Bio-based polyglyceryl esters and compositions containing same

Abstract

The present invention relates to bio-based polyglyceryl ester compounds and compositions, as well as formulations containing same, methods for preparing the bio-based polyglyceryl ester compositions of the invention, and uses thereof, including the use of the compounds and compositions of the invention in the formulation of products or components of products. The bio-based polyglyceryl ester compositions comprise one or more compounds of formula (I): TIFF2024537131000035.tif26170, where PG is a polyglyceryl group comprising greater than 40% hexaglycerol and higher polyglycerols and less than 60% pentaglycerol and lower polyglycerols, R is a linear or branched C5-C8 alkyl group, n=1-3, and substantially all of the carbon present in the one or more compounds of formula (I) is biobased.

Description

[Technical field]

[0001] [CROSS REFERENCE TO RELATED APPLICATIONS] This application claims priority to U.S. Provisional Patent Application No. 63 / 253,662, filed October 8, 2021, and is incorporated herein by reference.

[0002] The present invention relates to bio-based polyglyceryl ester compounds and compositions, formulations containing the compounds and compositions, methods of making and using the compounds, compositions and formulations, and applications thereof, including, inter alia, cosmetic applications. [Background technology]

[0003] Polyglycerols (PG) are readily esterified with fatty acids to produce polyglyceryl esters (PGEs), a well-known class of nonionic surfactants and emulsifiers frequently used as food ingredients and in cosmetic and personal care product formulations. PGEs, which consist of a hydrophilic PG group linked by an ester bond to a lipophilic / hydrophobic fatty acyl group, exhibit surface and interfacial activity due to their amphiphilic structure. PGE structures are typically designed to maximize surface and interfacial activity to provide optimal performance in functions such as emulsification, solubilization / microemulsification, detergency, foam generation, and foam stabilization. PGEs have the advantage of being synthesized in bulk without the need for solvents and are provided as 100% active, anhydrous materials that do not require protection from microbial contamination.

[0004] PGEs can be used as surfactants for the solubilization or microemulsification of water-insoluble species in aqueous media to produce stable clear or transparent solutions. PGEs are useful, for example, for solubilizing fragrances, essential oils, active ingredients, preservatives, and other ingredients that are poorly water-soluble into clear aqueous formulations.

[0005] Nonionic surfactants are known to have an inactivating effect on microbistatic ingredients (ingredients intended to inhibit the growth of microorganisms) and microbiocidal ingredients (ingredients intended to kill microorganisms). For example, polyethoxylated sorbitan esters or polysorbates are nonionic surfactants known to inhibit the antimicrobial activity of cosmetic preservatives. Summary of the Invention [Problem to be solved by the invention]

[0006] There is a need for non-ionic surfactants that can solubilize or microemulsify water-insoluble microbistatic and microbicidal components to produce clear solutions without inhibiting the biological effectiveness of such compounds, and it is desirable for such non-ionic surfactants to be selectively based on renewable carbon sources, i.e., plant-derived carbon, due to the market demand for more sustainable ingredients and the greater consumer appeal of so-called "natural" ingredients derived from renewable bio-based feedstocks. [Means for solving the problem]

[0007] Applicants have surprisingly discovered that the bio-based polyglyceryl ester compositions described herein have the correct balance between the hydrophilic and lipophilic properties of the polyglyceryl esters, thereby allowing the formation of stable, clear, aqueous solutions that do not inhibit the activity of microbistatic / microbiocidal compounds used in the formulations, for example, to protect against microbial contamination.

[0008] In some embodiments, the present invention relates to a bio-based polyglyceryl ester composition comprising: One or more of formula (I): [ka] where PG is a polyglyceryl group containing more than 40% hexaglycerol and higher polyglycerols and less than 60% pentaglycerol and lower polyglycerols; R is a linear or branched C5 to C8 alkyl group; n=1 to 3, In some embodiments, the present invention includes a mixture comprising one or more compounds of formula (I), wherein substantially all of the carbon present in the compound is bio-based.

[0009] In another embodiment, the invention relates to a self-dispersing concentrate. The concentrate comprises the composition described in the previous paragraph and a mid-chain end diol. Optionally, the concentrate comprises a mid-chain alkyl hydroxamic acid, a salt thereof, or a combination thereof. Optionally, the concentrate comprises glycerin and / or a C3-C4 diol.

[0010] In yet another embodiment, the present invention relates to a self-dispersing concentrate comprising: One or more of formula (I): [ka] where PG is a polyglyceryl group containing more than 40% hexaglycerol and higher polyglycerols and less than 60% pentaglycerol and lower polyglycerols; R is a linear or branched C5 to C8 alkyl group; n=1 to 3, about 30% to about 90% bio-based polyglyceryl ester, a mixture comprising a compound of formula (I), wherein substantially all of the carbon present in the one or more compounds of formula (I) is bio-based; About 5% to about 50% of a medium chain diol; about 0.1% to about 20% of a medium chain alkyl hydroxamic acid, a salt thereof, or a combination thereof; about 1% to about 75% of glycerin and / or a C3-C4 diol; Includes.

[0011] In yet another embodiment, the invention relates to a formulation comprising a composition or concentrate as described in any of the preceding paragraphs.

[0012] The present invention further relates to a method for preparing a bio-based polyglyceryl ester composition, the method comprising: One or more of formula (I): [ka] where PG is a polyglyceryl group containing more than 40% hexaglycerol and higher polyglycerols and less than 60% pentaglycerol and lower polyglycerols; R is a linear or branched C5 to C8 alkyl group; n=1 to 3, wherein substantially all of the carbon present in the compound of formula (I) is bio-based.

[0013] The present invention further relates to another method for preparing a self-dispersing concentrate, the method comprising: One or more of formula (I): [ka] where PG is a polyglyceryl group containing more than 40% hexaglycerol and higher polyglycerols and less than 60% pentaglycerol and lower polyglycerols; R is a linear or branched C5 to C8 alkyl group; n=1 to 3, preparing a bio-based polyglyceryl ester by mixing one or more compounds of formula (I) (wherein substantially all of the carbon present in the compound is bio-based); combining a bio-based polyglyceryl ester with a mid-chain end diol; Includes.

[0014] In yet another embodiment, the present invention relates to a method of preparing a formulation comprising the bio-based polyglyceryl ester composition and / or the self-dispersing concentrate described in any of the preceding paragraphs. [Brief description of the drawings]

[0015] [Figure 1] FIG. 1 shows the turbidity of Spectrastat™ G2 Natural (1%) in a 5% solution of Polyglyceryl-10 heptanoate as a function of the degree of esterification (DE) of Polyglyceryl-10 heptanoate. [Figure 2A] FIG. 14 shows the turbidity values ​​of the O / W microemulsions as a function of oil loading as prepared in Example 14. Formulations with turbidity values ​​above 100 NTU are considered thermodynamically unstable macroemulsions. [Figure 2B] FIG. 14 shows O / W microemulsion turbidity values ​​after 24 hours as a function of oil loading for Example 14. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] Before describing the compounds, compositions, and methods of the present invention in particular, it is to be understood that the present invention is not limited to the particular process, composition, or method described, as such may be modified. It is also to be understood that the terms used in the description are only for the purpose of describing the particular versions or embodiments, and are not intended to limit the scope of the present invention, which is limited only by the appended claims. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, the preferred methods, devices, and materials are described herein. All publications mentioned herein are incorporated by reference in their entirety. Nothing herein should be construed as an admission that the present invention is not entitled to antedate such disclosure by virtue of prior invention.

[0017] Also, it should be noted that as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a "cell" is a reference to one or more cells and equivalents thereof known to those skilled in the art.

[0018] Unless specified, "%" can refer to either weight percent or volume percent.

[0019] "Cosmetically acceptable" means suitable for use in contact with the skin without undue toxicity, incompatibility, instability, irritation, allergic response, and the like.

[0020] Where applicable, chemicals are designated by their INCI names following the International Nomenclature of Cosmetic Ingredients guidelines. Additional information, including suppliers and trade names, can be found in the appropriate INCI monographs in the International Cosmetic Ingredient Dictionary and Handbook, 16th Edition, published by the Personal Care Products Council of America (Washington, DC), or online at the INCIpedia of Personal Care Products of America (http: / / incipedia.personalcarecouncil.org).

[0021] Among many embodiments, the present invention includes bio-based compositions. The production of bio-based compositions requires the use of bio-based or "natural" feedstocks. Examples of bio-based compositions are those prepared from biologically derived feedstocks (e.g., by current sustainable agricultural practices such as fermentation, algae, plant or vegetable origin; e.g., obtained from plant sources, preferably using non-genetically modified organisms or biomass) and are non-petrochemically derived (e.g., obtained from sustainable tree and plant farms operating in the 21st century, as opposed to fossil sources such as petroleum, natural gas or coal). Such feedstocks are referred to herein as "natural" and "renewable" (i.e., "sustainable") and are known in the art as non-petroleum derived feedstocks. Moreover, such materials are formed by "new" carbon, rather than petroleum or other fossil fuel sources ("old" carbon). Such products are referred to herein as "natural" products and are known in the art as non-petrochemically derived or "bio" products. As used herein, the term "sustainable" refers to starting materials, reaction products, compositions and / or formulations that are derived from renewable sources. The term "sustainable" is therefore in contrast to "unsustainable" starting materials, reaction products, compositions and / or formulations that contain carbon from limited natural resources such as fossil fuels (e.g., oil or coal), natural gas, etc. For this reason, natural or bioproducts are non-petrochemically derived and / or are not derived from petrochemicals, but rather are produced from sustainable and renewable sources. True natural products (bioproducts) are formed using biomass (e.g., materials stored from carbon cycle processes in living plants, roots, etc., or released from animal respiration or waste, or by decomposition). When carbon is broken down and decomposed under pressure over millions of years, fossil fuels (sources of petrochemically derived carbon) are produced. Biocompounds herein are intended to include materials derived from carbon from recently existing (existing) plant sources / biomass and / or are sustainable, and materials derived from fossil fuels are expressly excluded.

