Metal oxide particulate ester dispersion comprising polyesters having

Abstract

The present invention relates to a non-aqueous based composition for dispersing metal oxide particles. The non-aqueous based composition comprises an ester dispersion medium and a broad molecular weight distribution (MWD) polyester dispersant, each preferably synthesized from 100% bio-based carbon. The ester dispersion medium includes a liquid ester selected from the group consisting of Formulae (I), (II), (III), (IV) and combinations thereof. The polyester dispersant has a polydispersity index (PDI) of greater than about 2.3. The present invention also relates to a non-aqueous-based dispersion comprising the above non-aqueous-based composition and metal oxide particles dispersed therein. The metal oxide particles may include zinc oxide, titanium oxide, or a combination thereof. Formulations using the compositions and dispersions and methods of making the same are also disclosed. # imgabs0 #

Description

[0001] Cross - reference to related applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 422,057, filed on November 3, 2022, and U.S. Provisional Application No. 63 / 422,063, filed on November 3, 2022, which are hereby incorporated by reference in their entirety. Technical field

[0003] The present invention relates to compositions, dispersions, and formulations comprising a non - aqueous ester and a polyester having a broad molecular weight distribution (MWD), optionally in combination with metal oxide particles, and methods for preparing the compositions and for using the compositions to prepare dispersions and formulations, and their applications, including, for example, personal care applications such as sunscreen formulations. Background art

[0004] Inorganic metal oxides, such as zinc oxide (ZnO) and titanium dioxide (TiO2), are important sunscreen ingredients because they can absorb and / or scatter UVB and UVA radiation, thus providing protection against sunburn and photo - damage (which can lead to premature aging and / or skin cancer). These metal oxides are most desirably supplied as sub - micron - sized particles that do not scatter visible light wavelengths on the skin and thus do not cause skin whitening. Metal oxide particles (“MOP”) are typically prepared and supplied in the form of free - flowing powders.

[0005] To effectively prepare sunscreen formulations containing ZnO and / or TiO2 MOP to provide a sufficient sun protection factor (“SPF”) value and not cause skin whitening, it is necessary to create a stable and non - caking MOP dispersion.

[0006] The formation of a dispersion requires the use of high - shear mixing or grinding to mechanically break up the powdered and / or any agglomerated MOP and disperse it into a liquid medium (i.e., the dispersion medium). The nature of the dispersion medium can be water - based or non - water - based. Wetting of the MOP by the dispersion medium to form a homogeneous state of dispersion generally requires a dispersant to prevent re - agglomeration of the MOP. [See, e.g., C. Agbo et al., A Review on the Mechanism of Pigment Dispersion, J. Disp. Sci. Tech., 2018, 39(6), 874 - 889.]

[0007] MOP is preferably dispersed in a non-aqueous fluid that is easy to apply to the skin and has a consumer-acceptable skin feel. Non-aqueous dispersion media for MOP (such as ZnO and TiO2) include various cosmetic-acceptable fluids that are commonly used as emollients in cosmetics and personal care products. Examples of such fluids include aliphatic hydrocarbons, triglycerides, benzoates, aliphatic esters, or combinations thereof, and silicones (such as cyclomethicone and dimethicone).

[0008] Given the increasing consumer preference for more natural and sustainable products, the non-aqueous dispersion medium is preferably derived from sustainable, renewable plant-based raw materials. An example of a dispersion medium of natural origin is caprylic / capric triglyceride, which is a triglyceride synthesized by the complete esterification of plant glycerol with a C8 (caprylic acid) and C 10 (capric acid) fatty acid mixture from coconut or palm kernel oil. Importantly, these triglycerides have not provided dispersions with a low enough viscosity to date. A lower viscosity is required to incorporate the desired high solid load of MOP. Other examples of plant-derived bio-based non-aqueous dispersion media include plant-derived oils such as jojoba oil or sunflower oil; fermentation-derived hydrocarbons such as hydrogenated farnesene; hydrocarbons derived from triglyceride oils (by hydrolysis to fatty acids, reduction to fatty alcohols, and dehydration / hydrogenation to hydrocarbons) such as coconut alkane; and esters derived from plant-derived saturated fatty acids and saturated fatty alcohols such as coco-caprylate / caprate derived from the esterification of hydrogenated coconut fatty alcohol with C8 / C 10 fatty acids.

[0009] Obtaining a stable MOP dispersion in a non-aqueous medium typically requires surface modification of the particles to make the hydrophilic inorganic surface hydrophobic and thus compatible with the relatively non-polar dispersion medium, i.e., the non-aqueous dispersion can wet the MOP surface. This 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 for MOP include fatty acids (such as isostearic acid), trialkoxyalkylsiloxanes (such as triethoxyoctylsilane), or silicones (such as methyl silicone or dimethicone). Surface modification of MOP typically requires additional process steps and / or unit operations to properly apply the surface treatment, see for example U.S. Patent No. 9,254,398 B2. Therefore, it is more efficient and economical to develop a dispersion system that can use un-surface-treated (i.e., uncoated) MOP.

[0010] Ideally, a flowable, low-viscosity particulate dispersion with a high MOP loading is produced, which can minimize the carry-over of excess dispersion medium into subsequent formulations (where a specific MOP dispersion is added). As described, when formulated at MOP loadings with a solid particle volume fraction greater than about 50%, conventional triglyceride dispersion media (such as caprylic / capric triglyceride and triheptanoin) typically produce MOP dispersions with undesirably high viscosities. See, for example, D.A. Brune et al., Model for the Viscosity of Particle Dispersions; Journal of Macromolecular Science - Rev. Macromol. Chem. Phys., C39(4), 561 - 642 (1999). Thus, to obtain stable and pourable MOP dispersions containing these triglycerides, it has hitherto regrettably been necessary to reduce the particle loading.

[0011] In addition, a dispersant is needed to provide steric stability to prevent particle agglomeration in the non-aqueous dispersion medium. Polymer dispersants are common, and polyhydroxystearic acid is a well-known dispersant for ZnO and TiO2 MOPs. [See, for example, B.J. 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.]

[0012] 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 must remain stable in the dispersion for extended periods. Low-viscosity dispersions are also desirable when formulated into sunscreen products as they make the product easier for consumers to dispense and apply.

[0013] Accordingly, stable, low-viscosity, high-solid-content MOP dispersions are needed. Due to the market demand for more sustainable ingredients and the greater consumer appeal for so-called "natural" ingredients derived from renewable biobased feedstocks, non-aqueous compositions should preferably be based on renewable carbon sources, i.e., plant-based carbon. Specifically, non-aqueous compositions are needed that contain one or more triglyceride esters prepared from renewable biobased carbon (more preferably 100% biobased carbon). Summary of the Invention

[0014] The non-aqueous compositions described and claimed herein meet these long-term needs and comprise an ester dispersion medium (EDM) and a broad MWD polyester dispersant (PEDA), to which MOP can be added to provide a uniform MOP dispersion.

[0015] Applicants have surprisingly found that an ester dispersion medium (preferably synthesized from 100% biobased carbon as described herein) in combination with a broad MWD PEDA provides a stable MOP dispersion with extremely low viscosity at relatively high particle loadings. Thus, stable, low-viscosity, high-solids-content MOP dispersions can be achieved using broad MWD PEDA and EDM based on 100% natural and renewable carbon.

[0016] In some embodiments, the invention relates to a non-aqueous composition. The non-aqueous composition comprises an ester and a polyester having a polydispersity index greater than about 2.3. The ester is selected from the group consisting of the following (i)-(v):

[0017] (i) A liquid ester of Formula I:

[0018]

[0019] 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; provided that if 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;

[0020] (ii) A liquid ester of Formula II:

[0021]

[0022] wherein R2 is a branched alkyl, a linear or branched alkenyl, or a linear or branched alkynyl, R3 is a linear or branched alkyl, a linear or branched alkenyl, or a linear or branched alkynyl, and R4 is a linear or branched alkyl, a linear or branched alkenyl, or a linear or branched alkynyl;

[0023] (iii) A liquid ester of Formula III:

[0024]

[0025] wherein R5 is a branched alkyl, a linear or branched olefin, or a linear or branched alkyne, R6 is a linear or branched alkyl, a linear or branched olefin, or a linear or branched alkyne, and R7 is a linear or branched alkyl, a linear or branched olefin, or a linear or branched alkyne; and

[0026] (iv) A liquid ester of Formula IV:

[0027]

[0028] wherein R8, R9, and R 10 are each independently selected from C5-C 18 linear, branched, saturated, or unsaturated alkyl groups having 5 to 18 carbon atoms; and

[0029] (v) combinations of the above esters.

[0030] The esters of the non-aqueous base composition in the preceding paragraph may have the formula I, and R is C5-C 17 branched or cyclic alkyl, linear, branched, or cyclic alkenyl, or linear, branched, or cyclic alkynyl; and R1 is C3-C 18 linear, branched, or cyclic alkyl, linear, branched, or cyclic alkenyl, or linear, branched, or cyclic alkynyl. The esters of formula I may include esters in which R and R1 are different.

[0031] The esters of the non-aqueous base composition described in any of the preceding paragraphs may have the formula II, and R2 is C3-C 18 branched alkyl, linear or branched alkenyl, or linear or branched alkynyl; R3 is C2-C8 linear or branched alkyl, linear or branched alkenyl, or linear or branched alkynyl; and R4 is C3-C 18 linear or branched alkyl, linear or branched alkenyl, or linear or branched alkynyl. The esters of formula II may include esters in which R2 and R4 are the same.

[0032] The esters of the non-aqueous base composition described in any of the preceding paragraphs may have the formula III, and R5 is C3-C 18 branched alkyl, linear or branched olefin, or linear or branched alkyne, R6 is C2-C8 linear or branched alkyl, linear or branched olefin, or linear or branched alkyne, and R7 is C3-C 18 linear or branched alkyl, linear or branched olefin, or linear or branched alkyne. The esters of formula III may include esters in which R5 and R7 are the same.

[0033] The esters of the non-aqueous base composition described in any of the preceding paragraphs may have the formula IV, and two or more of R8, R9, and R 10 are the same.

[0034] The esters of the non-aqueous base composition described in any of the preceding paragraphs may be selected from the group consisting of monoesters, diesters, triesters, and combinations thereof.

[0035] The esters of the non-aqueous base composition described in any of the preceding paragraphs may have a viscosity of less than about 100 cSt at 25°C.

[0036] The non-aqueous base composition described in any of the preceding paragraphs may have a viscosity of less than 500 cP.

[0037] The ester of the non-aqueous composition described in any preceding paragraph may be liquid at 25 °C. The ester may be 100% bio-based.

[0038] The non-aqueous composition described in any preceding paragraph, wherein the polyester has a polydispersity index (PDI) greater than about 2.4 or greater than about 2.5.

[0039] The polyester of the non-aqueous composition described in any preceding paragraph may comprise a terminal single carboxylic acid functional group. The polyester may comprise two terminal carboxylic acid functional groups.

[0040] The polyester of the non-aqueous composition described in any preceding paragraph may include a homopolymer derived from an AB hydroxycarboxylic acid monomer. The polyester may include a copolymer derived from an AA diol and a BB diacid or diester monomer.

[0041] The polyester of the non-aqueous composition described in any preceding paragraph may have a number average molecular weight (Mn) of less than about 10,000 g / mol. The polyester may have an acid value of at least 15 mg KOH / g.

[0042] The polyester of the non-aqueous composition described in any preceding paragraph is selected from the group consisting of: polyhydroxystearic acid, polyhydroxystearic acid stearate, polyhydroxystearyl succinate, polyhydroxystearyl sebacate, and combinations thereof. The carbon present in the polyester may be 100% bio-based.

[0043] In certain embodiments, the present invention relates to a non-aqueous composition consisting essentially of an ester and a polyester having a polydispersity index greater than about 2.3, the ester being selected from the group consisting of the following (i)-(v):

[0044] (i) A liquid ester of formula I:

[0045]

[0046] wherein R and R1 are each a linear, branched, or cyclic alkyl group; a linear, branched, or cyclic alkenyl group; or a linear, branched, or cyclic alkynyl group; provided that if one of R and R1 is a linear alkyl group, the other of R and R1 is a branched or cyclic alkyl group; a linear, branched, or cyclic alkenyl group; or a linear, branched, or cyclic alkynyl group;

[0047] (ii) A liquid ester of formula II:

[0048]

[0049] wherein R2 is a branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, R3 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, and R4 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group;

[0050] (iii) Liquid esters of formula III:

[0051]

[0052] wherein R5 is a branched alkyl, linear or branched alkene, or linear or branched alkyne, R6 is a linear or branched alkyl, linear or branched alkene, or linear or branched alkyne, and R7 is a linear or branched alkyl, linear or branched alkene, or linear or branched alkyne;

[0053] (iv) Liquid esters of formula IV:

[0054]

[0055] wherein R8, R9 and R 10 are each independently selected from C5-C 18 linear, branched, saturated or unsaturated alkyls containing 5 to 18 carbon atoms; and

[0056] (v) Combinations of the above esters.

[0057] In other specific embodiments, the present invention relates to a non-aqueous composition comprising an ester and a polyester having a polydispersity index greater than about 2.3, wherein the ester is selected from the group consisting of the following (i)-(v):

[0058] (i) Liquid esters of formula I:

[0059]

[0060] wherein R and R1 are each a linear, branched or cyclic alkyl; linear, branched or cyclic alkenyl; or linear, branched or cyclic alkynyl; provided that if one of R and R1 is a linear alkyl, the other of R and R1 is a branched or cyclic alkyl; linear, branched or cyclic alkenyl; or linear, branched or cyclic alkynyl;

[0061] (ii) Liquid esters of formula II:

[0062]

[0063] wherein R2 is a branched alkyl, linear or branched alkenyl, or linear or branched alkynyl, R3 is a linear or branched alkyl, linear or branched alkenyl, or linear or branched alkynyl, and R4 is a linear or branched alkyl, linear or branched alkenyl, or linear or branched alkynyl;

[0064] (iii) Liquid esters of formula III:

[0065]

[0066] wherein R5 is a branched alkyl, linear or branched olefin, or linear or branched alkyne, R6 is a linear or branched alkyl, linear or branched olefin, or linear or branched alkyne, and R7 is a linear or branched alkyl, linear or branched olefin, or linear or branched alkyne;

[0067] (iv) a liquid ester of formula IV:

[0068]

[0069] wherein R8, R9 and R 10 are each independently selected from C5-C 18 linear, branched, saturated or unsaturated alkyls having 5 to 18 carbon atoms; and

[0070] (v) a combination of the above esters.

