METAL OXIDE PARTICLE ESTER DISPERSIONS CONTAINING BROAD MOLECULAR WEIGHT DISTRIBUTION POLYESTER AND METHOD FOR PREPARING SAME

Abstract

The present invention relates to a non-aqueous composition for dispersing metal oxide particles. The non-aqueous composition comprises an ester dispersant and a broad molecular weight distribution (MWD) polyester dispersant, each preferably synthesized from 100% bio-based carbon. The ester dispersant comprises a liquid ester selected from the group consisting of Formula (I), Formula (II), Formula (III), Formula (IV), and combinations thereof. The polyester dispersant has a polydispersity index (PDI) greater than about 2.3. The present invention also relates to a non-aqueous dispersion comprising the non-aqueous composition and dispersed metal oxide particles. The metal oxide particles may comprise zinc oxide, titanium oxide, or a combination thereof. Formulations using the composition and dispersion, as well as methods of preparation, are also disclosed. TIFF2025537134000095.tif66170

Description

[Technical Field]

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS] This application claims priority to U.S. Provisional Patent Application No. 63 / 422,057, filed November 3, 2022, and U.S. Provisional Patent Application No. 63 / 422,063, filed November 3, 2022, each of which is incorporated herein by reference.

[0002] The present invention relates to compositions, dispersions, and formulations comprising non-aqueous esters and polyesters having broad molecular weight distributions (MWD), optionally in combination with metal oxide particles, as well as methods of preparing and using the compositions to prepare the dispersions and formulations, and their applications, including, inter alia, personal care applications, such as sunscreen formulations. [Background technology]

[0003] Inorganic metal oxides, such as zinc oxide (ZnO) and titanium dioxide (TiO2), are important sunscreen ingredients that provide protection from sunburn and photodamage, which can lead to premature aging and / or skin cancer, due to their ability to absorb and / or scatter UVB and UVA radiation. These metal oxides are most desirably supplied as submicron-sized particles that do not scatter visible light wavelengths on the skin and therefore do not cause a whitening appearance. Metal oxide particles (MOPs) are typically manufactured and supplied as free-flowing powders.

[0004] To effectively prepare sunscreen formulations containing ZnO and / or TiO2 MOPs that provide adequate sun protection factor (SPF) values ​​and do not whiten on the skin, it is necessary to create dispersions of the MOPs that are stable against aggregation.

[0005] Preparation of a dispersion involves mechanically breaking down powdered and / or any agglomerated MOPs using high shear mixing or milling and dispersing them in a liquid medium, i.e., a dispersion medium. The dispersion medium can be either aqueous or non-aqueous in nature. Wetting the MOPs with the dispersion medium to form a dispersed, homogeneous state typically requires a dispersant to prevent re-agglomeration of the MOPs [see, for example, Non-Patent Document 1].

[0006] MOPs are preferably dispersed in a non-aqueous fluid that is easily applied to the skin and has consumer-acceptable skin feel properties. Non-aqueous dispersion media for MOPs such as ZnO and TiO2 include a variety of cosmetically acceptable fluids typically used as emollients in cosmetics and personal care products. Examples of such fluids include aliphatic hydrocarbons, triglycerides, benzoates, fatty esters, or combinations thereof, and silicone fluids such as cyclomethicone and dimethicone.

[0007] Given the increasing consumer preference for more natural and sustainable products, it is preferred that the non-aqueous dispersion medium be derived from sustainable, renewable plant-derived feedstocks. One example of a naturally derived dispersion medium is caprylic / capric triglyceride, which is a C8 (caprylic) and C9 (C10) triglyceride derived from either coconut oil or palm kernel oil. 10These are triglycerides synthesized by the complete esterification of vegetable glycerin with a mixture of (capric) fatty acids. Importantly, these triglycerides have not previously provided dispersions with sufficiently low viscosity. Lower viscosities are necessary to incorporate the desired high solids loading of MOPs. Other examples of bio-based non-aqueous dispersion media derived from plants include plant-derived oils (e.g., Simmondsia chinensis (jojoba) seed oil or Helianthus annus (sunflower) seed oil), fermentation-derived hydrocarbons (e.g., hydrogenated farnesene), hydrocarbons derived from triglyceride oils (via hydrolysis to fatty acids, reduction to fatty alcohols, and dehydration / hydrogenation to hydrocarbons), such as coconut alkanes, and esters derived from plant-based saturated fatty acids and saturated fatty alcohols (e.g., C8 / C9). 10 Cococaprylate / caprate) derived from the esterification of hydrogenated coconut fatty alcohol with fatty acids.

[0008] To obtain a stable dispersion of MOPs in non-aqueous media, the particle surface must typically be modified to render the hydrophilic inorganic surface hydrophobic, thereby making it compatible with relatively non-polar dispersion media, i.e., capable of wetting the MOP surface. Such surface modification can be achieved by using a hydrophobic coating that adheres to the MOP surface through physical and / or covalent interactions. Examples of surface modifiers used in MOPs include fatty acids (e.g., isostearic acid), trialkoxyalkylsiloxanes (e.g., triethoxycaprylsilane), or silicones (e.g., methicone or dimethicone). Surface modification of MOPs typically requires additional process steps and / or unit operations to properly apply the surface treatment (see, e.g., U.S. Patent No. 5,929,293). Therefore, it is more efficient and economical to develop a dispersion system that can use untreated, i.e., uncoated, MOPs.

[0009] It is desirable to create a flowable, high-MOP-loaded, low-viscosity particle dispersion that can minimize excess dispersion medium carryover to subsequent formulations to which a particular MOP dispersion is added. As discussed above, conventional triglyceride dispersion media (e.g., caprylic / capric triglyceride and triheptanoin) typically result in undesirably high-viscosity MOP dispersions when formulated with MOP loads greater than about 50% solid particle volume fraction. See, e.g., "Stable, yet injectable, MOP dispersions using these triglycerides typically require a reduced particle load." Therefore, obtaining a stable, yet injectable, MOP dispersion using these triglycerides traditionally requires a reduced particle load.

[0010] Furthermore, the use of dispersants that provide steric stabilization against particle aggregation in non-aqueous dispersion media is necessary. Polymeric dispersants are common, and polyhydroxystearic acid is a well-known dispersant for ZnO and TiO2 MOPs [see, for example, Non-Patent Document 3].

[0011] Such non-aqueous dispersions preferably have a low viscosity (i.e., less than about 1000 cP) for ease of preparation and handling in subsequent formulation steps, and the dispersed solid particles should remain stable in the dispersion for extended periods of time. Low viscosity dispersions are also desirable when formulated into sunscreen products, as they provide a product that is easier for the consumer to dispense and apply.

[0012] Therefore, there is a need for stable, low-viscosity, high-solids MOP dispersions. Given the market demand for more sustainable ingredients and the growing consumer appeal of so-called "natural" ingredients derived from renewable bio-based feedstocks, non-aqueous compositions should be preferentially based on renewable carbon sources, i.e., plant-derived carbon. In particular, there is a need for non-aqueous compositions comprising one or more triglyceride esters prepared from renewable bio-based carbon, more preferably 100% bio-based carbon. [Prior art documents] [Patent documents]

[0013] [Patent Document 1] U.S. Patent No. 9,254,398 [Non-patent literature]

[0014] [Non-Patent Document 1] C. Agbo et al., A Review on the Mechanism of Pigment Dispersion, J. Disp. Sci. Tech., 2018, 39(6), 874-889. [Non-patent document 2] DA Brune et al., Model for the Viscosity of Particle Dispersions; Journal of Macromolecular Science-Rev. Macromol. Chem. Phys., C39(4), 561-642 (1999) [Non-patent document 3] BJ Naden et al. Adsorption of poly(hydroxystearic acid) to TiO2 nanoparticles, studied using gel permeation chromatography, Coll. Surf. A.: Physicochem. Eng. Aspects, 2015, 478, 36-44. Summary of the Invention

[0015] The non-aqueous compositions described and claimed herein meet these long-standing needs and include an ester dispersing medium (EDM) and a broad MWD polyester dispersant (PEDA) to which MOP(s) can be added to provide a homogeneous MOP dispersion.

[0016] Applicants have surprisingly found that combining an ester dispersion medium, preferably synthesized from 100% bio-based carbon as described herein, with a broad MWD PEDA provides stable MOP dispersions with very low viscosity at relatively high particle loadings. In this manner, stable, low viscosity, high solids MOP dispersions are achieved using EDM and a broad MWD PEDA based on 100% natural, renewable carbon.

[0017] In some embodiments, the present invention relates to a non-aqueous composition. The non-aqueous composition includes an ester and a polyester having a polydispersity index greater than about 2.3. The ester is (i) a liquid ester of formula I: [ka] (wherein R and R1 are each a linear, branched, or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl, and when one of R and R1 is a linear alkyl, the other of R and R1 is a branched or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl); (ii) Liquid esters of formula II: [ka] wherein R2 is branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; R3 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; and R4 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; (iii) Liquid esters of formula III: [ka] wherein R5 is a branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, R6 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, and R7 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; (iv) Liquid esters of formula IV: [ka] (Wherein R8, R9, and R 10 are each independently a C5-C 18 selected from linear, branched, saturated, or unsaturated alkyl groups; and (v) combinations of these; is selected from the group consisting of:

[0018] The ester of the non-aqueous composition described in the preceding paragraph can be of Formula I, wherein R is a C5-C 17 R1 is a branched or cyclic alkyl, a linear, branched or cyclic alkenyl, or a linear, branched or cyclic alkynyl, 18 The esters of formula I may include those in which R and R are different.

[0019] The ester of the non-aqueous composition described in any of the preceding paragraphs can be of Formula II, wherein R2 is C3-C 18 R3 is a C2 to C8 straight-chain or branched alkyl, straight-chain or branched alkenyl, or straight-chain or branched alkynyl; R4 is a C3 to C8 straight-chain or branched alkyl, straight-chain or branched alkenyl, or straight-chain or branched alkynyl; 18 The esters of Formula II may include those in which R2 and R4 are the same.

[0020] The ester of the non-aqueous composition described in any of the preceding paragraphs can be of Formula III, wherein R5 is a C3-C 18 R6 is a C2 to C8 straight-chain or branched-chain alkyl, a straight-chain or branched-chain alkene, or a straight-chain or branched-chain alkyne; R7 is a C3 to C8 straight-chain or branched-chain alkyl, a straight-chain or branched-chain alkene, or a straight-chain or branched-chain alkyne; 18 The ester of formula III may include those in which R5 and R7 are the same.

[0021] The ester of the non-aqueous composition described in any of the preceding paragraphs can be of Formula IV, wherein R, R, and R 10 Two or more of the are the same.

[0022] The ester of the non-aqueous composition described in any of the preceding paragraphs may be selected from the group consisting of monoesters, diesters, triesters, and combinations thereof.

[0023] The ester of the non-aqueous composition described in any of the preceding paragraphs can have a viscosity of less than about 100 cSt at 25°C.

[0024] The non-aqueous composition described in any of the preceding paragraphs may have a viscosity of less than 500 cP.

[0025] The ester of the non-aqueous composition described in any of the preceding paragraphs may be a liquid at 25° C. The ester may be 100% bio-based.

[0026] In the non-aqueous composition described in any of the preceding paragraphs, the polyester has a polydispersity index (PDI) greater than about 2.4, or greater than about 2.5.

[0027] The polyester of the non-aqueous composition described in any of the preceding paragraphs may include a single terminal carboxylic acid functional group. The polyester may include two terminal carboxylic acid functional groups.

[0028] The polyester of the non-aqueous composition described in any of the preceding paragraphs can comprise a homopolymer derived from AB hydroxycarboxylic acid monomers. The polyester can comprise a copolymer derived from AA diol and BB diacid or dibasic ester monomers.

[0029] The polyester of the non-aqueous composition described in any of the preceding paragraphs has a number average molecular weight (M) of less than about 10,000 g / mole. n The polyester may have an acid number of at least 15 mg KOH / g.

[0030] The polyester of the non-aqueous composition described in any of the preceding paragraphs can be selected from the group consisting of polyhydroxystearic acid, polyhydroxystearic acid stearate, polyhydroxystearyl succinate, polyhydroxystearyl sebacate, and combinations thereof. The carbon present in the polyester can be 100% bio-based.

[0031] In certain embodiments, the present invention essentially comprises: (i) a liquid ester of formula I: [ka] (wherein R and R1 are each a linear, branched, or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl, and when one of R and R1 is a linear alkyl, the other of R and R1 is a branched or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl; (ii) Liquid esters of formula II: [ka] wherein R2 is branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; R3 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; and R4 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; (iii) Liquid esters of formula III: [ka] wherein R5 is a branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; R6 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; and R7 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; (iv) Liquid esters of formula IV: [ka] (Wherein R8, R9, and R 10 are each independently a C5-C 18 selected from linear, branched, saturated, or unsaturated alkyl groups; and (v) combinations of these; an ester selected from the group consisting of a polyester having a polydispersity index greater than about 2.3; The present invention relates to a non-aqueous composition comprising:

[0032] In other specific embodiments, the present invention provides (i) a liquid ester of formula I: [ka] (wherein R and R1 are each a linear, branched, or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl, and when one of R and R1 is a linear alkyl, the other of R and R1 is a branched or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl); (ii) Liquid esters of formula II: [ka] wherein R2 is branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; R3 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; and R4 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; (iii) Liquid esters of formula III: [ka] wherein R5 is a branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, R6 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, and R7 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; (iv) Liquid esters of formula IV: [ka] (Wherein R8, R9, and R 10 are each independently a C5-C 18 selected from linear, branched, saturated, or unsaturated alkyl groups; and (v) combinations of these; an ester selected from the group consisting of a polyester having a polydispersity index greater than about 2.3; The present invention relates to a non-aqueous composition comprising:

[0033] In another embodiment, the present invention relates to a non-aqueous dispersion comprising a non-aqueous composition and a powder of metal oxide particles. The non-aqueous composition for the non-aqueous dispersion may be in accordance with the non-aqueous composition described in any of the preceding paragraphs.