[0022] The compositions and / or formulations of the present invention can be identified and distinguished from prior art compositions and / or formulations by their biobased carbon content. In some embodiments, the biobased carbon content can be measured by radiocarbon dating, which determines the relative age of materials composed of organic (i.e., carbon-containing) matter. Radiocarbon is the radioactive carbon found in the presence of carbon-14 (i.e., " 14 It is an unstable isotope of carbon known as 1H). 14 C releases radiant energy in the form of beta particles at a very consistent rate (i.e., radiocarbon has a half-life of 5730 years) and eventually decays into the more stable nitrogen-14( 14 Petroleum-based (i.e., petrochemical-derived) feedstocks are derived from plants and animals buried millions of years ago, so the radioactive carbon (i.e., 14 C) has been lost to radioactive decay. ASTM International Standards has established a test standard for determining the authenticity of "biobased compounds" using radiocarbon, which can be found in ASTM D6866-16. This standard distinguishes between newer carbon and carbon derived from fossil fuels or petroleum- and petrochemical-derived sources, i.e., "old carbon." In recent or present biomass, 14 Since the amount of C is known, the percentage of carbon that is derived from renewable sources can be estimated from the total organic carbon analysis, providing the necessary data to determine whether a compound is truly derived from a "natural" and / or "sustainable" ("renewable") feedstock source, or conversely, whether it is derived from an "old" sequestration compound (i.e., petrochemical-derived or petroleum-based source). The use of petroleum-based (also referred to as "fossil-based") feedstocks is generally recognized as unsustainable, i.e., old carbon is unsustainable, is not a renewable feedstock, and is not considered "natural" and / or "sustainable" in the art.

[0023] In some embodiments, the blends and / or compositions of the present invention comprise bio-based carbon as substantially all of the carbon present in the mixture of compounds, which can refer to a bio-based carbon content of at least 90%, at least 95%, or at least 98%.

[0024] In some embodiments, the compositions of the present invention have a solubility in water that is less than 50% of the present atmospheric solubility as determined according to ASTM D6866. 14 C content substantially equal 14 In some embodiments, the compositions of the present invention have a carbon content that is less than 100% of the carbon content of current atmospheric carbon as determined according to ASTM D6866. 14 C content of at least about 90%, at least about 95%, at least about 98%, or at least about 99% 14 In some embodiments, the compositions of the present invention comprise at least 10 C present in the composition as determined according to ASTM D6866. 12 At least about 0.8 per carbon atom 14 C atoms present in the composition 12 At least about 1.0 per carbon atom 14 C atoms or 10 present in the composition 12 At least about 1.2 carbon atoms per 14 Contains C atoms.

[0025] Alternatively, authenticity can be tested by detailed analysis of stable isotopes using mass spectrometry and evaluation of the ratios of Carbon-12 / Carbon-13 and / or Hydrogen-1 / Hydrogen-2 to distinguish between petroleum-derived products and truly natural and / or sustainable products. Such tests are available from several analytical service laboratories and are much quicker, more cost-effective, and more informative than radiocarbon testing methods.

[0026] Stable isotope analysis is based on the principle of kinetic isotope effect. The latter effect is well known to those skilled in the art of chemical kinetics. In the broadest sense, heavy isotopes of a particular element react slower than lighter isotopes (e.g., carbon-12 versus carbon-13). Thus, when a plant incorporates carbon dioxide into biomass, the ratio of carbon-12 to carbon-13 varies depending on the type of chemistry used in the plant to make the biomass (e.g., whether the plant undergoes a C3 or C4 photosynthetic pathway). This is generally referred to as δ 13 C / 12 C ratio (i.e., δ 13 C) and are referenced to a current carbon dioxide standard. In addition, a similar isotopic kinetic effect is observed when water is incorporated into new biomass, which is 2 H / 1 H ratio (i.e., δ 2 H). 13 C and δ 2 Using the combination of H ratios, one skilled in the relevant art can readily distinguish and verify the nature of the feedstock used to prepare the product being analyzed (i.e., whether it was petrochemically derived or derived from recently living or living algae, plants, or similar biological sources).

[0027] By "sustainable" herein, applicants refer to materials that are derived from renewable sources. In contrast, "unsustainable" refers to materials that are derived from limited natural resources, such as fossil fuels (e.g., petroleum, natural gas, coal, etc.).

[0028] Introduction The present invention relates to one or more compounds of formula (I): [ka] (In the formula, PG is a polyglyceryl group containing more than 40% hexaglycerol and higher polyglycerols and less than 60% pentaglycerol and lower polyglycerols; R is a linear C5-C8 alkyl group; n=1 to 3, The present invention relates to a bio-based polyglyceryl ester (PGE) composition comprising a mixture of compounds having the structure of formula (I):

[0029] Applicants have surprisingly discovered that in order to provide a PGE composition that provides a stable, clear, aqueous solution and does not inhibit the activity of the microbistatic / microbiocidal compounds used to protect against microbial contamination, it is necessary to establish a precise balance between the hydrophilic and lipophilic properties of the PGE composition.

[0030] The compositions of the present invention have significant hydrophilicity determined by the composition of the polyglyceryl moiety of the PGE, and also do not exceed a critical threshold of lipophilicity determined by the carbon chain length of the fatty acyl moiety and the degree of esterification (DE) of the PGE composition.

[0031] Polyglycerols with glyceryl repeating units In some embodiments, the present invention relates to esterified polyglycerols. Polyglycerols (PG) are complex polydisperse low molecular weight polyethers composed of repeating units based on anhydrous 3-carbon glycerol groups that can be linear, branched or cyclic in nature. Examples of such glyceryl repeating units can be found in G. Rokicki, G. et al. Green Chem. 2005, 7, 529-539, which is incorporated herein by reference, and include the following: (a) a linear 1,4(L 1,4 )PG repeat unit: [ka] (b) a linear 1,3(L 1,3 )PG repeat unit: [ka] (c) Dendritic (D)PG repeating units resulting in branched and cyclic PGs of formula (IIc): [ka] (d) Terminal 1,2 (T 1,2 ) unit (shown attached to the polyglyceryl moiety PG): [ka] and (e) the terminal 1,3 (T 1,3 ) unit (shown attached to the polyglyceryl moiety PG): [ka]

[0032] Individual PG molecules are classified into groups according to the degree of glyceryl polymerization (DP PG ), that is, PG molecules are described by the number of glyceryl repeat units present in the molecule, e.g., diglycerol has two glyceryl repeat units, triglycerol has three glyceryl repeat units, tetraglycerol has four glyceryl repeat units, etc. Polydisperse compositions composed of various PG molecules are characterized by the distribution of PG molecules present in the composition, which is determined by a particular DP PG It is well known to those skilled in the art that a PG composition can be defined in terms of the percentage of PG molecules having an average DP PG For example, the average DP PG Polydisperse PG compositions with various DP = 10 PG Although it is a polydisperse composition made up of individual PG molecules with DP values, it can be referred to as decaglycerol or by the INCI name Polyglycerol-10. PG Values ​​may be determined and reported by any of the techniques known to those of skill in the art, including hydroxyl number determination, gas chromatography (GC), gas chromatography-mass spectrometry (GC-MS), high performance liquid chromatography (HPLC), or HPLC with MS detection (HPLC-MS).

[0033] PG is extremely hydrophilic due to the presence of many pendant hydroxyl groups at primary and secondary positions. However, the hydroxyl value and hydrophilicity of PG decrease as the content of cyclic repeat units increases, since each cyclic repeat unit formed effectively consumes one pendant hydroxyl group. Bio-based PG can be produced by direct condensation polymerization of glycerol (refined glycerin) with water as a by-product, or by ring-opening polymerization of glyceryl carbonate (GC), a cyclic carbonate monomer synthesized from glycerol. Other routes to PG exist, for example, by polymerization of glycidol or epichlorohydrin, but these routes are less preferred because most glycidol and epichlorohydrin are derived from non-renewable feedstocks and these monomers present significant health and safety hazards. In embodiments herein, PG is not derived from polymerization of glycidol or epichlorohydrin.

[0034] Polyglycerol Ester Composition The hydrophilicity of the PGE composition is characterized by the PG distribution of the starting PG material before esterification and the hydroxyl value (OHV) of the PGE composition after esterification. A preferred PG distribution is composed of 40% or more of hexaglycerol and higher polyglycerols and 60% or less of pentaglycerol and lower polyglycerols, where the OHV of the PGE composition is greater than about 500 mg KOH / g. In embodiments herein, the PG as in formula (I) above is a polyglyceryl group comprising more than 40% of hexaglycerol and higher polyglycerols and less than 60% of pentaglycerol and lower polyglycerols. In some embodiments, the PG is a polyglyceryl group comprising more than 40% of hexaglycerol and higher polyglycerols, for example, more than 45%, more than 50%, more than 55%, or more than 60% of hexaglycerol and higher polyglycerols. In some embodiments, PG is a polyglyceryl group containing less than 60% pentaglycerol and lower polyglycerols, such as less than 55%, less than 50%, less than 45%, or less than 40% pentaglycerol and lower polyglycerols.