[0071] In other embodiments, the present invention relates to a non-aqueous dispersion comprising a non-aqueous composition and metal oxide particle powder. The non-aqueous composition of the non-aqueous dispersion can be the non-aqueous composition according to any of the preceding paragraphs.

[0072] The metal oxide particles of the non-aqueous dispersion in the preceding paragraph may include un-surface-modified metal oxide particles, for example, un-surface-modified particles.

[0073] The metal oxide particles of the non-aqueous dispersion according to any of the preceding paragraphs may include zinc oxide, titanium oxide, or a combination thereof.

[0074] The non-aqueous dispersion according to any of the preceding paragraphs may have a viscosity of less than about 1000 cP. The metal oxide particles may account for about 15 wt% to about 75 wt% of the non-aqueous dispersion, and the balance is the non-aqueous composition according to any of the preceding paragraphs. In some embodiments, the metal oxide particles account for about 40 wt% to about 60 wt% of the non-aqueous dispersion. Based on the total weight of the dispersion, the amount of polyester present may be about 3 wt% to about 5 wt%. The non-aqueous dispersion may be substantially free of silicone.

[0075] In certain embodiments, the non-aqueous dispersion comprises a plurality of metal oxide particles, an ester, and a polyester having a polydispersity index greater than about 2.3, wherein the ester is selected from the group consisting of the following (i)-(v):

[0076] (i) a liquid ester of formula I:

[0077]

[0078] wherein each of R and R1 is a linear, branched or cyclic alkyl group; a linear, branched or cyclic alkenyl group; or a linear, branched or cyclic alkynyl group; provided that if one of R and R1 is a linear alkyl group, the other of R and R1 is a branched or cyclic alkyl group; a linear, branched or cyclic alkenyl group; or a linear, branched or cyclic alkynyl group;

[0079] (ii) a liquid ester of formula II:

[0080]

[0081] wherein R2 is a branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, R3 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, and R4 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group;

[0082] (iii) a liquid ester of formula III:

[0083]

[0084] wherein R5 is a branched alkyl group, a linear or branched alkene, or a linear or branched alkyne, R6 is a linear or branched alkyl group, a linear or branched alkene, or a linear or branched alkyne, and R7 is a linear or branched alkyl group, a linear or branched alkene, or a linear or branched alkyne;

[0085] (iv) a liquid ester of formula IV:

[0086]

[0087] wherein R8, R9 and R 10 are each independently selected from C5-C 18 linear, branched, saturated or unsaturated alkyl groups containing 5 to 18 carbon atoms; and

[0088] (v) a combination of the above esters.

[0089] The ester of the non-aqueous dispersion described in the preceding paragraph may have the formula I, wherein R is a C5-C 17 branched or cyclic alkyl group, a linear, branched or cyclic alkenyl group, or a linear, branched or cyclic alkynyl group; R1 is a C3-C 18 linear, branched or cyclic alkyl group, a linear, branched or cyclic alkenyl group, or a linear, branched or cyclic alkynyl group. The ester of formula I may include esters with different R and R1.

[0090] The ester of the non-aqueous dispersion described in any of the preceding paragraphs may have the formula II, wherein R2 is a C3-C 18A branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group; R3 is a C2-C8 linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group; R4 is a C3-C 18 A linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group. The esters of formula II may include esters in which R2 and R4 are the same.

[0091] The esters of the non-aqueous base dispersions described in any of the preceding paragraphs may have formula III, wherein R5 is a C3-C 18 A branched alkyl group, a linear or branched alkene, or a linear or branched alkyne, R6 is a C2-C8 linear or branched alkyl group, a linear or branched alkene, or a linear or branched alkynyl group, R7 is a C3-C 18 A linear or branched alkyl group, a linear or branched alkene, or a linear or branched alkyne. The esters of formula III may include esters in which R5 and R7 are the same.

[0092] The esters of the non-aqueous base dispersions described in any of the preceding paragraphs may have formula IV, and two or more of R8, R9, and R 10 are the same.

[0093] The esters of the non-aqueous base dispersions described in any of the preceding paragraphs may be selected from monoesters, diesters, triesters, or combinations thereof.

[0094] The esters of the non-aqueous base dispersions described in any of the preceding paragraphs may have a viscosity of less than about 100 cSt at 25°C.

[0095] The viscosity of the non-aqueous base dispersions described in any of the preceding paragraphs may be less than 1000 cP.

[0096] The esters of the non-aqueous base dispersions described in any of the preceding paragraphs may be liquid at 25°C. The esters may be 100% bio-based.

[0097] The non-aqueous base dispersions described in any of the preceding paragraphs, wherein the polydispersity index (PDI) of the polyester is greater than about 2.4, or greater than about 2.5.

[0098] The polyesters of the non-aqueous base dispersions described in any of the preceding paragraphs may contain a single terminal carboxylic acid functional group. The polyesters may contain two terminal carboxylic acid functional groups. The polyesters may have a linear structure.

[0099] The polyesters of the non-aqueous base dispersions described in any of the preceding paragraphs may include homopolymers derived from AB hydroxycarboxylic acid monomers. The polyesters may include copolymers derived from AA diols and BB diacids or diester monomers.

[0100] The number average molecular weight (Mn) of the polyesters of the non-aqueous base dispersions described in any of the preceding paragraphs may be less than about 10,000 g / mol. The acid value of the polyesters may be at least 15 mg KOH / g.

[0101] The polyester of the non-aqueous dispersion described in any preceding paragraph may optionally 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 may be 100% biobased.

[0102] In certain embodiments, the dispersion consists essentially of a plurality of metal oxide particles, an ester, and a polyester having a polydispersity index greater than about 2.3, wherein the ester is selected from the group consisting of (i)-(v) below:

[0103] (i) an ester of Formula I:

[0104]

[0105] wherein R and R1 are each a linear, branched, or cyclic alkyl group; a linear, branched, or cyclic alkenyl group; or a linear, branched, or cyclic alkynyl group; provided that if one of R and R1 is a linear alkyl group, the other of R and R1 is a branched or cyclic alkyl group; a linear, branched, or cyclic alkenyl group; or a linear, branched, or cyclic alkynyl group;

[0106] (ii) an ester of Formula II:

[0107]

[0108] wherein R2 is a branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, R3 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, and R4 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group;

[0109] (iii) an ester of Formula III:

[0110]

[0111] wherein R5 is a branched alkyl group, a linear or branched olefin, or a linear or branched alkyne, R6 is a linear or branched alkyl group, a linear or branched olefin, or a linear or branched alkyne, and R7 is a linear or branched alkyl group, a linear or branched olefin, or a linear or branched alkyne;

[0112] (iv) a liquid ester of Formula IV:

[0113]

[0114] wherein R8, R9, and R 10 are each independently selected from C5-C 18 linear, branched, saturated, or unsaturated alkyl groups containing 5 to 18 carbon atoms; and

[0115] (v) combinations of the above esters.

[0116] In other specific embodiments, the non-aqueous dispersion consists of multiple metal oxide particles, an ester, and a polyester having a polydispersity index greater than about 2.3, wherein the ester is selected from the group consisting of the following (i)-(v):

[0117] (i) The ester of formula I:

[0118]

[0119] wherein R and R1 are each a linear, branched, or cyclic alkyl group; a linear, branched, or cyclic alkenyl group; or a linear, branched, or cyclic alkynyl group; provided that if one of R and R1 is a linear alkyl group, the other of R and R1 is a branched or cyclic alkyl group; a linear, branched, or cyclic alkenyl group; or a linear, branched, or cyclic alkynyl group;

[0120] (ii) The ester of formula II:

[0121]

[0122] wherein R2 is a branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, R3 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, and R4 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group;

[0123] (iii) The ester of formula III:

[0124]

[0125] wherein R5 is a branched alkyl group, a linear or branched alkene, or a linear or branched alkyne, R6 is a linear or branched alkyl group, a linear or branched alkene, or a linear or branched alkyne, and R7 is a linear or branched alkyl group, a linear or branched alkene, or a linear or branched alkyne;

[0126] (iv) The liquid ester of formula IV:

[0127]

[0128] wherein R8, R9, and R 10 are each independently selected from C5-C 18 linear, branched, saturated, or unsaturated alkyl groups containing 5 to 18 carbon atoms; and

[0129] (v) A combination of the above esters.

[0130] In still other embodiments, the present invention relates to formulations comprising the non-aqueous compositions or non-aqueous dispersions described in any of the preceding paragraphs. The formulations can be personal care products selected from the following or can be components of personal care products selected from the following: cosmetics, conditioners for hair, nails, skin or textiles, shampoos, hair styling products, oils or waxes for grooming beards, permanent wave solutions, hair dyes, facial cleansers or body washes, makeup removers, cleansing lotions, emollient lotions or creams, bar soaps, liquid soaps, shaving creams, foams or gels, sunscreen products, gels, lotions or creams for treating sunburn, deodorants or antiperspirants, moisturizing gels, shaving foams, facial powders, foundations, lipsticks, blushes, eyeliners, anti-wrinkle creams or anti-aging creams, eyeshadows, eyebrow pencils, mascaras, mouthwashes, toothpastes, oral care products, skin cleansing products, textile cleansing products, dishwashing products, hair or fur cleansing products, and skin care lotions or moisturizing creams. The formulation can be a sunscreen product or can be a component of a sunscreen product. The formulation can be an oil-in-water (O / W) emulsion or a water-in-oil (W / O) emulsion. The formulation can also comprise at least one additional ingredient selected from film-forming polymers, rheology-modifying polymers, waxes, emulsifiers, emollients, humectants, and combinations thereof.

[0131] The formulation can have a formulated viscosity such that, after storage at 50 °C for 4 weeks, the formulated viscosity increases by less than 20-fold.

[0132] The present invention also relates to a method for preparing a non-aqueous composition for dispersing metal oxide particle powders. The method comprises:

[0133] mixing an ester and a polyester to form a homogeneous solution, the polyester having a polydispersity index (PDI) greater than about 2.3, the ester being selected from the group consisting of the following (i)-(v):

[0134] (i) a liquid ester of formula I:

[0135]

[0136] wherein R and R1 are each a linear, branched or cyclic alkyl group; a linear, branched or cyclic alkenyl group; or a linear, branched or cyclic alkynyl group; provided that if one of R and R1 is a linear alkyl group, the other of R and R1 is a branched or cyclic alkyl group; a linear, branched or cyclic alkenyl group; or a linear, branched or cyclic alkynyl group;

[0137] (ii) a liquid ester of formula II:

[0138]

[0139] wherein R2 is a branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, R3 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, and R4 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group;

[0140] (iii) Liquid esters of formula III:

[0141]

[0142] wherein R5 is a branched alkyl, linear or branched olefin, or linear or branched alkyne, R6 is a linear or branched alkyl, linear or branched olefin, or linear or branched alkyne, and R7 is a linear or branched alkyl, linear or branched olefin, or linear or branched alkyne;

[0143] (iv) Liquid esters of formula IV:

[0144]

[0145] wherein R8, R9 and R 10 are each independently selected from C5-C 18 linear, branched, saturated or unsaturated alkyls containing 5 to 18 carbon atoms; and

[0146] (v) Combinations of the above esters.

[0147] The method may include the esters described in any of the preceding paragraphs, such as esters of formula I, formula II, formula III, formula IV and combinations thereof. The esters may be selected from monoesters, diesters, triesters and combinations thereof.

[0148] The method has a broad molecular weight distribution. The polyester may include the polyesters described in any of the preceding paragraphs.

[0149] The mixing process to form a homogeneous solution may include heating. The mixing process may include high-shear mixing.

[0150] The method may further include dispersing metal oxide particles in the homogeneous solution to form a non-aqueous dispersion. The metal oxide particles of the method may include the metal oxide particles described in any of the preceding paragraphs.

[0151] The method may further include adding at least one additional ingredient thereto to form a formulation. The at least one additional ingredient may be selected from film-forming polymers, rheology-modifying polymers, waxes, emulsifiers, emollients, humectants and combinations thereof. The formulation of the method may be a sunscreen. Description of the Drawings

[0152] Figure 1 Shows the variation of the dispersion viscosity with the polyester concentration for Examples E1 and Comparative Examples CE1-CE2 according to the embodiments herein. Detailed Description

[0153] Before describing the compounds, compositions, methods, etc. of the present invention, it should be understood that the present invention is not limited to the specific processes, compositions or methods described, as these may vary. It should also be understood that the terms used in the specification are only for describing a particular version or embodiment and are 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 may be used in the practice or testing of the embodiments of the present invention, the preferred methods, devices and materials are now described. All publications mentioned herein are incorporated herein by reference in their entirety. Nothing herein should be construed as an admission that the present invention is not entitled to antedate such disclosure by virtue of prior invention.

[0154] It must also be noted that, as used herein and in the appended claims, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a cell" refers to one or more cells and their equivalents known to those skilled in the art, and so on.

[0155] Unless otherwise indicated, "%" may refer to weight percent or volume percent.

[0156] Unless otherwise indicated, room temperature may refer to about 25 °C, or 25 °C, or a range from 22.5 °C to 27.5 °C, or a range from 20 °C to 30 °C.

[0157] Where applicable, symbols such as C x -C y represent a range of carbon atom numbers, including C x and C y and all groups therebetween. For example, C5-C9 includes each of pentyl, hexyl, heptyl, octyl and nonyl groups.

[0158] "Cosmetically acceptable" means suitable for use in contact with the skin and without undue toxicity, incompatibility, instability, irritation, allergic reaction, etc.

[0159] Where applicable, chemicals will be designated by their INCI names according to the guidelines of the International Nomenclature of Cosmetic Ingredients. Further information (including suppliers and trade names) can be found under the corresponding INCI monograph in the 16th Edition of the International Cosmetic Ingredient Dictionary and Handbook published by the Personal Care Products Council (Washington, D.C.), and also online at the Personal Care Products Council INCIpedia (https: / / incipedia.personalcarecouncil.org / ).