[0034] The metal oxide particles for the non-aqueous dispersion described in the preceding paragraph can include metal oxide particles that have not been surface-modified, for example, particles without any surface modification.

[0035] The metal oxide particles for the non-aqueous dispersion described in any of the preceding paragraphs can include zinc oxide, titanium oxide, or a combination thereof.

[0036] The non-aqueous dispersion described in any of the preceding paragraphs may have a viscosity of less than about 1000 cP. The metal oxide particles may comprise about 15% to about 75% by weight of the non-aqueous dispersion, with the remainder being the non-aqueous composition described in any of the preceding paragraphs. In some embodiments, the metal oxide particles comprise about 40% to about 60% by weight of the non-aqueous dispersion. The polyester may be present in an amount of about 3% to about 5% by weight, based on the total weight of the dispersion. The non-aqueous dispersion may be substantially free of silicone.

[0037] In certain embodiments, the non-aqueous dispersion comprises: a plurality of metal oxide particles; (i) a liquid ester of formula I: [ka] (wherein R and R1 are each a linear, branched, or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl, and when one of R and R1 is a linear alkyl, the other of R and R1 is a branched or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl); (ii) Liquid esters of formula II: [ka] wherein R2 is branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; R3 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; and R4 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; (iii) Liquid esters of formula III: [ka] wherein R5 is a branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, R6 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, and R7 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; (iv) Liquid esters of formula IV: [ka] (Wherein R8, R9, and R 10 are each independently a C5-C 18 selected from linear, branched, saturated, or unsaturated alkyl groups; and (v) combinations thereof; an ester selected from the group consisting of a polyester having a polydispersity index greater than about 2.3; Includes.

[0038] The ester of the non-aqueous dispersion described in the preceding paragraph can be of Formula I, wherein R is a C5-C 17 R1 is a branched or cyclic alkyl, a linear, branched or cyclic alkenyl, or a linear, branched or cyclic alkynyl, 18 The esters of formula I may include those in which R and R are different.

[0039] The ester of the non-aqueous dispersion described in any of the preceding paragraphs can be of Formula II, wherein R2 is C3-C 18 R3 is a C2 to C8 straight-chain or branched alkyl, straight-chain or branched alkenyl, or straight-chain or branched alkynyl; R4 is a C3 to C8 straight-chain or branched alkyl, straight-chain or branched alkenyl, or straight-chain or branched alkynyl; 18 The esters of Formula II may include those in which R2 and R4 are the same.

[0040] The ester of the non-aqueous dispersion described in any of the preceding paragraphs can be of Formula III, wherein R5 is C3-C 18 R6 is a C2 to C8 straight-chain or branched-chain alkyl, a straight-chain or branched-chain alkene, or a straight-chain or branched-chain alkyne; R7 is a C3 to C8 straight-chain or branched-chain alkyl, a straight-chain or branched-chain alkene, or a straight-chain or branched-chain alkyne; 18 The ester of formula III may include those in which R5 and R7 are the same.

[0041] The ester of the non-aqueous dispersion described in any of the preceding paragraphs can be of Formula IV, wherein R, R, and R 10 Two or more of the are the same.

[0042] The ester of the non-aqueous dispersion described in any of the preceding paragraphs may be selected from the group consisting of a monoester, a diester, a triester, or a combination thereof.

[0043] The ester of the non-aqueous dispersion described in any of the preceding paragraphs may have a viscosity of less than about 100 cSt at 25°C.

[0044] The non-aqueous dispersion described in any of the preceding paragraphs may have a viscosity of less than 1000 cP.

[0045] The ester of the non-aqueous dispersion described in any of the preceding paragraphs may be a liquid at 25° C. The ester may be 100% bio-based.

[0046] In the non-aqueous dispersion described in any of the preceding paragraphs, the polyester has a polydispersity index (PDI) greater than about 2.4, or greater than about 2.5.

[0047] The polyester of the non-aqueous dispersion described in any of the preceding paragraphs may contain a single terminal carboxylic acid functional group. The polyester may contain two terminal carboxylic acid functional groups. The polyester may be of linear structure.

[0048] The polyester of the non-aqueous dispersion described in any of the preceding paragraphs can comprise a homopolymer derived from AB hydroxycarboxylic acid monomers. The polyester can comprise a copolymer derived from AA diol and BB diacid or dibasic ester monomers.

[0049] The polyester of the non-aqueous dispersion described in any of the preceding paragraphs has a number average molecular weight (M) of less than about 10,000 g / mole. n The polyester may have an acid number of at least 15 mg KOH / g.

[0050] The polyester of the non-aqueous dispersion described in any of the preceding paragraphs can be selected from the group consisting of polyhydroxystearic acid, polyhydroxystearic acid stearate, polyhydroxystearyl succinate, polyhydroxystearyl sebacate, and combinations thereof. The carbon present in the polyester can be 100% bio-based.

[0051] In certain embodiments, the dispersion consists essentially of: a plurality of metal oxide particles; (i) an ester of formula I: [ka] (wherein R and R1 are each a linear, branched, or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl, and when one of R and R1 is a linear alkyl, the other of R and R1 is a branched or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl); (ii) Esters of Formula II: [ka] wherein R2 is branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; R3 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; and R4 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; (iii) Esters of Formula III: [ka] wherein R5 is a branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, R6 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, and R7 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; (iv) Liquid esters of formula IV: [ka] (Wherein R8, R9, and R 10 are each independently a C5-C 18 selected from linear, branched, saturated, or unsaturated alkyl groups; and (v) combinations thereof; an ester selected from the group consisting of a polyester having a polydispersity index greater than about 2.3; It consists of:

[0052] In other particular embodiments, the non-aqueous dispersion comprises: a plurality of metal oxide particles; (i) an ester of formula I: [ka] (wherein R and R1 are each a linear, branched, or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl, and when one of R and R1 is a linear alkyl, the other of R and R1 is a branched or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl); (ii) Esters of Formula II: [ka] wherein R2 is branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; R3 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; and R4 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; (iii) Esters of Formula III: [ka] wherein R5 is a branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, R6 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, and R7 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; (iv) Liquid esters of formula IV: [ka] (Wherein R8, R9, and R 10 are each independently a C5-C 18selected from linear, branched, saturated, or unsaturated alkyl groups; and (v) combinations thereof; an ester selected from the group consisting of a polyester having a polydispersity index greater than about 2.3; It consists of:

[0053] In yet another embodiment, the invention relates to a formulation comprising the non-aqueous composition or dispersion described in any of the preceding paragraphs, which formulation may be or be 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 removers, 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, mascaras, mouthwashes, toothpastes, oral care products, skin cleansing products, textile cleansing products, dish detergents, hair or fur cleansing products, and skin lotions or moisturizers. The formulation may be or be a component of a sunscreen. The formulation may be an oil-in-water (O / W) emulsion or a water-in-oil (W / O) emulsion. The formulation may further comprise at least one additional ingredient selected from the group consisting of a film-forming polymer, a rheology-modifying polymer, a wax, an emulsifier, an emollient, a moisturizer, or a combination thereof.

[0054] The formulation may have an as-formulated viscosity that increases less than 20-fold upon storage at 50° C. for 4 weeks.

[0055] The present invention further relates to a method for preparing a non-aqueous composition for dispersing a powder of metal oxide particles, the method comprising mixing an ester with a polyester having a polydispersity index (PDI) greater than about 2.3 to form a homogeneous solution, the ester being: (i) a liquid ester of formula I: [ka] (wherein R and R1 are each a linear, branched, or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl, and when one of R and R1 is a linear alkyl, the other of R and R1 is a branched or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl); (ii) Liquid esters of formula II: [ka] wherein R2 is branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; R3 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; and R4 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; (iii) Liquid esters of formula III: [ka] wherein R5 is a branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, R6 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, and R7 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; (iv) Liquid esters of formula IV: [ka] (Wherein R8, R9, and R 10are each independently a C5-C 18 selected from linear, branched, saturated, or unsaturated alkyl groups; and (v) combinations thereof; is selected from the group consisting of:

[0056] The method can include an ester as described in any of the preceding paragraphs, such as an ester of Formula I, Formula II, Formula III, Formula IV, and combinations thereof. The ester can be selected from the group consisting of monoesters, diesters, triesters, and combinations thereof.

[0057] This method has a broad molecular weight distribution. The polyester can include the polyesters described in any of the preceding paragraphs.

[0058] The mixing of the method to form a homogeneous solution may include heating. The mixing of the method may include high shear mixing.

[0059] The method can further include dispersing metal oxide particles in the homogeneous solution to form a non-aqueous dispersion. The metal oxide particles of the method can include the metal oxide particles described in any of the preceding paragraphs.

[0060] The method may further include adding at least one additional ingredient to form the formulation. The at least one additional ingredient may be selected from the group consisting of a film-forming polymer, a rheology-modifying polymer, a wax, an emulsifier, an emollient, a moisturizer, or a combination thereof. The formulation of this method may be a sunscreen. [Brief explanation of the drawings]

[0061] [Figure 1] FIG. 1 shows dispersion viscosity as a function of polyester concentration for Example E1 and Comparative Examples CE1 and CE2 according to an embodiment herein. DETAILED DESCRIPTION OF THE INVENTION

[0062] Before describing the compounds, compositions, and methods of the present invention in particular, it is to be understood that this invention is not limited to the particular processes, compositions, or methods described, as these may vary. It is also to be understood that the terminology used in the description is for the purpose of describing particular versions or embodiments only, and is not intended to limit the scope of the present invention, which is limited only by the appended claims. Unless otherwise defined, 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 now described. All publications mentioned herein are incorporated by reference in their entirety. Nothing herein should be construed as an admission that the invention is not entitled to antedate such disclosure by virtue of prior invention.

[0063] Also, 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, a reference to a "cell" is a reference to one or more cells and equivalents thereof known to those skilled in the art, and so forth.

[0064] Unless specified, "%" can refer to either weight percent or volume percent.

[0065] Unless otherwise specified, room temperature can refer to about 25°C or 25°C, or in the range of 22.5°C to 27.5°C, or in the range of 20°C to 30°C.

[0066] If applicable, C x ~C y indicates the range of carbon numbers, and C x and C y and all groups in between. For example, C5-C9 includes pentyl, hexyl, heptyl, octyl, and nonyl groups.

[0067] "Cosmetically acceptable" means suitable for use in contact with the skin without undue toxicity, incompatibility, instability, irritation, allergic reaction, and the like.

[0068] Where applicable, chemicals are designated by their INCI names in accordance with the International Nomenclature of Cosmetic Ingredients guidelines. Additional information, including suppliers and trade names, can be found in the appropriate INCI monograph in the International Cosmetic Ingredient Dictionary and Handbook, 16th Edition, published by the Personal Care Products Council (Washington, DC), or online at the Personal Care Products Council's INCIpedia (https: / / incipedia.personalcarecouncil.org).

[0069] Among many embodiments, the present invention includes biobased compositions. The production of biobased compositions requires the use of biobased or "natural" feedstocks. Examples of biobased compositions are those prepared from biologically derived feedstocks (e.g., through current sustainable agricultural practices such as fermentation, algae, plant, or vegetable sources; e.g., obtained from plant sources, preferably using non-genetically modified organisms or biomass) and are non-petrochemically derived (e.g., obtained from 21st-century sustainable tree and plant farms, 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. Furthermore, such materials are formed from "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 derived from renewable sources. Thus, the term "sustainable" is contrasted with "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, and the like. Thus, natural or bioproducts are non-petrochemically derived and / or not derived from petrochemicals, but rather from sustainable, 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 decomposition). Fossil fuels (sources of petrochemical-derived carbon) are produced when carbon decomposes and is broken down under pressure over millions of years. Biocompounds, as used herein, are intended to include and / or be sustainable materials derived from carbon from recently existing (or previously existing) plant sources / biomass; materials derived from fossil fuels are expressly excluded.

[0070] 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, 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 carbon-14 (i.e., " 14 It is an unstable isotope of carbon known as Cr(C). 14 C releases radiative energy in the form of beta particles at a very consistent rate (i.e., the half-life of radiocarbon is 5730 years) and eventually decays into the more stable nitrogen-14( 14 Because petroleum-based (i.e., petrochemical-derived) feedstocks are derived from plants and animals buried millions of years ago, the radiocarbon (i.e., 14 C) is 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 fuel or petroleum- and petrochemical-derived sources, i.e., "old carbon." In recent or present biomass, 14 Because the amount of C is known, the percentage of carbon derived from renewable sources can be estimated from the total organic carbon analysis, providing the data necessary to determine whether a compound is derived from a truly "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.

[0071] In some embodiments, the formulations 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%.

[0072] In some embodiments, the compositions of the present invention have a solubility in water that is less than that of current atmospheric pollutants as determined according to ASTM D6866. 14 C content substantially equivalent 14 In some embodiments, the compositions of the present invention comprise a C content of less than 100% of the carbon content of present 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 a C content of 10 C present in the composition as determined according to ASTM D6866. 12 At least about 0.8 carbon atoms per 14 C atoms present in the composition 12 At least about 1.0 carbon atoms per 14 C atoms, or 10 present in the composition 12 At least about 1.2 carbon atoms per 14 Contains C atoms.

[0073] By "sustainable" herein, applicants refer to materials that are derived from renewable sources. In contrast, "non-sustainable" refers to materials that are derived from limited natural resources, such as fossil fuels (e.g., petroleum, natural gas, coal, etc.).