[0035] With respect to the degree and distribution of esterification in PGE compounds according to formula (I), n is equal to 1-3. Most compounds will be monoesters (n=1). However, PGE compounds substituted with two or possibly more fatty acyl groups are also present in the composition. Compounds according to formula (I) have n values ​​of 1-3. In some embodiments, n=1, n=1-2, or n=1-3. In some embodiments, n=1-2. In some preferred embodiments, n=1 when the compound of formula (I) contains a monoester. Those skilled in the art will recognize that a PGE composition that is generally a monoester of the starting polyglycerol may actually contain a distribution of unsubstituted polyglycerols, polyglyceryl monoesters, polyglycerol diesters, and even polyglycerol triesters. For this reason, it is more practical to speak in terms of the average degree of esterification (DE) of the PGE composition rather than the individual PGE compounds.

[0036] The preferred lipophilicity of the PGE compositions is achieved by using bio-based fatty acids not exceeding C9, preferably bio-based fatty acids having C6-C8, and maintaining a DE of less than about 15%.

[0037] The PGE compositions of the present invention can be synthesized by a variety of methods known to those skilled in the art. A preferred route is direct esterification of bio-based PG (derived from the condensation polymerization of vegetable glycerol) with bio-based C6-C9 fatty acids. Preferred bio-based fatty acids include n-hexanoic acid (caproic acid), n-heptanoic acid (enanthic acid), n-octanoic acid (caprylic acid) and n-nonanoic acid (pelargonic acid). PG and fatty acids are charged to a reactor and heated to drive ester formation, with the resulting water of reaction being removed as a condensation by-product. The reaction is preferentially carried out at atmospheric pressure with an inert gas sparge, such as a nitrogen sparge, although a vacuum may be applied to the system to improve water removal, if desired. PGE compositions can also be synthesized by transesterification of simple esters (e.g., methyl or ethyl esters) of bio-based C6-C9 fatty acids, with the alcohol by-product of the reaction being removed by application of heat, inert gas sparge and / or vacuum.

[0038] The reaction is ideally carried out to reach a conversion where all of the fatty acids or their simple esters are consumed and converted to polyglyceryl esters. The residual fatty acid content is quantified as the acid value (AV), and the PGE compositions of the present invention have an AV of less than about 2.0 mg KOH / g.

[0039] Applicants have discovered that the preferred PGE compositions of the present invention can be characterized by their dynamic surface activity in aqueous solutions. The dynamic surface tension reduction, i.e., the reduction in surface tension as a function of time, is measured by bubble pressure tensiometry using the maximum bubble pressure (MBP) method. When the dynamic surface tension data obtained from the MBP experiment is plotted as a function of surface lifetime, the surface tension equilibrium rate constant (STERC) of a given surfactant at a particular concentration can be obtained by fitting the data to a first-order decay function such as equation (III).

[0040] The surface tension equilibrium rate constant (STERC) is calculated according to equation (III): Gamma t =γ eq +(γ i -γeq ) -t / K (III) (In the formula, Gamma t is the surface tension at time = t (in mN / m), Gamma eq is the equilibrium surface tension (in mN / m), Gamma i is the initial surface tension (in mN / m), t is the time in ms, K is the surface tension equilibrium rate constant (STERC) (ms -1 (unit) It is calculated according to:

[0041] STERC gives an indication of how rapidly a surface active species adsorbs to an air-water interface and reduces the surface tension of an aqueous solution. Compounds with lower STERC values ​​tend to adsorb more strongly at the air-water interface and remain there after adsorption compared to compounds with higher STERC values, the latter of which tend to adsorb and desorb more readily over the time scale of surface generation in MBP experiments. This adsorption-desorption phenomenon can also serve as a proxy for the tendency of surfactants to remain in a micellar state after micelles are formed.

[0042] Without wishing to be bound by theory, it is believed that surfactants that exhibit larger STERC values, i.e., that take longer to achieve equilibrium surface tension due to weaker adsorption at the air-water interface, also form more dynamic micelles due to enhanced micelle exchange and disassembly.Furthermore, it is believed that PGE compositions that exhibit larger STERC values ​​perform better as solubilizers of microbistatic / microbiocidal compounds because the more dynamic micellar behavior of these PGE compositions makes them less likely to inhibit the activity of these compounds via micelle encapsulation / sequestration, a phenomenon known as "neutralization."

[0043] Test Methods. Test methods used herein include the following: Acid value (AV): AOCS official method Te 2a-64, Hydroxyl value (OHV): AOCS official method Cd 13-60, Saponification value (SAP): AOCS official method Tl 2a-64, and Calculation of degree of esterification (DE): DE = [(SAP-AV) / (SAP+OHV)] x 100 DE(%)=[(SAP-AV) / (SAP+OHV)]×100 (IV).

[0044] Determination of Critical Micelle Concentration (CMC) by Equilibrium Surface Tension Measurements. Equilibrium surface tension values ​​for the determination of CMC values ​​were collected for each sample at each concentration by the Wilhelmy plate method using a standard 19.9 mm x 0.2 mm platinum plate on a high-resolution Kruss K100 tensiometer calibrated to ±0.00001 g (±0.002 mN / m) with NIST reference weights and calibrated against a pure distilled water standard surface tension of 72.50 mN / m ±0.05 mN / m. For the measurement of surface tension, the immersion distance of the plate was set at 3.00 mm until it returned to the surface, within ±0.01 mm. All tests were performed at 22°C ±0.2°C. For each surfactant, a 1.00% stock solution in pure water was prepared and added stepwise to the initial pure water to increase the surfactant concentration, with the surface tension measured after each concentration increase. Each surfactant was tested in duplicate at surfactant concentrations ranging from 0.001% to 0.500%. The CMC value was taken as the intersection of the regression line of the linearly dependent region with the line that passes through the plateau when the surface tension is plotted as a function of concentration.

[0045] Determination of STERC by Bubble Pressure Tensiometry. Dynamic surface tension was determined with a Kruss BP100 bubble pressure tensiometer using a 0.256 mm OD silanized glass capillary submerged to a depth of 1.00 cm for testing and buoyancy adjustment. The tensiometer is calibrated to 72.50 mN / m ± 0.1 mN / m in pure distilled water since the full dispersion range over the surface lifetime was in the range of 5 ms to 50,000 ms. All tests were performed at 22°C ± 0.2°C. Dynamic surface tension measurements were performed at the CMC. The STERC reported herein is determined at the CMC and is obtained by plotting the dynamic surface tension as a function of surface lifetime and fitting the data to the following equation to obtain a first order rate constant for the decrease in surface tension from the initial value to the equilibrium value:

[0046] (STERC) is as shown above and is represented by formula (III) repeated here: Gamma t =γ eq +(γ i -γ eq ) -t / K (III) (In the formula, Gamma t is the surface tension at time = t (in mN / m), Gamma eq is the equilibrium surface tension (in mN / m), Gamma i is the initial surface tension (in mN / m), t is the time in ms, K is the surface tension equilibrium rate constant (STERC) (ms -1 (unit) It is calculated according to:

[0047] Compositions containing bio-based polyglyceryl esters have a surface tension equilibrium rate constant (STERC) of, for example, about 2000 ms 2 as measured at a critical micelle concentration (CMC) determined in deionized water at 22° C. -1 These bio-based polyglyceryl ester compositions may have a STERC value of, for example, about 2000ms -1 ~ approx. 4000ms -1 , for example, about 2050ms -1~about 3500ms -1 Or about 2100ms -1 ~about 3250ms -1 On the lower end, the STERC values ​​of these bio-based polyglyceryl ester compositions can range from about 2000ms -1 Super, about 2050ms -1 More than or about 2100ms -1 In some embodiments, the bio-based polyglyceryl ester composition may have a molecular weight of about 2200 ms or more. -1 It has a STERC value of .

[0048] Turbidity measurements by nephelometric turbidity. Solutions and formulation clarity are reported as aqueous solution turbidity (AST) or formulation turbidity (FT) measured in nephelometric turbidity units (NTU). Turbidity values ​​were determined with an HF Scientific Micro 100 benchtop turbidity meter operating at room temperature (23°C ± 2°C). Aqueous solution turbidity is an inherent property of PGE compositions when routinely measured at 5% in deionized water at 23 ± 2°C.

[0049] Compositions comprising bio-based polyglyceryl esters may have low turbidity, such as an aqueous turbidity (AST) of less than about 10 NTU, measured at 5% in deionized water at 23±2° C. In some embodiments, the AST of the bio-based polyglyceryl ester compositions herein should be as low as possible. The AST of these bio-based polyglyceryl ester compositions may range, for example, from about 0 NTU to about 10 NTU, such as from 0 NTU to 5 NTU, from 0 NTU to 2.5 NTU, from 0 NTU to 2 NTU, or from 0 NTU to 1 NTU. In terms of upper limits, the AST may be less than 10 NTU, such as less than 5 NTU, less than 2.5 NTU, less than 2 NTU, less than 1.5 NTU, less than 1 NTU, or less than 0.5 NTU. In some embodiments, the bio-based polyglyceryl ester compositions have an AST of less than about 10 NTU, measured at 5% in deionized water at 23±2° C. In some embodiments, the AST is 0 or essentially 0, such as below the detection limit.