[0160] In numerous embodiments, the present invention includes biobased compositions. Biobased compositions must be produced using biobased or "natural" feedstocks. Examples of biobased compositions are compositions prepared from bioderived feedstocks (e.g., from current and sustainable agricultural activities such as fermentation, algae, plant or vegetable derived; e.g., from plant sources, preferably using non-genetically modified organisms or biomass and which is not petrochemically derived (e.g., from sustainable tree and plant farms active in the 21st century rather than fossil sources such as oil, 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. Additionally, such materials are formed from "new" carbon rather than from petroleum or other fossil fuel sources ("old" carbon). Such products are referred to herein as "natural" products and are known in the art as non-petrochemically derived or "biological" products. As used herein, the term "sustainable" refers to starting materials, reaction products, compositions, and / or formulations derived from renewable sources. Thus, "sustainable" is contrasted with "unsustainable" starting materials, reaction products, compositions, and / or formulations which contain carbon from finite natural resources such as fossil fuels (e.g., oil or coal), natural gas, etc. Thus, natural or biological products are not petrochemically derived and / or made from non-petrochemically derived sources but are sustainable and renewable. True natural products (biocompounds) are formed using biomass (e.g., materials stored in the carbon cycle processes in living plants, roots, etc., or materials released through animal respiration or feces or through decomposition). When carbon decomposes and degrades under pressure over millions of years, it produces fossil fuels (sources of petrochemically derived carbon). Biocompounds herein are intended to include materials derived from carbon of recently existing and / or sustainable plant sources / biomass and expressly exclude materials derived from fossil fuels.

[0161] The compositions and / or formulations of the present invention can be identified and distinguished from those of the prior art by their biobased carbon content. In some embodiments, the biobased carbon content can be measured by radiocarbon dating to determine the relative age of materials composed of organic (i.e., carbon-containing) substances. Radiocarbon is an unstable isotope of carbon called carbon-14 (i.e., " 14 14 14 14C is an unstable isotope which emits radiation energy in the form of beta particles at a very consistent rate (i.e., the half-life of radiocarbon is 5730 years) and ultimately decays into the more stable nitrogen-14 ( 14 14 14C) has been lost due to radioactive decay. ASTM International standards provide test criteria for using radiocarbon to determine the authenticity of "bio-based compounds", which can be found in ASTM D6866-16. This standard differentiates newer carbon from carbon derived from fossil fuels or petroleum and petrochemical sources (i.e., "old carbon"). The 14 C content in recent or current biomass is known and thus the percentage of carbon from renewable sources can be estimated by total organic carbon analysis, which provides the data needed to determine whether a compound is truly derived from "natural" and / or "sustainable" ("renewable") feedstock sources or instead from "old" sequestered compounds (i.e., petrochemical or petroleum-based sources). Using petroleum-based (also known as "fossil-based") feedstocks is generally considered unsustainable, i.e., old carbon is unsustainable, not a renewable feedstock, and not considered "natural" and / or "sustainable" in the art.

[0162] In some embodiments, the formulations and / or compositions of the present invention contain bio-based carbon as substantially all of the carbon present in the compound mixture, which can mean a bio-based carbon content of at least 90%, at least 95% or at least 98%.

[0163] In some embodiments, the compositions of the present invention contain 14 a C content that is substantially equal to the 14 C content in the current atmosphere, as determined by ASTM D6866. In some embodiments, the compositions of the present invention contain 14 a C content that is at least about 90%, at least about 95%, at least about 98% or at least about 99% of the 14 C content in the current atmosphere, as determined by ASTM D6866. In some embodiments, the compositions of the present invention contain at least about 0.8 12 C atoms per 10 14 carbon atoms present in the composition, at least about 1.0 12 C atoms per 10 14 carbon atoms present in the composition, or at least about 1.2 12 C atoms per 10 14 carbon atoms present in the composition, as determined by ASTM D6866.

[0164] What the applicant refers to as "sustainable" herein means materials from renewable sources. In contrast, "unsustainable" means materials from finite natural resources, such as fossil fuels (e.g., petroleum, natural gas, coal, etc.).

[0165] Introduction

[0166] The present invention relates to a non-aqueous composition comprising EDM and PEDA, wherein PEDA is characterized by a broad MWD. The non-aqueous compositions herein have a low enough viscosity to provide a uniform, high solids loading MOP dispersion. As described above, a stable, low viscosity, high solids content MOP dispersion can be achieved using a dispersion medium and dispersant based on 100% natural and renewable carbon. The applicant has surprisingly found that, as described herein, EDM (preferably synthesized from 100% biobased carbon) in combination with broad MWD PEDA provides a stable dispersion with extremely low viscosity at relatively high particle loadings. The EDM described herein includes esters comprising linear or branched, saturated or unsaturated alkyl groups.

[0167] The applicant has found that when used in a non-aqueous EDM, using PEDA with a high polydispersity index (PDI) value can provide a stable dispersion with lower viscosity than conventional dispersants.

[0168] Non-aqueous dispersion

[0169] The non-aqueous composition of the present invention comprises EDM and broad MWD PEDA. Metal oxide particles are added to the non-aqueous composition of the present invention to form a uniform non-aqueous dispersion of metal oxide particles with a high solids loading.

[0170] The non-aqueous composition of the present invention provides a "ready-to-use" dispersion system that is capable of forming low viscosity dispersions with a wide range of metal oxide particles. In particular, users of the non-aqueous dispersion do not require specialized mixing equipment or experience in fabricating stable non-aqueous dispersions.

[0171] In some embodiments, the non-aqueous composition of the present invention consists essentially of (i) one or more esters and (ii) a broad molecular weight distribution (MWD) polyester polymer. The basic and novel properties of such compositions of the present invention include the ability to form stable, low viscosity non-aqueous dispersions with a variety of metal oxide particles. In addition, the non-aqueous compositions described herein exhibit ease of processing, which is at least in part due to the achievement of low viscosity.

[0172] Metal oxide particles

[0173] Some embodiments of the present disclosure relate to dispersion compositions comprising metal oxide particles. The MOPs are preferably solid, white (or colorless), and odorless metal oxide particles. The MOPs herein may include zinc oxide (ZnO) and / or titanium dioxide (TiO2) particles. These are particularly useful in formulations such as sunscreen lotions. Some of the dispersions and / or formulations herein may additionally or alternatively comprise metal oxides including one or more of iron, copper, manganese, magnesium, cerium, vanadium, zirconium, aluminum, silicon, such as FeO, Fe2O3, Fe3O4, CeO2, V2O5, ZrO2, MnO2, MgO, Al2O3, SiO2, CaO, or combinations thereof, and other cosmetically acceptable metal oxides. Suitable metal oxides also include doped metal oxides (doped with the aforementioned metals and metal oxides). Other suitable metal oxide particles include coated particles (coated with, for example, the aforementioned metals and metal oxides). The MOPs have high purity, e.g., greater than 95%, greater than 96%, greater than 97%, greater than 98%, or greater than 99%.

[0174] In some embodiments, the surface of the metal oxide particles can be modified. Such surface modification, especially in the case of TiO2, can inhibit photocatalytic activity in subsequent formulations. Inorganic coatings such as alumina or silica are preferably used for any surface modification.

[0175] Alternatively, organic surface modification, while less preferred, is also acceptable. Surface modification with organic or hybrid organic-inorganic coatings derived from fossil-based carbon is not desirable due to poor sustainability and low consumer acceptance. Specifically, surface modification with silicone or siloxane is less preferred. For example, trialkoxyalkylsilanes (e.g., triethoxyoctylsilane) or silicones (e.g., methyl silicone or dimethyl silicone) are less preferred because of their negative environmental impact and / or negative consumer perception.

[0176] Any coating or surface modification of the particles as described above is included as part of the mass or weight of the particles herein (e.g., MOPs).

[0177] Unsurface-modified MOPs can also be used in the compositions and formulations described herein. In some embodiments, uncoated metal oxide particles are preferred. In certain embodiments, MOPs comprising uncoated ZnO are used in the compositions and formulations described herein.

[0178] The average particle size of the MOP is not limited, however, the average particle size of the MOP can preferably be in the sub-micron diameter range. For example, the metal oxide particles can be present in the composition with an average particle size of from 10 nm to 500 nm, such as from 10 nm to 400 nm, from 20 nm to 300 nm or from 30 nm to 150 nm. In terms of the upper limit, the average particle size of the MOP can be less than 500 nm, such as less than 400 nm, less than 300 nm or less than 150 nm. In terms of the lower limit, the average particle size of the MOP can be greater than 10 nm, such as greater than 20 nm or greater than 30 nm. In a preferred embodiment, the average particle size of the MOP is less than about 200 nm. These ranges and limitations can also apply to the formulations containing these compositions.

[0179] The MOP used in the compositions, dispersions and formulations described herein can exhibit a wide range of average particle size distributions. The average particle size distribution can, for example, be in the range of from about 10 nm to about 500 nm, such as in the range of 10 nm to 400 nm, 20 nm to 300 nm or 30 nm to 150 nm. In a preferred embodiment, the average particle size distribution is in the range of from about 30 nm to about 150 nm. The particles can be present in the form of clusters or aggregates. The MOP can exhibit a particle shape selected from spherical, rod-shaped, star-shaped, equiaxed, spherical, plate-shaped, flake or a combination thereof. In some preferred embodiments, the MOP (e.g., ZnO particles) is characterized as having a variety of shapes. [See, for example, 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.ht m#.]

[0180] In some or other embodiments, the MOP can be added to a non-aqueous composition to form a dispersion. In other words, a non-aqueous composition containing the EDM and wide MWD PEDA described herein is provided directly, or subsequently added to the MOP to form its dispersion and / or formulation.

[0181] Ester dispersion medium

[0182] Non-aqueous compositions for dispersing metal oxide particles, and dispersions and formulations herein, comprise a non-aqueous ester dispersion medium (EDM). The "ester dispersion medium" or simply "ester", which can be used interchangeably herein, is an ester having physical properties suitable for use as a dispersion medium. For example, the ester is a liquid (at room temperature, e.g., 25 °C) and / or the ester has a viscosity at 25 °C of less than about 100 cSt. Esters suitable for use as an ester dispersion medium can be branched esters, unsaturated esters, and / or triglyceride esters as described below.

[0183] In aspects herein, the ester comprises one or more selected R groups such that the ester is a liquid at 25 °C.

[0184] As described herein, the compositions, dispersions, and formulations of the present invention may contain other esters (not EDM as defined herein) in addition to the ester dispersion medium. Non-EDM esters that may be present include wax esters for constructing formulations and films, enhancing water resistance, etc. Examples of non-EDM esters include, but are not limited to, hydrogenated rapeseed oil, jojoba esters, hydrogenated jojoba oil, and synthetic beeswax.

[0185] The inventors surprisingly found that branched esters, unsaturated esters, and / or triglyceride esters are suitable for non-aqueous compositions of MOP dispersions because their combination with PEDA (described below) having a wide MWD can reduce the viscosity of the composition.

[0186] The non-aqueous composition may comprise an ester having a branched alkyl or unsaturated alkyl group. For the purposes herein, the branching point can be defined relative to any carbon or heteroatom in the molecule, or it can also refer to a stereocenter. For example, in certain embodiments, the methyl branching is at the 1-position, e.g., the methyl branching is at the carbon atom bearing the hydroxyl group of the alcohol, e.g., 1-methylheptanol, as shown below:

[0187]

[0188] In some embodiments, the non-aqueous composition for dispersing metal oxide particles comprises an ester of Formula I:

[0189]

[0190] wherein each of R and R1 is a linear, branched, or cyclic alkyl group; a linear, branched, or cyclic alkenyl group; or a linear, branched, or cyclic alkynyl group; provided that if one of R and R1 is a linear alkyl group, the other of R and R1 is a branched or cyclic alkyl group; a linear, branched, or cyclic alkenyl group; or a linear, branched, or cyclic alkynyl group. In some embodiments, R is a C5-C 17 branched or cyclic alkyl, linear, branched, or cyclic alkenyl, or linear, branched, or cyclic alkynyl; and R1 is a C3-C 18Linear, branched or cyclic alkyl, linear, branched or cyclic alkenyl, or linear, branched or cyclic alkynyl. In some embodiments, the ester has formula I and R and R1 are different. In some embodiments, R is preferably C 10 Unsaturated. R is even more preferably C 10 Terminal unsaturated. In some embodiments, R1 is preferably C6-C 12 Linearly saturated. R1 is even more preferably C7-C8 linearly saturated.

[0191] Examples of esters according to formula (I) include heptyl undecylenate according to structure (I-i) ( Natural, INOLEX Inc.)

[0192]

[0193] In addition to heptyl undecylenate as described above, other examples of esters include octyl undecylenate and / or decyl undecylenate.

[0194] In other embodiments, the non-aqueous composition for dispersing metal oxide particles comprises an ester of formula (II):

[0195]

[0196] wherein R2 is a branched alkyl, linear or branched alkenyl, or linear or branched alkynyl, R3 is a linear or branched alkyl, linear or branched alkenyl, or linear or branched alkynyl, and R4 is a linear or branched alkyl, linear or branched alkenyl, or linear or branched alkynyl. In some embodiments, R2 is C3-C 18 Branched alkyl, linear or branched alkenyl, or linear or branched alkynyl, R3 is a C2-C8 linear or branched alkyl, linear or branched alkenyl, or linear or branched alkynyl; and R4 is C3-C 18 Linear or branched alkyl, linear or branched alkenyl, or linear or branched alkynyl. In some embodiments, the ester has 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-C 18 , even more preferably branched C6-C 12 . In some embodiments, R3 is preferably linear C2-C8.

[0197] Examples of esters according to formula (II) include diisooctyl succinate according to structure (II-i) (SustOleo TM DCS, INOLEX Inc.)

[0198]

[0199] In other embodiments, the non-aqueous composition for dispersing metal oxide particles comprises an ester of formula (III):

[0200]

[0201] wherein R5 is a branched alkyl, linear or branched alkene, or linear or branched alkyne, R6 is a linear or branched alkyl, linear or branched alkene, or linear or branched alkyne, and R7 is a linear or branched alkyl, linear or branched alkene, or linear or branched alkyne. In some embodiments, R5 is a C3-C 18 branched alkyl, linear or branched alkene, or linear or branched alkyne, R6 is a C2-C8 linear or branched alkyl, linear or branched alkene, or linear or branched alkyne, and R7 is a C3-C 18 linear or branched alkyl, linear or branched alkene, or linear or branched alkyne. In some embodiments, the ester has formula III and R5 and R7 are the same.

