Bio-based glyceryl heptanoate ester composition, method for preparing and using the same

Abstract

The present invention relates to a bio-based glyceryl heptanoate composition, preferably a glyceryl monoheptanoate composition, a method for preparing the same, and uses thereof, including the use of the composition of the present invention in formulations for application as cosmetics and other personal care. The bio-based monoglyceryl monoester (MGME) composition is of the following chemical formula I, i.e. [Chemical Formula I] [R1, R2 and R3 are independently -H or -C(O)-C6alkyl] The composition comprises a mixture containing one or more of the compounds. The composition comprises glyceryl monoheptanoate in an amount of about 60 wt% or more and less than about 98 wt%. The carbons present in one or more of the compounds of Formula I are bio-based. The ET50 value of the composition exceeds 24 hours when the composition is tested as a 1% solution in water according to the EpiDerm skin irritation test (OECD 439). The invention also relates to a microbial growth inhibitory concentrate (MBC) comprising the disclosed composition.

Description

Technology Field

[0001] Cross-reference regarding related applications

[0002] This application claims priority to U.S. provisional application No. 63 / 109,657 (filed November 4, 2020), which is incorporated herein by reference.

[0003] field

[0004] The present invention relates to a bio-based glyceryl heptanoate composition and a method for preparing the same, and uses including the use of the composition in formulations for application as cosmetics and other personal care. Background Technology

[0005] Monoglyceryl monoesters (MGMEs), also known as monoglycerides, are compounds widely used across various fields of the cosmetics, pharmaceutical, and food industries due to their inherent properties, such as being non-toxic, non-ionic, and amphiphilic compounds [e.g., literature (Kabara, JJ Chemistry and Biology of Monoglycerides in Cosmetic Formulations, Ch. 12 in Glycerine: A Key Cosmetic Ingredient [See also Jungermann, E. and Sonntag, NOV, eds.; Marcel Dekker, Inc.: New York, 1991, pp 311-344) as well as the literature (Johnson, Jr. W. Int. J. Tox., 2004, 23(Suppl. 2), 55-94). It has been reported that MGME acts as a surfactant, emulsifier, skin softener, skin conditioning agent, and deodorant in cosmetic and personal care formulations.

[0006] MGMEs possessing acyl chains with 8 to 14 carbon atoms are particularly interesting and useful. These MGMEs are typically viscous fluids at room temperature or ductile solids with low melting points. Due to the inherent amphiphilic properties of MGMEs, they can be dispersed in aqueous media, where they exhibit self-assembly and surface activity at the interface. These amphiphilic materials are also highly suitable for interactions with amphiphilic substances, such as lipid bilayers that form the cell membranes of microorganisms. Consequently, C8–C 14 MGME has been confirmed to be used as an effective microbiostatic agent due to its inherent ability to increase cell membrane permeability, thereby disrupting cellular homeostasis and inhibiting microbial growth [e.g., literature (Kabara, J. Fatty Acids and Esters as Multifunctional Components, Ch. 5 in Preservative-Free and Self-Preserving Cosmetics and Drugs: Principles and Practice [See , Kabara and Orth, eds., Marcel Dekker, Inc.: New York, 1997, 119-138). The most common MGMEs for this purpose are linear C8~C with an even number of carbon atoms. 14 MGME, w-unsaturated C possessing an acyl chain (i.e., capryloyl, caproyl, lauroyl, or myristoyl) 11 It is MGME or a mixture thereof containing a chain (i.e., 10-undecenoyl).

[0007] C8~ C 14 The same properties that make MGME an effective surfactant, emulsifier, and microbial growth inhibitor are also these C8~C 14 MGME is made into an effective transdermal penetration enhancer, and the reason is C8~C 14This is because MGME interacts with the skin barrier lipid bilayer of the stratum corneum to partially fluidize it, thereby increasing the permeability of the skin barrier lipid bilayer to topically applied compounds. Therefore, C8-C 14 MGME is widely used as a transdermal absorption enhancer for the transdermal delivery of pharmaceutically active ingredients. However, C8~ C 14 The ability of MGME to modulate the permeability of the skin barrier can also cause skin irritation due to the permeability of MGME itself or the unintended enhancement of permeability of other topically applied ingredients, such as perfumes, sunscreens, and preservatives. Therefore, C8~C 14 There is a need to develop an MGME composition that retains the functional utility of MGME while reducing unwanted side effects, such as irritation.

[0008] C8~ C 14 Another desired mode of MGME is this C8~ C 14 C8~C, which makes MGME particularly useful for formulating products with reduced environmental impact. 14 It is related to the sustainability of MGME itself. In addition to being non-toxic and Generally Regarded As Safe (GRAS) compounds, these ingredients are easily biodegradable and derived from renewable plant-based feedstocks (i.e., C8–C 14It is considered highly sustainable because it can be synthesized from fatty acids and glycerin. Such fatty acids and glycerin can be derived from any plant-derived triglyceride oil (except coconut oil and palm kernel oil, which are the most common sources due to the high content of these acyls in their chain length). However, recent controversies surrounding the negative environmental and social impacts of oil palm cultivation and palm / palm kernel oil production have made these sources of fatty acids and glycerin less desirable from a commercial perspective, and market demand for ingredients based on alternative sources of these plant-derived feedstocks continues to increase.

[0009] Conventional ester (exchange) processes involving the reaction of glycerol with fatty acids or lipid esters to produce MGME result in an equilibrium distribution of glycerol ("free glycerin") and monoacyl, diacyl, and triacyl esters of glycerol. For example, refer to the literature of Kabara. For instance, if 1 mole of glycerol reacts with 1 molar equivalent of fatty acid with an average degree of glycerol esterification of 1.0 for monoesters, the resulting equilibrium mixture will contain approximately 40 mol% to 50 mol% monoester, 20 mol% to 30 mol% diester, 0 mol% to 10 mol% triester, and 20 mol% to 30 mol% free glycerol [Reference (Feuge, RO and Bailey, AE Modification of Vegetable Oils, VI. The Practical Preparation of Mono- and Diglycerides, Oil & Soap , 1946 , 23[Refer to (8), 259-264). An MGME product containing more than 80% monoester is typically obtained by fractionating the initial equilibrium reaction product mixture to remove free glycerin, diesters, and triesters, thereby providing a more concentrated monoester product. This fractionation is typically achieved through energy-intensive methods such as molecular distillation or short-path distillation to separate the components. If other separation methods are used before distillation to remove free glycerin, such as fractional distillation after extraction ("washing"), the monoester fraction can be isolated from the heavier diester and triester components.

[0010] What is needed at this point is an MGME composition produced from sustainable feedstocks and an improved method for producing and purifying it. means of solving the problem

[0011] The present invention is the following chemical formula I, i.e.

[0012] [Chemical Formula I]

[0013]

[0014] [In the formula, R1, R2 and R3 are independently -H or -C(O)-C6alkyl (e.g., n-heptanoyl)]

[0015] The present invention relates to a bio-based monoglyceryl monoester (MGME) composition comprising a mixture containing one or more compounds, wherein the composition comprises about 60 wt% or more to about 98 wt% or less of glyceryl monoheptanoate, and the carbon present in one or more of the compounds of Formula I is bio-based.

[0016] A composition such as that in the preceding paragraph contains glyceryl diheptanoate, glyceryl triheptanoate, or a combination thereof at a concentration of about 2 wt% to about 40 wt%.

[0017] It contains less than about 30% glycerol, as in any one or more of the preceding paragraphs.

[0018] The composition as in any one or more of the preceding paragraphs has an average degree of glyceryl esterification of about 0.7 to about 1.4.

[0019] At least 95% of the -C(O)-C6 alkyl groups present in a composition such as in any one or more of the preceding paragraphs are n-heptanoyl.

[0020] ET of a composition such as in any one or more of the preceding paragraphs 50 The value exceeds 24 hours when this composition is tested as a 1% solution in water according to the EpiDerm skin irritation test (OECD 439).

[0021] The MTT cell viability value after approximately 24 hours of the composition as in any one or more of the preceding paragraphs exceeds 50% when the composition is tested as a 1% solution in water according to the EpiDerm skin irritation test (OECD 439).

[0022] A composition such as that in any one or more of the preceding paragraphs further comprises a booster selected from the group consisting of one or more polyols, one or more glyceryl ethers, one or more chelating agents and combinations thereof.

[0023] A formulation containing a composition such as that in any one or more of the preceding paragraphs is preserved against microbial contamination for a period of at least 12 months, or at least 18 months, or at least 24 months.

[0024] A formulation comprising a composition such as that in any one or more of the preceding paragraphs is C8 to C 14Compared to a reference formulation containing the MGME composition at the same concentration by weight, it has equivalent or superior preservation ability against microbial contamination, because a C7 bio-based monoglyceryl monoester as described herein is present in the formulation.

[0025] The turbidity value of a formulation containing a composition as in any one or more of the preceding paragraphs is less than about 100 NTU.