[0074] Introduction The present invention relates to a non-aqueous composition comprising EDM and PEDA, wherein the PEDA is characterized by a broad MWD. ​​The non-aqueous composition herein has a sufficiently low viscosity to provide a homogeneous, high-solids-loaded MOP dispersion. As described above, the use of a 100% natural, renewable carbon-based carrier and dispersant provides a stable, low-viscosity, high-solids MOP dispersion. Applicants have surprisingly discovered that combining an EDM, preferably synthesized from 100% bio-based carbon, with a broad MWD PEDA, as described herein, provides a stable dispersion with very low viscosity at a relatively high particle load. The EDM described herein includes esters containing linear or branched, saturated or unsaturated alkyl groups.

[0075] Applicants have found that PEDAs with high polydispersity index (PDI) values, when used in non-aqueous EDMs, provide dispersions that are less viscous and more stable than conventional dispersants.

[0076] non-aqueous dispersion The non-aqueous compositions of the present invention herein include EDM and broad MWD PEDA. Metal oxide particles are added to the non-aqueous compositions herein to form a homogeneous non-aqueous dispersion with a high solids loading of the metal oxide particles.

[0077] The non-aqueous compositions of the present invention provide an "off-the-shelf" dispersion system that allows for the formation of low viscosity dispersions with a wide range of metal oxide particles. In particular, users of the non-aqueous dispersions do not require specialized mixing equipment or experience in making stable non-aqueous dispersions.

[0078] In some embodiments, the non-aqueous compositions of the present invention consist essentially of (i) one or more esters and (ii) a broad molecular weight distribution (MWD) polyester polymer. A fundamental and novel property of such compositions of the present invention is their ability to form stable, low-viscosity, non-aqueous dispersions containing a wide variety of metal oxide particles. Furthermore, the non-aqueous compositions described herein exhibit ease of processing, due, at least in part, to the low viscosities achieved.

[0079] metal oxide particles Some embodiments herein relate to dispersion compositions containing metal oxide particles. MOPs are preferably solid, white (or colorless), and odorless metal oxide particles. MOPs herein may include zinc oxide (ZnO) and / or titanium dioxide (TiO2) particles. These are particularly useful in formulations such as sunscreens. Some dispersions and / or formulations herein may additionally or alternatively include metal oxides containing one or more of iron, copper, manganese, magnesium, cerium, vanadium, zirconium, aluminum, and silicon, such as FeO, Fe2O3, Fe3O4, CeO2, VO5, ZrO2, MnO2, MgO, Al2O3, SiO2, CaO, or combinations thereof, and other cosmetically acceptable metal oxides. Suitable metal oxides also include doped metal oxides (those doped with the aforementioned metals and metal oxides). Other suitable metal oxide particles include coated particles (e.g., those coated with the aforementioned metals and metal oxides). MOPs are highly pure, for example, greater than 95%, greater than 96%, greater than 97%, greater than 98%, or greater than 99%.

[0080] In some embodiments, the surface of the metal oxide particles may be modified. Such surface modification, particularly in the case of TiO, may inhibit photocatalytic activity in subsequent formulations. For any surface modification, an inorganic coating, such as alumina or silica, is preferably used.

[0081] Alternatively, organic surface modification may be acceptable, although less preferred. Surface modification with organic coatings derived from fossil-based carbon or hybrid organic-inorganic coatings is undesirable due to their poor sustainability profile and poor consumer acceptance. Specifically, surface modification with silicones or siloxanes is less preferred. For example, trialkoxyalkylsiloxanes (e.g., triethoxycaprylsilane) or silicones (e.g., methicone or dimethicone) are less preferred due to their adverse environmental impact and / or negative consumer perception.

[0082] Any coating or surface modification of the particle, as described above, is included herein as part of the mass or weight of the particle (eg, MOP).

[0083] Non-surface-modified MOPs can also be used in the compositions and formulations described herein. In some embodiments, non-coated metal oxide particles are preferred. In certain embodiments, non-coated MOPs containing ZnO are used in the compositions and formulations described herein.

[0084] The average particle size of the MOPs is not limited, but the average particle size of the MOPs can preferably be submicron in diameter. The metal oxide particles can be present in the composition in an average particle size range of, for example, 10 nm to 500 nm, e.g., 10 nm to 400 nm, 20 nm to 300 nm, or 30 nm to 150 nm. Regarding the upper limit, the average particle size of the MOPs can be less than 500 nm, e.g., less than 400 nm, less than 300 nm, or less than 150 nm. Regarding the lower limit, the average particle size of the MOPs can be greater than 10 nm, e.g., greater than 20 nm, or greater than 30 nm. In a preferred embodiment, the average particle size of the MOPs is less than about 200 nm. These ranges and limitations also apply to formulations containing these compositions.

[0085] The MOPs used in the compositions, dispersions, and formulations described herein may exhibit a wide average particle size distribution range. The average particle size distribution may be, for example, from about 10 nm to about 500 nm, e.g., from 10 nm to 400 nm, from 20 nm to 300 nm, or from 30 nm to 150 nm. In preferred embodiments, the average particle size distribution is from about 30 nm to about 150 nm. The particles may exist as clusters or aggregates. The MOPs may exhibit a particle shape selected from spherical, rod-like, stellar, isometric, spherical, plate-like, platelet-like, or a combination thereof. In some preferred embodiments, the MOPs (e.g., ZnO particles) are characterized by having various shapes (see, e.g., Zinc oxide (nano form); What are the properties of ZnO nanoparticles?, https: / / ec.europa.eu / health / scientific_committees / opinions_layman / zinc-oxide / de / l-3 / 3.htm#).

[0086] In some or other embodiments, the MOP can be added to a non-aqueous composition to form a dispersion, i.e., a non-aqueous composition comprising an EDM and a broad MWD PEDA as described herein is provided directly or is subsequently added to the MOP to form a dispersion and / or formulation thereof.

[0087] Ester Dispersion Medium The non-aqueous compositions for dispersing metal oxide particles, as well as the dispersions and formulations herein, comprise a non-aqueous ester dispersant (EDM). As used interchangeably herein, an "ester dispersant" or simply an "ester" is an ester that has physical properties suitable for use as a dispersant, e.g., the ester is liquid (at room temperature, e.g., 25°C) and / or the ester has a viscosity of less than about 100 cSt at 25°C. Esters suitable as ester dispersants can be branched chain esters, unsaturated esters, and / or triglyceride esters, as described in more detail below.

[0088] In embodiments herein, the ester comprises one or more R groups selected such that the ester is a liquid at 25°C.

[0089] As contemplated herein, the compositions, dispersions, and formulations of the present invention may contain, in addition to ester dispersion media, other esters (non-EDM as defined herein). Non-EDM esters that may be present include waxy esters for structuring formulations and films, improving water repellency, etc. Examples of non-EDM esters include, but are not limited to, hydrogenated rapeseed oil, jojoba esters, hydrogenated jojoba oil, and synthetic beeswax.

[0090] The present inventors have surprisingly discovered that branched chain esters, unsaturated esters, and / or triglyceride esters are suitable for non-aqueous compositions for MOP dispersions due to their ability to reduce the viscosity of such compositions when combined with broad MWD PEDAs (described below).

[0091] The non-aqueous composition can include an ester having a branched alkyl group or an unsaturated alkyl group. For purposes herein, the branch point may be defined relative to any carbon or heteroatom in the molecule, or may refer to a stereocenter. For example, in certain embodiments, the methyl branch is located at the 1-position, e.g., the methyl branch is located on the carbon atom bearing the hydroxyl group of an alcohol, such as 1-methylheptyl alcohol, as shown below. [ka]

[0092] In some embodiments, the non-aqueous composition for dispersing metal oxide particles comprises an ester of Formula I: [ka] (wherein R and R1 are each a linear, branched, or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl, and when one of R and R1 is a linear alkyl, the other of R and R1 is a branched or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl). In some embodiments, R is a C5-C 17 R1 is a branched or cyclic alkyl, a linear, branched or cyclic alkenyl, or a linear, branched or cyclic alkynyl, 18 In some embodiments, the ester is of Formula I, wherein R and R are different. In some embodiments, R is preferably C 10 R is even more preferably C 10 In some embodiments, R1 is preferably C6-C 12 It is straight-chain saturated. R1 is even more preferably a C7 to C8 straight-chain saturated.

[0093] An example of an ester according to formula (I) includes heptyl undecylenate (LexFeel™ Natural, INOLEX, Inc.) according to structure (Ii). [ka]

[0094] In addition to the above-mentioned heptyl undecylenate, other examples of esters include octyl undecylenate and / or decyl undecylenate.

[0095] In other embodiments, the non-aqueous composition for dispersing metal oxide particles comprises an ester of formula (II): [ka] wherein R2 is a branched chain alkyl, a straight or branched chain alkenyl, or a straight or branched chain alkynyl; R3 is a straight or branched chain alkyl, a straight or branched chain alkenyl, or a straight or branched chain alkynyl; and R4 is a straight or branched chain alkyl, a straight or branched chain alkenyl, or a straight or branched chain alkynyl. In some embodiments, R2 is a C3-C 18 R3 is a C2 to C8 straight chain or branched chain alkyl, straight chain or branched chain alkenyl, or straight chain or branched chain alkynyl; R4 is a C3 to C8 straight chain or branched chain alkyl, straight chain or branched chain alkenyl, or straight chain or branched chain alkynyl; 18 In some embodiments, the ester is of Formula II, and R2 and R4 are the same. In some embodiments, R2 and R4 are preferably branched C4-C 18 , more preferably branched C5 to C 18 and even more preferably branched C6 to C 12 In some embodiments, R3 is preferably a straight chain C2-C8.

[0096] An example of an ester according to formula II includes diisooctyl succinate (SustOleo™ DCS, INOLEX, Inc.) according to structure (II-i). [ka]

[0097] In other embodiments, the non-aqueous composition for dispersing metal oxide particles comprises an ester of formula (III): [ka] wherein R5 is a branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; R6 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; and R7 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne. In some embodiments, R5 is a C3-C 18 R6 is a C2 to C8 straight-chain or branched alkyl, a straight-chain or branched alkene, or a straight-chain or branched alkyne; R7 is a C3 to C8 straight-chain or branched alkyl, a straight-chain or branched alkene, or a straight-chain or branched alkyne; 18 In some embodiments, the ester is of Formula III, wherein R5 and R7 are the same.

[0098] Examples of esters according to formula (III) include propylene glycol diisostearate and propylene glycol diundecylenate.

[0099] In yet other embodiments, the non-aqueous composition comprises an ester such as a triglyceride compound of formula (IV). [ka] (Wherein R8, R9, and R 10 are each independently 5 to 18 carbon atoms (C5 to C 18 In some embodiments, R, R, and R are selected from linear, branched, saturated, or unsaturated alkyl groups, including alkyl groups. 10 Two or more of the are the same.

[0100] An example of an ester according to formula (IV) is triheptanoin (SustOleo™ MCT, INOLEX, Inc.), which is a 100% natural non-palm oil medium chain triglyceride according to structure (IV-i). [ka]

[0101] Another example of a suitable triglyceride is caprylic / capric triglyceride (CCT), such as Lexol™ GT-865 MB from INOLEX, Inc., where R8, R9, and R1 of Structure IV are substituted. 10 are independently linear CH 15 or C9H 19 i.e., the triglycerides are either C8 acyl (caprylate) and C 10 Contains a mixture of acyl (caprate) ester moieties.

[0102] Typically, such triglyceride esters are not suitable for non-aqueous compositions for dispersing MOPs because the dispersion viscosity increases when combined with PEDA. Surprisingly, the present inventors have discovered that, in addition to the esters having branched or unsaturated alkyl groups described above, triglyceride esters are suitable for non-aqueous compositions for dispersing MOPs when used in combination with PEDAs having a broad MWD. ​​Therefore, the triglyceride esters disclosed herein are suitable as EDMs used in combination with PEDAs having a broad MWD.

[0103] The non-aqueous compositions for dispersing metal oxide particles herein may comprise an ester selected from the group consisting of: (i) a liquid ester of Formula I, (ii) a liquid ester of Formula II, (iii) a liquid ester of Formula III, (iv) a liquid ester of Formula IV, and combinations thereof. In some embodiments, the dispersions and / or formulations herein comprise a liquid ester of Formula I, Formula II, Formula III, Formula IV, and combinations thereof.

[0104] In some embodiments, the EDM of the non-aqueous compositions and / or dispersions herein has a viscosity of less than about 100 cSt at 25° C. In preferred embodiments, the EDM has a viscosity of less than about 50 cSt at 25° C. More preferably, the EDM has a viscosity of less than 25 cSt at 25° C.

[0105] The carbon present in the EDM described above can be 100% bio-based. In embodiments herein, the carbon atoms of the EDM comprise greater than about 50%, e.g., greater than 70%, greater than 80%, greater than 90%, greater than 95%, or greater than 99% bio-based carbon (see above). 14 (as determined by C radiocarbon dating or other methods known to one of skill in the art). In some embodiments, the EDM comprises 100% bio-based carbon. In some embodiments, substantially all of the carbon present in the compound of formula (IV) is bio-based. Preferred embodiments herein include those in which the EDM comprises 100% bio-based carbon.

[0106] The non-aqueous EDM optionally also contains one or more other non-aqueous organic fluids that are miscible with the primary ester component and acceptable for cosmetic use. Examples of suitable non-aqueous organic fluids include hydrocarbons, cyclic alkyl carbonates, dialkyl carbonates, dialkyl ketones, and the like.