[0202] Examples of esters according to formula (III) include propylene glycol diisostearate and propylene glycol undecylenate.

[0203] In still other embodiments, the non-aqueous composition comprises a triglyceride compound such as an ester of formula (IV):

[0204]

[0205] wherein R8, R9, and R 10 are each independently selected from C5-C 18 linear, branched, saturated or unsaturated alkyls containing 5 to 18 carbon atoms. In some embodiments, two or more of R8, R9, and R 10 are the same.

[0206] Examples of esters according to formula (IV) include triheptanoin (SustOleo TM MCT, INOLEX Inc.), which is a non-palm, 100% natural medium-chain triglyceride having the structure (IV-i):

[0207]

[0208] Another example of a suitable triglyceride is caprylic / capric triglyceride (CCT), such as Lexol TM GT-865MB from INOLEX Inc., wherein R8, R9, and R in structure IV 10 are independently linear C7H 15 or C9H 19 i.e., the triglyceride contains C8 acyl (caprylate) and C10 Mixture of acyl (caprate) ester moieties.

[0209] Typically, triglyceride esters as described above are not suitable for non-aqueous compositions for dispersing MOP due to their high dispersion viscosities when combined with PEDA. Very surprisingly, the inventors have found that, in addition to the esters having branched or unsaturated alkyl groups as described above, triglyceride esters are also suitable for non-aqueous compositions for dispersing MOP when used in combination with wide MWD PEDA. Thus, the triglyceride esters disclosed herein are suitable as EDMs for use in combination with wide MWD PEDA.

[0210] The non-aqueous compositions herein for dispersing metal oxide particles can comprise esters selected from the group consisting of: (i) liquid esters of Formula I, (ii) liquid esters of Formula II, (iii) liquid esters of Formula III, (iv) liquid esters of Formula IV, and combinations thereof. In some embodiments, the dispersions and / or formulations herein comprise liquid esters of Formula I, Formula II, Formula III, Formula IV, and combinations thereof.

[0211] 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 a preferred embodiment, 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.

[0212] As described above, the carbon present in the EDM can be 100% biobased. In embodiments herein, the carbon atoms of the EDM comprise greater than about 50% biobased carbon, such as greater than 70%, greater than 80%, greater than 90%, greater than 95%, or greater than 99% (as determined by 14 the C radiocarbon dating method as described above or other methods known to those skilled in the art). In some embodiments, the EDM comprises 100% biobased carbon. In some embodiments, substantially all of the carbon present in the compound of Formula (IV) is biobased. Preferred embodiments herein include the EDM comprising 100% biobased carbon.

[0213] The non-aqueous EDM can also optionally comprise one or more other non-aqueous organic fluids that can be mixed with the main ester component and can be used for cosmetic applications. Examples of suitable non-aqueous organic fluids include hydrocarbons, cyclic alkyl carbonates, dialkyl carbonates, dialkyl ketones, and the like.

[0214] When this document describes a composition and / or dispersion as "non-aqueous", it means that the composition (and / or dispersion) is substantially free of added water, preferably containing less than about 3 wt% water, more preferably less than about 1 wt% water, even more preferably less than about 0.5 wt% water, and most preferably less than about 0.1 wt% water. The non-aqueous composition (and / or dispersion) may contain a small amount of accidental water (e.g., from absorbing environmental humidity) or processing conditions (e.g., incomplete drying after washing).

[0215] Polyester dispersant

[0216] The non-aqueous compositions for dispersing metal oxide particles and the dispersions and formulations herein may comprise a polyester dispersant (PEDA) having a broad MWD. "Polyester dispersant" and "polyester" are used interchangeably herein, where the polyester dispersant (PEDA) has a broad MWD and performs specific functions as defined below. Surprisingly, it has been found that EDMs (including those containing triglyceride esters as described above) are suitable for the compositions and MOP dispersions herein using PEDA with a broad MWD.

[0217] As described herein, the compositions of the present invention may comprise other polyesters (not PEDA as defined herein) in addition to PEDA (broad molecular weight distribution PEDA). Other non-PEDA polyesters may include, for example, polyester film formers for improving water resistance, etc.

[0218] The non-aqueous composition comprises a linear aliphatic polyester insoluble in water. In some embodiments, the polyester is carboxyl-functional, in other words, one or more chain ends are capped with a carboxylic acid structural moiety. The PEDA herein has terminal carboxylic acid functionality. Thus, the PEDA described herein can be a carboxylic acid-capped polyester dispersant. For example, the PEDA may comprise a single terminal carboxylic acid functionality or two terminal carboxylic acid functionalities.

[0219] The polyesters in the embodiments herein can be characterized by the polydispersity index (PDI), which is determined by size exclusion chromatography (SEC), gel permeation chromatography (GPC), or matrix-assisted laser desorption / ionization time-of-flight (MALDI-TOF) mass spectrometry, and is defined as the ratio of the weight-average molecular weight (M w ) to M n , i.e., PDI = M w / M n . [See, e.g., Introduction toPhysical Polymer Science, 3rd Edition by L.H. Sperling, Chapter 3, Wiley-Interscience, 2001]

[0220] For a given polyester, a larger PDI value corresponds to a broader MWD. The PDI value (in terms of the lower limit) of the polyesters herein can be greater than about 2, such as greater than 2.0, greater than 2.2, or greater than 2.4. In a preferred embodiment, the polydispersity index (PDI) of the polyester is greater than about 2.3, greater than about 2.4, or more preferably greater than about 2.5. For example, the polydispersity index (PDI) range of the polyesters used herein can be from 2.0 to 3.0, from 2.2 to 2.8, or from 2.3 to 2.7.

[0221] The PEDA applicable to the compositions, dispersions, and formulations herein can be characterized by the number average molecular weight (M n ) value, which is determined by size exclusion chromatography (SEC) or gel permeation chromatography (GPC). The number average molecular weight (M n ) of the polyesters described herein is less than about 10,000 g / mol. The M n value of the polyester can, for example, be in the range of about 750 g / mol to 10,000 g / mol, such as in the range of 750 g / mol to 5,000 g / mol, 750 g / mol to 2,500 g / mol, or 800 g / mol to 2,500 g / mol.

[0222] The PEDA herein can be characterized by the acid value (measured by the 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 can, for example, be from about 15 mg KOH / g to about 100 mg KOH / g, such as from 20 mg KOH / g to 90 mg KOH / g, from 25 mg KOH / g to 80 mg KOH / g, or from 30 mg KOH / g to 75 mg KOH / g. The acid value (in terms of the lower limit) of the PEDA can be greater than about 15 mg KOH, such as greater than 20 mg KOH, greater than 25 mg KOH / g, or greater than 30 mg KOH / g. The acid value (in terms of the upper limit) of the PEDA can be less than about 100 mg KOH, such as less than 90 mg KOH, less than 80 mg KOH / g, or less than 75 mg KOH / g.

[0223] In some embodiments, the non-aqueous composition for dispersing MOP used in the dispersions and / or formulations herein comprises a polyester homopolymer derived from the polycondensation of hydroxyalkanoic acids of formula (V):

[0224]

[0225] wherein R is selected from linear, branched, saturated, or unsaturated alkyl groups containing 5 to 23 carbon atoms (C5-C 23 ) and R' is selected from H or alkyl groups containing 1 to 22 carbon atoms (C1-C22 ) linear, branched, cyclic, saturated or unsaturated alkyl or acyl groups.

[0226] Examples of polyesters according to formula (V) include polyhydroxystearic acid (the structure is shown in (V-i) below), polyhydroxystearic acid stearate (polyhydroxystearic acid in which some or all of the hydroxyl groups react with stearic acid to form stearate), polyhydroxystearyl succinate (polyhydroxystearic acid in which some or all of the hydroxyl groups react with succinic acid to form succinic acid monoester and / or diester), polyhydroxystearyl sebacate (polyhydroxystearic acid in which some or all of the hydroxyl groups react with sebacic acid to form sebacic acid monoester and / or diester), polyricinoleic acid, and carboxyl-terminated lactones (estolides) derived from oleic acid, such as coconut oleate lactone. The monoesters of polyhydroxystearyl succinate and polyhydroxystearyl sebacate are shown in Figures V-ii and V-iii, respectively. The copolymers of the diesters polyhydroxystearyl succinate and polyhydroxystearyl sebacate are shown in Figure V-iv, where R 10 = succinyl [C(O)(CH2)2C(O)] or sebacoyl [C(O)(CH2)8C(O)] and R 11 = C 17 H 34 .

[0227]

[0228]

[0229] In some embodiments, the polyester can be a polyester copolymer derived from the polycondensation of two or more difunctional monomers (such as diols and diacids or diesters (such as methyl esters)) according to structure (VI):

[0230]

[0231] where R is selected from linear, branched, cyclic, saturated or unsaturated alkyl groups containing 2 to 34 carbon atoms (C2-C 34 ); R' is selected from linear, branched, saturated or unsaturated alkyl groups containing 2 to 34 carbon atoms (C2-C 34 ); and R'' is selected from H or linear, branched, cyclic, saturated or unsaturated alkyl or acyl groups containing 1 to 22 carbon atoms (C1-C 22 ). The acid-functional monomer must be present in excess to ensure that most of the polyester copolymer chain ends are carboxyl-functional. One end of the polyester copolymer can be capped with an ester group, but at least one chain end includes a carboxylic acid functional group. Alternatively, the hydroxyl-functional polyester can be COOH-capped, for example, by a post-polymerization reaction with an acid anhydride (such as succinic anhydride).

[0232] For example, 1,2-pentanediol (pentanediol, R' = 1,2-substituted n-pentyl) can be copolymerized with a slightly molar excess of sebacic acid to produce carboxyl-terminated telechelic (functionally terminated at both ends) poly(1,2-pentanediol sebacate). Examples of the polyester according to formula (VI) include the pentanediol / sebacic acid copolymer according to structure (VI-i):

[0233]

[0234] wherein R is an 1,8-substituted n-octyl and R' is a 1,2-substituted n-pentyl.

[0235] 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 other embodiments, the carboxylic acid-terminated polyester includes a homopolymer derived from an AB hydroxycarboxylic acid monomer. In other embodiments, the carboxylic acid-terminated polyester includes a copolymer derived from an AA diol and a BB diacid or diester (such as a methyl ester) monomer. In a preferred embodiment, PEDA does not contain an unsaturated structural moiety in the polymer backbone or as a side chain group, i.e., PEDA does not contain a C═C double bond susceptible to oxidative degradation.

[0236] The carboxylic acid-terminated polyester may be selected from polyhydroxystearic acid, polyhydroxystearic acid stearate, polyhydroxystearyl succinate, polyhydroxystearyl sebacate, and combinations thereof.

[0237] The polyester dispersant as described above contains biobased carbon. In the embodiments herein, the carbon atoms of the polyester contain greater than about 90%, such as greater than 95%, greater than 96%, greater than 97%, greater than 98%, or greater than 99% biobased carbon (as determined by 14 the radiocarbon dating method of C or other methods known to those skilled in the art as described above). In some embodiments, the polyester contains 100% biobased carbon. In some embodiments, substantially all of the carbon present in the compounds of formula (V), (VI), or combinations thereof is biobased. The polyester is preferably composed of renewable biobased carbon. In a preferred embodiment, the carboxylic acid-terminated polyester contains 100% biobased carbon.

[0238] Preparation / method of the dispersion

[0239] The non-aqueous dispersions of the present disclosure advantageously may contain a high loading of metal oxide particles. The weight fraction of metal oxide particles contained in the non-aqueous dispersion ranges from about 15 wt% to about 75 wt%, based on the total weight of the non-aqueous dispersion, for example, 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%. In terms of the lower limit, the dispersion may 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%, or greater than 45 wt% or greater than 50 wt%. In a preferred embodiment, the MOP fraction in the dispersion is greater than 40 wt% or greater than 45 wt%.

[0240] The non-aqueous dispersions of the present disclosure desirably contain a high loading of metal oxide particles, and this is also true in terms of volume fraction. The non-aqueous dispersion contains a volume fraction of solid particles of metal oxide particles that ranges from about 20 vol% to about 80 vol% based on the total volume of the non-aqueous dispersion, 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%. In terms of the lower limit, the dispersion may 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 a preferred embodiment, the MOP fraction in the dispersion is greater than 50 vol%, greater than 60 vol%, or greater than 70 vol%.

[0241] The amount (or concentration) of polyester in the dispersion is selected to produce the lowest possible dispersion viscosity range. These dispersion compositions contain polyester in the range of about 1.00 wt% to about 10.00 wt%, for example 1.00 wt% to 7 wt%, 2.00 wt% to 6.00 wt% or 3.00 wt% to 5.00 wt%. In a preferred embodiment, the dispersion composition contains polyester in the range of 3.00 wt% to 5.00 wt%. The amount of polyester required to achieve a stable, low-viscosity dispersion generally increases as the loading of MOP in the dispersion increases.

[0242] The methods of the present disclosure include preparing a non-aqueous composition for dispersing metal oxide particles. In some embodiments, the method includes adding one or more components to the non-aqueous composition to form a non-aqueous dispersion and / or formulation.

[0243] The dispersion can be prepared according to any technique familiar 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 a polyester in an ester to form a homogeneous solution. Subsequently, the method includes adding metal oxide particles to the homogeneous solution (or mixture), and thoroughly mixing and shearing to ensure a homogeneous non-aqueous dispersion. Heating can be used to improve the dissolution of the polyester in the ester. In addition to or in place of heating, high-shear mixing can also be performed using a rotor-stator homogenizer, a Cowles blade, a colloid mill, or other high-shear devices to ensure optimal dispersion and stabilization of the metal oxide particles.

[0244] In some embodiments, the method includes mixing an EDM and a PEDA having a broad MWD to form a homogeneous solution (or mixture). The ester includes esters selected from the above formulas (I), (II), (II), (IV), and combinations thereof. The method can include the triglyceride in formula IV as described in detail 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.

[0245] The method can include a polydispersity index (PDI) of the polyester greater than about 2.3, about 2.4, or about 2.5. The polyester can contain a single terminal carboxylic acid functional group. In other embodiments, the method includes the polyester containing two terminal carboxylic acid functional groups.

[0246] The method can include the polyester having a number average molecular weight (Mn) of less than about 10,000 g / mol. The polyester can have an acid value of at least 15 mg KOH / g. The method can include the polyester selected from polyhydroxystearic acid, polyhydroxystearic acid stearate, polyhydroxystearyl succinate, polyhydroxystearyl sebacate, and combinations thereof. The carbon present in the polyester is 100% biobased.