[0026] A formulation comprising a composition such as that in any one or more of the preceding paragraphs comprises water, surfactants, e.g., anionic, cationic, nonionic, and amphoteric surfactants, emulsifiers, skin softeners, moisturizers, conditioning agents for hair, skin, or nails, chelating agents, active agents, bleaches or whitening agents, additional pH adjusters, perfumes, colorants, exfoliants, antioxidants, plant ingredients, plant extracts, mica, smectite, thickeners, rheology modifiers, cannabinoids, oils, dyes, waxes, amino acids, nucleic acids, vitamins, hydrolyzed proteins and their derivatives, glycerin and its derivatives, enzymes, anti-inflammatory agents and other medicines, biocides, antifungals, preservatives, antioxidants, UV absorbers, dyes and pigments, preservatives, UV blocking agents, antiperspirants, oxidizing agents, pH balancing agents, moisturizers, peptides It further comprises at least one component selected from the group consisting of derivatives thereof, anti-aging active substances, hair growth promoters, cellulite-preventing active substances, and combinations thereof.

[0027] A method for preserving a formulation against microbial contamination includes the step of adding a sufficient amount of a composition such as in any one or more of the preceding paragraphs.

[0028] The microbial growth inhibitory concentrate (MBC) comprises a bio-based monoglyceryl monoester composition such as in any one or more of the preceding paragraphs, and at least one of glycerin and C3-C4 diol.

[0029] Microbial growth inhibitor concentrates such as those in any one or more of the preceding paragraphs contain a bio-based monoglyceryl monoester composition in an amount of about 30 wt% to about 85 wt%.

[0030] Microbial growth inhibitor concentrates such as those in any one or more of the preceding paragraphs contain glycerin, C3-C4 diol, or a combination thereof in an amount of about 1 wt% to about 70 wt%.

[0031] A composition, formulation, or microbial growth inhibitory concentrate such as in any one or more of the preceding paragraphs further comprises one or more polyols selected from the group consisting of glycerin, propanediol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-hexanediol, 1,2-heptanediol, 2,3-octanediol, caprylyl glycol, decylene glycol, sorbitol, sorbitan, and combinations thereof.

[0032] A composition, formulation, or microbial growth inhibitor concentrate such as in any one or more of the preceding paragraphs further comprises one or more glyceryl ethers selected from the group consisting of hexylglycerin, cyclohexylglycerin, heptylglycerin, caprylylglyceryl ether, methylheptylglycerin, ethylhexylglycerin, and combinations thereof.

[0033] A composition, formulation, or microbial growth inhibitor concentrate such as in any one or more of the preceding paragraphs further comprises one or more chelating agents selected from the group consisting of heptanohydroxylase and its salt, caprylohydroxylase (caprylhydroxylase) and its salt, pelagohydroxylase and its salt, citric acid and its salt, caprohydroxylase and its salt, tetrasodium glutamate diacetate, phytic acid and its salt, gluconic acid and its salt, galacturonic acid and its salt, galactaric acid and its salt, and combinations thereof.

[0034] The present invention relates to a method for preserving a formulated product without compromising performance, particularly the efficacy of inhibiting microbial growth, and C8~C 14 Provides a sustainable, plant-based MGME composition that overcomes the problem of irritation associated with MGME.

[0035] Surprisingly, when a C7 acyl group with an odd number of carbons is selected, the cytotoxicity and irritation potential of MGME are dramatically reduced while maintaining its microbial growth inhibitory efficacy. Furthermore, it was confirmed that if the MGME composition contains some or all of the diester and triester components, the cytotoxicity and irritation potential of the C7MGME composition are further reduced without diminishing its microbial growth inhibitory efficacy. The C7MGME composition of the present invention also provides transparency and translucency of transparent formulations, unlike traditional C8~C 14 It was confirmed that it improves the transparency and translucency of formulations prepared with MGME.

[0036] In order for the sustainability benefit of the C7MGME composition to be guaranteed, the C7 acid, i.e., n-heptanoic acid, must be derived from a plant-based feedstock; in other words, the C7 acid, i.e., n-heptanoic acid, must be bio-based n-heptanoic acid or "bio-heptanoic acid." Bio-heptanoic acid is ricinoleic acid, i.e., ricinus communis ( Ricinus communisUnsaturated C derived from the saponification of castor oil obtained from the fruit of ) 18 It is derived from the thermal decomposition of hydroxy fatty acids. The thermal decomposition of ricinoleic acid or its corresponding methyl ester, methyl ricinoleate, produces heptaldehyde and either undecylenic acid or methylundecylenate. Bioheptaldehyde is readily converted to bioheptanoic acid through catalytic oxidation, the resulting bioheptanoic acid having a linear saturated C7 acid with a purity of over 99% (and is commercially available, for example, by Arkema under the trade name Oleris® n-heptanoic acid).

[0037] It is particularly important to use bioheptanoic acid because it does not contain branched C7 acids or unsaturated impurities. For example, n-heptanoic acid obtained from petrochemical feedstocks via the oxo method may contain 3.5 wt% or less of 2-methylhexanoic acid (Oxea n-heptanoic acid sales manual). When petrochemical-based heptanoic acid is used to produce a C7MGME composition, branched and / or unsaturated alkanic acid impurities are undesirable because residual unreacted branched and / or unsaturated fatty acids in the resulting C7MGME composition can impart an unwanted odor. Brief explanation of the drawing

[0038] FIG. 1 shows EpiDerm as a function of exposure time and 1% solution of the MGME composition of Examples 2 and 3 and Comparative Examples 2 and 3. TM A diagram showing cell viability data in a graph is provided. Specific details for implementing the invention

[0039] First of all, prior to the description of the compounds, compositions, and methods, it will be understood that the invention described and claimed herein is not limited to the specific methods, compositions, or methodologies described and may vary. It will also be understood that the terms used in the description of the invention are intended only to describe specific versions or embodiments and are not intended to limit the scope of the invention, which is limited only by the claims of the appended claims. Unless otherwise defined, all scientific and technical terms used herein have the same meaning as commonly understood by those skilled in the art. Although any methods and materials similar or equivalent to the methods and materials described herein may be used to practice or test embodiments of the invention, preferred methods, devices, and materials are described below. All patent applications and other publications cited or mentioned herein are incorporated by reference in their entirety. Nothing in this application should be construed as an admission that the invention as listed in the claims of the appended claims has no right to precede these disclosure(s) by prior art.

[0040] As used herein and in the appended claims, the use of “a,” “an,” and / or “the” is intended to include both singular and plural forms (e.g., “one or more”) unless the context clearly indicates otherwise. That is, for example, a reference to “cell” is to refer to one or more cells and their equivalents known to those skilled in the art.

[0041] Unless otherwise specified, "%" may refer to weight %, volume %, or unit volume weight %, and the associated units will be obvious to those skilled in the art based on the context.

[0042] "Acceptable as a cosmetic" means that it does not provide excessive toxicity, incompatibility, instability, irritation, and allergic reactions, and is suitable for use in contact with skin, preferably human skin.

[0043] Where applicable, chemical substances are specified by their own INCI names in accordance with the guidelines of the International Nomenclature of Cosmetic Ingredients. Additional information, including suppliers and product names, is available in the International Cosmetic Ingredient Dictionary and Handbooks published by the Personal Care Products Council (Washington, DC) or accessible online via the Personal Care Products Council Online INFOBASE (http: / / online.personalcarecouncil.org). International Cosmetic Ingredient Dictionary and Handbook It can be examined in a suitable INCI paper of the 16th edition.

[0044] Among a number of embodiments, the present invention comprises a bio-based C7MGME composition. A bio-based or "natural" feedstock must be used to produce the bio-based MGME composition. An example of a bio-based MGME composition is one produced from a bio-derived feedstock (e.g., one obtained from current and sustainable agricultural activities, e.g., fermentation, algae, plants, or vegetables; e.g., preferably derived from vegetable sources using non-genetically modified organisms or biomass), and is not derived from petrochemicals (e.g., not derived from fossil sources, e.g., petroleum, natural gas, or coal, but from tree and plant farms sustainably practiced in the 21st century). Such feedstocks are referred to herein as "natural" and "renewable" (i.e., "sustainable"), and in the art as non-petroleum-derived feedstocks. Furthermore, such materials are produced by "new" carbon and are not produced from 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-petrochemical derived products or “bio” products. The term “sustainable” as used herein refers to cases where starting materials, reaction products, compositions, and / or formulations are derived from renewable sources. Thus, the term “sustainable” is in contrast to the term “unsustainable,” which refers to cases where any starting materials, reaction products, compositions, and / or formulations contain carbon derived from limited natural resources, such as fossil fuels (e.g., petroleum or coal) and natural gas. Therefore, natural or bio products are not derived from petrochemicals and / or are not derived from petrochemicals but are rather produced from sustainable and renewable resources.True natural products (biocompounds) are generated using biomass (materials stored through the carbon cycle in, for example, living plants and roots, or released through the respiration or excretion of animals, or released through decomposition). Fossil fuels (carbon sources derived from petrochemicals) are generated when carbon breaks down or decays under pressure over millions of years. The biocompounds of this invention are intended to include materials derived from carbon in currently existing / currently existing (or recently existing / currently existing) sustainable plant sources / biomass, and expressly exclude materials derived from fossil fuels.