[0107] By describing a composition and / or dispersion herein as "non-aqueous," we mean that the composition (and / or dispersion) is substantially free of added water, preferably containing less than about 3% by weight water, more preferably less than about 1% by weight water, even more preferably less than about 0.5% by weight water, and most preferably less than about 0.1% by weight water. Non-aqueous compositions (and / or dispersions) may contain trace amounts of incidental water (e.g., due to absorption of ambient moisture) or water due to processing conditions (e.g., incomplete drying after washing).

[0108] Polyester Dispersant Non-aqueous compositions for dispersing metal oxide particles, as well as dispersions and formulations herein, can include broad MWD polyester dispersants (PEDAs). As used herein, "polyester dispersant" and "polyester" are used interchangeably, and polyester dispersants (PEDAs) have broad MWDs and perform specific functions as defined below. Surprisingly, it has been found that EDMs, including those containing the triglyceride esters described above, are suitable for compositions and MOP dispersions herein that use broad MWD PEDAs.

[0109] As contemplated herein, the compositions of the present invention may further include other polyesters (non-PEDA as defined herein) in addition to the broad MWD PEDA. The additional non-PEDA polyesters may include, for example, polyester film formers to, among other things, improve water resistance.

[0110] The non-aqueous composition comprises a water-insoluble linear aliphatic polyester. In some embodiments, the polyester is carboxy-functional, i.e., one or more chain ends are terminated with a carboxylic acid moiety. The PEDA herein may have a terminal carboxylic acid functional group. Thus, the PEDA described herein may be a carboxylic acid-terminated polyester dispersant. For example, the PEDA may contain a single terminal carboxylic acid functional group, or two terminal carboxylic acid functional groups.

[0111] Polyesters as embodied herein may be characterized by their polydispersity index (PDI) as determined by size exclusion chromatography (SEC), gel permeation chromatography (GPC), or matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, and by their weight average molecular weight (M w ) and M n The ratio of PDI to M w / M n [See Introduction to Physical Polymer Science, 3rd Edition by L.H. Sperling, Chapter 3, Wiley-Interscience, 2001.]

[0112] Higher PDI values ​​correspond to broader MWDs for a given polyester. The PDI values ​​for polyesters herein may be, in terms of lower limits, greater than about 2, e.g., greater than 2.0, greater than 2.2, or greater than 2.4. In preferred embodiments, the polyesters have a polydispersity index (PDI) greater than about 2.3, greater than about 2.4, or more preferably greater than about 2.5. The polyesters used herein may have a polydispersity index (PDI) in the range of, for example, 2.0 to 3.0, 2.2 to 2.8, or 2.3 to 2.7.

[0113] PEDA suitable for the compositions, dispersions, and formulations herein has a number average molecular weight (M) determined by size exclusion chromatography (SEC) or gel permeation chromatography (GPC). n The polyesters described herein may be characterized by a number average molecular weight (M) value of less than about 10,000 g / mol. n ) Polyester M n Values ​​can range, for example, from about 750 g / mol to 10,000 g / mol, e.g., from 750 g / mol to 5,000 g / mol, from 750 g / mol to 2,500 g / mol, or from 800 g / mol to 2,500 g / mol.

[0114] The PEDA herein may be characterized by its acid value (measured by AOCS Official Method Te 2a-64). In some embodiments, the PEDA has an acid value of at least 15 mg KOH / g. The acid value of the PEDA may be, for example, in the range of about 15 mg KOH / g to about 100 mg KOH / g, e.g., 20 mg KOH / g to 90 mg KOH / g, 25 mg KOH / g to 80 mg KOH / g, or 30 mg KOH / g to 75 mg KOH / g. The acid value of the PEDA may be, at its lower limit, greater than about 15 mg KOH / g, e.g., greater than 20 mg KOH / g, greater than 25 mg KOH / g, or greater than 30 mg KOH / g. The acid value of the PEDA may be, at its upper limit, less than about 100 mg KOH / g, e.g., less than 90 mg KOH / g, less than 80 mg KOH / g, or less than 75 mg KOH / g.

[0115] In some embodiments, the non-aqueous composition for dispersing MOP for use in the dispersions and / or formulations herein comprises a polyester homopolymer derived from the condensation polymerization of a hydroxyalkanoic acid of formula (V): [ka] (wherein R is a group having 5 to 23 carbon atoms (C5 to C 23 ), and R' is selected from H or alkyl groups having 1 to 22 carbon atoms (C1 to C 22 ) is selected from linear, branched, cyclic, saturated or unsaturated alkyl or acyl groups including

[0116] Examples of polyesters according to formula (V) include polyhydroxystearic acid (structure shown in (Vi) below), polyhydroxystearic acid stearate (polyhydroxystearic acid in which some or all of the hydroxyl groups have reacted with stearic acid to give stearic acid esters), polyhydroxystearyl succinate (polyhydroxystearic acid in which some or all of the hydroxyl groups have reacted with succinic acid to give succinic acid monoesters and / or diesters), and polyhydroxystearyl sebacate (polyhydroxystearic acid in which some or all of the hydroxyl groups have reacted with sebacic acid to give sebacic acid monoesters and / or diesters), polyricinoleic acid, and carboxy-terminated estolides derived from oleic acid, such as cocooleate estolides. Monoesters of polyhydroxystearyl succinate and monoesters of polyhydroxystearyl sebacate are shown in Figures V-ii and V-iii below, respectively. Diesters of polyhydroxystearyl succinate and polyhydroxystearyl sebacate are shown in Figure V-iv below (where R 10 = succinoyl [C(O)(CH2)2C(O)] or sebacoyl [C(O)(CH2)8C(O)], and R 11 =C 17 H 34 ). [ka]

[0117] In some embodiments, the polyester may be a polyester copolymer derived from the condensation polymerization of two or more difunctional monomers, such as a diol and a diacid or dibasic ester (e.g., methyl ester), according to structure (VI): [ka] (wherein R is a group having 2 to 34 carbon atoms (C2 to C 34 ), and R' is selected from linear, branched, cyclic, saturated, or unsaturated alkyl groups containing 2 to 34 carbon atoms (C2 to C 34 ), and R″ is selected from H or a group having 1 to 22 carbon atoms (C1 to C 22 The acid-functional monomer is selected from linear, branched, cyclic, saturated, or unsaturated alkyl or acyl groups, including carboxyl groups. An excess of acid-functional monomer is required to ensure that the majority of the polyester copolymer chain ends are carboxyl functional. The polyester copolymer may be end-capped with an ester group, but contains carboxylic acid functionality on at least one chain end. Alternatively, hydroxy-functional polyesters may be COOH-end-capped via post-polymerization reaction with an anhydride, such as succinic anhydride.

[0118] For example, copolymerization of 1,2-pentanediol (pentylene glycol, R' = 1,2-substituted n-pentyl) with sebacic acid in a slight molar excess can give carboxy-terminated telechelic (double-end functionalized) poly(1,2-pentylene sebacate). An example of a polyester according to formula (VI) is a pentylene glycol / sebacic acid copolymer according to structure (VI-i): [ka] where R is a 1,8-substituted n-octyl and R' is a 1,2-substituted n-pentyl.

[0119] In some embodiments, the polyester is a carboxylic acid-terminated polyester, including a linear polyester terminated with one carboxylic acid group. In other embodiments, the carboxylic acid-terminated polyester includes a linear polyester terminated with two carboxylic acid groups, or a telechelic linear polyester terminated with carboxylic acid groups at both chain ends. In yet other embodiments, the carboxylic acid-terminated polyester includes a homopolymer derived from AB hydroxycarboxylic acid monomers. In yet other embodiments, the carboxylic acid-terminated polyester includes a copolymer derived from AA diol and BB diacid or dibasic (e.g., methyl ester) monomers. In preferred embodiments, the PEDA does not contain unsaturation within the polymer backbone or as pendant groups, i.e., the PEDA does not contain C=C double bonds susceptible to oxidative degradation.

[0120] The carboxylic acid terminated polyester may be selected from the group consisting of polyhydroxystearic acid, polyhydroxystearic acid stearate, polyhydroxystearyl succinate, polyhydroxystearyl sebacate, and combinations thereof.

[0121] The polyester dispersant described above comprises bio-based carbon. In embodiments herein, the carbon atoms of the polyester comprise greater than about 90%, e.g., greater than 95%, greater than 96%, greater than 97%, greater than 98%, or greater than 99% bio-based carbon (as described above). 14 (as determined by C radiocarbon dating or other methods known to those skilled in the art). In some embodiments, the polyester comprises 100% bio-based carbon. In some embodiments, substantially all of the carbon present in the compound of Formula (V), Formula (VI), or combinations thereof is bio-based. Preferably, the polyester is composed of renewable bio-based carbon. In a preferred embodiment, the carboxylic acid terminated polyester comprises 100% bio-based carbon.

[0122] Dispersion preparation / method The non-aqueous dispersions herein can advantageously contain a high loading of metal oxide particles. The non-aqueous dispersions contain a weight fraction of metal oxide particles in the range of about 15 wt% to about 75 wt%, e.g., 25 wt% to 75 wt%, 30 wt% to 75 wt%, 35 wt% to 75 wt%, 40 wt% to 75 wt%, 45 wt% to 75 wt%, 50 wt% to 75 wt%, or 40 wt% to 60 wt%, based on the total weight of the non-aqueous dispersion. Regarding lower limits, the dispersions can contain a weight fraction of metal oxide particles greater than 15 wt%, greater than 25 wt%, greater than 30 wt%, greater than 35 wt%, greater than 40 wt%, greater than 45 wt%, or greater than 50 wt%. In preferred embodiments, the MOP fraction in the dispersion is greater than 40 wt%, or greater than 45 wt%.

[0123] The non-aqueous dispersion herein desirably contains a high loading of metal oxide particles, also in terms of volume fraction. The non-aqueous dispersion contains a solid particle volume fraction of metal oxide particles in the range of about 20 vol% to about 80 vol%, for example, 25 vol% to 75 vol%, 30 vol% to 70 vol%, 35 vol% to 70 vol%, 40 vol% to 70 vol%, 45 vol% to 65 vol%, or 50 vol% to 65 vol%, based on the total volume of the non-aqueous dispersion. Regarding lower limits, the dispersion can contain a volume fraction of metal oxide particles greater than 20 vol%, greater than 25 vol%, greater than 30 vol%, greater than 35 vol%, greater than 40 vol%, greater than 45 vol%, or greater than 50 vol%. In preferred embodiments, the MOP fraction in the dispersion is greater than 50 vol%, greater than 60 vol%, or greater than 70 vol%.

[0124] The level (or concentration) of polyester in the dispersion is selected to achieve the lowest possible dispersion viscosity. The dispersion composition comprises about 1.00 wt. % to about 10.00 wt. % of the polyester, e.g., 1.00 wt. % to 7 wt. %, 2.00 wt. % to 6.00 wt. %, or 3.00 wt. % to 5.00 wt. % of the polyester. In a preferred embodiment, the dispersion composition comprises 3.00 wt. % to 5.00 wt. % of the polyester. The amount of polyester required to achieve a stable, low-viscosity dispersion generally increases as the loading of MOP in the dispersion increases.

[0125] The methods herein include preparing a non-aqueous composition for dispersing metal oxide particles. In some embodiments, the methods include adding one or more components to the non-aqueous composition to form a non-aqueous dispersion and / or formulation.

[0126] The dispersion can be prepared according to any technique well known to those skilled in the art of pigment dispersions. The dispersion is preferably prepared by first preparing a non-aqueous composition. The non-aqueous composition can be prepared by dissolving the polyester in the ester to form a homogeneous solution. The method then involves adding the metal oxide particles to the homogeneous solution (or mixture) while applying sufficient mixing and shear to ensure a homogeneous non-aqueous dispersion. Heat may be applied to improve dissolution of the polyester in the ester. In addition to, or instead of, heating, high shear mixing using a rotor-stator homogenizer, Cowles blade, colloid mill, or other high shear device can be performed to ensure optimal dispersion and stabilization of the metal oxide particles.

[0127] In some embodiments, the method includes mixing EDM and broad MWD PEDA to form a homogeneous solution (or mixture). The esters include those selected from Formula (I), Formula (II), Formula (II), Formula (IV), and combinations thereof, as described above. The method can include a triglyceride, such as Formula IV, detailed above. The method can include an ester having a viscosity of less than about 100 cSt at 25°C. The carbon present in the ester is 100% biobased.

[0128] The method may include the polyester having a polydispersity index (PDI) of greater than about 2.3, about 2.4, or about 2.5. The polyester may include a single terminal carboxylic acid functional group. In other embodiments, the method includes the polyester including two terminal carboxylic acid functional groups.

[0129] The method comprises: providing a polyester having a number average molecular weight (M) of less than about 10,000 g / mole; nThe polyester may have an acid number of at least 15 mg KOH / g. The method may include the polyester being selected from the group consisting of polyhydroxystearic acid, polyhydroxystearic acid stearate, polyhydroxystearyl succinate, polyhydroxystearyl sebacate, and combinations thereof. The carbon present in the polyester is 100% biobased.

[0130] The non-aqueous dispersions described herein preferably exhibit low viscosity for ease of processing (e.g., mixing, pumping, etc.), handling, and application. In some embodiments, the methods include those in which the non-aqueous dispersion has a viscosity of less than about 1000 cP. The viscosity of the dispersion composition can be, in terms of upper limits, less than about 1000 cP, e.g., less than 1000 cP, less than 900 cP, less than 750 cP, less than 500 cP, less than 300 cP, or less than 200 cP.

[0131] These low-viscosity non-aqueous metal oxide particle dispersions have a ratio of inorganic solid particles, i.e., metal oxide particles, to ester dispersion medium, ranging from about 1 to 0.33 (1:0.33) to about 1 to 5 (1:5), by weight. In a preferred embodiment, the non-aqueous dispersion has a ratio of inorganic particles to ester of about 1 to about 0.67 (1:0.67). In a more preferred embodiment, the non-aqueous dispersion has a ratio of inorganic particles to ester of about 1 to about 1 (1:1).