[0247] The non-aqueous dispersion described herein preferably has a low viscosity for easy processing (such as mixing, pumping, etc.), handling, and application. In some embodiments, the method includes a viscosity of the non-aqueous dispersion less than about 1000 cP. The viscosity of the dispersion composition (in terms of the upper limit) is less than about 1000 cP, such as 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.

[0248] In these low-viscosity non-aqueous metal oxide particle dispersions, the weight ratio of the inorganic solid particles, metal oxide particles to the ester dispersion medium ranges from about 1 to 0.33 (1:0.33) to about 1 to 5 (1:5). In a preferred embodiment, the weight ratio of the inorganic particles to the ester in the non-aqueous dispersion is about 1 to about 0.67 (1:0.67). In a more preferred embodiment, the weight ratio of the inorganic particles to the ester in the non-aqueous dispersion is about 1 to about 1 (1:1).

[0249] The non-aqueous dispersions and formulations containing the non-aqueous dispersions can be free or substantially free of silicones, such as methyl silicone, dimethyl silicone, cyclopentasiloxane, etc. "Silicone-free" compositions and formulations contain less than about 1 wt%, preferably less than about 0.5 wt%, more preferably less than about 0.1 wt% of silicone components, or most preferably do not contain a measurable concentration or amount of silicone.

[0250] The non-aqueous dispersion should exhibit stability during preparation, which means that sedimentation, separation, or a sharp change in viscosity should not occur from the time of preparation to use. This generally means that the dispersion remains stable for several days to several weeks after preparation. The ability to easily redisperse the sedimented solids by stirring the sedimented dispersion (e.g., using a stirrer or oscillator) is also a favorable indicator of the dispersion stability, such as in cases where a lower solid loading is required and the colloidal packing and / or yield value are insufficient to prevent sedimentation.

[0251] The method can include pre-preparing a homogeneous solution for subsequent addition of MOP, i.e., the MOP component can be considered optional and added later to form the non-aqueous dispersion. Thus, the method can also include dispersing metal oxide particles in a mixture to form a non-aqueous dispersion. The metal oxide particles can include zinc oxide, titanium oxide, combinations thereof, and other metal oxides listed above.

[0252] The non-aqueous dispersion can be substantially free of silicones.

[0253] The non-aqueous dispersion composition can be used directly or for formulating a final product. For example, the dispersion can be formulated into various product forms, such as oil-in-water (O / W) emulsions, water-in-oil (W / O) emulsions, creams, lotions, pastes, sprays, sticks, etc.

[0254] The method can also include adding at least one additional ingredient thereto to form a formulation. The at least one additional ingredient is selected from film-forming polymers (such as polyester-7, polyester-10, trimethylpentanediol / adipic acid / glycerol crosslinked polymer, adipic acid / diethylene glycol crosslinked polymer, ethyl cellulose, acrylate copolymer (such as Avalure from Lubrizol TMAC series, polyurethane-62, PPG-17 / IPDI / DMPA copolymer), rheology modifying polymers (such as acrylate copolymers, carbomers, acrylate / C 10-30 alkyl acrylate crosslinked polymer, acrylate / polyoxyethylene-25 behenyl methacrylate copolymer, sodium acrylate / sodium acryloyldimethyltaurate copolymer, acrylate / vinyl neodecanoate crosslinked polymer, hydroxypropyl methylcellulose, hydroxyethyl cellulose, polyurethane-79), waxes (such as Cera Alba (beeswax), candelilla wax, carnauba wax, microcrystalline wax), emulsifiers (such as cetearyl alcohol polyoxyethylene-12 ether, PEG-100 stearate, glyceryl stearate, rapeseed glyceride, rapeseed alcohol, lauryl polyoxyethylene-4 ether, potassium cetyl phosphate), emollients (such as petrolatum, mineral oil, sunflower oil, squalene, almond oil), humectants (such as glycerin, urea, betaine), pH adjusters, antioxidants, fragrances, multifunctional ingredients, preservation techniques or combinations thereof. In some embodiments, the formulation is a sunscreen.

[0255] Other components can be provided, including those known in the field of sunscreen formulations, or components for personal care compositions (such as cosmetics). The composition can optionally contain, for example, surfactants, buffers, fragrances, colorants, dyes, viscosity regulators, water, oils, emulsifiers, preservatives, antioxidants, emollients, thickeners, gelling agents, vitamins, humectants, alcohols, plant extracts, and powders. Other suitable additives or components can include one or more oils in the product, such as almond oil, castor oil, coconut oil, corn oil, cottonseed oil, rapeseed oil, linseed oil, nut oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower oil, jojoba oil, or combinations of these oils.

[0256] Surfactants can be included in the personal care composition, such as anionic surfactants, zwitterionic surfactants, cationic surfactants, nonionic surfactants, or combinations thereof. Other exemplary components or additives can include, but are not limited to, lipids, additional alcohols, waxes, pigments, vitamins, fragrances, bleaching 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, plant extracts, abrasives and / or exfoliants (chemical or mechanical), anticaking agents, antioxidants, binders, biological additives, buffers, swelling agents, chelating agents, chemical additives, denaturants, topical analgesics, film formers, humectants, opacifiers, pH adjusters, preservatives, propellants, reducing agents, sunscreens, skin tanning agents, essential oils, skin sensates, or combinations thereof.

[0257] The personal care composition of the present invention may also comprise one or more optical brighteners, as described in U.S. Patent Publication No. 2011 / 0104078A1, which is incorporated herein by reference, and also includes, for example, triazine-stilbene (disulfonated, tetrasulfonated or hexasulfonated), coumarin, imidazoline, oxadiazole, triazole, benzoxazoline and diphenylstilbene.

[0258] The scope of the present invention also includes a method for protecting the skin, hair and / or nails of a mammal from damage caused by exposure to light in the UV wavelength range, which comprises applying the composition as described above to the skin, hair or nails. "Skin" includes the outer skin of living mammals, reptiles, amphibians, birds and other animals, as well as processed skin, such as leather or suede. "Hair" includes the hair, fur, wool and other filamentous keratinized structures of mammals and other animals. Similarly, "nails" includes the claws, hooves and similar structures of mammals and other animals.

[0259] The scope of the present invention also includes a method for improving the aesthetics of a light protection preparation by using the composition, to avoid an oily and / or greasy feel and to prevent significant loss or separation of the components when the skin is wet, moist or otherwise wetted.

[0260] Formulation

[0261] In some embodiments, the present invention relates to a dispersion composition comprising metal oxide particles, which can be used in formulations for various applications. The dispersion composition or formulation is a personal care product, a household care product, a textile care product, an institutional care product, a pharmaceutical product, a veterinary product, a food or an industrial product or can be a component of these products. In some embodiments, the composition can be used in a formulation or can be a component of a personal care product. Personal care products include cosmetics, hair, nail, skin or textile conditioners, shampoos, hair styling products, oils or waxes for grooming beards, perming solutions, hair dyes, facial cleansers or shower gels, makeup removers, cleansing milks, emollient lotions or creams, soaps, liquid soaps, shaving creams, foams or gels, sunscreens, gels, lotions or creams for treating sunburn, deodorants or antiperspirants, moisturizing gels, shaving foams, facial powders, foundations, lipsticks, blushes, eyeliner creams, anti-wrinkle creams or anti-aging creams, eyeshadows, eyebrow pencils, mascaras, mouthwashes, toothpastes, oral care products, skin cleansing products, textile cleansing products, dishwashing products, hair or fur cleansing products, and skin care lotions or moisturizers. In a preferred embodiment, the formulation is a sunscreen.

[0262] The formulations of the present invention can be used, for example, as skin creams, facial moisturizers, sunscreen lotions, nourishing creams, day creams or night creams. Typical embodiments are creams, gels such as, but not limited to, hydrogels, aqueous dispersion gels, oleogels; emulsions, alcohols and water / alcohol solutions, emulsions in various forms such as, but not limited to, oil-in-water (O / W), water-in-oil (W / O), mixed emulsions, PIT emulsions, Pickering emulsions, microemulsions, nanoemulsions; aerosol foams, non-aerosol foams, aerosol sprays, non-aerosol sprays, pump sprays, serums, roll-ons, pastes, balms or stick formulations. These compositions can also contain mild surfactants, co-emulsifiers, superfatting agents, pearlescent waxes, thickening agents, thickeners, polymers, silicone compounds, fats, waxes, stabilizers, bioactive ingredients, deodorant active ingredients, antidandruff agents, film formers, swelling agents, hydrotropes, preservatives, insect repellents, tanning agents, artificial self-tanning agents (such as dihydroxyacetone), stabilizers, aromatic oils, dyes, antibacterial agents, water-based and non-water-based plant extracts, etc. as further auxiliaries and additives. Those skilled in the art can determine the amounts of cosmetic or dermatological auxiliaries and carrier substances and fragrances that can be used in each case based on the nature of the product under discussion. In a preferred embodiment according to the present invention, the composition is a sunscreen preparation or sunscreen with an SPF of 30 or higher. The SPF is determined according to the standard ISO 24444:2019 "In Vivo Determination of the Sun Protection Factor (SPF)" and in accordance with the provisions in "Over-the-counter sunscreen drug products; required labeling based oneffectiveness testing", Food and Drug Administration, Code of Federal Regulations, Title 21, §201.327.

[0263] In some embodiments, the sunscreen active agent 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 and can be from about 0.5 wt% to about 75 wt% of the composition, preferably from about 5 wt% to about 70 wt% of the composition, and most preferably from about 10 wt% to about 40 wt% of the composition, although this amount can be adjusted according to the desired final effect and based on the selected active ingredients known in the art.

[0264] In some cases, the disclosed compositions may expressly exclude one or more of the above ingredients in this section, e.g., by claim language. For example, the claim language can be modified to state that the disclosed compositions, formulations, methods, etc. do not use or do not contain one or more of the above optional ingredients.

[0265] The dispersion compositions and formulations described herein exhibit stability over time and temperature.

[0266] The dispersion compositions and formulations disclosed herein can, for example, have a formulated viscosity that increases less than 1.3-fold when stored at 25 °C for 2 weeks, or less than 2-fold when stored at 25 °C for 4 weeks. At higher storage temperatures, the dispersion compositions and formulations disclosed herein can, for example, have a formulated viscosity that increases less than 1.4-fold when stored at 45 °C for 2 weeks, or less than 8.3-fold when stored at 45 °C for 4 weeks. At higher storage temperatures, the dispersion compositions and formulations disclosed herein can, for example, have a formulated viscosity that increases less than 2.2-fold when stored at 50 °C for 2 weeks, or less than 19.3-fold when stored at 50 °C for 4 weeks.

[0267] These detailed descriptions serve to illustrate the above general descriptions and embodiments that form part of the present invention. These detailed descriptions are for illustrative purposes only and are not intended to limit the scope of the present invention.

[0268] Examples

[0269] Dispersion Preparation. MOP dispersions were prepared according to the following procedure. The ester dispersion medium and polyester dispersant were charged into a glass beaker of appropriate size and gently mixed and heated until the polyester liquefied (about 50 - 60 °C). The ester and polyester were mixed at 2000 - 2500 rpm using a Silverson L5M-A high shear rotor / stator laboratory for about one minute, or until a clear (transparent) and homogeneous solution was obtained. MOP was added to this ester - polyester mixture and mixed at 5000 - 5500 rpm for five minutes to obtain a homogeneous dispersion. Generally, the mixing speed was adjusted as needed according to the dispersion viscosity. Care was taken to ensure that all of the MOP was uniformly incorporated into the dispersion and that there was no undispersed MOP.

[0270] Brookfield Viscosity Determination. The dispersion viscosity was determined using a Brookfield DV1 type digital viscometer. The spindle and rotational speed were selected to ensure that the viscosity reading was obtained within a torque window of 10 - 80% of the maximum torque range. For most dispersions, the viscosity was recorded using the RV spindle 3 at a rotational speed of 10 - 100 rpm.

[0271] Kinematic viscosity measurement. The kinematic viscosity (unit: cSt (centistokes)) was measured using an Anton Paar Stabinger viscometer (model: SVM 3001) that meets the requirements of ASTM method D7042.

[0272] Rheological parameters. Rheological parameters G', 平台 , G", 频率 , yield stress, and viscosities at 0.1 s -1 and 1 s -1 were measured using a TA Instruments Discovery HR-20 rheometer with a standard 50 mm cone-plate geometry with a 2° angle and 52 mm gap at a Peltier-controlled temperature of 25 °C. The yield stress value was determined by the modulus crossover method through amplitude sweep testing (at 1 rad / s), where where % strain 交叉 and G' 交叉 are the values at which G' and G" cross each other, i.e., G' 交叉 = G". 交叉 . [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, -Escalona A, A, ME, Lafuente P (1996) Comparison of the rheological properties of metallocene-catalyzed and conventional high-density polyethylenes. Macromolecules 29:960 - 965.] The plateau value G' of the storage modulus G' and the amplitude range with linear response (required for frequency sweep testing) were also determined by amplitude sweep testing. Frequency dependence (flow and relaxation kinetics) was determined by measuring the storage modulus (G') and loss modulus (G") through frequency sweep testing (% strain in the linear range, 0.03% strain to 0.1% strain for the compositions measured). G" 平台 was determined based on the measurement results at a frequency of 1 rad / s. Viscosity and shear thinning behavior were determined by flow curve measurement, i.e., viscosity vs shear rate (s 频率 ). -1 ) measurement.

[0273] In vitro UV transmittance measurement. The UV transmittance values of the compositions containing metal oxide particles (MOP) were measured for wavelengths from 250 - 450 nm using a Labsphere UV-2000 ultraviolet transmittance analyzer; the protocol applied conformed to the broad-spectrum and UV1 / UV determination of the US FDA method (2011). Specifically, 18.75 mg (milligrams) of the composition was evenly applied on a 5 x 5 cm 2 polymethyl methacrylate (PMMA) plate. Before transmittance measurement, the treated plate was placed in a dark place and allowed to stand for 15 minutes. The transmittance was measured at five positions on each of the three treated PMMA plates for each composition (using an untreated PMMA plate as a reference), and the average of these 15 measurements was used to determine the in vitro UV transmittance of the composition at a wavelength of 340 nm.