[0050] Microbiological Challenge Testing (MCT) of Formulations to Determine Preservative Efficacy. To determine the preservative efficacy of the formulations against bacteria, yeasts and molds, challenge tests were conducted according to the United States Pharmacopeia (USP) and PCPC official test methods. Such tests are referenced in the Personal Care Products Council Technical Guidelines, Microbiology Guidelines, 2018 Edition, published by the Personal Care Products Council, Washington, DC, and references cited therein, which are incorporated herein by reference.

[0051] The PGE compositions of the present invention are useful for preparing aqueous formulations, particularly clear or translucent formulations, containing poorly water-soluble or insoluble hydrophobic compounds, such as fragrances, essential oils, active ingredients, preservative ingredients, and other ingredients that are poorly water-soluble, in clear aqueous formulations. Formulations prepared using the PGE compositions exhibit excellent transparency and preservative efficacy against microbial contamination.

[0052] Formulations containing the PGE compositions herein may contain additional components or ingredients such as surfactants including anionic, nonionic, cationic and zwitterionic surfactants, emollients, humectants, conditioning agents, active agents, bleaching or whitening agents, fragrances, colorants, exfoliants, antioxidants, botanicals, mica, smectites, rheology modifiers, thickeners, cannabinoids, oils, dyes, waxes, amino acids, nucleic acids, vitamins, hydrolyzed proteins and derivatives thereof, glycerin derivatives (e.g., glyceride esters), enzymes, anti-inflammatory and other agents, bactericides, antifungals, disinfectants, antioxidants, UV absorbers, dyes and pigments, preservatives, sunscreen actives, antiperspirant actives, oxidants, pH balancing agents, moisturizers, peptides and derivatives thereof, anti-aging actives, hair growth agents, anti-cellulite actives, and combinations thereof.

[0053] The PGE composition or formulation may be, or may be a component of, a personal care product, a home care product, a fabric care product, an institutional care product, a pharmaceutical product, an animal product, a food product, or an industrial product. In some embodiments, the composition may be used in the formulation of, or may be a component of, a personal care product. Personal care products include cosmetics, hair, nail, skin or fabric conditioners, shampoos, hair styling products, oils or waxes for grooming facial hair, permanent wave solutions, hair coloring agents, face or body washes, makeup remover products, cleansing lotions, emollient lotions or creams, bar soaps, liquid soaps, shaving creams, foams or gels, sunscreens, gels, lotions or creams for treating sunburn, deodorants or antiperspirants, moisturizing gels, shaving foams, face powders, foundations, lipsticks, blushes, eyeliners, wrinkle or anti-aging creams, eye shadows, eyebrow pencils, mascara, mouthwashes, toothpastes, oral care products, skin cleansing products, fabric cleaning products, dishwashing products, hair or fur cleaning products, and lotions or moisturizers.

[0054] The PGE composition can be used directly in a formulation, such as a personal care product formulation. The amount of the PGE composition can be present in the formulation in a range of, for example, about 0.01 wt% to about 33 wt%, such as 0.025 wt% to 25 wt%, 0.1 wt% to 15 wt%, or 0.2 wt% to 10 wt%. In terms of the upper limit, the amount of the PGE can be less than 33 wt%, such as less than 25 wt%, less than 15 wt%, or less than 10 wt%. In terms of the lower limit, the amount of the PGE composition can be greater than 0.01 wt%, such as greater than 0.025 wt%, greater than 0.1 wt%, or greater than 0.2 wt%.

[0055] Formulations containing PGE compositions have lower formulation turbidity (FT) values, e.g., less than about 100 NTU, when measured in water at 23±2°C. The FT of formulations containing PGE compositions herein should be as low as possible. The FT of these formulations can range, e.g., from about 0 NTU to about 100 NTU, e.g., from 0 NTU to 50 NTU, from 0 NTU to 25 NTU, from 0 NTU to 10 NTU, or from 0 NTU to 5 NTU. In terms of upper limits, the FT can be less than 100 NTU, e.g., less than 50 NTU, less than 25 NTU, less than 10 NTU, less than 5 NTU, less than 2.5 NTU, or less than 1 NTU. In some embodiments, formulations containing PGE compositions have a FT of less than about 10 NTU, when measured at 5% in deionized water at 23±2°C. In some embodiments, the FT is 0 or essentially 0, e.g., below the detection limit.

[0056] Self-dispersing concentrate (SDC) The PGE compositions of the present invention can also be used to make self-dispersing concentrates (SDCs), which are useful for preparing clear or translucent oil-in-water (O / W) microemulsions of poorly soluble or insoluble hydrophobic compounds in water. SDCs, when dissolved in water, show exceptional clarity, typically less than 10 NTU, and form thermodynamically stable O / W microemulsions with good clarity, typically less than 100 NTU.

[0057] The SDC of the present invention is useful for preparing clear or translucent aqueous formulations containing poorly soluble or insoluble hydrophobic compounds in water, such as fragrances, essential oils, active ingredients, preservative ingredients, and other ingredients that are poorly water soluble, in a clear aqueous formulation. Formulations prepared with SDC exhibit excellent clarity and preservative efficacy against microbial contamination.

[0058] In some embodiments, the present invention relates to SDC comprising bio-based polyglyceryl esters that can be used in formulations for various applications. The SDC composition or formulation can be, or be a component of, a personal care product, a home care product, a fabric care product, an institutional care product, a pharmaceutical product, an animal product, a food product, or an industrial product. In some embodiments, the composition can be used in, or be a component of, a personal care product formulation. Personal care products include cosmetics, hair, nail, skin or fabric conditioners, shampoos, hair styling products, oils or waxes for grooming facial hair, permanent wave solutions, hair coloring agents, face or body washes, makeup remover products, cleansing lotions, emollient lotions or creams, bar soaps, liquid soaps, shaving creams, foams or gels, sunscreens, gels, lotions or creams for treating sunburn, deodorants or antiperspirants, moisturizing gels, shaving foams, face powders, foundations, lipsticks, blushes, eyeliners, wrinkle or anti-aging creams, eye shadows, eyebrow pencils, mascara, mouthwashes, toothpastes, oral care products, skin cleansing products, fabric cleaning products, dishwashing products, hair or fur cleaning products, and lotions or moisturizers.

[0059] The SDCs disclosed herein are suitable for use in formulations as microemulsion systems for water-insoluble ingredients or as vehicles for introducing poorly soluble or water-insoluble ingredients into the formulation. In some embodiments, the formulations are thermodynamically stable O / W microemulsions.

[0060] In some cases, SDCs may be useful for preparing formulation concentrates that can be easily combined with other ingredients and diluted with water to obtain a finished formulation. In some cases, SDCs have the advantage of being "cold processable", i.e., they do not require heat to disperse in aqueous solution. In embodiments, these SDCs may include a bio-based polyglyceryl ester composition as described above, and additionally a mid-chain end diol (MCTD). The bio-based polyglyceryl ester of these embodiments may be a composition of formula (I) as described above. These compositions may be used in or be a component of formulations for personal care products or other applications as described above. The bio-based polyglyceryl ester may act synergistically with other ingredients, such as MCTD.

[0061] For use in cosmetic, toiletry and pharmaceutical applications, the most preferred diols for use in the concentrates or formulations described herein are medium chain length linear vicinal diols that exhibit microbiocidal and / or antimicrobial activity at relatively low use levels. In some embodiments, the medium chain length is C4 to C8 for the diols. 10Such diols include 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol (caprylyl glycol) and 1,2-decanediol. Other vicinal diols useful in the compositions described herein include molecules derived from glycerin. Glycerin can be substituted at the 1 or 3 positions with other molecules, leaving two adjacent hydroxyl groups. For example, glyceryl monoethers such as ethylhexylglycerin, available from INOLEX, Inc. as Lexgard™ E, or methylheptylglycerin, available from INOLEX, Inc. as Lexgard™ MHG Natural MB, are useful liquid vicinal diols with antimicrobial properties. Glyceryl monoesters, such as glyceryl monolaurate, glyceryl monocaprate, glyceryl monopelargonate, glyceryl monoheptanoate, or glyceryl monocaprylate, which is commercially available as LEXGARD™ GMCY from INOLEX, Inc. (Philadelphia, Pa.), are also useful antimicrobial vicinal diols.

[0062] In some embodiments, the mid-chain end diol is at least one of a glyceryl monoester, a glyceryl monoether, a 1,2-alkanediol, and combinations thereof. The mid-chain end diol may be a glyceryl monoester selected from the group consisting of glyceryl monolaurate, glyceryl monocaprate, glyceryl monopelargonate, glyceryl monocaprylate, glyceryl monoheptanoate, and glyceryl monoundecylenate. The mid-chain end diol may be a glyceryl monoether selected from the group consisting of ethylhexylglycerin, methylheptylglycerin, caprylyl glyceryl ether, heptylglycerin, hexylglycerin, or cyclohexylglycerin. The mid-chain end diol may be a 1,2-alkanediol selected from the group consisting of 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol (caprylyl glycol) and 1,2-decanediol.