[0132] Non-aqueous dispersions and formulations containing non-aqueous dispersions may be free or substantially free of silicones such as methicone, dimethicone, cyclopentasiloxane, etc. "Silicone-free" compositions and formulations contain less than about 1% by weight, preferably less than about 0.5% by weight, more preferably less than about 0.1% by weight of silicone components, or most preferably no measurable concentration or amount of silicone.

[0133] The non-aqueous dispersion should be stable upon preparation, meaning that no settling, separation, or dramatic change in viscosity should occur from the time of preparation to the time of use. This typically means that the dispersion is stable for days to weeks after preparation. The ability to easily redisperse the settled solids by agitating the settled dispersion, for example, using a mixer or shaker, is also a favorable indicator of dispersion stability when lower solids loading is desired, for example, so that there is insufficient colloidal packing and / or yield value to prevent settling.

[0134] The method may include preparing a homogeneous solution in advance so that the MOP can be added later, i.e., the MOP components may have the option of being added later to form the non-aqueous dispersion. Thus, the method may further include dispersing metal oxide particles in the mixture to form the non-aqueous dispersion. The metal oxide particles may include zinc oxide, titanium oxide, combinations thereof, as well as other metal oxides listed above.

[0135] The non-aqueous dispersion may be substantially free of silicone.

[0136] The composition of the non-aqueous dispersion may be used as is or may be used to formulate a final product. For example, the dispersion may be formulated into a variety of product formats, such as oil-in-water (O / W) emulsions, water-in-oil (W / O) emulsions, creams, lotions, pastes, sprays, sticks, etc.

[0137] The method may further include adding at least one additional ingredient to form the formulation. The at least one additional ingredient may be a film-forming polymer (polyester-7, polyester-10, trimethylpentanediol / adipic acid / glycerin crosspolymer, adipic acid / diglycol crosspolymer, ethylcellulose, acrylates copolymer (e.g., Avalure™ AC series by Lubrizol), polyurethane-62, PPG-17 / IPDI / DMPA copolymer, etc.), a rheology-modifying polymer (acrylates copolymer, carbomer, acrylates / C10-30 alkyl acrylate crosspolymer, acrylates / beheneth-25 methacrylate copolymer, sodium acrylate / sodium acryloyldimethyl taurate copolymer, acrylates / vinyl neodecanoate crosspolymer, hydroxypropyl methylcellulose, hydroxyethyl cellulose, polyurethane-79, etc.), a wax (cera alba (beeswax), Euphorbia cerifera (candelilla) wax, Copernicia prunifera (copernicia japonica) wax, or the like). Prunifera (carnauba) wax, microcrystalline wax, etc.), emulsifiers (ceteareth-12, PEG-100 stearate, glyceryl stearate, brassica glycerides, brassica alcohol, laureth-4, potassium cetyl phosphate, etc.), emollients (petrolatum, mineral oil, sunflower oil, squalene, almond oil, etc.), humectants (glycerin, urea, betaine, etc.), pH adjusters, antioxidants, fragrances, multifunctional ingredients, preservative technologies, or combinations thereof. In some embodiments, the formulation is a sunscreen.

[0138] Other components may also be provided, including components known in the art of sunscreen formulations or components for use in personal care compositions, such as cosmetics. The compositions may optionally include, for example, surfactants, buffers, fragrances, colorants, dyes, viscosity modifiers, water, oils, emulsifiers, preservatives, antioxidants, emollients, thickeners, gelling agents, vitamins, moisturizers, alcohol, plant extracts, and powders. Other suitable additives or components may include one or more oils in the product, such as, for example, almond oil, castor oil, coconut oil, corn (maize) oil, cottonseed oil, canola oil, linseed oil, hempseed oil, nut oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower oil, jojoba oil, or a combination of these oils.

[0139] The personal care composition may include surfactants such as, for example, anionic surfactants, zwitterionic surfactants, cationic surfactants, nonionic surfactants, or combinations thereof. Other exemplary components or additives may include, but are not limited to, lipids, additional alcohols, waxes, pigments, vitamins, fragrances, whitening agents, antibacterial agents, anti-inflammatory agents, antifungal agents, thickeners, gums, starches, chitosan, polymeric materials, cellulosic materials, glycerin, proteins, amino acids, keratin fibers, fatty acids, siloxanes, botanical extracts, abrasives and / or exfoliants (chemical or mechanical), anti-caking agents, antioxidants, binders, biological additives, buffers, bulking agents, chelating agents, chemical additives, denaturants, topical analgesics, film formers, moisturizers, opacifiers, pH adjusters, preservatives, propellants, reducing agents, sunscreens, skin darkening agents, essential oils, skin sensates, or combinations thereof.

[0140] The personal care compositions of the present invention may also include one or more optical brighteners as described in U.S. Patent Application Publication No. 2011 / 0104078, which is incorporated herein by reference, including, for example, triazine-stilbenes (di-, tetra-, or hexa-sulfonated), coumarins, imidazolines, diazoles, triazoles, benzoxazolines, and biphenylstilbenes.

[0141] Also within the scope of the present invention is a method for protecting mammalian skin, hair, and / or nails from damage caused by exposure to ultraviolet wavelength light by applying a composition as described above to the skin, hair, or nails. "Skin" includes the outer coat of living mammals, reptiles, amphibians, birds, and other animals, as well as processed hides such as leather or suede. "Hair" includes hair, fur, wool, and other thread-like keratinized structures of mammals or other animals. Similarly, "nail" includes claws, hooves, and similar structures of mammals and other animals.

[0142] Also within the scope of the present invention is a method for improving the aesthetics of photoprotective formulations by using the compositions in a manner that avoids the feeling of oiliness and / or stickiness when the skin is moist, damp, or otherwise wet, without significant loss or separation of ingredients.

[0143] formulation In some embodiments, the present invention relates to dispersion compositions comprising metal oxide particles that can be used in formulations for a variety of applications. The dispersion compositions or formulations can be, or be components of, personal care products, home care products, fabric care products, institutional care products, pharmaceuticals, veterinary products, foods, or industrial products. In some embodiments, the compositions can be used in the formulation of, or be components of, personal care products. Personal care products include cosmetics, hair, nail, skin or fabric conditioners, shampoos, hair styling products, oils or waxes for grooming facial hair, permanent wave liquids, hair colorants, face or body washes, makeup removers, 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, mascaras, mouthwashes, toothpastes, oral care products, skin cleansing products, textile cleansing products, dish detergents, hair or fur cleansing products, and skin lotions or moisturizers. In a preferred embodiment, the formulation is a sunscreen.

[0144] The formulations herein can be used, for example, as skin protection creams, facial moisturizers, sunscreen lotions, nourishing creams, day creams, or night creams. Exemplary embodiments include creams, gels (including, but not limited to, hydrogels, hydrodispersed gels, and oil gels); lotions, alcoholic and aqueous / alcoholic solutions, various forms of emulsions (including, but not limited to, oil-in-water (O / W), water-in-oil (W / O), mixed emulsions, PIT emulsions, Pickering emulsions, microemulsions, and nanoemulsions); aerosol foams, non-aerosol foams, aerosol sprays, non-aerosol sprays, pump sprays, serums, roll-ons, pastes, balsams, or stick preparations. These compositions may also contain, as further adjuvants and additives, mild surfactants, co-emulsifiers, superfatting agents, pearlescent waxes, thickeners, thickeners, polymers, silicone compounds, fats, waxes, stabilizers, bioactive ingredients, deodorant active ingredients, antidandruff agents, film-forming agents, swelling agents, hydrotropic agents, preservatives, insect repellents, tanning agents, artificial self-tanning agents (e.g., dihydroxyacetone), stabilizers, perfume oils, dyes, antimicrobial agents, aqueous and non-aqueous plant extracts, etc. The amounts of cosmetic or dermatological adjuvants, carrier substances, and fragrances that can be used in each case can be determined by those skilled in the art depending on the nature of the product. In a preferred embodiment according to the present invention, the composition is a sunscreen formulation or sunscreen with an SPF of 30 or more. SPF is determined in accordance with ISO 24444:2019 standard, "In Vivo Determination of the Sun Protection Factor (SPF)," and is specified in the Food and Drug Administration, Code of Federal Regulations, Title 21, §201.327, "Over-the-counter sunscreen drug products; required labeling based on effectiveness testing."

[0145] In some embodiments, the sunscreen active(s) and / or metal oxide are present in the formulation in an amount effective to provide sun protection consistent with the desired SPF of the composition, which may be from about 0.5% to about 75% by weight of the composition, preferably from about 5% to about 70% by weight of the composition, and most preferably from about 10% to about 40% by weight of the composition, although the amount may be adjusted based on the active ingredients selected to suit the desired end effect, as is known in the art.

[0146] In some cases, this section may explicitly exclude one or more of the above-mentioned components from the disclosed compositions, e.g., by claim language. For example, claim language may be modified to state that the disclosed compositions, formulations, methods, etc. do not utilize or include any one or more of the above-mentioned components.

[0147] The dispersion compositions and formulations described herein exhibit stability as a function of time and temperature.

[0148] Dispersion compositions and formulations disclosed herein can, for example, have an as-formulated viscosity that increases less than 1.3-fold after two weeks of storage at 25° C., or less than two-fold after four weeks of storage at 25° C. At higher storage temperatures, dispersion compositions and formulations disclosed herein can, for example, have an as-formulated viscosity that increases less than 1.4-fold after two weeks of storage at 45° C., or less than 8.3-fold after four weeks of storage at 45° C. At even higher storage temperatures, dispersion compositions and formulations disclosed herein can, for example, have an as-formulated viscosity that increases less than 2.2-fold after two weeks of storage at 50° C., or less than 19.3-fold after four weeks of storage at 50° C.

[0149] These detailed descriptions serve to illustrate the above general description and embodiments that form part of the present invention. These detailed descriptions are presented for purposes of example only and are not intended to limit the scope of the invention. [Example]

[0150] Dispersion Preparation. Examples of MOP dispersions were prepared according to the following procedure. The ester dispersant and polyester dispersant were placed in an appropriately sized glass beaker and heated with gentle mixing until the polyester was liquefied (approximately 50°C-60°C). The ester and polyester were mixed using a Silverson L5M-A laboratory high shear rotor / stator at 2000-2500 rpm for approximately 1 minute or until a clear, homogeneous solution was obtained. The MOP was added to the ester-polyester mixture and mixed at 5000-5500 rpm for 5 minutes to obtain a uniform dispersion. Generally, the mixing speed was adjusted as needed depending on the dispersion viscosity. Care was taken to ensure that all MOP was uniformly incorporated into the dispersion and that no undispersed MOP was present.

[0151] Brookfield Viscosity Determination. A Brookfield Model DV1 Digital Viscometer was used to determine dispersion viscosity. The spindle and rotation speed were selected to ensure that viscosity readings were taken within a torque window of 10% to 80% of the maximum torque range. For most dispersions, viscosity was recorded using an RV spindle 3 at rotation speeds of 10 rpm to 100 rpm.

[0152] Kinematic Viscosity Determination. Kinematic viscosity was determined in cSt (centistokes) using an Anton Paar Stabinger viscometer, model SVM 3001, meeting the requirements of ASTM method D7042.

[0153] Rheological parameters. Rheological parameter G' プラトー , G'' 周波数 , yield stress, and 0.1s -1 and 1s -1 Viscosity at 25°C was measured using a TA Instruments Discovery HR-20 rheometer using a standard 50 mm cone-plate geometry at a Peltier controlled temperature of 25°C, an angle of 2 degrees, and a gap of 52 μm. Yield stress values ​​were obtained from amplitude sweep tests (at 1 rad / s) using the modulus crossover method, yield stress = % strain.クロスオーバー / 100×√2G' クロスオーバー (Here, the distortion クロスオーバー and G' クロスオーバー is the value where G' and G'' intersect with each other, i.e., G' クロスオーバー =G'' クロスオーバー The plateau value of the storage modulus G' is determined using the shear flow function (see, for example, Utracki LA, Schlund B (1987) Linear low density polyethylenes and their blends. Part 2. Shear flow of LLDPE's. Polym Eng Sci 27:367-379; and Vega JF, Munoz-Escalona A, Santamaria A, Munoz ME, Lafuente P (1996) Comparison of the rheological properties of metallocene-catalyzed and conventional high-density polyethylenes. Macromolecules 29:960-965). プラトー The amplitude range of the linear response (required for frequency sweep testing) was also determined by amplitude sweep testing. The frequency dependence (kinetics of flow and relaxation) was determined by measuring both the storage modulus (G') and loss modulus (G'') in frequency sweep testing (% strain in the linear region, 0.03% strain to 0.1% strain for the measured compositions). G'' 周波数 was determined from measurements at a frequency of 1 rad / s. The viscosity and shear thinning behavior were determined from flow curve measurements (i.e., viscosity vs. shear rate (s -1 ) measurement).

[0154] In vitro UV transmittance measurements. The UV transmittance of compositions containing metal oxide particles (MOPs) was measured using a Labsphere UV-2000 UV transmittance analyzer for wavelengths between 250 nm and 450 nm. The protocol applied complies with the US FDA regulations (2011) for broad spectrum and UV1 / UV measurements. Specifically, 18.75 mg (milligrams) of the composition was measured in a 5 x 5 cm 2 The compositions were uniformly coated onto polymethyl methacrylate (PMMA) plates. The treated plates were left in the dark for 15 minutes before transmittance measurements. Transmittance was measured at five locations on each of three treated PMMA plates per composition (an untreated PMMA plate was used as a reference), and the average of these 15 measurements was used to determine the in vitro UV transmittance of that composition at a wavelength of 340 nm.