[0274] Dispersion compositions. Table 1 shows the dispersion composition Example E1 and Comparative Examples CE1 and CE2 prepared according to the above method and the indicated amounts.

[0275] Example E1 and Comparative Examples CE1, CE2

[0276] Dispersion compositions with low MW (CE1), high MW (CE2), and broad MWD (E1) were used.

[0277] The MOP in Table 1 is zinc oxide, 10 (EverCare). For CE1, at amounts of 2.00 wt%, 3.00 wt%, 4.00 wt%, 5.00 wt%, and 6.00 wt%, the polyester was polyhydroxystearic acid Dispersun DSP-OL300 (Innospec), or for CE2, at amounts of 3.00 wt%, 4.00 wt%, 5.00 wt%, and 6.00 wt%, the polyester was polyhydroxystearic acid Dispersun DSP-OL 100 (Innospec), or for E1, at amounts of 2.00 wt%, 3.00 wt%, 4.00 wt%, 5.00 wt%, and 6.00 wt%, the polyester was a 50 / 50 mixture of polyhydroxystearic acid Dispersun DSP-OL300 (Innospec) and Dispersun DSP-OL 100 (Innospec). The weight ratio range of MOP to PEDA in all compositions was from about 25:1 to about 8:1. The MOP and EDM components were the same in Example E1 and Comparative Examples CE1 and CE2, while the PEDA was different. The EDM was heptyl undecylenate, LexFeel TM Natural (INOLEX, Inc.).

[0278]

[0279] The dispersion composition of Example E1 was prepared using a wide MWD PHSA (PEDA). The dispersion composition of Comparative Example CE1 was prepared using a low MW PHSA (PEDA). The dispersion composition of Comparative Example CE2 was prepared using a high MW PHSA (PEDA).

[0280] Table 2 shows the dispersion viscosity values of Example E1 and Comparative Examples CE1 and CE2, where the amounts of polyester are 2.00 wt%, 3.00 wt%, 4.00 wt%, 5.00 wt% and 6.00 wt%.

[0281] As shown in Table 2, within the entire PEDA concentration range tested, the viscosity values of Example E1 were lower than those of Comparative Examples CE1 and CE2. These results are shown graphically in Figure 1 .

[0282]

[0283] Benefits of polyesters with high PDI values (wide MWD PEDA).

[0284] Table 3 details the polymer characterization data of three different polyhydroxystearic acid (PHSA) polyesters. The acid value was used to quantify the carboxyl chain-end functionality of each polyester. Polyesters with higher acid values had higher levels of carboxylic acid chain-ends. The molecular weight of the polyesters was determined by end-group analysis (EGA) and gel permeation chromatography (GPC). The number-average molecular weight (M n ) and number-average degree of polymerization (DP n ) values determined by EGA and GPC showed good agreement. The slightly higher values obtained by GPC were attributed to the use of a polystyrene molecular weight calibration standard rather than direct calibration vs. a polyhydroxystearic acid standard of known MW. GPC also produced weight-average molecular weight values (M w ) and information on the MW distribution (MWD), characterized by the polydispersity index (PDI). The PDI values of the high molecular weight and low molecular weight PHSA polyesters ranged from 2.08 - 2.26. The high molecular weight and low molecular weight PHSA polyesters had narrow molecular weight distributions. By preparing a 50 / 50 wt% / wt% mixture of high molecular weight and low molecular weight PHSA materials, a PHSA with a wider MWD was prepared; this wide MWD PHSA exhibited M n and M wThe median value, and the PDI value is significantly larger, being 2.57. The PHSA polyesters used are as follows: low MW is Dispersun DSP-OL 300 (Innospec), high MW is Dispersun DSP-OL 100 (Innospec), and wide MWD is a 50 / 50 by weight mixture of low MW and high MW PHSA polyesters.

[0285] Polyester characterization data.

[0286]

[0287] The polyesters listed in Table 3 were used to prepare the MOP dispersions of ZnO in the examples, as shown in Table 4 (and as shown in Table 1).

[0288] Examples E2–E5 and Comparative Examples CE3–CE10: Benefits of high PDI polyesters (i.e., wide MWD PHSA / PEDA) for reducing the viscosity of the dispersion.

[0289] Table 4 shows the compositions of various dispersions prepared using the different polyesters listed in Table 3, which are heptyl undecylenate (such as E2, CE3, and CE4), or diisooctyl succinate (such as E3, CE5, and CE6), or triheptanoin (C7 triglyceride) (such as E4, CE7, and CE8), or caprylic / capric triglyceride (C8 / C 10 triglyceride) (such as E5, CE9, and CE10). The polyester and ester concentrations in the dispersions were kept constant at 4.00 wt% and 45.95 wt% respectively, and the remainder contained ZnO MOP. Table 4 also reports the viscosity of each dispersion.

[0290] In all cases, the dispersions prepared using wide MWD PHSA polyesters (Examples E2 - E5) exhibited lower viscosities than the examples prepared using low or high MW PHSA polyesters with lower PDI values (i.e., narrower MWD). When wide MWD PHSA was used instead of low or high MW PHSA polyesters, the percentage reduction in viscosity of various esters is detailed in Table 5.

[0291] Viscosity of the dispersion composition.

[0292] Table 4. Dispersion composition (CE3 - CE10 and E2 - E5) and its viscosity Formulation Wt% (as supplied)

[0293]

[0294] Table 5. Reduction of dispersion viscosity using wide MWD PHSA (E2 - E5) vs low MW PHSA (CE3, CE5, CE7, CE9) and vs high MW PHSA (CE4, CE6, CE8, CE10) for four different esters (EDM).

[0295] Dispersion viscosity is reduced when using wide MWD PHSA polyesters.

[0296]

[0297] The percentage reduction of low MWD PHSA dispersions vs. low MW or high MW PHSA dispersions in Table 5 ranges from 8% to 93%.

[0298] The results shown in Tables 4 and 5 demonstrate that the combination of using wide molecular weight distribution polyesters with esters (including triglycerides) according to the present invention to prepare low viscosity MOP dispersions has a surprising effect. This effect is shown compared to low molecular weight and high molecular weight polyesters.

[0299] Ester dispersion medium data at the time of supply is shown in Table 6 below.

[0300]

[0301] The results shown in Tables 7 and 8 demonstrate the utility of the compositions and formulations of the present invention disclosed herein on the other hand. Table 7 details Example formulation E6, which uses an ester (such as heptyl undecylenate in E1) as the ester dispersion medium in combination with wide MWD PEDA (polyhydroxystearic acid), as described in the polyester characterization data in Table 3 above. Table 7 also includes Comparative formulation CE11, which contains the same ester as E6 but is combined with low molecular weight PEDA (Dispersun DSP - OL 300 (Innospec)), as described in Table 3 above.

[0302] Table 8 lists the viscosities of E6 and CE11, which were measured after formulation and after storage at room temperature, 45 °C, and 50 °C for two and four weeks respectively. Although both formulations E6 and CE11 show an increase in viscosity with increasing storage time, the rate of increase in viscosity of CE11 is significantly higher than that of E6. After storage at 45 °C and 50 °C for four weeks, the viscosity of CE11 is far higher than 100,000 cP, which renders the formulation unusable, while the viscosity of E6 after storage at these temperatures for four weeks is completely within the usable range.

[0303] Formulations containing wide MWD PEDA (E6) and low molecular weight polyester (CE11).

[0304]

[0305]

[0306] Table 9-11 details the example formulations respectively. In Examples E7-E9, a combination of an ester dispersion medium (i.e., glyceryl triheptanoate in E7 and E8, and glyceryl caprylate / caprate in E9) and polyhydroxystearic acid (PHSA, 4 wt%) was used as a polyester dispersant with a broad molecular weight distribution, as described by the polyester characterization data in Tables 1-3 above. In Comparative Examples CE12-CE14, the same esters as in the examples of the present invention were used, but a polyester dispersant with a narrow molecular weight distribution was used. E7 and CE12 were made into water-in-oil (W / O) emulsions; E8 and CE13 were made into oil-in-water (O / W) emulsions, and E9 and CE14 were made into water-in-oil (W / O) emulsions.

[0307] The preparation of the sunscreen formulations was as follows. Zinc oxide was dispersed into a mixture of polyester (PHSA) and ester (EDM), homogenized for 1 minute at 1000 rpm and for 2 minutes at 2500 rpm according to the formulations detailed herein (Silverson L5M-A, General Purpose Head).

[0308] Then the remaining oil phase components were added and heated to 70-75 °C while mixing with a propeller mixer at 100 rpm.

[0309] In a separate container, the main batch components were mixed and heated to 70-75 °C while mixing with a propeller mixer at 100 rpm.

[0310] Then the main batch components were added to the oil phase and homogenized for 5 minutes at 2500 rpm.

[0311] Then the formulation was transferred for propeller mixing at 250 rpm, cooled, and the remaining components were added at 40 °C and mixing was continued for 5 minutes.

[0312] Mixing was continued until the temperature reached ≤30 °C.

[0313]

[0314]

[0315]

[0316] To demonstrate the benefits of the present invention, the finished formulation viscosities and in vitro UV transmittance values of sunscreen formulations generated using different MOP dispersions according to Tables 9 - 11 were analyzed. Importantly, Examples E7 - E9 of the present invention exhibited lower viscosities and lower in vitro UV transmittance compared to Comparative Examples CE12 - CE14. By achieving a high level of well - dispersed ZnO particles in the formulation while providing improved sensory, tactile, and spreading behavior (e.g., reduced viscosity, storage modulus, loss modulus, and yield stress values), a sunscreen formulation with sufficient sun protection performance (e.g., low UV transmittance) can be created.

[0317] As described above, two types of sunscreen formulations were prepared, oil - in - water emulsions (such as E8) and water - in - oil emulsions (such as E7 and E9).

[0318] Table 12 shows the data of Examples (E7 to E9) and Comparative Examples (CE12 to CE14) of the present invention to study the effect of different ester / polyester MWD combinations on the rheological properties of finished sunscreen formulations using ZnO particle dispersions. The in vitro UV transmittance values were also measured and listed in Table 12.

[0319]

[0320] ＊ Broad MWD (BMW D is 50:50 OL - 100:OL - 300 (w / w).

[0321] ＊＊ Narrow MWD (NMWD) is Dispersun DSP - OL300.

[0322] The rheological parameters listed in Table 12 indicate that the viscosities, storage moduli, loss moduli (G′, G″), and yield stress values of Examples E7 - E9 of the present invention are lower compared to Comparative Examples CE12 - CE14. Rheological parameters characterize the feel, tactile, and spreading behavior of materials. Sunscreen formulations are typically very thick, greasy, and difficult to spread, i.e., they exhibit high viscosities, storage moduli, loss moduli, and yield stress values. It is desirable to manufacture sunscreen formulations with sufficient sun protection performance but with improved feel, tactile, and spreading behavior. The Examples of the present invention in Table 12 exhibit this improved behavior compared to the corresponding Comparative Examples listed in the same table. Specifically, G′ of the Examples of the present invention 平台 is 2 to 4 times lower than that of the Comparative Examples, G″ 频率 is 2 to 3 times lower, the yield stress is 1.5 to 4 times lower, the viscosity at 0.1 s -1 is 6.6% to 66% lower, and the viscosity at 1 s -126% to 300% lower in viscosity. The quality of the MOP dispersion is very important for achieving good sun protection and SPF values at a given MOP usage level. The in vitro UV transmittance values of the examples of the present invention are 6% to 34% lower than the in vitro UV transmittance values of the comparative examples. Table 13 lists the % reduction in rheological and UV transmittance parameters of examples E7 to E9 of the present invention compared to their corresponding comparative examples CE12 to CE14, where x is the parameter value of an example or comparative example of the present invention from Table 12 above.

[0323]

[0324] Table 13 shows that, compared to the narrow molecular weight distribution polyester, the % reduction in G' of the wide molecular weight distribution polyester of the present invention 平台 is on average 68%; the % reduction in G'' 频率 is on average 64%; the % reduction in yield stress is on average 60%; the % reduction in viscosity at 0.1 s -1 is on average 35%; the % reduction in viscosity at 1 s -1 is on average 50%; the % reduction in UV transmittance is on average 18%. The sunscreen formulations according to the examples herein provide reduced UV transmittance (e.g., high SPF factor) while having increased spreadability.

[0325] Embodiments

[0326] Among other embodiments, the following embodiments are disclosed.

[0327] Clause 1. A non-aqueous composition for dispersing metal oxide particles, the composition comprising a polyester having a polydispersity index greater than about 2.3 and an ester selected from the group consisting of the following (i)-(v):

[0328] (i) A liquid ester of formula I:

[0329]

[0330] wherein R and R1 are each a linear, branched or cyclic alkyl group; a linear, branched or cyclic alkenyl group; or a linear, branched or cyclic alkynyl group; provided that if one of R and R1 is a linear alkyl group, the other of R and R1 is a branched or cyclic alkyl group; a linear, branched or cyclic alkenyl group; or a linear, branched or cyclic alkynyl group.

[0331] (ii) A liquid ester of formula II:

[0332]

[0333] wherein R2 is a branched alkyl, linear or branched alkenyl, or linear or branched alkynyl; R3 is a linear or branched alkyl, linear or branched alkenyl, or linear or branched alkynyl; and R4 is a linear or branched alkyl, linear or branched alkenyl, or linear or branched alkynyl;

[0334] (iii) a liquid ester of formula III:

[0335]

[0336] wherein R5 is a branched alkyl, linear or branched alkene, or linear or branched alkyne; R6 is a linear or branched alkyl, linear or branched alkene, or linear or branched alkyne; and R7 is a linear or branched alkyl, linear or branched alkene, or linear or branched alkyne; and

[0337] (iv) a liquid ester of formula IV:

[0338]

[0339] wherein R8, R9 and R 10 are each independently selected from C5-C 18 linear, branched, saturated or unsaturated alkyls containing 5 to 18 carbon atoms; and

[0340] (v) a combination of the above esters.

[0341] Clause 2. The non-aqueous composition according to Clause 1, wherein the ester has formula I and R is a C5-C 17 branched or cyclic alkyl, linear, branched or cyclic alkenyl, or linear, branched or cyclic alkynyl; and R1 is a C3-C 18 linear, branched or cyclic alkyl, linear, branched or cyclic alkenyl, or linear, branched or cyclic alkynyl.