[0063] It is known that vicinal diols are effective against bacteria and yeasts in preserving cosmetics, toiletries and medicines, but are weak against fungi. In the book D. Steinberg, Preservatives for Cosmetics. 2nd ed, (2006), pg. 102, the authors state that vicinal diols "have the weakest activity of all against fungi." In the article D. Smith et al., "The Self-Preserving Challenge," Cosmetic & Toiletries, No. 1, 115, No. 5 (May 2000), it is stated that vicinal diols have activity against bacteria, but "limited activity against Aspergillus." Aspergillus niger, also known as Aspergillus brasiliensis, is one of the organisms used in PCPC challenge testing; therefore, products described herein that have vicinal diols as the only preservative ingredient may not pass a PCPC challenge test satisfactorily.

[0064] The compositions of these embodiments may also include a chelating agent. Chelating agents suitable for use with the compositions, formulations, products and methods of the present invention include C6-C 10 Examples of suitable chelating agents include, but are not limited to, alkylhydroxamic acid or its alkylhydroxamate salts, tetrasodium glutamate diacetate, phytic acid or its salts, gluconic acid or its salts, galacturonic acid or its salts, galactaric acid or its salts, and combinations thereof. In some embodiments, the chelating agent is caprylhydroxamic acid, a hydroxamate salt of caprylhydroxamic acid, or a combination thereof. In some embodiments, the chelating agent consists essentially of caprylhydroxamic acid, a hydroxamate salt of caprylhydroxamic acid, or a combination thereof. The addition of a chelating agent, such as an alkylhydroxamic acid chelating agent, provides additional efficacy against fungi.

[0065] The SDC comprises at least the following components: a bio-based polyglyceryl ester composition as described above and a mid-chain terminated diol. Optionally, the SDC can comprise a mid-chain alkyl hydroxamic acid, a salt thereof, or a combination thereof. Optionally, the SDC can comprise glycerin and / or a C3-C4 diol. Examples of optional C3-C4 diols include propanediol, 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, methylpropanediol, and combinations thereof.

[0066] The SDC may comprise from about 30% to about 90% of the bio-based polyglyceryl ester composition of formula (I) and from about 5% to about 50% of a mid-chain terminal diol. In some embodiments, the concentrate further comprises from about 0.1% to about 20% of a mid-chain alkyl hydroxamic acid, salt thereof, or combination thereof. In some embodiments, the concentrate additionally or alternatively comprises from about 1% to about 75% of glycerin and / or a C3-C4 diol. Other optional ingredients may be included in the SDC, as described below.

[0067] The SDC may comprise a bio-based polyglyceryl ester composition of formula (I), such as a composition of formula (I), in the range of about 30 wt% to about 90 wt%, such as 40 wt% to 85 wt%, 45 wt% to 80 wt%, or 50 wt% to 75 wt%. In terms of the upper limit, the amount of the composition of formula (I) may be less than 90 wt%, such as less than 85 wt%, less than 80 wt%, or less than 75 wt%. In terms of the lower limit, the amount of the composition of formula (I) may be greater than 30 wt%, such as greater than 40 wt%, greater than 45 wt%, or greater than 50 wt%.

[0068] The SDC contains the mid-chain terminal diol in the range of about 5 wt% to about 50 wt%, for example, 7.5 wt% to 40 wt%, 10 wt% to 30 wt%, or 10 wt% to 25 wt%. With respect to the upper limit, the amount of the mid-chain terminal diol can be less than 50 wt%, for example, less than 40 wt%, less than 30 wt%, or less than 25 wt%. With respect to the lower limit, the amount of the mid-chain terminal diol can be more than 5 wt%, for example, more than 7.5 wt% or more than 10 wt%. The ratio of the polyglyceryl ester to the mid-chain terminal diol in the SDC is about 1:1 to about 10:1, preferably about 2:1 to about 8:1, and more preferably about 2:1 to about 7:1.

[0069] The SDC comprises a medium chain alkyl hydroxamic acid, a salt thereof, or a combination thereof in the range of about 0.1 wt% to about 20 wt%, for example, 0.5 wt% to 17.5 wt%, 1.0 wt% to 15 wt%, or 2.0 wt% to 10 wt%. In terms of the upper limit, the amount of the medium chain alkyl hydroxamic acid, a salt thereof, or a combination thereof can be less than 20 wt%, for example, less than 17.5 wt%, less than 15 wt%, or less than 10 wt%. In terms of the lower limit, the amount of the medium chain terminal diol medium chain alkyl hydroxamic acid, a salt thereof, or a combination thereof can be greater than 0.1 wt%, for example, greater than 0.5 wt%, greater than 1.0 wt%, or greater than 2.0 wt%.

[0070] SDC contains glycerin and / or C3-C4 diol in the range of about 1.0 wt% to about 75 wt%, for example, 2.5 wt% to 50 wt%, 5 wt% to 50 wt%, or 5 wt% to 25 wt%. In terms of the upper limit, the amount of glycerin and / or C3-C4 diol can be less than 75 wt%, for example, less than 50 wt% or less than 25 wt%. In terms of the lower limit, the amount of glycerin and / or C3-C4 diol can be more than 1.0 wt%, for example, more than 2.5 wt% or more than 5 wt%.

[0071] Optionally, the SDC includes additional components or ingredients such as organic acids and / or polyols. The SDC may include an organic acid selected from the group consisting of benzoic acid, sorbic acid, p-anisic acid, levulinic acid, salicylic acid, citric acid, lactic acid, succinic acid, malonic acid, malic acid, fumaric acid, anisic acid, glycolic acid, salts thereof, and combinations thereof. The SDC may include a polyol selected from the group consisting of sorbitol, sorbitan, isosorbide, and combinations thereof. The SDC is a polyol selected from the group consisting of medium chain (C6-C8) polyols of the amino acid glycine. 10 ) fatty acid amides, such as capryloyl glycine or salts thereof. In some embodiments, the SDC is substantially anhydrous, i.e., water is not intentionally added to the SDC during preparation, and the SDC contains less than about 2% water, e.g., incidental moisture from processing or absorption from the atmosphere.

[0072] These components may be considered optional. In some cases, this section may explicitly exclude one or more of the above-mentioned components from the disclosed compositions, for example, by claim language. For example, the claim language may be modified to state that the disclosed compositions, formulations, methods, etc. do not utilize or include one or more of the above-mentioned optional components.

[0073] The SDC can then be used in subsequent formulations, such as in personal care product formulations. The amount of SDC can be present in the formulation in a range of, for example, about 0.1 wt% to about 50 wt%, such as 0.25 wt% to 30 wt%, 0.5 wt% to 15 wt%, or 1.0 wt% to 10 wt%. On the upper limit, the amount of SDC can be less than 50 wt%, such as less than 30 wt%, less than 15 wt%, or less than 10 wt%. On the lower limit, the amount of SDC can be greater than 0.1 wt%, such as greater than 0.25 wt%, greater than 0.5 wt%, or greater than 1.0 wt%.

[0074] Formulations containing SDC with bio-based polyglyceryl ester and mid-chain end diol have lower formulation turbidity (FT) values, e.g., less than about 100 NTU, when measured in water at 23±2°C. The FT of formulations containing SDC herein should be as low as possible. The FT of these SDC formulations can range, e.g., from about 0 NTU to about 100 NTU, e.g., from 0 NTU to 50 NTU, from 0 NTU to 25 NTU, from 0 NTU to 10 NTU, or from 0 NTU to 5 NTU. On the upper end, the FT can be less than 100 NTU, e.g., less than 50 NTU, less than 25 NTU, less than 10 NTU, less than 5 NTU, less than 2.5 NTU, or less than 1 NTU. In some embodiments, the SDC has an FT of less than about 10 NTU when measured at 5% in deionized water at 23±2°C. In some embodiments, the FT is 0 or essentially 0, e.g., below the detection limit.

[0075] Optionally, the formulations comprising SDC herein may contain additional components or ingredients such as surfactants including anionic, nonionic, cationic and zwitterionic surfactants, emollients, humectants, conditioning agents, active agents, bleaching or whitening agents, fragrances, colorants, exfoliants, antioxidants, botanicals, mica, smectites, rheology modifiers, thickeners, cannabinoids, oils, dyes, waxes, amino acids, nucleic acids, vitamins, hydrolyzed proteins and derivatives thereof, glycerin derivatives (e.g., glyceride esters), enzymes, anti-inflammatory and other agents, bactericides, antifungals, disinfectants, antioxidants, UV absorbers, dyes and pigments, preservatives, sunscreen actives, antiperspirant actives, oxidants, pH balancing agents, moisturizers, peptides and derivatives thereof, anti-aging actives, hair growth agents, anti-cellulite actives, and combinations thereof.

[0076] Methods for preparing compositions and concentrates containing bio-based polyglyceryl ester compositions The methods of the present invention relate to the preparation of bio-based polyglyceryl ester compositions and self-dispersing concentrates, as well as formulations and / or components that include the bio-based polyglyceryl ester compositions and self-dispersing concentrates.