[0155] Dispersion Compositions Table 1 shows the dispersion compositions of Example E1 and Comparative Examples CE1 and CE2 prepared according to the methods described above in the amounts indicated.

[0156] Example E1 and Comparative Examples CE1 and CE2 Dispersion compositions using low MW (CE1), high MW (CE2), and wide MWD (E1) The MOP in Table 1 was Zano™ 10 (EverCare), a zinc oxide. In amounts of 2.00 wt%, 3.00 wt%, 4.00 wt%, 5.00 wt%, and 6.00 wt%, the polyester was Dispersun DSP-OL300 (Innospec), a polyhydroxystearic acid (for CE1), or in amounts of 3.00 wt%, 4.00 wt%, 5.00 wt%, and 6.00 wt%, the polyester was Dispersun DSP-OL100 (Innospec), a polyhydroxystearic acid (for CE2), or in amounts of 2.00 wt%, 3.00 wt%, 4.00 wt%, 5.00 wt%, and 6.00 wt%, the polyester was a 50 / 50 mix of Dispersun DSP-OL300 (Innospec), a polyhydroxystearic acid, and Dispersun DSP-OL100 (Innospec), for E1. The weight ratio of MOP to PEDA in all compositions ranged from about 25:1 to about 8:1. The MOP and EDM components were common to Example E1 and Comparative Examples CE1 and CE2, but the PEDA was different. The EDM was LexFeel™ Natural (INOLEX, Inc.), which is heptyl undecylenate.

[0157] [Table 1]

[0158] The dispersion composition of Example E1 was prepared using a broad MWD PHSA (PEDA). The dispersion composition of Example CE1 was prepared using a low MW PHSA (PEDA). The dispersion composition of Example CE2 was prepared using a high MW PHSA (PEDA).

[0159] The dispersion viscosity values ​​for Example E1 and Comparative Examples CE1 and CE2 are shown in Table 2 for polyester amounts of 2.00 wt%, 3.00 wt%, 4.00 wt%, 5.00 wt%, and 6.00 wt%.

[0160] As shown in Table 2, Example E1 exhibits lower viscosity values ​​relative to Comparative Examples CE1 and CE2 over the entire range of PEDA concentrations tested. These results are shown graphically in FIG.

[0161] [Table 2]

[0162] Advantages of high PDI polyester (wide MWD PEDA) Table 3 details the polymer property data for three different polyhydroxystearic acid (PHSA) polyesters. Acid number was used to quantify the amount of carboxylic chain end functionality for each polyester. Polyesters with higher acid number values ​​possess greater levels of carboxylic acid chain ends. The molecular weights of the polyesters were determined by end group analysis (EGA) and gel permeation chromatography (GPC). The number average molecular weights (M) determined by EGA and GPC were: n ) and number average degree of polymerization (DP n ) values ​​demonstrated good agreement. The slightly higher values ​​obtained by GPC are due to the use of polystyrene molecular weight calibration standards rather than direct calibration against polyhydroxystearic acid standards of known MW. GPC allowed the determination of weight average molecular weight values ​​(M w Information on the molecular weight distribution (MWD), characterized as the molecular weight (MW), and polydispersity index (PDI), was also obtained. High and low molecular weight PHSA polyesters exhibited PDI values ​​ranging from 2.08 to 2.26. High and low molecular weight PHSA polyesters have narrow molecular weight distributions. PHSAs with broader MWDs were created by preparing 50 / 50 wt% / wt% blends of high and low MW PHSA materials. This broad MWD PHSA was characterized by the M n and M wThe PDI value was 2.57, which was significantly higher. The PHSA polyesters used were as follows: low MW Dispersun DSP-OL300 (Innospec), high MW Dispersun DSP-OL100 (Innospec), and broad MWD, a 50 / 50 (by weight) blend of low and high MW PHSA polyesters.

[0163] Polyester property data

[0164] [Table 3]

[0165] The polyesters listed in Table 3 were used to prepare MOP dispersions of ZnO in the examples in Table 4 (as well as Table 1).

[0166] Examples E2-E5 and Comparative Examples CE3-CE10: Benefits of High PDI Polyesters (i.e., Broad MWD PHSA / PEDA) to Reduce Dispersion Viscosity Table 4 shows the various polyesters listed in Table 3 in combination with heptyl undecylenate in E2 and CE3 and CE4, or diisooctyl succinate in E3 and CE5 and CE6, or triheptanoin (C7 triglyceride) in E4 and CE7 and CE8, or caprylic / capric triglyceride (C8 / C9) in E5 and CE9 and CE10. 10 The compositions of various dispersions prepared using either ZnO MOP or ZnO MOP (triglycerides) are shown in Table 4. In the dispersions, the concentrations of polyester and ester were kept constant at 4.00 wt.% and 45.95 wt.%, respectively, with the remainder comprising the ZnO MOP. The viscosity of each dispersion is also shown in Table 4.

[0167] In all examples, the dispersions prepared using broad MWD PHSA polyesters (Examples E2-E5) exhibited lower viscosities than examples prepared using either low-MW PHSA polyesters or high-MW PHSA polyesters with lower PDI values ​​(i.e., narrower MWDs). The percent reduction in viscosity for various esters when broad MWD PHSAs were used in place of either low-MW or high-MW PHSA polyesters is shown in Table 5.

[0168] Viscosity of the dispersion composition

[0169] [Table 4]

[0170] Table 5. Reduction in dispersion viscosity when using broad MWD PHSAs (E2-E5) versus low MW PHSAs (CE3, CE5, CE7, CE9) and high MW PHSAs (CE4, CE6, CE8, CE10) for four different esters (EDM).

[0171] Reduced dispersion viscosity using broad MWD PHSA polyester

[0172] [Table 5]

[0173] In Table 5, the percent reduction for dispersions using low MWD PHSAs ranges from 8% to 93% relative to dispersions using either low MW PHSAs or high MW PHSAs.

[0174] The results shown in Tables 4 and 5 demonstrate the surprising effectiveness of using broad molecular weight polyesters in combination with esters according to the present invention, including triglycerides, in preparing low viscosity MOP dispersions, as compared to both low and high molecular weight polyesters.

[0175] Data for the supplied ester dispersion media is provided in Table 6 below.

[0176] [Table 6]

[0177] The results shown in Tables 7 and 8 demonstrate another aspect of the utility of the inventive compositions and formulations disclosed herein. Table 7 details example formulation E6, which utilized an ester (heptyl undecylenate, the same as E1) as the ester dispersant in combination with a broad MWD PEDA (polyhydroxystearic acid), as described in the polyester property data in Table 3 above. Table 7 also includes comparative formulation CE11, which contains the same ester as E6, but in combination with a low molecular weight PEDA, Dispersun DSP-OL300 (Innospec), as described in Table 3 above.

[0178] Table 8 lists the viscosities of E6 and CE11 determined upon formulation and after 2 and 4 weeks of storage at room temperature, 45°C, and 50°C, respectively. Both formulations E6 and CE11 show an increase in viscosity with increasing storage time, however, the rate of viscosity increase for CE11 is significantly higher than that of E6. After 4 weeks of storage at 45°C and 50°C, the viscosity of CE11 is well above 100,000 cP, making the formulation unusable, whereas the viscosity of E6 after 4 weeks at these temperatures is well within the usable range.

[0179] Formulations containing broad MWD PEDA (E6) and low molecular weight polyester (CE11)

[0180] [Table 7]

[0181] [Table 8]

[0182] Tables 9-11 provide formulation details for each example. Examples E7-E9 use an ester dispersant (i.e., triheptanoin for E7 and caprylic / capric triglyceride for E9) in combination with polyhydroxystearic acid (PHSA, 4 wt%) as a polyester dispersant with a broad molecular weight distribution, as described in the polyester property data in Tables 1-3 above. Comparative Examples CE12-CE14 use the same ester as the inventive examples, but with a narrow molecular weight distribution polyester dispersant. E7 and CE12 were made as water-in-oil (W / O) emulsions, E8 and CE13 were made as oil-in-water (O / W) emulsions, and E9 and CE14 were made as water-in-oil (W / O) emulsions.

[0183] An example sunscreen formulation was prepared as follows: Zinc oxide was dispersed into a mixture of polyester (PHSA) and ester (EDM) according to the formulation detailed herein and homogenized (Silverson L5M-A general purpose head) at 1000 rpm for 1 minute and 2500 rpm for 2 minutes.

[0184] The remaining oil phase components were then added and heated to 70°C to 75°C while mixing at 100 rpm using a propeller mixer.

[0185] In a separate vessel, the main batch ingredients were combined and heated to 70°C-75°C while mixing with a propeller mixer at 100 rpm.

[0186] The main batch ingredients were then added to the oil phase and homogenized at 2500 rpm for 5 minutes.

[0187] The formulation was then transferred to a propeller mixer at 250 rpm, allowed to cool, and the remaining ingredients were added at 40° C. and mixed for a further 5 minutes.

[0188] Mixing was continued until the temperature was below 30°C.

[0189] [Table 9]

[0190] [Table 10]

[0191] [Table 11]

[0192] To demonstrate the benefits of the present invention, sunscreen formulations made according to Tables 9-11 using different MOP dispersions were analyzed for finished formulation viscosity and in vitro UV transmittance values. Importantly, Inventive Examples E7-E9 demonstrated lower viscosity and lower in vitro UV transmittance values ​​compared to Comparative Examples CE12-CE14. It would be desirable to create sunscreen formulations that provide improved feel, texture, and spreading behavior (e.g., reduced viscosity, storage and loss moduli, and yield stress values) while providing sufficient sun protection properties (e.g., low UV transmittance) by achieving high levels of well-dispersed ZnO particles in the formulation.

[0193] As described above, two sunscreen formulations were made: an oil-in-water emulsion such as E8, and a water-in-oil emulsion such as E7 and E9.

[0194] Table 12 presents data for inventive examples (E7-E9) and comparative examples (CE12-CE14) to examine the effect of various ester / polyester MWD combinations on the rheological properties of finished sunscreen formulations using ZnO particle dispersions. In vitro UV transmittance values ​​were also measured and are listed in Table 12.

[0195] [Table 12]

[0196] The rheological parameters listed in Table 12 show that the viscosity, storage and loss moduli (G', G"), and yield stress values ​​are all lower for Inventive Examples E7-E9 compared to Comparative Examples CE12-CE14. Rheological parameters characterize materials in terms of feel, texture, and spreading behavior. Sunscreen formulations are typically very thick, sticky, and difficult to spread, i.e., they exhibit high viscosity, storage and loss moduli, and yield stress values. It is desirable to produce sunscreen formulations that have adequate sun protection properties but improved feel, texture, and spreading behavior. The Inventive Examples in Table 12 show improved behavior relative to the respective Comparative Examples listed in the same table. Specifically, the Inventive Examples have lower G' values ​​relative to the Comparative Examples. プラトー is half to one-fourth, and G'' 周波数 is half to one-third, the yield stress is two-thirds to one-quarter, and the 0.1s -1 Viscosity is 6.6% to 66% lower at 1s -1 The viscosity at room temperature is 26% to 300% lower. The dispersion quality of the MOP is important to achieve good sun protection and SPF values ​​at a given use level of the MOP. The in vitro UV transmittance of the inventive examples is 6% to 34% lower than the in vitro UV transmittance of the comparative examples. Table 13 shows the % reduction in rheological and UV transmittance parameters of inventive examples E7 to E9 and their respective comparative examples CE12 to CE14, where % reduction = (x 比較例 -x 本発明 ) / x 比較例 ×100 (where x is the parameter value of either the present invention or the comparative example in Table 12 above).

[0197] [Table 13]

[0198] Table 13 shows that in the examples using broad molecular weight distribution polyesters according to the present invention, the G' プラトー The percent reduction in G' is an average of 68 percent.周波数 The percent reduction in yield stress averaged 60 percent, and the percent reduction in 0.1s -1 The percent reduction in viscosity at 1s is an average of 35 percent. -1 The figures show an average percent reduction in viscosity of 50 percent and an average percent reduction in UV transmittance of 18 percent. Sunscreen formulations according to embodiments herein provide reduced UV transmittance (e.g., higher SPF factors) while increasing spreadability.

[0199] Embodiment Among other things, the following embodiments are disclosed:

[0200] Item 1. A non-aqueous composition for dispersing metal oxide particles, the composition comprising: (i) a liquid ester of formula I: [ka] (wherein R and R1 are each a linear, branched, or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl, and when one of R and R1 is a linear alkyl, the other of R and R1 is a branched or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl); (ii) Liquid esters of formula II: [ka] wherein R2 is branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; R3 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; and R4 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; (iii) Liquid esters of formula III: [ka] wherein R5 is a branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, R6 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, and R7 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; (iv) Liquid esters of formula IV: [ka] (Wherein R8, R9, and R 10 are each independently a C5-C 18 selected from linear, branched, saturated, or unsaturated alkyl groups; and (v) combinations of these; an ester selected from the group consisting of a polyester having a polydispersity index greater than about 2.3; A non-aqueous composition comprising:

[0201] Item 2. The ester is represented by formula I, and R is C5 to C 17 branched or cyclic alkyl, straight, branched or cyclic alkenyl, or straight, branched or cyclic alkynyl, and R1 is C3 to C 18 Item 2. The non-aqueous composition of item 1, wherein the alkyl group is a straight-chain, branched-chain, or cyclic alkyl, a straight-chain, branched-chain, or cyclic alkenyl, or a straight-chain, branched-chain, or cyclic alkynyl.