[0342] Clause 3. The non-aqueous composition according to Clause 1, wherein the ester has formula I and R and R1 are different.

[0343] Clause 4. The non-aqueous composition according to Clause 1, wherein the ester has formula II and R2 is a C3-C 18 branched alkyl, linear or branched alkenyl or linear or branched alkynyl; R3 is a C2-C8 linear or branched alkyl, linear or branched alkenyl or linear or branched alkynyl; and R4 is a C3-C 18 linear or branched alkyl, linear or branched alkenyl or linear or branched alkynyl.

[0344] Clause 5. The non-aqueous composition according to Clause 1, wherein the ester has formula II and R2 and R4 are the same.

[0345] Clause 6. The non-aqueous composition according to Clause 1, wherein the ester has the formula III and R5 is C3-C 18 branched alkyl, linear or branched alkene or linear or branched alkyne, R6 is C2-C8 linear or branched alkyl, linear or branched alkene or linear or branched alkyne, and R7 is C3-C 18 linear or branched alkyl, linear or branched alkene or linear or branched alkyne.

[0346] Clause 7. The non-aqueous composition according to Clause 1, wherein the ester has the formula III and R5 and R7 are the same.

[0347] Clause 8. The non-aqueous composition according to Clause 1, wherein the ester has the formula IV and two or more of R8, R9 and R 10 are the same.

[0348] Clause 9. The non-aqueous composition according to Clause 1, wherein the ester is selected from the group consisting of monoesters, diesters, triesters or combinations thereof.

[0349] Clause 10. The non-aqueous composition according to Clause 1, wherein the ester has a viscosity at 25 °C of less than about 100 cSt.

[0350] Clause 11. The non-aqueous composition according to Clause 1, wherein the non-aqueous composition has a viscosity of less than 500 cP.

[0351] Clause 12. The non-aqueous composition according to Clause 1, wherein the carbon present in the ester is 100% biobased.

[0352] Clause 13. The non-aqueous composition according to Clause 1, wherein the polyester has a polydispersity index (PDI) greater than about 2.4.

[0353] Clause 14. The non-aqueous composition according to Clause 1, wherein the polyester has a polydispersity index (PDI) greater than about 2.5.

[0354] Clause 15. The non-aqueous composition according to Clause 1, wherein the polyester contains a single terminal carboxylic acid functional group.

[0355] Clause 16. The non-aqueous composition according to Clause 1, wherein the polyester contains two terminal carboxylic acid functional groups.

[0356] Clause 17. The non-aqueous composition according to Clause 1, wherein the polyester comprises a homopolymer derived from an AB hydroxycarboxylic acid monomer.

[0357] Clause 18. The non-aqueous composition according to Clause 1, wherein the polyester comprises a copolymer derived from an AA diol and a BB diacid or a di-monomer.

[0358] Clause 19. The non-aqueous composition according to Clause 1, wherein the polyester is selected from the group consisting of polyhydroxystearic acid, polyhydroxystearic acid stearate, polyhydroxystearyl succinate, polyhydroxystearyl sebacate, and combinations thereof.

[0359] Clause 20. The non-aqueous composition according to Clause 1, wherein the polyester comprises polyhydroxystearic acid.

[0360] Clause 21. The non-aqueous composition according to Clause 1, wherein the polyester has a number average molecular weight (Mn) of less than about 10,000 g / mol.

[0361] Clause 22. The non-aqueous composition according to Clause 1, wherein the polyester has an acid value of at least 15 mg KOH / g.

[0362] Clause 23. The non-aqueous composition according to Clause 1, wherein the carbon present in the polyester is 100% bio-based.

[0363] Clause 24. A non-aqueous composition for dispersing metal oxide particles, the composition consisting essentially of an ester and a polyester having a polydispersity index greater than about 2.3, wherein the ester is selected from the group consisting of the following (i)-(v):

[0364] (i) A liquid ester of Formula I:

[0365]

[0366] wherein each of R and R1 is a linear, branched, or cyclic alkyl group; a linear, branched, or cyclic alkenyl group; or a linear, branched, or cyclic alkynyl group; provided that if one of R and R1 is a linear alkyl group, the other of R and R1 is a branched or cyclic alkyl group; a linear, branched, or cyclic alkenyl group; or a linear, branched, or cyclic alkynyl group;

[0367] (ii) A liquid ester of Formula II:

[0368]

[0369] wherein R2 is a branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, R3 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, and R4 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group;

[0370] (iii) A liquid ester of Formula III:

[0371]

[0372] wherein R5 is a branched alkyl, linear or branched alkene, or linear or branched alkyne, R6 is a linear or branched alkyl, linear or branched alkene, or linear or branched alkyne, and R7 is a linear or branched alkyl, linear or branched alkene, or linear or branched alkyne;

[0373] (iv) a liquid ester of formula IV:

[0374]

[0375] wherein R8, R9 and R 10 are each independently selected from C5-C 18 linear, branched, saturated or unsaturated alkyls containing 5 to 18 carbon atoms; and

[0376] (v) a combination of the above esters.

[0377] Clause 25. A non-aqueous composition for dispersing metal oxide particles, the composition consisting of an ester and a polyester having a polydispersity index greater than about 2.3, wherein the ester is selected from the group consisting of the following (i)-(v):

[0378] (i) a liquid ester of formula I:

[0379]

[0380] wherein R and R1 are each a linear, branched or cyclic alkyl; linear, branched or cyclic alkenyl; or linear, branched or cyclic alkynyl; wherein if one of R and R1 is a linear alkyl, the other of R and R1 is a branched or cyclic alkyl; linear, branched or cyclic alkenyl; or linear, branched or cyclic alkynyl;

[0381] (ii) a liquid ester of formula II:

[0382]

[0383] wherein R2 is a branched alkyl, linear or branched alkenyl, or linear or branched alkynyl, R3 is a linear or branched alkyl, linear or branched alkenyl, or linear or branched alkynyl, and R4 is a linear or branched alkyl, linear or branched alkenyl, or linear or branched alkynyl;

[0384] (iii) a liquid ester of formula III:

[0385]

[0386] wherein R5 is a branched alkyl, linear or branched alkene, or linear or branched alkynyl, R6 is a linear or branched alkyl, linear or branched alkene, or linear or branched alkynyl, and R7 is a linear or branched alkyl, linear or branched alkene, or linear or branched alkynyl;

[0387] (iv) Liquid esters of formula IV:

[0388]

[0389] wherein R8, R9 and R 10 are each independently selected from C5-C 18 linear, branched, saturated or unsaturated alkyl groups having 5 to 18 carbon atoms; and

[0390] (v) Combinations of the above esters.

[0391] Clause 26. A non-aqueous dispersion comprising a plurality of metal oxide particles, an ester, and a polyester having a polydispersity index greater than about 2.3, wherein the ester is selected from the group consisting of the following (i)-(v):

[0392] (i) Liquid esters of formula I:

[0393]

[0394] wherein R and R1 are each a linear, branched or cyclic alkyl group; a linear, branched or cyclic alkenyl group; or a linear, branched or cyclic alkynyl group; provided that if one of R and R1 is a linear alkyl group, the other of R and R1 is a branched or cyclic alkyl group; a linear, branched or cyclic alkenyl group; or a linear, branched or cyclic alkynyl group;

[0395] (ii) Liquid esters of formula II:

[0396]

[0397] wherein R2 is a branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, R3 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, and R4 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group;

[0398] (iii) Liquid esters of formula III:

[0399]

[0400] wherein R5 is a branched alkyl group, a linear or branched alkene, or a linear or branched alkyne, R6 is a linear or branched alkyl group, a linear or branched alkene, or a linear or branched alkyne, and R7 is a linear or branched alkyl group, a linear or branched alkene, or a linear or branched alkyne;

[0401] (iv) Liquid esters of formula IV:

[0402]

[0403] wherein R8, R9 and R 10Each independently selected from C5-C containing 5 to 18 carbon atoms 18 linear, branched, saturated or unsaturated alkyl; and

[0404] (v) a combination of the above esters.

[0405] Clause 27. The non-aqueous dispersion according to Clause 26, wherein the ester is selected from the group consisting of monoesters, diesters, triesters, or combinations thereof.

[0406] Clause 28. The non-aqueous dispersion according to Clause 26, wherein the ester has the formula I, and R is C5-C 17 branched or cyclic alkyl, linear, branched or cyclic alkenyl, or linear, branched or cyclic alkynyl; and R1 is C3-C 18 linear, branched or cyclic alkyl, linear, branched or cyclic alkenyl, or linear, branched or cyclic alkynyl.

[0407] Clause 29. The non-aqueous dispersion according to Clause 26, wherein the ester has the formula I and R and R1 are different.

[0408] Clause 30. The non-aqueous dispersion according to Clause 26, wherein the ester has the formula II, and R2 is C3-C 18 branched alkyl, linear or branched alkenyl, or linear or branched alkynyl; R3 is C2-C8 linear or branched alkyl, linear or branched alkenyl, or linear or branched alkynyl; and R4 is C3-C 18 linear or branched alkyl, linear or branched alkenyl, or linear or branched alkynyl.

[0409] Clause 31. The non-aqueous dispersion according to Clause 26, wherein the ester has the formula II, and R2 and R4 are the same.

[0410] Clause 32. The non-aqueous dispersion according to Clause 26, wherein the ester has the formula III, and R5 is C3-C 18 branched alkyl, linear or branched olefin or linear or branched alkyne, R6 is C2-C8 linear or branched alkyl, linear or branched olefin or linear or branched alkyne, and R7 is C3-C 18 linear or branched alkyl, linear or branched olefin or linear or branched alkyne.

[0411] Clause 33. The non-aqueous dispersion according to Clause 26, wherein the ester has the formula III, and R5 and R7 are the same.

[0412] Clause 34. The non-aqueous dispersion according to Clause 26, wherein the ester has the formula IV, and two or more of R8, R9 and R 10 are the same.

[0413] Clause 35. The non-aqueous dispersion according to Clause 26 has a viscosity of less than 1000 cP.

[0414] Clause 36. The non-aqueous dispersion according to Clause 26, wherein the ester has a viscosity of less than about 100 cSt at 25 °C.

[0415] Clause 37. The non-aqueous dispersion according to Clause 26, wherein the carbon present in the ester is 100% bio-based.

[0416] Clause 38. The non-aqueous dispersion according to Clause 26, wherein the polyester has an acid value of at least 15 mg KOH / g.

[0417] Clause 39. The non-aqueous dispersion according to Clause 26, wherein the polyester contains a single terminal carboxylic acid functional group.

[0418] Clause 40. The non-aqueous dispersion according to Clause 26, wherein the polyester contains two terminal carboxylic acid functional groups.

[0419] Clause 41. The non-aqueous dispersion according to Clause 26, wherein the polyester has a linear structure.

[0420] Clause 42. The non-aqueous dispersion according to Clause 26, wherein the carbon present in the polyester is 100% bio-based.

[0421] Clause 43. The non-aqueous dispersion according to Clause 26, wherein the polyester is selected from the group consisting of polyhydroxystearic acid, polyhydroxystearic acid stearate, polyhydroxystearyl succinate, polyhydroxystearyl sebacate, and combinations thereof.

[0422] Clause 44. The non-aqueous dispersion according to Clause 26, wherein the metal oxide particles are not surface-modified.

[0423] Clause 45. The non-aqueous dispersion according to Clause 26, wherein the metal oxide particles include zinc oxide, titanium oxide, or a combination thereof.

[0424] Clause 46. The non-aqueous dispersion according to Clause 26, wherein the metal oxide particles account for about 15 wt% to about 75 wt% of the non-aqueous dispersion.

[0425] Clause 47. The non-aqueous dispersion according to Clause 26, wherein the metal oxide particles account for about 40 wt% to about 60 wt% of the non-aqueous dispersion.

[0426] Clause 48. The non-aqueous dispersion according to Clause 26, wherein the non-aqueous dispersion is substantially free of silicone.

[0427] Clause 49. A non-aqueous dispersion mainly composed of multiple metal oxide particles, an ester, and a polyester with a polydispersity index greater than about 2.3, wherein the ester is selected from the group consisting of the following (i)-(v):

[0428] (i) A liquid ester of Formula I:

[0429]

[0430] wherein R and R1 are each a linear, branched, or cyclic alkyl group; a linear, branched, or cyclic alkenyl group; or a linear, branched, or cyclic alkynyl group; provided that if one of R and R1 is a linear alkyl group, the other of R and R1 is a branched or cyclic alkyl group; a linear, branched, or cyclic alkenyl group; or a linear, branched, or cyclic alkynyl group;

[0431] (ii) A liquid ester of Formula II:

[0432]

[0433] wherein R2 is a branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, R3 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, and R4 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group;

[0434] (iii) A liquid ester of Formula III:

[0435]

[0436] wherein R5 is a branched alkyl group, a linear or branched olefin, or a linear or branched alkyne, R6 is a linear or branched alkyl group, a linear or branched olefin, or a linear or branched alkyne, and R7 is a linear or branched alkyl group, a linear or branched olefin, or a linear or branched alkyne;

[0437] (iv) A liquid ester of Formula IV:

[0438]

[0439] wherein R8, R9, and R 10 are each independently selected from C5-C 18 linear, branched, saturated, or unsaturated alkyl groups containing 5 to 18 carbon atoms; and

[0440] (v) A combination of the above esters.

[0441] Clause 50. A non-aqueous dispersion composed of multiple metal oxide particles, an ester, and a polyester with a polydispersity index greater than about 2.3, wherein the ester is selected from the group consisting of the following (i)-(v):

[0442] (i) A liquid ester of Formula I:

[0443]

[0444] wherein each of R and R1 is a linear, branched or cyclic alkyl group; a linear, branched or cyclic alkenyl group; or a linear, branched or cyclic alkynyl group; provided that if one of R and R1 is a linear alkyl group, the other of R and R1 is a branched or cyclic alkyl group; a linear, branched or cyclic alkenyl group; or a linear, branched or cyclic alkynyl group;

[0445] (ii) a liquid ester of formula II:

[0446]

[0447] wherein R2 is a branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, R3 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, and R4 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group;

[0448] (iii) a liquid ester of formula III:

[0449]

[0450] wherein R5 is a branched alkyl group, a linear or branched alkene, or a linear or branched alkyne, R6 is a linear or branched alkyl group, a linear or branched alkene, or a linear or branched alkyne, and R7 is a linear or branched alkyl group, a linear or branched alkene, or a linear or branched alkyne;

[0451] (iv) a liquid ester of formula IV:

[0452]

[0453] wherein R8, R9 and R 10 are each independently selected from C5-C 18 linear, branched, saturated or unsaturated alkyl groups containing 5 to 18 carbon atoms; and

[0454] (v) a combination of the above esters.