[0077] The method of preparing a bio-based polyglyceryl ester composition includes mixing one or more compounds of formula (I), which is described in detail above. Mixing can be performed in a flask, reactor, or other vessel known in the art and may include stirring. Mixing may include heating to a temperature of about 150° C. to 250° C. and may include the use of a nitrogen sparge. Condensed water is removed during mixing. Mixing allows the compounds to react until a desired conversion is achieved, as indicated by an acid number. Mixing and reacting may include mixing for about 8 hours to 36 hours. In some embodiments, a conversion is achieved, as indicated by an acid number of less than 2.0 mg KOH / g.

[0078] The method may include that n in formula (I) is 1, 2 or 3. In some embodiments, n=1. R in formula (I) may be a linear or branched C5-C8 alkyl group. In some embodiments, R is a linear C5-C8 alkyl group. In some embodiments, R is a linear C6 alkyl group and RCO is derived from bio-based n-heptanoic acid.

[0079] The method may include that PG of formula (I) can be a polyglyceryl group comprising greater than 60% hexaglycerols and higher polyglycerols and less than 40% pentaglycerols and lower polyglycerols. In some embodiments, the method includes that PG is a polyglyceryl group comprising greater than 60% hexaglycerols and higher polyglycerols and less than 40% pentaglycerols and lower polyglycerols.

[0080] The method may include the biobased polyglyceryl ester composition having a hydroxyl number of greater than 500 mg KOH / g and a degree of esterification (DE) of less than about 15%. In some embodiments, the method includes the composition having an acid number (AV) of less than about 2 mg KOH / g.

[0081] The method comprises providing a biobased polyglyceryl ester composition having a molecular weight of about 2000 ms as measured at a critical micelle concentration (CMC) determined in deionized water at 22° C. -1 The surface tension equilibrium rate constant (STERC) may include having a surface tension equilibrium rate constant (STERC) of greater than or equal to 100 nm.

[0082] The method can include the biobased polyglyceryl ester composition having an aqueous solution turbidity of less than about 10 NTU when measured at 5% in deionized water at 23±2° C.

[0083] A method of preparing a self-dispersing concentrate comprising a bio-based polyglyceryl ester composition can include mixing one or more compounds of formula (I). Mixing and formula (I) are described in detail above. Following mixing, the method includes combining the bio-based polyglyceryl ester with a mid-chain end diol. The method can include that n in formula (I) is 1-3. In some cases, n=1. In some cases, R is a linear C5-C8 alkyl group. In certain embodiments, R is a linear C6 alkyl group and RCO is derived from bio-based n-heptanoic acid. PG can be a polyglyceryl group comprising greater than 60% hexaglycerol and higher polyglycerols and less than 40% pentaglycerol and lower polyglycerols.

[0084] In some embodiments, the combination comprises about 30% to about 90% bio-based polyglyceryl ester and about 5% to about 50% of a medium chain diol blend.

[0085] The combination in the method of preparing a self-dispersing concentrate may further comprise a medium chain alkyl hydroxamic acid, a salt thereof, or a combination thereof, hi some embodiments, the combination comprises about 0.1% to about 20% of a medium chain alkyl hydroxamic acid, a salt thereof, or a combination thereof.

[0086] The combination in the method of preparing a self-dispersing concentrate may further comprise glycerin and / or a C3-C4 diol, hi some embodiments, the combination comprises from about 1% to about 75% glycerin and / or a C3-C4 diol.

[0087] The method may include preparing a formulation from the bio-based polyglyceryl ester composition and / or SDC. Depending on the end-use formulation, further additional ingredients, as described above, may be additionally combined. The formulation or composition may be a component of a personal care product, a home care product, a fabric care product, an institutional care product, a pharmaceutical product, an animal product, a food product, or an industrial product. Personal care products that can be made by the process herein include cosmetics, hair, nail, skin or fabric conditioners, shampoos, hair styling products, oils or waxes for grooming facial hair, permanent wave solutions, hair coloring agents, face or body washes, makeup remover products, cleansing lotions, emollient lotions or creams, bar soaps, liquid soaps, shaving creams, foams or gels, sunscreens, gels, lotions or creams for treating sunburn, deodorants or antiperspirants, moisturizing gels, shaving foams, face powders, foundations, lipsticks, blushes, eyeliners, wrinkle or anti-aging creams, eye shadows, eyebrow pencils, mascara, mouthwashes, toothpastes, oral care products, skin cleansing products, fabric cleaning products, dishwashing products, hair or fur cleaning products, and toners or moisturizers.

[0088] These detailed descriptions serve to illustrate the above general description and the embodiments which form a part of the present invention. These detailed descriptions are presented for illustrative purposes only and are not intended to limit the scope of the invention. EXAMPLES

[0089] Example 1: Synthesis of Polyglyceryl-10 Heptanoate Composition. Polyglyceryl-10 heptanoate PGE composition was synthesized as follows: To a 1 liter, 4-neck round bottom flask equipped with an overhead mechanical stirrer, heating mantle, temperature controller, condenser / receiver and nitrogen sparge was added bio-based polyglycerin-10 (Pure Vegetable Polyglycerine-10, Spiga Nord SpA, 598 g, 0.78 mol) conforming to the specifications in Table 1 and bio-heptanoic acid (Oleris™ n-Heptanoic Acid, Arkema, 152 g, 1.17 mol). The contents of the flask were stirred at moderate speed and heated to 200° C. with nitrogen sparge at a rate of 0.10 L / min. The reaction was maintained under these conditions and condensed water was removed. The reaction was allowed to proceed until the desired conversion was achieved (indicated by an acid number of less than 2.0 mg KOH / g), which took approximately 18 hours. The reactor was then cooled to 80° C. and the contents were removed and stored in a suitable container.

[0090] [Table 1]

[0091] Examples 2 to 6: Synthesis of Polyglyceryl-10 Heptanoate Compositions. Examples 2 to 6 were prepared in the same manner as Example 1, except that the molar ratio of bioheptanoic acid to polyglycerin-10 was changed according to the values ​​listed in Table 2.

[0092] Example 7: Synthesis of Polyglyceryl-10 Hexanoate Composition. Polyglyceryl-10 Hexanoate PGE composition was synthesized as follows: A 1-liter, 4-neck round bottom flask equipped with an overhead mechanical stirrer, heating mantle, temperature controller, condenser / receiver, and nitrogen sparge was charged with bio-based polyglycerin-10 (Pure Vegetable Polyglycerine-10, Spiga Nord SpA, 607 g, 0.8 mol) and biohexanoic acid (Hexanoic acid, natural, >98%, Sigma Aldrich, 93 g, 0.8 mol) conforming to the specifications in Table 1. The contents of the flask were stirred at a moderate rate and heated to 200° C. with nitrogen sparge at a rate of 0.10 L / min. The reaction was held under these conditions and condensed water was removed. The reaction was allowed to proceed until the desired conversion (indicated by an acid value of less than 2.0 mg KOH / g) was achieved, which took approximately 20 hours. The reactor was then cooled to 80° C. and the contents removed into suitable containers for storage.

[0093] Example 8: Synthesis of Polyglyceryl-10 Caprylate Composition. Polyglyceryl-10 Caprylate PGE composition was synthesized as follows: A 1-liter, 4-neck round bottom flask equipped with an overhead mechanical stirrer, heating mantle, temperature controller, condenser / receiver, and nitrogen sparge was charged with bio-based polyglycerin-10 (Pure Vegetable Polyglycerine-10, Spiga Nord SpA, 607 g, 0.8 mol) conforming to the specifications in Table 1 and biocaprylic acid (Caprylic Acid, 99%, FA C0899, Unilever Oleochemical, 112 g, 0.8 mol). The contents of the flask were stirred at a moderate rate and heated to 200° C. with nitrogen sparge at a rate of 0.10 L / min. The reaction was held under these conditions and condensed water was removed. The reaction was allowed to proceed until the desired conversion (indicated by an acid value of less than 2.0 mg KOH / g) was achieved, which took approximately 15 hours. The reactor was then cooled to 80° C. and the contents removed into suitable containers for storage.

[0094] [Table 2]

[0095] Comparative Example 1: Synthesis of Polyglyceryl-4 Heptanoate Composition Polyglyceryl-4 heptanoate PGE composition was synthesized according to the procedure of Example 1, except that bio-based polyglycerin-4 (Pure Vegetable Polyglycerine-4, Spiga Nord SpA) conforming to the specifications in Table 3 was used in a 1:1 molar ratio with bio-heptanoic acid.

[0096] [Table 3]

[0097] Comparative Example 2: Synthesis of Polyglyceryl-6 Heptanoate Composition. Polyglyceryl-6 heptanoate PGE composition was synthesized according to the procedure of Example 1, except that bio-based polyglycerin-6 (Pure Vegetable Polyglycerine-6, Spiga Nord SpA) conforming to the specifications in Table 1 was used in a 1:1 molar ratio with bio-heptanoic acid.

[0098] Comparative Example 3: Commercially available polyglyceryl-10 caprylate. A commercially available sample of polyglyceryl-10 caprylate PGE composition (SY-Glyster MCA-750, decaglycerol monocaprylate) was obtained from Sakamoto Pharmaceutical Co., Ltd. and used as received.

[0099] Comparative Example 4: Commercially Available Heptyl Glucoside. A commercially available sample of heptyl glucoside, a C7 alkyl polyglucoside surfactant (Sepiclear G7), was obtained from Seppic, Inc. and used as received. This material is provided as a 70%-75% solution in water. Heptyl glucoside is an alkyl polyglucoside (not a PGE) and is a very effective solubilizer for the preparation of O / W microemulsions (see U.S. Pat. No. 9,080,132) and is included herein as a comparative performance benchmark.