[0045] The compositions of the present invention can be identified from and distinguished from the compositions of the prior art based on their bio-based carbon content. In some embodiments, the bio-based carbon content may be measured by radiocarbon dating to determine the relative age of a material composed of organic matter (i.e., carbon-containing material). Radiocarbon is carbon-14 (i.e., " 14 It is an unstable isotope of carbon known as "C". 14 C is an unstable isotope that emits radioactive energy in the form of beta particles at a very consistent rate (i.e., the half-life of radiocarbon is 5,730 years), and ultimately the more stable nitrogen-14 ( 14 It decays into N). Since petroleum-based (i.e. derived from petrochemicals) feedstocks originate from plants and animals buried millions of years ago, the radiocarbon of these feedstocks (i.e.) 14 C) was lost due to radioactive decay. ASTM international standards provide test standards using radiocarbon to confirm the authenticity of "bio-based compounds" (which can be found in ASTM D6866-16). This standard distinguishes carbon derived from fossil fuels or petroleum and petrochemicals (i.e., "old carbon") from newer carbon. Among recent, or current biomass14 Since the amount of C is known, the percentage of carbon derived from renewable sources can be estimated from the total organic carbon analysis, which provides the data necessary to determine whether a compound is truly derived from a “natural” and / or “sustainable” (“renewable”) feedstock source or whether a compound is derived inversely from a compound separated “old” (i.e., derived from petrochemicals or petroleum-based sources). The use of petroleum-based (also referred to as “fossil-based”) feedstocks is generally accepted as unsustainable; in other words, old carbon is an unsustainable feedstock, not a renewable one, and furthermore, is not considered “natural” and / or “sustainable” in the field.

[0046] In some embodiments, the composition of the present invention comprises bio-based carbon as almost all of the carbon present in the mixture of compounds, which may refer to a bio-based carbon content of at least 90%, at least 95%, or at least 98%. In some embodiments, the composition of the present invention comprises an all-bio-based MGME and an all-bio-based reactant, which is determined to have a bio-based carbon content of at least about 98%, at least about 99%, at least about 99.5%, or about 100%.

[0047] In some embodiments, the composition of the present invention is 14 C as determined according to ASTM D6866, in modern 1-day standby 14 C content (present-day atmospheric 14 It contains an amount nearly equal to C content. In some embodiments, the composition of the present invention 14 C in the modern atmosphere as established according to ASTM D6866 14It contains an amount of at least about 90%, at least about 95%, at least about 98%, or at least about 99% of the C content. In some embodiments, the composition of the present invention is, as determined according to ASTM D6866, 10 present in the composition 12 At least about 0.8 per carbon atom 14 C atoms, 10 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 per carbon atom 14 It contains C atoms.

[0048] As a method to distinguish the authenticity of bio-based feedstocks, a more recent method uses mass spectrometry, and 12 C / 13 C ratio and / or 1 H / 2 A method is used to analyze stable isotopes in detail by evaluating the H ratio. This test is available through several analytical service testing facilities and provides more rapid, cost-effective, and detailed information compared to radiocarbon testing methods. Stable isotope analysis is based on the principle of the dynamic isotope effect. This dynamic isotope effect is widely known to those skilled in the art of chemical mechanics. In the broadest sense, a middle isotope of a specific element is an isotope lighter than that middle isotope of this element (e.g., 13 Contrasting with C 12 It reacts more slowly compared to C). Therefore, as plants incorporate carbon dioxide into their own biomass 12 C 13 The proportion of C will vary depending on the type of chemicals used by the plant to produce biomass (e.g., whether the plant follows the C3 or C4 photosynthetic pathway). This is usually δ 13 C / 12 C ratio (i.e., δ)13 It is reported as C) and is referred to as the current carbon dioxide standard. Furthermore, when water is incorporated into neobiomass, a similar dynamic isotope effect is observed, which is δ 2 H / 1 H ratio (i.e., δ 2 It is measured as H). δ 13 C ratio and δ 2 When combinations of H ratios are used, one thing familiar to the relevant field is that it is possible to easily distinguish and certify the nature of the feedstock used to manufacture the product under analysis (i.e., whether it originated from petrochemicals or from algae, plants, or similar bio-sources that were alive until recently or are currently alive).

[0049] Bio-based monoglyceryl monoester composition. The following chemical formula I, that is

[0050] [Chemical Formula I]

[0051]

[0052] [In the formula, R1, R2 and R3 are independently -H or -C(O)-C6alkyl (e.g., n-heptanoyl)]

[0053] A bio-based monoglyceryl monoester (MGME) composition containing the compound can be prepared, for example, by the reaction of bio-based glycerin and bio-based n-heptanoic acid (bio-heptanoic acid).

[0054] In some embodiments, the C7MGME composition of the present invention may be synthesized according to any of the methods known to those skilled in the art of glyceryl ester synthesis [e.g., refer to DE 102008013023 A1, which describes the synthesis of glyceryl esters of octanoic acid]. A preferred route for the C7MGME composition of the present invention is a route in which bio-based glycerin is directly esterified with bioheptanoic acid and water, a coagulation byproduct, is removed to induce termination of the esterification reaction. Maintaining the molar ratio of bioheptanoic acid to glycerin to 1 or less (≤1) is advantageous for the formation of monoester products and limits the formation of diester and triester byproducts in the resulting mixture; therefore, bioheptanoic acid is a limiting reagent in the synthesis. The ratio of bioheptanoic acid to glycerin is preferably about 0.4 to about 1.0, and more preferably about 0.4 to about 0.6. In some embodiments, the ratio of bioheptanoic acid to glycerin is about 0.5.

[0055] The reaction is carried out by filling a reaction vessel with glycerin and bioheptanoic acid and heating it under an inert atmosphere, such as nitrogen, with appropriate stirring to ensure thorough mixing of the reactants. The reaction is carried out at a temperature of about 75°C to about 300°C, preferably about 150°C to about 250°C, and most preferably about 175°C to about 225°C. Once the desired reaction temperature is reached, the reaction may be carried out under atmospheric pressure with inert gas spraying or under vacuum, thereby inducing conversion to esters through the removal of condensation byproducts, namely water. If desired, an esterification catalyst may be used to improve reaction kinetics and shorten reaction time. Examples of such catalysts include acid catalysts, such as methanesulfonic acid, ethanesulfonic acid, and p - Toluenesulfonic acid, etc., and transition metal catalysts, e.g., tetrasulfonic acid n- Includes butyl titanate and tin-containing octanoate, etc. In a preferred embodiment, the reaction proceeds without the aid of a catalyst.

[0056] In some embodiments, C1-C4 esters of bioheptanoic acid, such as methyl heptanoate or ethyl heptanoate, may be used as starting materials. In these embodiments, the reaction proceeds as an ester exchange reaction between the heptanoate ester and bio-based glycerin, in which case the reaction is terminated as the reaction proceeds accompanied by the removal of C1-C4 alcohols, such as methanol or ethanol, which are coagulation byproducts. Another ester exchange route for the C7MGME composition of the present invention is the ester exchange of a bio-based glyceryl diheptanoate ester and / or triheptanoate ester, i.e., a glyceryl ester composition having an average degree of esterification of 2.0 or higher, in which case the bio-based glycerin reduces the average degree of glyceryl esterification to less than 1.5, preferably to about 0.7 to about 1.4. For example, bio-based glyceryl triheptanoate, such as triheptanoin, can be transesterified with bio-based glycerin, and as a result, a composition is produced that includes a distribution of free glycerin as well as monoester, diester, and triester byproducts.

[0057] The unrefined reaction product resulting from the condensation of bioheptanoic acid (or a simple ester thereof) and bio-based glycerin will comprise a mixture of free glycerin, glyceryl monoheptanoate, glyceryl diheptanoate, and glyceryl triheptanoate. Any glyceryl ester purification method known to those skilled in the art may be used to further refine the unrefined reaction product to obtain the C7MGME composition of the present invention. For example, the unrefined reaction product may be subjected to steam stripping under vacuum, thereby removing unreacted bioheptanoic acid or volatile byproducts that may have imparted an unwanted odor to the composition. The unrefined reaction product may also be extracted with a solvent, i.e., washed, to remove any fraction of the reaction product. For example, water extraction may be used to remove unreacted glycerin from the C7MGME composition. In some embodiments, ionic salts, such as sodium chloride, potassium chloride, and calcium chloride, etc., may be added to the aqueous extraction phase to promote phase separation of the glycine-concentrated aqueous layer and the ester-concentrated organic layer. The extraction and separation processes may be enhanced through heating, mixing, centrifugation, etc. The organic layer may be dried by removing all residual water by performing heat, vacuum, and / or inert gas spraying after the ester-concentrated organic layer is separated from the glycerin-concentrated aqueous phase.

[0058] The C7MGME composition of the present invention may be further fractionated to increase the monoester content in the composition. Techniques such as molecular distillation, e.g., single-row distillation, wiped film distillation, etc., may be used to remove unreacted glycerin and to separate monoesters from heavier diester and tryster byproducts. The C7MGME composition may also be refined through treatment with processing aids, such as activated carbon and diatomite, and filtration to improve properties such as color and odor.

[0059] Another route for glyceryl esters that can be used to synthesize the C7MGME composition of the present invention is to react bioheptanoic acid with glycidol derived from bio-based glycerin. In this reaction, nucleotropic attack on the epoxide ring in glycidol causes ring opening, and as a result, 2,3-dihydroxypropyl ester of heptanoic acid, namely glyceryl monoheptanoate, is produced in very high yield, while corresponding diester and triester byproducts are produced in low yield.

