the negative control, suggesting that both hydroxyalkanoate esters (Ex2 and Ex4) are considered mild. [Table 1]

[0048] Formulation Series 1 To clarify the advantages of hydroxyalkanoate esters, a prototype of a basic sulfate-free shampoo formulation was developed. This formulation contains the main surfactant, the anionic compound AOS, at 10 wt% activity, and the auxiliary surfactant, usually amphoteric (CAPB or AFC), at 2 wt% activity, both constituting the main chassis in a 5:1 ratio (AOS:CAPB or AFC). The hydroxyalkanoate ester is present at a 1 wt% activity level. To increase viscosity, 3 wt% NaCl was added. Finally, as a pH adjuster, a 50 wt% aqueous citric acid solution was added until the pH reached 5.5-6.

[0049] Unless otherwise stated, all content in Table 1 below is expressed in wt% (100% of the active compound per 10 units of the total weight of each composition). [Table 2]

[0050] The formulation was prepared under a cold process, i.e., with a simple mixture of the components in the order described above, and completed by adding salt and adjusting the pH using a disperser (IKA Eurostar 200). The final formulation was yellowish in color and had no noticeable odor.

[0051] In addition to viscosity measurements and stability studies, both versions of the sulfate-free shampoo (including CAPB or AFC) were subjected to foam analysis, intracellular lipid (sebum) removal tests, and zein mildness tests.

[0052] Viscosity (η) The viscosity of a formulation depends on several factors: chassis components (anionic / amphoteric / nonionic), the concentration of chassis components, the ratio of chassis components, the salt concentration, and the addition of adjuvants / other components.

[0053] Viscosity was measured using an Anton Paar MCR302 rheometer. The inclusion of hydroxyalkanoate esters had a positive effect on viscosity in all cases. This result also indicates that substitution of CAPB with AFC was beneficial in increasing viscosity in formulations containing hydroxyalkanoate esters. Replacing CAPB with AFC doubled the viscosity of formulations using Ex2 and tripled the viscosity of formulations using Ex4 (Table 2). [Table 3]

[0054] stability Stability testing is useful for predicting the shelf life of a product. The purpose of stability testing is to ensure that cosmetics maintain their intended physical, chemical, and microbiological qualities, as well as their functionality and aesthetic appearance, when stored under appropriate conditions. In addition, all sulfate-free formulations were subjected to accelerated stability testing at room temperature and 50°C for 12 weeks. Until the end of the test, all formulations were considered stable, with no changes in viscosity, appearance, or pH.

[0055] Foam analysis A sulfate-free prototype was subjected to foam analysis using DFA with a Kruss camera module. DFA measures the foaming properties of a liquid, as well as the stability of the foam, which either rapidly decays or persists for a long time, based on the detection of reproducible foaming and height. It also measures the liquid content and analyzes the foam structure.

[0056] Foam was generated by passing air through 50 mL of a 0.1 wt% aqueous solution of the formulation (0.3 L / min for 20 seconds). Foam measurement was performed over a total of 300 seconds (including the airflow time). Measurements were performed at room temperature.

[0057] The following parameters were considered.

[0058] ·V 泡沫 Maximum = Maximum volume of foam • BC initial = initial number of bubbles ("flash bubbles") • BC final = final number of bubbles ("foam stability") [Table 4]

[0059] The maximum foam volume, initial bubble count (flash foam), and final bubble count (foam stability) of formulations containing hydroxyalkanoate esters were equivalent to or better than those of the same formulations without hydroxyalkanoate esters. This indicates that flash foam with a larger foam volume, a high bubble count (smaller bubbles), and stable foam can be generated by adding hydroxyalkanoate esters to the formulation.

[0060] Intracellular lipid (sebum) removal test The objective of this study is to determine how the application of a sample affects intracellular lipids at the cellular level on sebaceous gland cells in vitro. Lipid droplets are found in all eukaryotes, and the accumulation of lipid droplets is a normal function of cells. The lipid surface of the skin originates from keratinocytes and sebaceous gland cells. Therefore, sebaceous glands secrete lipids onto the surface of the stratum corneum. The intracellular lipid assay consists of culturing cells in the absence (negative control) and in the presence of the product. After incubation time, oil red staining, a diazolisochrome dye that enables lipid staining, helps determine the difference in intracellular lipid levels between the product and the negative control. Briefly, cells are cultured in the absence and presence of the product. The sample, diluted to a predetermined concentration in cell culture medium, is added to the cells and incubated for 24 hours. Intracellular lipids are measured using oil red staining. [Table 5]

[0061] This sample induces a significant decrease in intracellular lipid levels compared to the negative control.

[0062] Results using hydroxyalkanoates showed that when the CAPB chassis was present, the sample induced a significant decrease in intracellular lipid levels compared to the negative control and the comparative example without hydroxyalkanoates. A lower sebum removal value indicates better cleansing properties.

[0063] Formulation Series 2 To clarify the advantages of hydroxyalkanoate esters, a prototype basic sulfate-based shampoo formulation was developed. This formulation consists of the anionic surfactants SLES (5.6 wt%) and SLS (4.8 wt%); and the co-surfactant, usually amphoteric (e.g., CAPB 1.20 wt%). Hydroxyalkanoate esters are present at different activity levels (0-3 wt%). Finally, as a pH adjuster, a 40-50 wt% aqueous solution of citric acid was added until the pH reached 5.5-6.5. NaCl was added to the formulation in stages to examine its effect on viscosity.