[0100] Comparative Example 5: Commercially available Polyglyceryl-10 Caprylic / Capric Acid. A commercially available sample of Polyglyceryl-10 Caprylic / Capric Acid PGE composition (Polyaldo 10-1-CC K) was obtained from Arxada (formerly Lonza) and used as received.

[0101] Characterization data (AV, OHV, SAP, and DE) for Examples 1-8 and Comparative Examples 1-4 are reported in Table 2. Only the OHV was determined for Comparative Example 4, since it is an ether and not an ester. Water solubility and clarity of the bio-based PGE compositions were evaluated by preparing 5% and 10% aqueous solutions of the PGE compositions in deionized water. The data are reported in Table 2. Examples 1-8 prepared with polyglycerin-10 were readily water soluble and formed clear solutions with AST values ​​less than 7.0 NTU and good clarity. Comparative Examples 1 and 2 prepared with polyglycerin-4 and polyglycerin-6, respectively, were insoluble in water and did not form clear solutions. Examples 1-8 demonstrate the importance of selecting polyglycerin precursors composed of 40% or more hexaglycerol and higher polyglycerols and 60% or less pentaglycerol and lower polyglycerols to ensure solubility and clarity. Comparative Examples 3 and 4 formed clear solutions with low turbidity values.

[0102] [Table 4]

[0103] Example 9: Determination of CMC and STERC values. The values ​​of CMC and STERC at CMC were determined for several PGE compositions of the present invention (Examples 2, 4, and 6-8) and comparative examples. The results are reported in Table 4. The STERC values ​​of the PGE compositions of the present invention were -1 The comparative PGE composition of Comparative Example 3 is 2000s -1 The commercially available performance benchmark, heptyl glucoside, shown in Comparative Example 4, has a STERC of 3226 ms -1STERC was shown.

[0104] Example 10: Solubilization of a multifunctional preservative system. Spectrastat™ G2 Natural is a 100% biobased multifunctional preservative system from INOLEX, Inc., composed of glyceryl caprylate, caprylhydroxamic acid, and glycerin. Spectrastat™ G2 Natural is poorly soluble in water and does not form a clear solution. The solubilization performance of Examples 1-8 and Comparative Examples 3 and 4 was evaluated by determining the FT of 1% Spectrastat™ G2 Natural in an aqueous solution containing 5% solubilizer (note that Comparative Example 4 was used at 5% as supplied, resulting in approximately 3.5% active heptyl glucoside). Turbidity values ​​are reported in Table 5.

[0105] [Table 5]

[0106] Examples 2, 4, 5, 6 and 8, when used at 5%, formed clear formulations of 1% Spectrastat™ G2 Natural with FT values ​​of less than 9.0 NTU. Polyglyceryl-10 hexanoate of Example 7 did not form clear solutions at 5%, but when used at 7%, Example 7 produced a 1% formulation of Spectrastat™ G2 Natural with a turbidity of 6.54 NTU. The reduced efficiency of Example 7 is due to the shorter C6 fatty acid ester of Polyglyceryl-10 hexanoate, making it less lipophilic than the C7 and C8 fatty acid esters of the other Examples. Polyglyceryl-10 heptanoate of Examples 1 and 3 formed opaque emulsions, while the commercial polyglyceryl-10 caprylate of Comparative Example 3 formed a cloudy translucent formulation with a turbidity of 57.1 NTU. Heptyl glucoside of Comparative Example 4 showed the highest transparency with a turbidity value of 4.21 NTU.

[0107] FIG. 1 shows the turbidity of 1% formulations of Spectrastat™ G2 Natural at 5% formulations of various polyglyceryl-10 heptanoates as a function of DE for a series of polyglyceryl-10 heptanoate examples. For polyglyceryl-10 heptanoate compositions, ideal solubilization performance is achieved when the PGE composition has an OHV of greater than 528 mg KOH / g and a DE of 8%-11%. Polyglyceryl-10 caprylate of Example 8 also exhibited OHV and DE values ​​in this range, forming a clear formulation with a FT of 5.04 NTU. Examples 1 and 3 are too hydrophobic (low OHV, too much DE) and too hydrophilic (not enough DE), respectively, to function well as an O / W microemulsifier for Spectrastat™ G2 Natural. Similarly, the commercial polyglyceryl-10 caprylate of Comparative Example 3 does not perform well and produces a cloudy solution because it exhibits a lower OHV (492 mg KOH / g) and excessive DE (13.3%) compared to the polyglyceryl-10 caprylate of Example 8 (OHV=617 mg KOH / g and DE=9.4%).

[0108] Example 11: Preservative efficacy of solubilized multifunctional preservative systems. The effect of various solubilizers on preservative efficacy was evaluated by preparing the formulations shown in Table 6 using the following procedure: Water (95% of the total water required for the batch) was charged to an appropriately sized beaker of known tare weight equipped with an overhead mechanical stirrer and anchor-type blade. Mixing was started at low to medium speed and the designated solubilizer was added to the water and mixed until completely dissolved. Spectrastat™ G2 Natural was added to the batch and mixed until a uniformly mixed homogenous solution was formed. The pH of the formulation was adjusted to pH 6.6±0.2 using a 10% solution of citric acid. The remaining water was qs to 100% and the batch was mixed until uniform before being removed to an appropriate container for storage.

[0109] [Table 6]

[0110] Table 6 reports the turbidity values ​​of the formulations, along with the OHV, DE, and STERC data for each solubilizer evaluated. Formulation A (no solubilizer) formed an opaque dispersion with a turbidity greater than 100 NTU. Formulation B, using the performance benchmark of heptyl glucoside from Comparative Example 4, and Formulation D, using Polyglyceryl-10 heptanoate from Example 2, both formed clear solutions with turbidity values ​​of 5.2 and 5.7, respectively. Formulation C, using the commercial polyglyceryl-10 caprylate from Comparative Example 3, formed a hazy solution with a turbidity of 57.1.

[0111] MCTs were conducted according to USP and PCPC official test methods to determine the preservative efficacy of Spectrastat™ G2 Natural in the formulations. The results are shown in Tables 7A-7D. Formulations A and B showed good preservative efficacy, achieving strong reductions of five microorganisms by day 14. Formulation C, prepared with the comparative PGE composition, showed weak preservative efficacy against most microorganisms, and the MCT was discontinued on day 14. Formulation D, prepared with the PGE composition of the present invention, showed significantly stronger preservative efficacy than Formulation C, achieving a greater reduction in microbial growth. The improved preservative efficacy of Formulation D compared to Formulation C is attributed to the higher STERC value of the PGE composition of the present invention (2115ms -1 vs. 1964ms -1 ).

[0112] [Table 7A]

[0113] [Table 7B]

[0114] [Table 7C]

[0115] [Table 7D]

[0116] Example 12. Preparation of Self-Dispersing Concentrates (SDCs). The SDCs shown in Table 8 were prepared by combining and mixing the specified amounts of each component at 40° C.-45° C. until a uniform, homogeneous composition was obtained.

[0117] [Table 8]

[0118] Example 13: Preservative efficacy of micellar water formulations. The effect of various solubilizers on preservative efficacy was evaluated by preparing the micellar water formulations shown in Table 9 using the following procedure: Water (95% of the total water required for the batch) was charged to an appropriately sized beaker of known tare weight equipped with an overhead mechanical stirrer and anchor-type blade. Mixing was started at low to medium speed and the designated solubilizer was added to the water and mixed until completely dissolved. A multi-functional preservative system including glyceryl heptanoate (45%), caprylhydroxamic acid (10%) and propanediol (45%) was added to the batch and mixed until a uniformly mixed homogenous solution was formed. The pH of the formulation was adjusted to pH 6.6±0.2 using a 10% solution of citric acid. The remaining water was qs to 100% and the batch was mixed until uniform before being removed to an appropriate container for storage. For Formulation H, instead of adding the multi-function preservative system and solubilizer separately, the SCD of Example 12D was added to the batch. All micellar waters were clear, transparent solutions with turbidity values ​​below 4.0 NTU (Table 9).

[0119] [Table 9]

[0120] MCT was performed according to USP and PCPC official test methods to determine the preservative efficacy of the micellar water formulations. The results are shown in Tables 10A-10D. All formulations demonstrated good preservative efficacy, achieving a strong reduction of 5 microorganisms by day 14, and meeting the preservative efficacy success criteria according to the USP, PCPC, and EP official guidelines. Formulations F and G prepared with the PGE composition of the present invention (Example 2), and Formulation H prepared with the SDC of the present invention (Example 12A) both achieved a desirable combination of clarity and preservative efficacy, meeting the performance benchmark of Formulation E prepared with heptyl glucoside (Comparative Example 3).

[0121] [Table 10A]

[0122] [Table 10B]

[0123] [Table 10C]

[0124] [Table 10D]

[0125] Example 14. Preparation of O / W Microemulsions with SDC. To demonstrate the utility of the SDC of the present invention for the preparation of O / W microemulsion formulations, the formulations shown in Table 11 were prepared using the SDCs of Examples 12B, 12C, and 12D. The formulations were prepared at a 20 g scale by loading the appropriate amount of each component into a 20 mL scintillation vial and then mixing on a vortex mixer until uniform. The microemulsions were allowed to settle until no air bubbles were present in the solution, and then the turbidity was measured. The turbidity measurements were repeated after aging the microemulsions for 24 hours. Solutions with turbidity values ​​above 100 NTU at the time of preparation were considered to be thermodynamically unstable macroemulsions and were not further evaluated for turbidity at 24 hours.