[0060] The bio-based C7MGME composition contains glyceryl monoheptanoate in a range of about 60 wt% to about 98 wt%, e.g., 65 wt% to 95 wt%, 65 wt% to 85 wt%, or 65 wt% to 75 wt%. In terms of the upper limit, the amount of glyceryl monoheptanoate may be less than 98 wt%, e.g., less than 95 wt%, less than 85 wt%, or less than 75 wt%. In terms of the lower limit, the amount of glyceryl monoheptanoate may be 60 wt% or more, e.g., 65 wt% or more.

[0061] In some embodiments, the composition of the present invention comprises a limited amount of glyceryl diheptanoate and / or glyceryl triheptanoate. The bio-based C7MGME composition comprises glyceryl diheptanoate in a range of about 1 wt% to about 40 wt%, e.g., 1 wt% to 30 wt%, 2 wt% to 30 wt%, 2.5 wt% to 30 wt%, or 5 wt% to 25 wt%. In terms of the upper limit, the amount of glyceryl diheptanoate may be less than 40 wt%, e.g., less than 35 wt%, less than 30 wt%, or less than 25 wt%. In terms of the lower limit, the amount of glyceryl diheptanoate may be 1 wt% or more, e.g., 2 wt% or more, 2.5 wt% or more, or 5 wt% or more.

[0062] The bio-based C7MGME composition contains glyceryl triheptanoate in a range of about 0 wt% to about 10 wt%, e.g., 0 wt% to 6 wt%, 0 wt% to 4 wt%, or 1 wt% to 4 wt%. In terms of the upper limit, the amount of glyceryl triheptanoate may be less than 10 wt%, e.g., less than 6 wt%, less than 4 wt%, or less than 2 wt%. In terms of the lower limit, the amount of glyceryl triheptanoate may be 0 wt% or more, e.g., 1 wt% or more.

[0063] The bio-based C7MGME composition comprises glyceryl diheptanoate and glyceryl triheptanoate in a total combined amount in the range of about 2 wt% to about 40 wt%, e.g., 2 wt% to 35 wt%, 2 wt% to 30 wt%, or 2 wt% to 25 wt%. In terms of the upper limit, the total combined amount of glyceryl diheptanoate and glyceryl triheptanoate may be less than 40 wt%, e.g., less than 35 wt%, less than 30 wt%, or less than 25 wt%. In terms of the lower limit, the total combined amount of glyceryl diheptanoate and glyceryl triheptanoate may be 2 wt% or more, e.g., 3 wt% or more, 4 wt% or more, or 5 wt% or more.

[0064] The bio-based C7MGME composition comprises glycerol in the range of about 0 wt% to about 30 wt%, e.g., 1 wt% to 30 wt%, 2 wt% to 20 wt%, 2 wt% to 15 wt%, or 2 wt% to 10 wt%. In terms of the upper limit, the amount of glycerol may be less than 30 wt%, e.g., less than 20 wt%, less than 15 wt%, or less than 10 wt%. In terms of the lower limit, the amount of glycerol may be 0 wt% or more, e.g., 1 wt% or more, or 2 wt% or more. In some embodiments, the composition of the present invention substantially does not contain glycerol (i.e., contains less than about 2 wt%, preferably less than about 1 wt%, or most preferably less than 0.5 wt% of glycerol in the composition).

[0065] The degree of esterification (DE) of the MGME composition is referred to as the average glyceryl DE by those skilled in the art, where the average glyceryl DE is the ratio of (number of glyceryl ester groups in the composition) to (number of glyceryl ester groups + number of non-esterified hydroxyl groups) x 3, where "3" is the total number of hydroxyl groups on the glycerol molecule that can be used for esterification. Therefore, the DE of non-esterified glycerol is 0, and the DE of glyceryl triester (triglyceride) is 3. The average glyceryl DE can also be calculated based on the weighted average of glycerol, glyceryl monoester (monoglyceride), glyceryl diester (diglyceride), and glyceryl triester (triglyceride) present in the MGME composition. The composition of the present invention may be modified to have a desired average glyceryl DE suitable for any particular formulation or application. In some embodiments, the average degree of glyceryl esterification of the composition of the present invention is about 0.7 to about 1.4, about 0.8 to about 1.4, about 0.9 to about 1.4, about 1.0 to about 1.4, about 0.9 to about 1.3, or about 1.0 to about 1.3. With respect to the upper limit, the average degree of glyceryl esterification may be less than 1.4, e.g., less than 1.3, less than 1.2, or less than 1.1. With respect to the lower limit, the average degree of glyceryl esterification may be 0.7 or more, e.g., 0.8 or more, 0.9 or more, or 1.0 or more.

[0066] In some embodiments, the alkyl portions of the glyceryl ester acyl side chains R1, R2, and R3 present in the composition of the present invention are preferably linear. In some embodiments, at least 95% of the alkyl portions of the glyceryl ester acyl side chains R1, R2, and R3 present in the composition of the present invention are linear, at least 98% are linear, or at least 99% are linear. In some embodiments, the glyceryl ester side chains present in the composition of the present invention do not substantially have branched R1, R2, or R3 groups.

[0067] The composition of the present invention has optical properties, odor, and skin sensitivity that are superior to other compositions, specifically other glyceryl ester compositions, such as optical properties, odor, and skin sensitivity.

[0068] Formulation.The compositions of the present invention may be incorporated into a number of finished consumer and industrial formulations, such as personal care, home and facility care, pharmaceutical, veterinary care, oral care, textile care, metalworking, food processing, and industrial formulations. In one embodiment of the present invention, a bio-based C7MGME composition or a composition comprising a bio-based C7MGME composition is incorporated into a formulation, such as a personal care formulation. An embodiment includes incorporating into the formulation together with at least one other ingredient. Suitable formulations and additional ingredients known to those skilled in the art are listed in the 16th edition of the International Dictionary of Cosmetic Ingredients and Handbook, published by the American Cosmetic Council (Washington, DC) or accessible online via the American Cosmetic Council Online INFOBASE (http: / / online.personalcarecouncil.org). Formulations and ingredients permitted for use in formulations for human use include water, surfactants, e.g., anionic, cationic, nonionic, and amphoteric surfactants, emulsifiers, skin softeners, moisturizers, conditioning agents for hair, skin, or nails, chelating agents, active agents, bleaches or whitening agents, pH adjusters, perfumes, colorants, exfoliants, antioxidants, plant ingredients, e.g., plant extracts, mica, smectite, thickeners, rheology modifiers, cannabinoids, oils, dyes, waxes, amino acids, nucleic acids, vitamins, hydrolyzed proteins and their derivatives, glycerin and its derivatives, enzymes, anti-inflammatory agents and other medicinal agents, biocides, antifungals, preservatives, antioxidants, UV absorbers, dyes and pigments, preservatives, UV blocking agents, antiperspirants, oxidizing agents, pH balancers, moisturizers, peptides and their derivatives, anti-aging active substances, It may include hair growth promoters, cellulite-preventing active substances, etc., but is not limited thereto.

[0069] The formulation may comprise one or more bio-based C7MGME compositions. In a preferred embodiment, the type and amount of the bio-based C7MGME composition used in the embodiments of the formulation will impart an antimicrobial effect or a microbial growth inhibitory effect to the formulation to preserve the formulation against microbial contamination or to improve antimicrobial efficacy on surfaces, e.g., skin, hair, etc. Therefore, one embodiment comprises a formulation comprising at least one bio-based C7MGME composition and at least one other component. Another aspect of the present invention comprises a method for mitigating microbial contamination, comprising the step of combining an effective amount of at least one entirely bio-based C7MGME composition and at least one other component to form a microbial growth inhibitory concentrate (MBC), wherein the microbial growth inhibitory concentrate (MBC) may be added to the formulation to preserve the formulation against microbial contamination or to improve antimicrobial efficacy on surfaces. As an embodiment of the formulation and / or MBC, the following chemical formula I, i.e.

[0070] [Chemical Formula I]

[0071]

[0072] [In the formula, R1, R2 and R3 are independently -H or -C(O)-C6alkyl (e.g., n-heptanoyl)]

[0073] It includes a bio-based C7MGME composition containing a bio-based MGME.

[0074] The bio-based C7MGME composition of the present invention may be present in a formulation at a concentration of about 0.05% to about 10% based on the weight of the formulation. The bio-based C7MGME composition may be present in a formulation, such as a formulation for personal care products, in an amount ranging from about 0.05 wt% to about 10 wt%, for example, 0.1 wt% to 5 wt%, 0.25 wt% to 4 wt%, or 0.25 wt% to 2.5 wt%. In terms of the upper limit, the amount of the bio-based C7MGME composition may be less than 10 wt%, for example, less than 5 wt%, less than 4 wt%, or less than 2.5 wt%. In terms of the lower limit, the amount of the bio-based C7MGME composition may be 0.05 wt% or more, for example, 0.1 wt% or more, 0.2 wt% or more, or 0.25 wt% or more. In any embodiment, the composition of the present invention is present in the formulation at a concentration of about 0.25% to about 2.5% based on the weight of the formulation.