[0202] Item 3. The non-aqueous composition of item 1, wherein the ester is of formula I, and R and R1 are different.

[0203] Item 4. The ester is represented by formula II, and R2 is C3 to C 18 R3 is a C2 to C8 straight-chain or branched alkyl, straight-chain or branched alkenyl, or straight-chain or branched alkynyl; R4 is a C3 to C8 straight-chain or branched alkyl, straight-chain or branched alkenyl, or straight-chain or branched alkynyl; 18Item 2. The non-aqueous composition of item 1, wherein the alkyl group is a straight-chain or branched-chain alkyl, a straight-chain or branched-chain alkenyl, or a straight-chain or branched-chain alkynyl.

[0204] Item 5. The non-aqueous composition of item 1, wherein the ester is of formula II, and R2 and R4 are the same.

[0205] Item 6. The ester is represented by formula III, and R5 is C3 to C 18 R6 is a C2 to C8 straight-chain or branched alkyl, a straight-chain or branched alkene, or a straight-chain or branched alkyne; R7 is a C3 to C8 straight-chain or branched alkyl, a straight-chain or branched alkene, or a straight-chain or branched alkyne; 18 Item 1. The non-aqueous composition of item 1, wherein the alkyl group is a linear or branched chain alkyl, a linear or branched chain alkene, or a linear or branched chain alkyne.

[0206] Item 7. The non-aqueous composition of item 1, wherein the ester is of formula III, and R5 and R7 are the same.

[0207] Item 8. The ester is of formula IV, and R8, R9, and R 10 The non-aqueous composition of item 1, wherein two or more of:

[0208] Item 9. The non-aqueous composition of item 1, wherein the ester is selected from the group consisting of monoesters, diesters, triesters, and combinations thereof.

[0209] Item 10. The non-aqueous composition of item 1, wherein the ester has a viscosity of less than about 100 cSt at 25°C.

[0210] Item 11. The non-aqueous composition of Item 1, wherein the non-aqueous composition has a viscosity of less than 500 cP.

[0211] Item 12. The non-aqueous composition of item 1, wherein the carbon present in the ester is 100% bio-based.

[0212] Item 13. The non-aqueous composition of item 1, wherein the polyester has a polydispersity index (PDI) of greater than about 2.4.

[0213] Item 14. The non-aqueous composition of item 1, wherein the polyester has a polydispersity index (PDI) of greater than about 2.5.

[0214] Item 15. The non-aqueous composition of item 1, wherein the polyester contains a terminal single carboxylic acid functional group.

[0215] Item 16. The non-aqueous composition of item 1, wherein the polyester comprises two terminal carboxylic acid functional groups.

[0216] Item 17. The non-aqueous composition of item 1, wherein the polyester comprises a homopolymer derived from an AB hydroxycarboxylic acid monomer.

[0217] Item 18. The non-aqueous composition of item 1, wherein the polyester comprises a copolymer derived from an AA diol and a BB diacid or dibasic monomer.

[0218] Item 19. The non-aqueous composition of item 1, wherein the polyester is selected from the group consisting of polyhydroxystearic acid, polyhydroxystearic acid stearate, polyhydroxystearyl succinate, polyhydroxystearyl sebacate, and combinations thereof.

[0219] Item 20. The non-aqueous composition of item 1, wherein the polyester comprises polyhydroxystearic acid.

[0220] Item 21. The polyester has a number average molecular weight (M n Item 1. The non-aqueous composition of item 1.

[0221] Item 22. The non-aqueous composition of item 1, wherein the polyester has an acid value of at least 15 mg KOH / g.

[0222] Item 23. The non-aqueous composition of item 1, wherein the carbon present in the polyester is 100% bio-based.

[0223] Item 24. A non-aqueous composition for dispersing metal oxide particles, the composition essentially comprising: (i) a liquid ester of formula I: [ka] (wherein R and R1 are each a linear, branched, or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl, and when one of R and R1 is a linear alkyl, the other of R and R1 is a branched or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl); (ii) Liquid esters of formula II: [ka] wherein R2 is branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; R3 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; and R4 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; (iii) Liquid esters of formula III: [ka] wherein R5 is a branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, R6 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, and R7 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; (iv) Liquid esters of formula IV: [ka] (Wherein R8, R9, and R 10 are each independently a C5-C 18selected from linear, branched, saturated, or unsaturated alkyl groups; and (v) combinations of these; an ester selected from the group consisting of a polyester having a polydispersity index greater than about 2.3; A non-aqueous composition comprising:

[0224] Item 25. A non-aqueous composition for dispersing metal oxide particles, the composition comprising: (i) a liquid ester of formula I: [ka] (wherein R and R1 are each a linear, branched, or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl, and when one of R and R1 is a linear alkyl, the other of R and R1 is a branched or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl); (ii) Liquid esters of formula II: [ka] wherein R2 is branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; R3 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; and R4 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; (iii) Liquid esters of formula III: [ka] wherein R5 is a branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, R6 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, and R7 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; (iv) Liquid esters of formula IV: [ka] (Wherein R8, R9, and R 10 are each independently a C5-C 18 selected from linear, branched, saturated, or unsaturated alkyl groups; and (v) combinations of these; an ester selected from the group consisting of a polyester having a polydispersity index greater than about 2.3; A non-aqueous composition comprising:

[0225] Item 26. A non-aqueous dispersion, a plurality of metal oxide particles; (i) a liquid ester of formula I: [ka] (wherein R and R1 are each a linear, branched, or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl, and when one of R and R1 is a linear alkyl, the other of R and R1 is a branched or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl); (ii) Liquid esters of formula II: [ka] wherein R2 is branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; R3 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; and R4 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; (iii) Liquid esters of formula III: [ka] wherein R5 is a branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, R6 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, and R7 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; (iv) Liquid esters of formula IV: [ka] (Wherein R8, R9, and R 10 are each independently a C5-C 18 selected from linear, branched, saturated, or unsaturated alkyl groups; and (v) combinations of these; an ester selected from the group consisting of a polyester having a polydispersity index greater than about 2.3; A non-aqueous dispersion comprising:

[0226] Item 27. The non-aqueous dispersion of item 26, wherein the ester is selected from the group consisting of a monoester, a diester, a triester, or a combination thereof.

[0227] Item 28. The ester is of formula I, and R is C5 to C 17 branched or cyclic alkyl, straight, branched or cyclic alkenyl, or straight, branched or cyclic alkynyl, and R1 is C3 to C 18 Item 27. The non-aqueous dispersion according to Item 26, wherein the alkyl group is a linear, branched, or cyclic alkyl, a linear, branched, or cyclic alkenyl, or a linear, branched, or cyclic alkynyl.

[0228] Item 29. The non-aqueous dispersion of item 26, wherein the ester is of formula I, and R and R1 are different.

[0229] Item 30. The ester is of formula II, and R2 is C3 to C 18R3 is a C2 to C8 straight-chain or branched alkyl, straight-chain or branched alkenyl, or straight-chain or branched alkynyl; R4 is a C3 to C8 straight-chain or branched alkyl, straight-chain or branched alkenyl, or straight-chain or branched alkynyl; 18 Item 27. The non-aqueous dispersion according to Item 26, wherein the alkyl group is a linear or branched chain alkyl, a linear or branched chain alkenyl, or a linear or branched chain alkynyl.

[0230] Item 31. The non-aqueous dispersion of item 26, wherein the ester is of formula II, and R2 and R4 are the same.

[0231] Item 32. The ester is of formula III, and R5 is C3 to C 18 R6 is a C2 to C8 straight-chain or branched alkyl, a straight-chain or branched alkene, or a straight-chain or branched alkyne; R7 is a C3 to C8 straight-chain or branched alkyl, a straight-chain or branched alkene, or a straight-chain or branched alkyne; 18 Item 27. The non-aqueous dispersion according to Item 26, wherein the alkyl group is a linear or branched chain alkyl, a linear or branched chain alkene, or a linear or branched chain alkyne.

[0232] Item 33. The non-aqueous dispersion of item 26, wherein the ester is of formula III, and R5 and R7 are the same.

[0233] Item 34. The ester is of formula IV, wherein R8, R9, and R 10 Item 27. The non-aqueous dispersion of item 26, wherein two or more of the above are the same.

[0234] Item 35. The non-aqueous dispersion of item 26, having a viscosity of less than 1000 cP.

[0235] Item 36. The non-aqueous dispersion of item 26, wherein the ester has a viscosity of less than about 100 cSt at 25°C.

[0236] Item 37. The non-aqueous dispersion of item 26, wherein the carbon present in the ester is 100% bio-based.

[0237] Item 38. The non-aqueous dispersion of item 26, wherein the polyester has an acid value of at least 15 mg KOH / g.

[0238] Item 39. The non-aqueous dispersion of item 26, wherein the polyester contains a terminal single carboxylic acid functional group.

[0239] Item 40. The non-aqueous dispersion of item 26, wherein the polyester contains two terminal carboxylic acid functional groups.

[0240] Item 41. The non-aqueous dispersion of Item 26, wherein the polyester has a linear structure.

[0241] Item 42. The non-aqueous dispersion of item 26, wherein the carbon present in the polyester is 100% bio-based.

[0242] Item 43. The non-aqueous dispersion of item 26, wherein the polyester is selected from the group consisting of polyhydroxystearic acid, polyhydroxystearic acid stearate, polyhydroxystearyl succinate, polyhydroxystearyl sebacate, and combinations thereof.

[0243] Item 44. The nonaqueous dispersion of Item 26, wherein the metal oxide particles are not surface-modified.

[0244] Item 45. The non-aqueous dispersion of item 26, wherein the metal oxide particles comprise zinc oxide, titanium oxide, or a combination thereof.

[0245] Item 46. The non-aqueous dispersion of Item 26, wherein the metal oxide particles constitute about 15% by weight to about 75% by weight of the non-aqueous dispersion.

[0246] Item 47. The non-aqueous dispersion according to Item 26, wherein the metal oxide particles constitute about 40% by weight to about 60% by weight of the non-aqueous dispersion.

[0247] Item 48. The non-aqueous dispersion of Item 26, wherein the non-aqueous dispersion is substantially free of silicone.

[0248] Item 49. A non-aqueous dispersion, essentially: a plurality of metal oxide particles; (i) an ester of formula I: [ka] (wherein R and R1 are each a linear, branched, or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl, and when one of R and R1 is a linear alkyl, the other of R and R1 is a branched or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl); (ii) Esters of Formula II: [ka] wherein R2 is branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; R3 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; and R4 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; (iii) Esters of Formula III: [ka] wherein R5 is a branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, R6 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, and R7 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; (iv) Liquid esters of formula IV: [ka] (Wherein R8, R9, and R 10 are each independently a C5-C 18 selected from linear, branched, saturated, or unsaturated alkyl groups; and (v) combinations thereof; an ester selected from the group consisting of a polyester having a polydispersity index greater than about 2.3; A non-aqueous dispersion comprising:

[0249] Item 50. A non-aqueous dispersion, a plurality of metal oxide particles; (i) an ester of formula I: [ka] (wherein R and R1 are each a linear, branched, or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl, and when one of R and R1 is a linear alkyl, the other of R and R1 is a branched or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl); (ii) Esters of Formula II: [ka] wherein R2 is branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; R3 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; and R4 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; (iii) Esters of Formula III: [ka] (wherein R5 is a branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; R6 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; and R7 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne). (iv) Liquid esters of formula IV: [ka] (Wherein R8, R9, and R 10 are each independently a C5-C 18 selected from linear, branched, saturated, or unsaturated alkyl groups; and (v) combinations thereof; an ester selected from the group consisting of a polyester having a polydispersity index greater than about 2.3; A non-aqueous dispersion comprising:

[0250] Item 51. A formulation comprising the non-aqueous dispersion of any of items 26, 49, or 50, wherein the formulation 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 removers, 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, textile cleansing products, dishwashing detergents, hair or fur cleansing products, and skin lotions or moisturizers.

[0251] Item 52. The formulation of Item 51, wherein the formulation is a sunscreen or is a component of a sunscreen.

[0252] Item 53. The formulation of Item 51, wherein the formulation is an oil-in-water (O / W) emulsion or a water-in-oil (W / O) emulsion.

[0253] Item 54. The formulation of item 51, further comprising at least one additional ingredient selected from the group consisting of film-forming polymers, rheology-modifying polymers, waxes, emulsifiers, emollients, moisturizers, and combinations thereof.

[0254] Item 55. The formulation of Item 51, which has a viscosity as formulated, and the viscosity as formulated increases by less than 20 times when stored at 50°C for 4 weeks.

[0255] Item 56. A method for preparing a non-aqueous composition for dispersing metal oxide particles, the method comprising mixing an ester with a polyester having a polydispersity index (PDI) greater than about 2.3 to form a homogeneous solution, wherein the ester is: (i) a liquid ester of formula I: [ka] (wherein R and R1 are each a linear, branched, or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl, and when one of R and R1 is a linear alkyl, the other of R and R1 is a branched or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl); (ii) Liquid esters of formula II: [ka] wherein R2 is branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; R3 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; and R4 is straight or branched alkyl, straight or branched alkenyl, or straight or branched alkynyl; (iii) Liquid esters of formula III: [ka] wherein R5 is a branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, R6 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne, and R7 is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; (iv) Liquid esters of formula IV: [ka] (Wherein R8, R9, and R 10 are each independently a C5-C 18 selected from linear, branched, saturated, or unsaturated alkyl groups; and (v) combinations thereof; The method is selected from the group consisting of:

[0256] Item 57. The method of claim 56, wherein the ester is selected from the group consisting of monoesters, diesters, triesters, and combinations thereof.