[0126] [Table 11]

[0127] Turbidity data for formulations prepared using SDC as a microemulsifier are shown in Table 12. As the ratio of polyglyceryl-10 heptanoate:methylheptylglycerin increases from 5:1 (Example 12B) to 7:1 (Example 12D), the oil solubilization capacity of the system is observed to increase, as evidenced by the maximum amount of orange oil the system can solubilize before the turbidity exceeds 100 NTU. Although SDC in Example 12D (7:1) has the lowest oil solubilization capacity in the series, it produces O / W microemulsions with higher transparency, as indicated by the lower turbidity value at a given oil loading. The transparency data suggests that as the ratio of polyglyceryl-10 heptanoate:methylheptylglycerin decreases from 7:1 to 5:1, the droplet size of the microemulsion decreases, since smaller droplets scatter less light and result in lower turbidity values ​​at a given oil loading. Figures 2A and 2B show the turbidity of O / W microemulsions as a function of oil loading for three different SDCs both at the time of preparation of the microemulsions and after 24 hours. O / W microemulsion formulations with turbidity values ​​below 100 NTU were observed to remain stable and clear for several weeks after preparation, indicating the formation of a thermodynamically stable microemulsion system.

[0128] [Table 12]

[0129] Example 15. Comparison of the PGE composition of the present invention with a commercially available PGE composition for solubilizing a multifunctional preservative system

[0130] [Table 13]

[0131] Micellar water formulations containing either a PGE composition of the present invention (Example 2) or a commercially available PGE composition (Comparative Example 5) were prepared and evaluated for formulation turbidity. The data in Table 13 show that the PGE composition of the present invention having heptanoic acid (C7) ester functionality is superior to the caprylic acid (C8) and capric acid (C9) esters. 10 ) is demonstrated to result in dramatically clearer formulations with turbidity values ​​below 10 NTU compared to commercially available PGE compositions having a mixture of ester functional groups.

[0132] Example 16: Solubilization of essential oils in micellar water formulations Examples 16A-16H shown in Table 14 are micellar water formulations containing essential oils and ZeaStat™, a multifunctional preservative ingredient composed of caprylhydroxamic acid and propanediol. These examples demonstrate the utility of the PGE composition of the present invention of Example 2 for the preparation of clear micellar water formulations containing fragrant essential oils. In each case, a minimum of 5.00% of the PGE composition was required to microemulsify 0.5% of the essential oil in the formulation, as indicated by FT values ​​of less than 10 NTU. These formulations did not require the use of a mid-chain end diol in combination with the PGE composition to obtain formulations with turbidity values ​​of less than 10 NTU, thus demonstrating the ability of the PGE composition of the present invention to provide clear microemulsions of essential oils.

[0133] [Table 14]

[0134] The present invention is not limited in scope by the specific embodiments described herein. Indeed, various modifications of the invention in addition to those described herein will become apparent to those skilled in the art from the foregoing description and drawings. Such modifications are intended to be included within the scope of the appended claims.

[0135] It should be further understood that all values ​​are approximate and are provided for illustration purposes. All references cited and discussed herein are incorporated by reference in their entirety to the same extent as if each reference was individually incorporated by reference.

Claims

1. 1. A bio-based polyglyceryl ester microemulsifier composition comprising: One or more of formula (I): 【Chemical 1】 where PG is a polyglyceryl group containing more than 40% hexaglycerol and higher polyglycerols and less than 60% pentaglycerol and lower polyglycerols; R is a linear C6 alkyl group, RCO is derived from n-heptanoic acid, n=1 to 3, wherein substantially all of the carbon present in said one or more compounds of formula (I) is bio-based; having a degree of esterification (DE) of 6.5% or more and less than 15%; composition.

2. The composition of claim 1 , wherein n=1.

3. 3. The composition of claim 1 or 2, wherein PG is a polyglyceryl group comprising greater than 60% hexaglycerol and higher polyglycerols and less than 40% pentaglycerol and lower polyglycerols.

4. 3. The composition of claim 1 or 2 having a hydroxyl number greater than 500 mg KOH / g.

5. A composition described in claim 1 or 2 having an acid value of less than 2 mg KOH / g.

6. 2000 ms measured at critical micelle concentration (CMC) determined in deionized water at 22°C －１ 3. The composition of claim 1 or 2, having a surface tension equilibrium rate constant (STERC) of greater than 0.

1.

7. 3. The composition of claim 1 or 2, having an aqueous solution turbidity of less than 10 NTU measured at 5% in deionized water at 23±2°C.

8. A medium-chain terminal diol, a medium chain alkyl hydroxamic acid, a salt thereof, or a combination thereof; glycerin and / or C3-C4 diols, The composition of claim 1 or 2, further comprising at least one of:

9. The composition of claim 1 or 2, having a degree of esterification (DE) of 8% to 11%.

10. The composition of claim 1 or 2, consisting solely of a mixture comprising one or more compounds of formula (I), glycerin, and water.

11. A formulation comprising the composition of claim 1 or 2.

12. 12. The formulation of claim 11, which is or is a component of a personal care product, a home care product, a fabric care product, an institutional care product, a pharmaceutical product, an animal product, a food product, or an industrial product.

13. 12. The formulation of claim 11, which is or is a component of a personal care product selected from the group consisting of cosmetics, hair, nail, skin or fabric conditioners, shampoos, hair styling products, oils or waxes for grooming facial hair, permanent wave solutions, hair colorants, face or body washes, makeup remover products, cleansing lotions, emollient lotions or creams, bar soaps, liquid soaps, shaving creams, foams or gels, sunscreens, gels, lotions or creams for treating sunburn, deodorants or antiperspirants, moisturizing gels, shaving foams, face powders, foundations, lipsticks, blushers, eyeliners, wrinkle or anti-aging creams, eye shadows, eyebrow pencils, mascara, mouthwashes, toothpastes, oral care products, skin cleansing products, fabric cleaning products, dishwashing products, hair or fur cleaning products, and toners or moisturizers.

14. One or more of formula (I): 【Chemistry 2】 where PG is a polyglyceryl group containing more than 40% hexaglycerol and higher polyglycerols and less than 60% pentaglycerol and lower polyglycerols; R is a linear C6 alkyl group, RCO is derived from n-heptanoic acid, n=1 to 3, a 30% to 90% bio-based polyglyceryl ester microemulsifier that is a mixture comprising a compound of Formula (I), wherein substantially all of the carbon present in the one or more compounds of Formula (I) is bio-based, and having a degree of esterification (DE) of 6.5% or greater and less than 15%; 5% to 50% of a mid-chain end diol; 0.1% to 20% of a medium chain alkyl hydroxamic acid, a salt thereof, or a combination thereof; 1% to 75% glycerin and / or C ３ ~C ４ Diol and A microemulsifying system comprising:

15. 15. The microemulsification system of claim 14, wherein the mid-chain terminal diol is selected from the group consisting of alkanediols, glyceryl ethers, and glyceryl esters.

16. The mid-chain terminal diol is C ５ ~C １０ 1,2-alkanediol, C ６ ~C １２ Alkyl glyceryl ether, C ６ ~C １２ 16. The microemulsifying system of claim 15, selected from acyl monoglyceryl monoesters and combinations thereof.

17. C ６ ~C １２ 17. The microemulsifying system according to any one of claims 14 to 16, comprising a medium chain alkylhydroxamic acid selected from alkylhydroxamic acids, salts thereof and combinations thereof.

18. C selected from propanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, methylpropanediol, and combinations thereof ３ ~C ４ The microemulsion system according to any one of claims 14 to 16, comprising a diol.

19. A microemulsification system described in any one of claims 14 to 16, having an aqueous solution turbidity value of less than 10 NTU.

20. The microemulsification system according to any one of claims 14 to 16, wherein the ratio of polyglyceryl ester to mid-chain terminal diol is 1:1 to 10:1, preferably 2:1 to 8:1, more preferably 2:1 to 7:

1.

21. 1. A method for preparing a bio-based polyglyceryl ester microemulsifier composition, comprising: One or more of formula (I): 【Chemistry 3】 where PG is a polyglyceryl group containing more than 40% hexaglycerol and higher polyglycerols and less than 60% pentaglycerol and lower polyglycerols; R is a linear C6 alkyl group, RCO is derived from n-heptanoic acid, n=1 to 3, wherein substantially all of the carbon present in said one or more compounds of formula (I) is bio-based; The composition has a degree of esterification (DE) of greater than or equal to 6.5% and less than 15%.

22. 22. The method of claim 21, further comprising combining the bio-based polyglyceryl ester microemulsifier composition with a mid-chain end diol.

23. 23. The method of claim 22, wherein the combination comprises 30% to 90% of the bio-based polyglyceryl ester microemulsifier composition and 5% to 50% of a mid-chain end diol.

24. The combination is a medium chain alkyl hydroxamic acid, a salt thereof, or a combination thereof; Glycerin and / or C ３ ~C ４ diol, 24. The method of claim 22 or 23, further comprising at least one of:

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