[0075] Embodiments of the formulation may take the form of, for example, a solution; a conditioner for hair, nails, skin, or fabric; a shampoo; a hairspray; an oil or wax for mustaches / beards; a hair styling product; a permanent wave solution; a hair dye; a glaze; a skin lotion; a face and body wash; a makeup remover; a cleansing lotion; a skin softening lotion / cream; a bar soap; a shaving cream; a sunscreen; a burn treatment; a deodorant; a moisturizing gel; shaving foam; a face powder; a foundation; a lipstick, a blush; an eyeliner; a cream for anti-wrinkle and anti-aging; an eyeshadow; an eyebrow pencil; a mascara; a mouthwash; a toothpaste; an oral care composition; a skin cleansing composition; a fabric washing composition; a dishwashing cleaning composition; a cleaning composition for hair or fur; a deodorant or antiperspirant; a color cosmetic; or a hair styling composition (though not limited thereto). Any embodiment may also include a micelle solution comprising water and at least one surfactant or oil-in-water emulsion, and may further include other forms suitable for delivery for use with the entirely bio-based C7MGME composition, such as an aqueous solution or dispersion, or a non-aqueous solution or a solid / semi-solid mixture.

[0076] In the formulation and method for reducing microbial contamination and exhibiting preservation ability against it as described herein, the pH value may be, for example, in the range of about 2 to about 10, for example, 3 to 9 or 4 to 8. With respect to the upper limit, the pH value may be less than 10, for example, less than 9, less than 7, less than 6.5, less than 6, or less than 5.6. With respect to the lower limit, the pH value may be 2 or more, for example, 3 or more, 4 or more, or 5 or more. In any embodiment, the pH value is preferably less than about 6.5, more preferably less than about 6, and most preferably less than about 5.6.

[0077] booster.In some embodiments, the formulations of the present invention may contain a booster, which is a compound that can be added to enhance the antimicrobial and / or preservative efficacy of a bio-based C7MGME composition by enhancing, for example, the bacteriostatic and / or fungistatic activity of the bio-based C7MGME. As boosters suitable for use with the compositions of the present invention, preferably all bio-based, they include, but are not limited to, polyols, glyceryl ethers, chelating agents, and combinations thereof.

[0078] Suitable polyols include C3 to C, which may include 1,2-alkanediols, 2,3-alkanediols, and mixtures thereof. 10 It includes, but is not limited to, diols. In some embodiments, one or more polyols are proximal C3 to C, also known as medium chain terminal diols. 10 It includes diols. Non-limiting representative examples of polyols for use with the composition of the present invention include glycerin, propanediol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-hexanediol, 1,2-heptanediol, 2,3-octanediol, caprylyl glycol, decylene glycol, sorbitol and sorbitan, etc., and mixtures thereof.

[0079] Suitable glyceryl ethers are typically C6 to C 10 It is a monoether of glycerol having one or more alkyl groups. Non-limiting representative examples of glyceryl ethers for use with the composition of the present invention include hexylglycerin, cyclohexylglycerin, heptylglycerin, caprylylglyceryl ether, methylheptylglycerin and ethylhexylglycerin, etc., and mixtures thereof.

[0080] As chelating agents, bio-based C6~C 10Alkylhydroxamic acids, such as heptanohydroxamic acid, caprylohydroxamic acid (caprylhydroxamic acid), pelagohydroxamic acid, caprohydroxamic acid, and mixtures thereof, and their corresponding alkylhydroxamate salts are included, but not limited thereto. Caprylohydroxamic acid (caprylhydroxamic acid) or its corresponding hydroxamate salt is preferred. Additional non-limiting examples of chelating agents that can be used as boosters include tetrasodium glutamate diacetate, citric acid / citrate salt, phytic acid / phytate salt, glutonic acid / gluconate salt, galacturonic acid / galacturonate salt, galactaric acid / galactate salt, and mixtures thereof.

[0081] Boosters may also include organic acids, such as 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. Other boosters include the amino acid glycine, such as the medium-length chain (C6–C2) of capryloyl glycine. 10 It includes a fatty amide or a salt thereof.

[0082] The booster may be present in the range of about 0.05 wt% to about 15 wt% (based on the total weight of the formulation), e.g., 0.075 wt% to 10 wt% or 0.1 wt% to 5 wt%. In terms of the upper limit, the amount of the booster may be less than 15 wt%, e.g., less than 10 wt% or less than 5 wt%. In terms of the lower limit, the amount of the booster may be 0.05 wt% or more, e.g., 0.75 wt% or more or 0.1 wt% or more.

[0083] In this regard, the booster may be present in a formulation containing the microbial growth inhibitor concentrate of the present invention.

[0084] Microbial growth inhibitor concentrate.A formulation of C7MGME containing a booster as described above may also be prepared as a microbial growth inhibitor concentrate (MBC) to be added to the composition to protect the composition against microbial contamination and growth. The MBC comprises at least the following components, namely, a bio-based C7MGME composition as described above, glycerin, and at least one of a C3-C4 diol. The C3-C4 diol may be selected from 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.

[0085] MBC may comprise about 30 wt% to about 85 wt%, for example, about 5 wt% to about 50 wt% of the bio-based C7MGME composition of the present invention, and at least one of glycerin or C3-C4 diol. MBC comprises the bio-based C7MGME composition comprising a compound of Formula I in a range of about 30 wt% to about 85 wt%, for example, 35 wt% to 80 wt%, 40 wt% to 80 wt%, or 45 wt% to 75 wt%. In terms of the upper limit, the amount of the bio-based C7MGME composition may be less than 85 wt%, for example, less than 80 wt% or less than 75 wt%. In terms of the lower limit, the amount of the bio-based C7MGME composition may be 30 wt% or more, for example, 35 wt% or more, 40 wt% or more, or 45 wt% or more.

[0086] MBC contains glycerin, C3-C4 diol, or a combination thereof in a range of about 1 wt% to about 75 wt%, e.g., 1 wt% to 70 wt%, 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 at least one of glycerin and C3-C4 diol may be less than 75 wt%, e.g., less than 70 wt%, less than 50 wt%, or less than 25 wt%. In terms of the lower limit, the amount of at least one of glycerin and C3-C4 diol may be 1.0 wt% or more, e.g., 2.5 wt% or more, or 5 wt% or more.

[0087] In some embodiments, the MBC optionally comprises about 0.1 wt% to about 20 wt% of a medium-length chain alkylhydroxamic acid, a salt thereof, or a combination thereof. The MBC may comprise the medium-length alkylhydroxamic acid, a salt thereof, or a combination thereof in the range of about 0.1 wt% to about 25 wt%, e.g., 1.0 wt% to 20 wt%, 2.5 wt% to 20 wt%, 5.0 wt% to 17.5 wt%, or 5.0 wt% to 15 wt%. With respect to the upper limit, the amount of the medium-length chain alkylhydroxamic acid, a salt thereof, or a combination thereof may be less than 25 wt%, e.g., less than 20 wt%, less than 17.5 wt%, or less than 15 wt%. In terms of the lower limit, the amount of medium-length chain alkylhydroxy acid, its salt, or a combination thereof may be 0.1 wt% or more, e.g., 1.0 wt% or more, 2.5 wt% or more, or 5.0 wt% or more.

[0088] Other optional components as described below may be included in the MBC. The MBC may optionally contain any of the aforementioned other booster compounds, such as glyceryl ethers, organic acids, chelating agents, and combinations thereof (but not limited thereto), all of which are preferably bio-based. In some embodiments, the MBC is substantially anhydrous, that is, no water is intentionally added to the MBC during manufacturing, and the MBC contains only about 2 wt% of water, such as moisture that is incidentally present due to absorption from processing or the atmosphere.

[0089] MBC may subsequently be used in a subsequent formulation, for example, a formulation for personal care products. MBC may be present in the formulation in an amount ranging from about 0.1 wt% to about 10 wt%, for example, 0.25 wt% to 7.5 wt%, 0.5 wt% to 5 wt%, or 0.75 wt% to 2.5 wt%. In terms of the upper limit, the amount of MBC may be less than 10 wt%, for example, less than 7.5 wt%, less than 5 wt%, or less than 2.5 wt%. In terms of the lower limit, the amount of MBC may be 0.1 wt% or more, for example, 0.25 wt% or more, 0.5 wt% or more, or 0.75 wt% or more.

[0090] The pH value of a formulation containing MBC as described herein may be, for example, in the range of about 2 to about 10, e.g., 3 to 9, 4 to 8, 5 to 8, 5.5 to 7.5, or 6 to 7. In terms of the upper limit, the pH value may be less than 10, e.g., less than 9, less than 8, less than 7.5, or less than 7. In terms of the lower limit, the pH value may be 2 or more, e.g., 3 or more, 4 or more, 5 or more, 5.5 or more, or 6 or more. In any embodiment, the pH value is about 5 to about 8, preferably about 5.5 to about 7.5, or more preferably about 6 to about 7.

[0091] The bio-based C7MGME composition of the present invention or the formulation containing MBC of the present invention may have superior microbial resistance or preservation ability. In some embodiments, the formulation containing the composition of the present invention is substantially preserved against microbial contamination for a period of at least 12 months, at least 18 months, or at least 24 months. Embodiments of formulations and / or compositions and methods for mitigating and preserving microbial contamination may further include reducing microorganisms by up to 90% within one week to one month. In some embodiments, the composition of the present invention may be used to reduce microorganisms in the formulation by at least 90% within 7 days. In some embodiments, the present invention includes a method of adding the composition to a formulation to reduce or remove 99% of the bacteria within 7 days and / or a method of reducing or removing 90% of yeast and fungi from the formulation by 90% within 7 days.