[0064] All content values ​​in Table 6 below are given in wt%, and are expressed as 100% of the active compound. [Table 6]

[0065] Table 7 shows the results of foam analysis using the procedure described above. The initial number of bubbles (flash foam) and the final number of bubbles (foam stability) of the formulation containing hydroxyalkanoate esters are higher compared to the same formulation without hydroxyalkanoate esters. The high number of bubbles (small bubbles) in the flash foam indicates that stable foam can be generated by adding hydroxyalkanoate esters to the formulation. [Table 7]

[0066] Effect of salt on the stability and viscosity of formulations Increasing the viscosity of sulfate surfactant-based formulations is easily achieved by adding NaCl due to the thickening effect of salt. NaCl was gradually added to the formulation, and the viscosity was measured at each step using a Brookfield viscometer (DV-I Prime, SPDL 3 or 7; 1-100 rpm). [Table 8]

[0067] Formulation Series 3 To clarify the advantages of hydroxyalkanoate esters, a prototype of a basic sulfate-free shampoo formulation was developed. This formulation contains the anionic surfactant AOS (15 wt%); two auxiliary surfactants, amphoteric CAPB (5 wt%) and nonionic (DecyGluc 2 wt%). The hydroxyalkanoate esters are present at different activity levels (0-3 wt%). Finally, as a pH adjuster, a 40-50 wt% aqueous solution of citric acid was added until the pH reached 5.5-6.5.

[0068] All content values ​​in Table 9 below are given in wt%, and are expressed as 100% of the active compound. [Table 9]

[0069] Table 10 shows the results of foam analysis using the procedure described above. The maximum foam volume, initial number of bubbles (flash foam), and final number of bubbles (foam stability) of the formulation containing the hydroxyalkanoate ester were higher compared to the same formulation without the hydroxyalkanoate ester. This indicates that a larger foam volume, high number of bubbles (small bubbles), and stable flash foam can be generated by adding the hydroxyalkanoate ester to the formulation. [Table 10]

[0070] Table 11 shows the test results for NaCl stability and viscosity using the procedure described above. [Table 11]

[0071] Formulation Series 4 To clarify the advantages of hydroxyalkanoate esters, a prototype of a basic sulfate-free shampoo formulation was developed. This formulation consists of four surfactants: SLSarc (1.8 wt%), DSLSS (5.41 wt%), SCI (3.18 wt%), and CAPB (4.55 wt%). The hydroxyalkanoate esters are present at different activity levels (0-3 wt%). Finally, a 40-50 wt% aqueous solution of citric acid was added as a pH adjuster until the pH reached 5.5-6.5.

[0072] All content values ​​in Table 12 below are given in wt% and are expressed as 100% of the active compound. [Table 12]

[0073] Table 13 shows the results of foam analysis using the procedure described above. The maximum foam volume, initial number of bubbles (flash foam), and final number of bubbles (foam stability) of the formulation containing the hydroxyalkanoate ester were higher compared to the same formulation without the hydroxyalkanoate ester. This indicates that a larger foam volume, high number of bubbles (small bubbles), and stable flash foam can be generated by adding the hydroxyalkanoate ester to the formulation. [Table 13]

[0074] Table 14 shows the results of the NaCl stability and viscosity tests using the procedure described above. [Table 14]

[0075] Formulation Series 5 Table 15 provides a series of other formulations that were prepared and tested. [Table 15]

[0076] Formulation Series 6 Tables 16 and 17 provide a series of other formulations that were prepared and tested. [Table 16] [Table 17]

[0077] Formulation Series 12 To clarify the advantages of hydroxyalkanoate esters, a prototype basic hair conditioner formulation was developed. This formulation consists of a cationic surfactant (2 wt%), an aliphatic alcohol (5 wt%), and a hydroxyalkanoate ester (1 wt%).

[0078] Conditioner preparation procedure The required amounts of incroquat behenyl TMC-85 (2 wt%) and cetearyl alcohol (5 wt%) were weighed and added to dH2O (125 g). The contents were mixed in an IKA T25 easy-wash digital disperser / homogenizer at 5000 RPM at 75°C until all was dissolved. The pH was checked, and if it exceeded the acceptable pH range (4-4.5), it was adjusted using 10 wt% citric acid aqueous solution and 40 wt% NaOH aqueous solution. The mixture was weighed and divided in half into two beakers. Water was added to one beaker (CFEx 8) until the formulation reached 90 g. Ex 2 (1 g) was added to the other beaker (FEx 18), and dH2O was added until the formulation reached 90 g. The contents of both CFEx 8 and FEx 18 were mixed independently using an IKA T25 at 10000 RPM. After thorough mixing, the pH was checked again and adjusted as needed. Water was added until the mixture reached 100g, and then it was mixed one last time. Due to the high viscosity of both mixtures, the mixer was moved around in the beaker to ensure homogenization. CFEx 18 was noticeably more viscous than FEx 8, which did not contain Ex 2.

[0079] Table 18 shows the components and their wt% values. [Table 18]

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