[0257] Item 58. The ester is of formula I, wherein R is C5 to C 17 branched or cyclic alkyl, straight, branched or cyclic alkenyl, or straight, branched or cyclic alkynyl, and R1 is C3 to C 18 57. The method of claim 56, wherein the alkyl group is a straight-chain, branched-chain, or cyclic alkyl, a straight-chain, branched-chain, or cyclic alkenyl, or a straight-chain, branched-chain, or cyclic alkynyl.

[0258] Item 59. The method of item 56, wherein the ester is of formula I and R and R1 are different.

[0259] Item 60. The ester is of formula II, and R2 is C3 to C 18 R3 is a C2 to C8 straight-chain or branched alkyl, straight-chain or branched alkenyl, or straight-chain or branched alkynyl; R4 is a C3 to C8 straight-chain or branched alkyl, straight-chain or branched alkenyl, or straight-chain or branched alkynyl;18 57. The method of claim 56, wherein the alkyl group is a straight or branched chain alkyl, a straight or branched chain alkenyl, or a straight or branched chain alkynyl.

[0260] Item 61. The method of item 56, wherein the ester is of formula II and R2 and R4 are the same.

[0261] Item 62. The ester is of formula III, and R5 is C3 to C 18 R6 is a C2-C8 straight-chain or branched-chain alkyl, a straight-chain or branched-chain alkene, or a straight-chain or branched-chain alkyne; R7 is a C3-C8 straight-chain or branched-chain alkyl, a straight-chain or branched-chain alkene, or a straight-chain or branched-chain alkyne; 18 57. The method of claim 56, wherein the alkyl group is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne.

[0262] Item 63. The method of item 56, wherein the ester is of formula III and R5 and R7 are the same.

[0263] Item 64. The ester is of formula IV, wherein R8, R9, and R 10 57. The method of claim 56, wherein two or more of

[0264] Item 65. The method of item 56, wherein the ester has a viscosity of less than about 100 cSt at 25°C.

[0265] Item 66. The method of item 56, wherein the carbon present in the ester is 100% bio-based.

[0266] Item 67. The method of item 56, wherein the polyester has an acid number of at least 15 mg KOH / g.

[0267] Item 68. The method of item 56, wherein the polyester comprises a terminal single carboxylic acid functional group.

[0268] Item 69. The method of item 56, wherein the polyester comprises two terminal carboxylic acid functional groups.

[0269] Item 70. The method of item 56, wherein the polyester has a linear structure.

[0270] Item 71. The method of item 56, wherein the carbon present in the polyester is 100% bio-based.

[0271] Item 72. The method of item 56, wherein the polyester is selected from the group consisting of polyhydroxystearic acid, polyhydroxystearic acid stearate, polyhydroxystearyl succinate, polyhydroxystearyl sebacate, and combinations thereof.

[0272] Item 73. The method of item 56, further comprising dispersing a plurality of metal oxide particles in the non-aqueous composition to form a non-aqueous dispersion.

[0273] Item 74. The method of item 73, wherein the non-aqueous dispersion has a viscosity of less than 1000 cP.

[0274] Item 75. The method of item 73, wherein the metal oxide particles are not surface-modified.

[0275] Item 76. The method of item 73, wherein the metal oxide particles comprise zinc oxide, titanium oxide, or a combination thereof.

[0276] Item 77. The method of Item 73, wherein the metal oxide particles constitute about 15% by weight to about 75% by weight of the non-aqueous dispersion.

[0277] Item 78. The method of Item 73, wherein the metal oxide particles constitute about 40% by weight to about 60% by weight of the non-aqueous dispersion.

[0278] Item 79. The method of item 73, wherein the non-aqueous dispersion is substantially free of silicone.

[0279] Clause 80. The method of clause 73, further comprising adding at least one additional ingredient to form a formulation.

[0280] Clause 81. The method of clause 73, wherein the at least one additional ingredient is selected from the group consisting of film-forming polymers, rheology-modifying polymers, waxes, emulsifiers, emollients, moisturizers, and combinations thereof.

[0281] Item 82. The method of item 73, wherein the preparation is a sunscreen.

[0282] 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 be 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.

[0283] It should be further understood that all values ​​are approximate and are provided for illustrative purposes. All references cited and discussed herein are incorporated by reference in their entirety to the same extent as if each reference were incorporated by individual reference.

[0284] References -C. Agbo et al., A Review on the Mechanism of Pigment Dispersion, J. Disp. Sci. Tech., 2018, 39(6), 874-889 -DA Brune et al., Model for the Viscosity of Particle Dispersions; Journal of Macromolecular Science - Rev. Macromol. Chem. Phys., C39(4), 561-642 (1999). -BJ Naden et al. Adsorption of poly(hydroxystearic acid) to TiO2nanoparticles, studied using gel permeation chromatography, Coll. Surf. A.: Physicochem. Eng. Aspects, 2015, 478, 36-44. -Zinc oxide (nano form); What are the properties of ZnO nanoparticles?, https: / / ec.europa.eu / health / scientific_committees / opinions_layman / zinc-oxide / de / l-3 / 3.htm#. -Utracki LA, Schlund B (1987) Linear low density polyethylenes and their blends. Part 2. Shear flow of LLDPE's. Polym Eng Sci 27:367-379. -Vega JF, Munoz-Escalona A, Santamaria A, Munoz ME, Lafuente P (1996) Comparison of the rheological properties of metallocene-catalyzed and conventional high-density polyethylenes. Macromolecules 29:960-965. -U.S. Patent No. 9,254,398 -U.S. Patent Application Publication No. 2011 / 0104078

Claims

1. 1. A non-aqueous composition for dispersing metal oxide particles, the composition comprising: (i) A liquid ester of formula I: 【Chemistry 1】 (Wherein R and R １ are each a linear, branched, or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl; and R and R １ When one of R and R is a straight chain alkyl, １ the other is branched or cyclic alkyl; straight-chain, branched, or cyclic alkenyl; or straight-chain, branched, or cyclic alkynyl; (ii) Liquid esters of formula II: 【Chemistry 2】 (In the formula, R ２ is a branched chain alkyl, a straight or branched chain alkenyl, or a straight or branched chain alkynyl, and R ３ is a straight or branched chain alkyl, a straight or branched chain alkenyl, or a straight or branched chain alkynyl; R ４ is a straight or branched chain alkyl, a straight or branched chain alkenyl, or a straight or branched chain alkynyl; (iii) Liquid esters of formula III: 【Transformation 3】 (In the formula, R ５ is a branched alkyl, a straight or branched alkene, or a straight or branched alkyne; R ６ is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; R ７ is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; (iv) Liquid esters of formula IV: 【Chemistry 4】 (In the formula, R ８ , R ９ , and R １０ are each independently a C containing 5 to 18 carbon atoms ５ ~C １８ straight-chain, branched-chain, saturated, or unsaturated alkyl groups); and (v) combinations thereof; an ester selected from the group consisting of a polyester having a polydispersity index greater than about 2.3; A non-aqueous composition comprising:

2. A non-aqueous dispersion, (i) A liquid ester of formula I: 【Transformation 5】 (Wherein R and R １ are each a linear, branched, or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl; and R and R １ When one of R and R is a straight chain alkyl, １ the other is branched or cyclic alkyl; straight-chain, branched, or cyclic alkenyl; or straight-chain, branched, or cyclic alkynyl; (ii) Liquid esters of formula II: 【Transformation 6】 (In the formula, R ２ is a branched chain alkyl, a straight or branched chain alkenyl, or a straight or branched chain alkynyl, and R ３ is a straight or branched chain alkyl, a straight or branched chain alkenyl, or a straight or branched chain alkynyl; R ４ is a straight or branched chain alkyl, a straight or branched chain alkenyl, or a straight or branched chain alkynyl; (iii) Liquid esters of formula III: 【Transformation 7】 (In the formula, R ５ is a branched alkyl, a straight or branched alkene, or a straight or branched alkyne; R ６ is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; R ７ is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; (iv) Liquid esters of formula IV: 【Transformation 8】 (In the formula, R ８ , R ９ , and R １０ are each independently a C containing 5 to 18 carbon atoms ５ ~C １８ straight-chain, branched-chain, saturated, or unsaturated alkyl groups); and (v) combinations thereof; an ester selected from the group consisting of a polyester having a polydispersity index greater than about 2.3; a composition comprising: a plurality of metal oxide particles dispersed in the composition; A non-aqueous dispersion comprising:

3. The ester is In formula I, R is C ５ ~C １７ is a branched or cyclic alkyl, a linear, branched or cyclic alkenyl, or a linear, branched or cyclic alkynyl of the formula １ But C ３ ~C １８ straight-chain, branched or cyclic alkyl, straight-chain, branched or cyclic alkenyl, or straight-chain, branched or cyclic alkynyl; Formula II, wherein R ２ is C ３ ~C １８ is a branched chain alkyl, a straight or branched chain alkenyl, or a straight or branched chain alkynyl of the formula ３ is C ２ ~C ８ is a straight-chain or branched-chain alkyl, straight-chain or branched-chain alkenyl, or straight-chain or branched-chain alkynyl of ４ is C ３ ~C １８ straight-chain or branched-chain alkyl, straight-chain or branched-chain alkenyl, or straight-chain or branched-chain alkynyl; Formula III, wherein R ５ But C ３ ~C １８ is a branched alkyl, a straight or branched alkene, or a straight or branched alkyne of the formula ６ But C ２ ~C ８ is a linear or branched alkyl, a linear or branched alkene, or a linear or branched alkyne of the formula ７ But C ３ ~C １８ a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; and combinations of these, The non-aqueous composition of claim 1 or the non-aqueous dispersion of claim 2, selected from the group consisting of:

4. 3. The non-aqueous composition of claim 1 or the non-aqueous dispersion of claim 2, wherein the ester is selected from the group consisting of monoesters, diesters, triesters, and combinations thereof.

5. 3. The non-aqueous composition of claim 1 or the non-aqueous dispersion of claim 2, wherein the ester has a viscosity of less than about 100 cSt at 25°C.

6. 3. The non-aqueous composition of claim 1 or the non-aqueous dispersion of claim 2, wherein the polyester comprises a single terminal carboxylic acid functional group, two terminal carboxylic acid functional groups, a homopolymer derived from an AB hydroxycarboxylic acid monomer, a copolymer derived from an AA diol and a BB diacid or dibasic monomer, or a combination thereof.

7. 3. The non-aqueous composition of claim 1 or the non-aqueous dispersion of claim 2, wherein the polyester is selected from the group consisting of polyhydroxystearic acid, polyhydroxystearic acid stearate, polyhydroxystearyl succinate, polyhydroxystearyl sebacate, and combinations thereof.

8. The polyester has a number average molecular weight (M ｎ 3. The non-aqueous composition of claim 1 or the non-aqueous dispersion of claim 2, wherein the polyester has an acid number of at least 15 mg KOH / g.

9. 10. The non-aqueous composition of claim 1, wherein the carbon present in the ester is 100% bio-based and the carbon present in the polyester is 100% bio-based.

10. 3. The non-aqueous composition of claim 1 or the non-aqueous dispersion of claim 2, wherein the non-aqueous composition has a viscosity of less than 500 cP or the non-aqueous dispersion has a viscosity of less than 1000 cP.

11. 3. The non-aqueous dispersion of claim 2, wherein the metal oxide particles are not surface-modified or the metal oxide particles comprise zinc oxide, titanium oxide, or a combination thereof.

12. 3. The non-aqueous dispersion of claim 2, wherein the plurality of metal oxide particles constitutes from about 15% to about 75% by weight of the non-aqueous dispersion, or the plurality of metal oxide particles constitutes from about 40% to about 60% by weight of the non-aqueous dispersion.

13. 10. A formulation comprising the non-aqueous composition of claim 1 or the non-aqueous dispersion of claim 2, wherein the formulation 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 removers, 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, textile cleansing products, dish detergents, hair or fur cleansing products, and skin lotions or moisturizers.

14. 14. The formulation of claim 13, wherein the formulation is a sunscreen or a component of a sunscreen, or the formulation is an oil-in-water (O / W) emulsion or a water-in-oil (W / O) emulsion.

15. 1. A method for preparing a non-aqueous composition for dispersing metal oxide particles, the method comprising mixing an ester with a polyester having a polydispersity index (PDI) greater than about 2.3 to form a homogeneous solution, the ester comprising: (i) A liquid ester of formula I: 【Chemistry 9】 (Wherein R and R １ are each a linear, branched, or cyclic alkyl; a linear, branched, or cyclic alkenyl; or a linear, branched, or cyclic alkynyl; and R and R １ When one of R and R is a straight chain alkyl, １ the other is branched or cyclic alkyl; straight-chain, branched, or cyclic alkenyl; or straight-chain, branched, or cyclic alkynyl; (ii) Liquid esters of formula II: 【Chemistry 10】 (In the formula, R ２ is a branched chain alkyl, a straight or branched chain alkenyl, or a straight or branched chain alkynyl, and R ３ is a straight or branched chain alkyl, a straight or branched chain alkenyl, or a straight or branched chain alkynyl; R ４ is a straight or branched chain alkyl, a straight or branched chain alkenyl, or a straight or branched chain alkynyl; (iii) Liquid esters of formula III: 【Chemistry 11】 (In the formula, R ５ is a branched alkyl, a straight or branched alkene, or a straight or branched alkyne; R ６ is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; R ７ is a straight or branched chain alkyl, a straight or branched chain alkene, or a straight or branched chain alkyne; (iv) Liquid esters of formula IV: 【Chemistry 12】 (In the formula, R ８ , R ９ , and R １０ are each independently a C containing 5 to 18 carbon atoms ５ ~C １８ straight-chain, branched-chain, saturated, or unsaturated alkyl groups); and (v) combinations thereof; The method is selected from the group consisting of:

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