[0092] In some embodiments, formulations containing the composition of the present invention surprisingly contain the same amount or same concentration of C8~C 14It exhibits preservation ability against microbial contamination to a degree substantially similar to that of formulations containing glyceryl esters (e.g., glyceryl caprylate). In other words, since a C7 bio-based monoglyceryl monoester as described herein is present in the formulation, the formulation is, C8~C 14 Compared to a reference formulation containing the MGME composition at the same weight-based concentration, it has the same or superior preservation ability against microbial contamination.

[0093] In some embodiments, formulations containing the composition of the present invention are C8 to C as measured by nephelometric turbidimetry. 14It exhibits superior optical transparency compared to formulations containing glyceryl esters (e.g., glyceryl caprylate) in equal amounts or concentrations. In some embodiments, formulations containing the composition of the present invention exhibit modulotable turbidity. Turbidity can be measured by methods known in the art, such as the method described in ISO 7027 (© International Organization for Standardization), and can be measured using an instrument, such as an HF Scientific Micro 100 Benchtop Turbidity Meter operating at room temperature (23°C ± 2°C). In some embodiments, the turbidity value of the formulation containing the composition of the present invention is less than about 100 Nepelometric Turbidity Units ("NTU"), less than about 75 NTU, less than about 50 NTU, less than about 25 NTU, or less than about 10 NTU, as measured by ISO 7027 or similar methods. In some embodiments, the turbidity of a formulation comprising a C7 bio-based monoglyceryl monoester as described herein may be less than about 10 units of turbidity measurement (NTU). Since the formulation can be easily formulated into a final-use product intended to be transparent or clear, turbidity is important. Therefore, the turbidity of the formulation of the present invention should be as low as possible for the given formulation.

[0094] Examples

[0095] Example 1. Comparison of Bioheptanoic Acid and Petrochemical Heptanoic Acid

[0096] To determine the content of branched impurities present only in petrochemical heptanoic acid (i.e., non-bio-based / non-renewable heptanoic acid), not only chromatographic analysis 14 C The source of C7 heptanoic acid was identified by radiocarbon dating.

[0097] According to ASTM D6866 14 C Radiocarbon dating is castor oil-derived bioheptanoic acid (Arkema's Oleris®n -Heptanoic acid) contained 100% bio-based carbon, whereas C7 acid (Oxea) after the hydroformation of 1-hexene n Petrochemical heptanoic acid produced from oxidation to heptanoic acid (-heptanoic acid) was found to contain 0% bio-based carbon.

[0098] Samples of bioheptanoic acid and petrochemical heptanoic acid were reacted with methanol in the presence of boron trifluoride (BF3) to produce methyl ester derivatives of the alkanes. Subsequently, the resulting methyl ester composition was extracted with heptane and analyzed by gas chromatography using the Total Fatty Acid Methyl Ester (FAME) method based on the AOCS process method Ce 1h-05. A Thermo Electron 1310 gas chromatography system equipped with an FID detector, Chromeleon software (version 7.2.10), and a Restek MX-5 column (0.53 mm ID, 30 m, membrane thickness 0.5 μm) was used. The injection and detector temperatures were set to 300°C, with an initial temperature of 100°C and a final temperature of 300°C, at a heating rate of 8°C / min. The injection volume was 1.0 μL, in which case the He carrier flow rate was 5 mL / min and the split injection flow rate was 10 mL / min.

[0099] GC analysis revealed that bioheptanoic acid consists of over 99% linear C7 fatty acids and contains only trace amounts (about 0.1%) of linear C6 fatty acids (impurities). In contrast, petrochemical heptanoic acid contained a significant amount of branched C7 alkanic acid impurities, namely 2-methylhexanoic acid (present at about 2.9%).

[0100] [Table 1]

[0101]

[0102] Example 2. Synthesis of C7MGME composition GH70

[0103] Glycerin (9669 g, 105.1 mol) and bioheptanoic acid (Oleris® n-heptanoic acid, Arkema, 6831 g, 52.55 mol) were added to a 22-liter, four-necked, round-bottom flask equipped with an overhead mechanical stirring device and temperature control, and subjected to nitrogen stripping. The contents of the flask were heated to 200°C while stirring at a medium speed. The reaction mixture was left at 200°C for 2 hours, after which vacuum was applied to the system to remove condensed water. The reaction was allowed to proceed until the desired conversion rate was achieved (approximately 9 hours), as confirmed by an acid value of less than 1.0 mg KOH / g. The reactor was then cooled to 80°C. Steam was stripped into the reactor for 2 hours at 80°C under a vacuum of 5 mm Hg. Following steam stripping, the reactor was cooled to 70°C under a vacuum of 5 mm Hg. Next, the reactor was placed under atmospheric pressure, and the contents were transferred to a storage container in preparation for subsequent processing.

[0104] After adding an equal amount of deionized (DI) water to the reaction contents, the mixture was heated to 85°C–90°C and mixed vigorously for 15 minutes. Mixing was stopped, and the mixture was allowed to separate into two layers. The bottom aqueous layer containing free glycerin was separated and set aside for glycerin recovery. The washing process was repeated using an equal amount of DI water as in the first separation, except that 0.5% potassium chloride was added in this case. In this second separation, the bottom aqueous layer was discarded. The organic phase (top layer) was placed in a 4-neck round-bottom glass flask, heated to 90°C, and then dried under a vacuum of 5 mm Hg while mixing at a low-to-medium speed for 5 hours. Afterward, the product in the reactor was cooled to room temperature, transferred to a suitable container, and stored.

[0105] The bio-based glyceryl heptanoate MGME composition produced therefrom contained 70.4 wt% glyceryl monoheptanoate, 25.1 wt% glyceryl diheptanoate, 2.9 wt% glyceryl triheptanoate, and 1.2 wt% free glycerin. The product of Example 2 was named GH70, which indicates a glyceryl heptanoate MGME composition containing nominally about 70 wt% glyceryl monoheptanoate ester and having an average degree of glyceryl esterification of 1.29.

[0106] Example 3. Preparation of C7MGME composition GH90

[0107] The GH70 product of Example 2 was filled into a feed flask and then fed into a wiped membrane evaporator (operated at 140°C and under a vacuum of 1 mm Hg). The GH70 product was fractionated to obtain a C7MGME composition containing 91.7 wt% glyceryl monoheptanoate, 6.2 wt% glyceryl diheptanoate, and 0 wt% glyceryl triheptanoate. Example 3 was named GH90, which indicates a glyceryl heptanoate MGME composition containing nominally about 90 wt% glyceryl monoheptanoate ester and an average degree of glyceryl esterification of 1.04.

[0108] Comparative Examples 2 and 3. Preparation of C8MGME compositions GC70 and GC90

[0109] A C8MGME composition was prepared using a method similar to that described in Examples 2 and 3; however, bio-based C8-caprylic acid was used instead of bio-heptanoic acid. The comparative examples produced therefrom were as follows:

[0110] Comparative Example 2. A C8MGME composition comprising GC70 (nominally about 70 wt% glyceryl monocaprylate ester), i.e., 72.0 wt% glyceryl monocaprylate, 22.9 wt% glyceryl dicaprylate, 2.1 wt% glyceryl tricaprylate, and 1.3 wt% free glycerin, with an average degree of glyceryl esterification of 1.22.

[0111] Comparative Example 3. A C8MGME composition comprising GC88 (nominally about 88 wt% glyceryl monocaprylate ester), i.e., 89.2 wt% glyceryl monocaprylate, 7.7 wt% glyceryl dicaprylate, 0.1 wt% glyceryl tricaprylate, and 2.9 wt% free glycerin, with an average degree of glyceryl esterification of 1.05.

[0112] Example 4. Improved skin mildness of the C7MGME composition

[0113] MatTek EpiDerm using the MTT assay to measure cell viability (as a function of time) of 3-D skin tissue equivalents exposed to an aqueous solution of the MGME composition TM The skin irritation of the MGME composition was evaluated using the skin irritation test (OECD TG 439). For additional details regarding the experiment of this assessment, refer to the publication by Faller et al. (Predictive ability of reconstructed human epidermis equivalents for the assessment of skin irritation of cosmetics). Tox. In Vitro , 2002 , 16(5), 557-572) and Walters et al. (In Vitro Assessment of Skin Irritation Potential of Surfactant-based Formulations by Using a 3-D Skin Reconstructed Tissue Model and Cytokine Response, Altern. Lab Anim It is described in ., 2016, 44(6), 523-532). Cell viability as a function of time is a measure of cytotoxicity and is correlated with the stimulating potential of the chemical composition. The exposure time at which cell viability reaches 50% (ET 50 The value (as announced) is a characteristic quantification means indicating the potential for skin irritation. The ET of the chemical composition 50 Since the higher the value, the lower the cytotoxicity of the composition will be; ET 50 The composition with the larger value is ET 50 It was considered to have less irritation than compositions with smaller values.

[0114] [Table 2]

[0115]

[0116] Table 2 lists the cell viability values ​​as a function of exposure time to a 1.0 wt% solution of the MGME composition for Examples 2 and 3 and Comparative Examples 2 and 3; and the ET calculated from this data 50 Values ​​are also listed. "SD" as used in Table 2 refers to the relative standard deviation calculated from the cell viability (%) value evaluated by performing the experiment twice per tissue sample using each of the exemplary comparative compositions of Examples 2 to 3 and Comparative Examples 2 to 3.

[0117] Figure 1 is a graph showing cell viability values ​​as a function of exposure time. Due to the significantly greater cytotoxicity of Comparative Example 3, ET 50Note that as part of an effort to obtain data that is more conducive to the accurate calculation of values, an exposure time of 1 hour was applied instead of 16 hours.

[0118] The C7MGME compositions of Examples 2 and 3 (GH70 and GH90) exhibited significantly higher cell viability over all exposure times compared to the corresponding C8MGME compositions of Comparative Examples 2 and 3 (GC70 and GC88). This was quite surprising considering that only a single methylene (-CH2-) unit within the lipid acyl chain differed between the compositions. ET for Examples 2 and 3 50 While both values ​​were longer than 24 hours, Comparative Examples 2 and 3 had ET values ​​of less than 20.1 hours and 1 hour, respectively. 50 The values ​​were shown, which indicate that the C8MGME compositions of Comparative Examples 2 and 3 have significantly greater stimulating potential compared to the C7MGME compositions.

[0119] The data in Table 1 and Figure 1 also show that cytotoxicity and irritation potential decreased when the monoester content of the MGME composition was lower and, consequently, the fractions of diester and tryster content increased. For example, Example 2 (GH70) showed higher cell viability values ​​compared to Example 3 (GH90) at all time points, indicating that MGME compositions containing higher levels of diester and tryster had lower cytotoxicity and irritation potential. A similar trend was observed in the C8MGME compositions of Comparative Examples 2 and 3. Therefore, MGME compositions containing very high monoester content (where monoesters constitute about 90% or more) were less desirable in terms of reducing skin irritation potential.

[0120] Example 5. Micellar water formulation comprising a C7MGME composition

[0121] [Table 3]

[0122]

[0123] Micellar water was prepared according to the composition of Table 3 using the following procedure: Water was filled into a beaker of suitable size equipped with an overhead mechanical stirrer and an anchor-type blade. Mixing was initiated at a low-to-medium speed, polysorbate 20, butylene glycol, and glyceryl heptanoate (GH70, Example 1) were added to the ash, and then mixed until a clear and homogeneous solution was produced. The pH of the ash was adjusted to 5.4 ± 0.2 using citric acid (20% aqueous solution) and sodium hydroxide (10% aqueous solution). After mixing the ash until homogeneous, it was transferred to a suitable container and stored.

[0124] Comparative Example 4 - Micellar water formulation not containing C7MGME composition.

[0125] Comparative Example 4 was prepared according to the procedure performed in Example 5, except that only glyceryl heptanoate was excluded from the formulation.

[0126] Comparative Example 5 - Micellar water comprising a C8MGME composition.

[0127] Comparative Example 5 was prepared according to the procedure performed in Example 5, except that glyceryl caprylate (GC70, Comparative Example 2) was used instead of glyceryl heptanoeate.

[0128] Visual observation of the micellar water formulations revealed that while the transparency of the formulation was maintained upon the addition of the C7MGME composition, a cloudy formulation was produced upon the addition of the comparative C8MGME composition. Thermo Scientific TM Orion TMTurbidity measurements were performed using the AQUAfast AQ3010 Turbidity Meter, and the turbidity values ​​were reported in Net Turbidity Units (NTU). It was observed that these values ​​correlated with the results of visual observation of the formulation's condition.

[0129] Microbiological challenge testing (MCT) for micellar water formulations to confirm preservation efficacy:

[0130] To confirm the preservation efficacy of the formulations in Table 3, an attack test was performed in compliance with the USP and PCPC compendial test methodology [refer to the literature (Personal Care Products Council Technical Guidelines, Microbiology Guidelines (2018 Edition, published by Personal Care Products Council (Washington, DC)) and cited references)]. The results are shown in Tables 4a through 4c. The tables represent the logarithmic values ​​of the number of live organisms measured after the expiration time interval. The row heading "Inoculation Level" indicates the initial number of organisms present at the start of the test.

[0131] Comparative Example 4, which did not contain the MGME composition, did not meet the USP 51 and PCPC acceptance criteria for bacterial reduction within 7 days. Example 5, containing GH70, demonstrated preservation efficacy, bacterial and yeast growth inhibition, and mold growth inhibition equivalent to that of Comparative Example 5, which contained GH88, meeting the USP and PCPC acceptance criteria and the USP 51 acceptance criteria. The results for Example 5 and Comparative Example 5 demonstrate that the shorter C7 acyl chain of the less irritating GH70 did not impair the preservation efficacy of the MGME composition.

[0132] [Table 4a]

[0133]

[0134] [Table 4b]

[0135]

[0136] [Table 4c]

[0137]

[0138] Example 6. Natural lotion formulation containing C7MGME composition GH70

[0139] A lotion containing 100% bio-based ingredients was prepared according to the composition of Table 5 using the following procedure: Water and glycerin were filled into a beaker of suitable size equipped with an overhead mechanical stirrer, an anchor-type blade, and a heating plate. Mixing was initiated at low to medium speeds, and xanthan gum was slowly sifted and added to the aqueous phase, followed by mixing until uniformly dispersed (until no lumps were present). The mixture was then heated to 80°C. The oil phase components were combined in a separate beaker and heated to 80°C while mixing at low speeds until homogeneous. At 80°C, the oil phase mixture was added to the aqueous phase mixture, while mixing was carried out at medium to high speeds. Upon reaching a homogeneous state, the mixture was allowed to cool to approximately 75°C and subsequently homogenized at 3500 rpm for 3 minutes. After homogenization. The mixture was stirred at a medium speed and allowed to cool to about 45°C to about 50°C. Glyceryl heptanoate (GH70, Example 2) was added at 45°C to 50°C. When cooled to room temperature (23°C ± 2°C), the pH of the ash was adjusted to 6.5 ± 0.2 using citric acid (20% aqueous solution). The ash was mixed until homogeneous, then transferred to a suitable container and stored.

[0140] Example 7. Natural lotion formulation containing C7MGME composition GH90

[0141] Example 7 was prepared according to the procedure performed in Example 6, except that the C7MGME composition (GH90) of Example 3 was used instead of GH70.

[0142] [Table 5]

[0143]

[0144] Comparative Example 6. Natural lotion formulation not containing MGME composition

[0145] Comparative Example 6 was prepared according to the procedure performed in Example 6, except that a medium-length chain MGME composition was not added to the formulation.

[0146] Comparative Example 7. Natural lotion formulation containing C8 MGME composition GC70

[0147] Comparative Example 7 was prepared according to the procedure performed in Example 6, except that the C8 MGME composition (GC70) of Comparative Example 2 was used instead of GH70.

[0148] Comparative Example 8. Natural lotion formulation containing C8 MGME composition GC88

[0149] Comparative Example 8 was prepared according to the procedure performed in Example 6, except that the C8 MGME composition (GC88) of Comparative Example 3 was used instead of GH70.

[0150] Microbiological attack test on natural lotion formulations to confirm preservation efficacy:

[0151] To confirm the preservation efficacy of the formulations in Table 5, an attack test was performed in compliance with the USP and PCPC overview test methods. The results are shown in Tables 6a through 6e.

[0152] [Table 6a]

[0153]

[0154] [Table 6b]

[0155]

[0156] [Table 6c]

[0157]

[0158] [Table 6d]

[0159]

[0160] [Table 6e]

[0161]

[0162] Comparative Example 6, prepared without using a medium-length chain MGME composition, did not show adequate preservation efficacy against bacteria and yeast and did not meet the acceptance criteria of USP 51 and PCPC, whereas Examples 5–6 and Comparative Examples 7–8, prepared using a medium-length chain MGME composition, achieved broad preservation efficacy against bacteria, yeast, and mold. Example 7, formulated with the C7MGME composition (GH90) of Example 3, showed superior preservation efficacy against mold compared to Comparative Example 8, formulated with the C8MGME composition (GC88, Comparative Example 3), which has nearly the same monoester content.

[0163] Examples 8 and 9 - Microbial Growth Inhibitor Concentrate (MBC)

[0164] MBC shown in Table 7 was prepared by combining and mixing each component in the amounts specified in Table 7 and mixing at 40°C to 45°C until a uniform and homogeneous composition was obtained.

[0165] [Table 7]

[0166]

[0167] Examples 10 and 11 - Preservation of micellar water formulations containing MBC

[0168] Examples 10 and 11 containing the MBC of Examples 8 and 9, respectively, and the micellar water formulation of Comparative Example 9, which does not contain MBC (see Table 8), were prepared according to the procedure described above (see Example 5).

[0169] [Table 8]

[0170]

[0171] To confirm the preservation efficacy of the formulations in Table 8, microbiological challenge tests were performed in compliance with the USP and PCPC general test methods. The results are shown in Tables 9a through 9c. Comparative Example 9, prepared without the use of the MBC composition, did not show adequate preservation efficacy against bacteria and yeast and did not meet the USP 51 and PCPC acceptance criteria, whereas Examples 10 and 11, prepared with the MBC composition, achieved broad preservation efficacy against bacteria, yeast, and mold and met the general acceptance criteria.

[0172] [Table 9a]

[0173]

[0174] [Table 9b]

[0175]

[0176] [Table 9c]

[0177]

[0178] Examples 12 and 13 - Preservation of natural lotion formulations containing MBC

[0179] Natural lotion formulations of Examples 12 and 13 containing the MBC of Examples 8 and 9, respectively, and Comparative Example 10 not containing MBC (see Table 10) were prepared according to the aforementioned procedure (see Example 6). MBC was added to the formulation at 45°C to 50°C, and the emulsion was cooled while mixing appropriately.

[0180] [Table 10]

[0181]

[0182] To confirm the preservation efficacy of the formulations in Table 10, microbiological challenge tests were performed in compliance with the USP and PCPC general test methods. The results are shown in Tables 11a to 11c. Comparative Example 10, prepared without the use of the MBC composition, did not show adequate preservation efficacy against bacteria and yeast and did not meet the USP 51 and PCPC acceptance criteria, whereas Examples 12 to 13, prepared with the MBC composition, achieved broad preservation efficacy against bacteria, yeast, and mold and met the general acceptance criteria.

[0183] [Table 11a]

[0184]

[0185] [Table 11b]

[0186]

[0187] [Table 11c]

[0188]

[0189] Examples 14 and 15 - Natural shampoo containing MBC

[0190] Natural shampoo formulations of Examples 14 and 15 containing the MBC of Examples 8 and 9, respectively, and Comparative Example 11 not containing MBC (see Table 12) were prepared according to the following procedure: Water (90% of the total ash content), lauryl glucoside, sodium cocoyl glutamate, cocamidopropyl betaine, and MBC as specified in Table 12 were filled into a beaker of suitable size equipped with an overhead mechanical stirrer. The ash was mixed at low to medium speed until the contents were homogeneous, then the pH was adjusted to 5.1 ± 0.1 using citric acid (10% aqueous solution), and the remainder was made to 100 wt% by adding a sufficient amount of water.

[0191] [Table 12]

[0192]

[0193] To confirm the preservation efficacy of the formulations in Table 12, microbiological challenge tests were performed in compliance with the USP and PCPC general test methods. The results are shown in Tables 13a to 13c. Comparative Example 11, prepared without the use of the MBC composition, did not show adequate preservation efficacy against bacteria and yeast and did not meet the USP 51 and PCPC acceptance criteria, whereas Examples 14 to 15, prepared with the MBC composition, achieved broad preservation efficacy against bacteria, yeast, and mold and met the general acceptance criteria.

[0194] [Table 13a]

[0195]

[0196] [Table 13b]

[0197]

[0198] [Table 13c]

[0199]

[0200] Examples 16 and 17 - Preservation of UV protection formulations containing MBC

[0201] UV protection formulations of Examples 16 and 17 containing the MBC of Examples 8 and 9, respectively, and Comparative Example 11 not containing MBC (see Table 14) were prepared according to the following procedure: Water, glycerin-xanthan gum premix, butylene glycol, tetrasodium EDTA, and MBC were filled into a beaker of suitable size equipped with an overhead mechanical stirrer and a heating plate as specified in Table 14. This aqueous phase was heated to 80°C and then mixed until homogeneous. The oil phase components were combined in a separate beaker, heated to 80°C, and then mixed until homogeneous. When the two phases were at 80°C and homogeneous, the oil phase was added to the aqueous phase, and mixing was carried out at medium-high speed, resulting in the formation of an emulsion. The emulsion was homogenized at 3500 rpm for 3 minutes. The ash was mixed and allowed to cool to 45°C. During cooling, Simulgel NS and silicon were added to the formulation and mixed until homogeneous. When cooled to room temperature (23°C ± 2°C), the pH of the ash was adjusted to 6.5 ± 0.2 using citric acid (10% aqueous solution) and sodium hydroxide (10% aqueous solution). After mixing the ash until homogeneous, it was transferred to a suitable container and stored.

[0202] [Table 14]

[0203]

[0204] To confirm the preservation efficacy of the formulations in Table 14, microbiological challenge tests were performed in compliance with the USP and PCPC general test methods. The results are shown in Tables 15a through 15c. Comparative Example 12, prepared without the use of the MBC composition, did not show adequate preservation efficacy against bacteria and yeast and did not meet the USP 51 and PCPC acceptance criteria, whereas Examples 14 and 15, prepared with the MBC composition, achieved broad preservation efficacy against bacteria, yeast, and mold and met the general acceptance criteria.

[0205] [Table 15a]

[0206]

[0207] [Table 15b]

[0208]

[0209] [Table 15c]

[0210]

Claims

Claim 1 The following chemical formula I, i.e., chemical formula I A bio-based monoglyceryl monoester preservation composition comprising one or more compounds, wherein in Formula I, R1, R2, and R3 are independently -H or -C(O)-C6 alkyl, and one or more compounds comprise 65 wt% or more to less than 75 wt% of glyceryl monoheptanoate; 2 wt% to 35 wt% of glyceryl diheptanoate, glyceryl triheptanoate, or a combination thereof; and less than 30 wt% of glycerol, wherein at least 98% of the -C(O)-C6 alkyl groups present in one or more compounds are n-heptanoyl, and the carbon present in one or more compounds of Formula I is bio-based. Claim 2 A composition according to claim 1, wherein the glyceryl diheptanoate, glyceryl triheptanoate, or a combination thereof is at a concentration of 2 wt% to 30 wt%. Claim 3 The composition according to claim 1 or 2, wherein the composition comprises less than 20 wt% glycerol. Claim 4 A composition according to claim 1 or 2, wherein the average degree of glyceryl esterification of the composition is 1.0 to 1.

4. Claim 5 A composition according to claim 1 or 2, wherein at least 99% of the -C(O)-C6 alkyl groups present in the composition are n-heptanoyl. Claim 6 In claim 1 or 2, the ET of the composition 50 The value is a composition exceeding 24 hours when this composition is tested as a 1 wt% solution in water according to the Epiderma skin irritation test (OECD 439). Claim 7 A composition according to claim 1 or 2 in which the MTT % cell viability value after 24 hours of the composition exceeds 50% when the composition is tested as a 1 wt% solution in water according to the Epiderma skin irritation test (OECD 439). Claim 8 A composition according to claim 1, further comprising a booster selected from the group consisting of one or more polyols, one or more glyceryl ethers, one or more chelating agents, and combinations thereof. Claim 9 A formulation comprising a composition according to claim 1, wherein the formulation is preserved against microbial contamination for a period of at least 12 months, or at least 18 months, or at least 24 months, and the formulation is C8~C 14 A formulation having equivalent or superior preservation ability against microbial contamination compared to a reference formulation containing a monoglyceryl monoester composition at the same concentration by weight, the reason being that the composition according to claim 1 is present in said formulation, or a formulation having a turbidity value of less than 100 NTU. Claim 10 A formulation according to claim 9, further comprising at least one ingredient selected from the group consisting of water, surfactants including anionic, cationic, nonionic, and amphoteric surfactants, emulsifiers, skin softeners, moisturizers, conditioning agents for hair, skin, or nails, chelating agents, active preparations including UV blocking agents and antiperspirants, bleaching agents or whitening agents, pH adjusters or balancers, perfumes, colorants including dyes and pigments, exfoliants, plant ingredients, mica, smectite, thickeners or rheology modifiers, cannabinoids, oils, waxes, amino acids, nucleic acids, vitamins, hydrolyzed proteins and derivatives thereof, enzymes, anti-inflammatory agents and other medicines, microbial killers, antifungal agents, preservatives, antioxidants, UV absorbers, preservatives, oxidizing agents, moisturizers, peptides and derivatives thereof, anti-aging active substances, hair growth promoters, anti-cellulite active substances, and combinations thereof. Claim 11 A method for preserving a formulation against microbial contamination, comprising the step of adding a sufficient amount of the composition according to claim 1 or 2 to the formulation. Claim 12 A microbial growth inhibitory concentrate comprising 30 wt% to 85 wt% of a bio-based monoglyceryl monoester preservation composition according to claim 1, and 1 wt% to 70 wt% of at least one of glycerin and C3 to C4 diol. Claim 13 A composition according to claim 8, further comprising one or more polyols selected from the group consisting of glycerin, propanediol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-hexanediol, 1,2-heptanediol, 2,3-octanediol, caprylyl glycol, decylene glycol, sorbitol, sorbitan, and combinations thereof. Claim 14 A composition according to claim 8, further comprising one or more glyceryl ethers selected from the group consisting of hexylglycerin, cyclohexylglycerin, heptylglycerin, caprylylglyceryl ether, methylheptylglycerin, ethylhexylglycerin, and combinations thereof. Claim 15 A composition according to claim 8, further comprising one or more chelating agents selected from the group consisting of heptanohydroxamic acid and its salt, caprylohydroxamic acid (caprylhydroxamic acid) and its salt, pelargohydroxamic acid and its salt, citric acid and its salt, caprohydroxamic acid and its salt, tetrasodium glutamate diacetate, phytic acid and its salt, gluconic acid and its salt, galacturonic acid and its salt, galactaric acid and its salt, and combinations thereof. Claim 16 A formulation according to claim 9, further comprising one or more polyols selected from the group consisting of glycerin, propanediol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-hexanediol, 1,2-heptanediol, 2,3-octanediol, caprylyl glycol, decylene glycol, sorbitol, sorbitan, and combinations thereof. Claim 17 A microbial growth inhibitory concentrate according to claim 12, further comprising one or more polyols selected from the group consisting of glycerin, propanediol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-hexanediol, 1,2-heptanediol, 2,3-octanediol, caprylyl glycol, decylene glycol, sorbitol, sorbitan, and combinations thereof.

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