[0455] Clause 51. A preparation comprising the non-aqueous dispersion according to any one of Clauses 26, 49 or 50, wherein the preparation is a personal care product or a component of a personal care product, and the personal care product is selected from the group consisting of: cosmetics, softeners for hair, nails, skin or textiles, shampoos, hair styling products, oils or waxes for grooming beards, perming solutions, hair dyes, facial or body cleansers, makeup remover products, cleansing lotions, emollient lotions or creams, bar soaps, liquid soaps, shaving creams, foams or gels, sunscreen products, gels, lotions or creams for treating sunburn, deodorants or antiperspirants, moisturizing gels, shaving foams, facial powders, foundations, lipsticks, blushes, eyeliner pastes, anti-wrinkle creams or anti-aging creams, eyeshadows, eyebrow pencils, mascaras, mouthwashes, toothpastes, oral care products, skin cleansing products, textile cleansing products, tableware cleansing products, hair or fur cleansing products, and skin care lotions or moisturizing creams.

[0456] Clause 52. The preparation according to Clause 51, wherein the preparation is a sunscreen product or a component of a sunscreen product.

[0457] Clause 53. The preparation according to Clause 51, wherein the preparation is an oil-in-water (O / W) emulsion or a water-in-oil (W / O) emulsion.

[0458] Clause 54. The preparation according to Clause 51, further comprising at least one additional ingredient selected from the group consisting of film-forming polymers, rheology-modifying polymers, waxes, emulsifiers, emollients, humectants, and combinations thereof.

[0459] Clause 55. The preparation according to Clause 51, having a formulated viscosity, wherein after storage at 50 °C for 4 weeks, the formulated viscosity increases by less than 20-fold.

[0460] Clause 56. A method for preparing a non-aqueous composition for dispersing metal oxide particles, the method comprising mixing an ester and a polyester to form a homogeneous solution, the polyester having a polydispersity index (PDI) greater than about 2.3, and the ester being selected from the group consisting of the following (i)-(v):

[0461] (i) A liquid ester of Formula I:

[0462]

[0463] wherein R and R1 are each a linear, branched or cyclic alkyl group; a linear, branched or cyclic alkenyl group; or a linear, branched or cyclic alkynyl group; provided that if one of R and R1 is a linear alkyl group, the other of R and R1 is a branched or cyclic alkyl group; a linear, branched or cyclic alkenyl group; or a linear, branched or cyclic alkynyl group;

[0464] (ii) A liquid ester of Formula II:

[0465]

[0466] wherein R2 is a branched alkyl, linear or branched alkenyl, or linear or branched alkynyl; R3 is a linear or branched alkyl, linear or branched alkenyl, or linear or branched alkynyl; and R4 is a linear or branched alkyl, linear or branched alkenyl, or linear or branched alkynyl;

[0467] (iii) a liquid ester of formula III:

[0468]

[0469] wherein R5 is a branched alkyl, linear or branched alkene, or linear or branched alkyne; R6 is a linear or branched alkyl, linear or branched alkene, or linear or branched alkyne; and R7 is a linear or branched alkyl, linear or branched alkene, or linear or branched alkyne; and

[0470] (iv) a liquid ester of formula IV:

[0471]

[0472] wherein R8, R9 and R 10 are each independently selected from C5-C 18 linear, branched, saturated or unsaturated alkyls containing 5 to 18 carbon atoms; and

[0473] (v) a combination of the above esters.

[0474] Clause 57. The method according to Clause 56, wherein the ester is selected from the group consisting of a monoester, a diester, a triester, and combinations thereof.

[0475] Clause 58. The method according to Clause 56, wherein the ester has formula I, and R is a C5-C 17 branched or cyclic alkyl, linear, branched or cyclic alkenyl, or linear, branched or cyclic alkynyl; and R1 is a C3-C 18 linear, branched or cyclic alkyl, linear, branched or cyclic alkenyl, or linear, branched or cyclic alkynyl.

[0476] Clause 59. The method according to Clause 56, wherein the ester has formula I and R and R1 are different.

[0477] Clause 60. The method according to Clause 56, wherein the ester has formula II, and R2 is a C3-C 18 branched alkyl, linear or branched alkenyl or linear or branched alkynyl; R3 is a C2-C8 linear or branched alkyl, linear or branched alkenyl or linear or branched alkynyl; and R4 is a C3-C 18 linear or branched alkyl, linear or branched alkenyl or linear or branched alkynyl.

[0478] Clause 61. The method according to Clause 56, wherein the ester has Formula II and R2 and R4 are the same.

[0479] Clause 62. The method according to Clause 56, wherein the ester has Formula III, and R5 is a C3-C 18 branched alkyl, linear or branched alkene or linear or branched alkyne, R6 is a C2-C8 linear or branched alkyl, linear or branched alkene or linear or branched alkyne, and R7 is a C3-C 18 linear or branched alkyl, linear or branched alkene or linear or branched alkyne.

[0480] Clause 63. The method according to Clause 56, wherein the ester has Formula III and R5 and R7 are the same.

[0481] Clause 64. The method according to Clause 56, wherein the ester has Formula IV, and two or more of R8, R9 and R 10 are the same.

[0482] Clause 65. The method according to Clause 56, wherein the ester has a viscosity of less than about 100 cSt at 25 °C.

[0483] Clause 66. The method according to Clause 56, wherein the carbon present in the ester is 100% biobased.

[0484] Clause 67. The method according to Clause 56, wherein the polyester has an acid value of at least 15 mg KOH / g.

[0485] Clause 68. The method according to Clause 56, wherein the polyester contains a single terminal carboxylic acid functional group.

[0486] Clause 69. The method according to Clause 56, wherein the polyester contains two terminal carboxylic acid functional groups.

[0487] Clause 70. The method according to Clause 56, wherein the polyester has a linear structure.

[0488] Clause 71. The method according to Clause 56, wherein the carbon present in the polyester is 100% biobased.

[0489] Clause 72. The method according to Clause 56, wherein the polyester is selected from the group consisting of polyhydroxystearic acid, polyhydroxystearic acid stearate, polyhydroxystearyl succinate, polyhydroxystearyl sebacate, and combinations thereof.

[0490] Clause 73. The method according to Clause 56, which further comprises dispersing a plurality of metal oxide particles into the non-aqueous composition to form a non-aqueous dispersion.

[0491] Clause 74. The method according to Clause 73, wherein the non-aqueous dispersion has a viscosity of less than 1000 cP.

[0492] Clause 75. The method according to Clause 73, wherein the metal oxide particles are not surface-modified.

[0493] Clause 76. The method according to Clause 73, wherein the metal oxide particles include zinc oxide, titanium oxide, or a combination thereof.

[0494] Clause 77. The method according to Clause 73, wherein the metal oxide particles account for about 15 wt% to about 75 wt% of the non-aqueous dispersion.

[0495] Clause 78. The method according to Clause 73, wherein the metal oxide particles account for about 40 wt% to about 60 wt% of the non-aqueous dispersion.

[0496] Clause 79. The method according to Clause 73, wherein the non-aqueous dispersion is substantially free of silicone.

[0497] Clause 80. The method according to Clause 73, which further comprises adding at least one additional component therein to form a formulation.

[0498] Clause 81. The method according to Clause 73, wherein the at least one additional component is selected from the group consisting of film-forming polymers, rheology-modifying polymers, waxes, emulsifiers, emollients, humectants, and combinations thereof.

[0499] Clause 82. The method according to Clause 73, wherein the formulation is a sunscreen.

[0500] The scope of the present invention is not limited by the specific embodiments described herein. In fact, it will be apparent to those skilled in the art from the foregoing description and drawings that various modifications of the present invention are possible in addition to those described herein. Such modifications are intended to fall within the scope of the appended claims.

[0501] It should also be understood that all values are approximate and are for descriptive purposes only. All references cited and discussed in this specification are hereby incorporated by reference in their entirety as if each reference were individually incorporated herein to the same extent.

[0502] References:

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[0504] -D.A.Brune et al.,Model for the Viscosity of Particle Dispersions;Journal of Macromolecular Science-Rev.Macromol.Chem.Phys.,C39(4),561-642(1999).

[0505] -B.J.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.

[0506] -Zinc oxide(nano form);What are the properties of ZnO nanoparticles?,

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[0508] -Utracki LA,Schlund B(1987)Linear low density polyethylenes and theirblends.Part 2.Shear flow of LLDPE’s.Polym Eng Sci 27:367-379.

[0509] -Vega JF, -Escalona A,Santamaría A, ME,Lafuente P(1996)Comparison of the rheological properties of metallocene-catalyzed andconventional high-density polyethylenes.Macromolecules 29:960-965.

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[0511] -U.S.Patent Publication No.2011 / 0104078 A1.

Claims

1. A non-aqueous composition for dispersing metal oxide particles, the composition comprising an ester selected from the group consisting of the following (i)-(v) and a polyester having a polydispersity index greater than about 2.3: (i) A liquid ester of formula I: wherein R and R1 are each a linear, branched or cyclic alkyl group; a linear, branched or cyclic alkenyl group; or a linear, branched or cyclic alkynyl group; provided that if one of R and R1 is a linear alkyl group, the other of R and R1 is a branched or cyclic alkyl group; a linear, branched or cyclic alkenyl group; or a linear, branched or cyclic alkynyl group; (ii) A liquid ester of formula II: wherein R2 is a branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, R3 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, and R4 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group; (iii) A liquid ester of formula III: wherein R5 is a branched alkyl group, a linear or branched alkene, or a linear or branched alkyne, R6 is a linear or branched alkyl group, a linear or branched alkene, or a linear or branched alkyne, and R7 is a linear or branched alkyl group, a linear or branched alkene, or a linear or branched alkyne; (iv) A liquid ester of formula IV: wherein R8, R9 and R 10 are each independently selected from C5-C 18 linear, branched, saturated or unsaturated alkyl groups having 5 to 18 carbon atoms; and (v) A combination of the above esters.

2. A non-aqueous dispersion comprising a composition and a plurality of metal oxide particles dispersed in the composition, the composition comprising an ester selected from the group consisting of the following (i)-(v) and a polyester having a polydispersity index greater than about 2.3: (i) A liquid ester of formula I: wherein R and R1 are each a linear, branched or cyclic alkyl group; a linear, branched or cyclic alkenyl group; or a linear, branched or cyclic alkynyl group; provided that if one of R and R1 is a linear alkyl group, the other of R and R1 is a branched or cyclic alkyl group; a linear, branched or cyclic alkenyl group; or a linear, branched or cyclic alkynyl group; (ii) A liquid ester of formula II: wherein R2 is a branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, R3 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, and R4 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group; (iii) A liquid ester of formula III: wherein R5 is a branched alkyl group, a linear or branched alkene, or a linear or branched alkyne, R6 is a linear or branched alkyl group, a linear or branched alkene, or a linear or branched alkyne, and R7 is a linear or branched alkyl group, a linear or branched alkene, or a linear or branched alkyne; (iv) A liquid ester of formula IV: wherein R8, R9 and R 10 are each independently selected from C5-C 18 linear, branched, saturated or unsaturated alkyl groups having 5 to 18 carbon atoms; and (v) A combination of the above esters.

3. The non-aqueous composition according to claim 1 or the non-aqueous dispersion according to claim 2, wherein, The ester is selected from the group consisting of: Formula I and R is C5-C 17 branched or cyclic alkyl, linear, branched or cyclic alkenyl, or linear, branched or cyclic alkynyl; and R1 is C3-C 18 linear, branched or cyclic alkyl, linear, branched or cyclic alkenyl, or linear, branched or cyclic alkynyl; Formula II and R2 is C3-C 18 branched alkyl, linear or branched alkenyl, or linear or branched alkynyl; R3 is C2-C8 linear or branched alkyl, linear or branched alkenyl, or linear or branched alkynyl; and R4 is C3-C 18 linear or branched alkyl, linear or branched alkenyl, or linear or branched alkynyl; Formula III and R5 is C3-C 18 branched alkyl, linear or branched alkene, or linear or branched alkyne, R6 is C2-C8 linear or branched alkyl, linear or branched alkene, or linear or branched alkyne, and R7 is C3-C 18 linear or branched alkyl, linear or branched alkene, or linear or branched alkyne; A combination of the above esters.

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

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

6. The non-aqueous composition according to claim 1 or the non-aqueous dispersion according to 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 a di-monomer; or a combination thereof.

7. The non-aqueous composition according to claim 1 or the non-aqueous dispersion according to 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 non-aqueous composition according to claim 1 or the non-aqueous dispersion according to claim 2, wherein, The number average molecular weight (Mn) of the polyester is less than about 10,000 g / mol, or the acid value of the polyester is at least 15 mg KOH / g.

9. The non-aqueous composition according to claim 1, wherein The carbon present in the ester is 100% biobased, and the carbon present in the polyester is 100% biobased.

10. The non-aqueous composition according to claim 1 or the non-aqueous dispersion according to claim 2, wherein, The viscosity of the non-aqueous based composition is less than 500 cP or the viscosity of the non-aqueous based dispersion is less than 1000 cP.

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

12. The non-aqueous based dispersion according to claim 2, wherein the plurality of metal oxide particles account for about 15 wt% to about 75 wt% of the non-aqueous based dispersion, or wherein the plurality of metal oxide particles account for about 40 wt% to about 60 wt% of the non-aqueous based dispersion.

13. A formulation comprising the non-aqueous composition according to claim 1 or the non-aqueous dispersion according to claim 2, wherein, The formulation is a personal care product or a component of a personal care product, and the personal care product is selected from the group consisting of: cosmetics, softeners for hair, nails, skin or textiles, shampoos, hair styling products, oils or waxes for grooming beards, perming solutions, hair dyes, facial cleansers or body washes, makeup removers, cleansing lotions, emollient lotions or creams, bar soaps, liquid soaps, shaving creams, foams or gels, sunscreen products, gels, lotions or creams for treating sunburns, deodorants or antiperspirants, moisturizing gels, shaving foams, face powders, foundations, lipsticks, blushes, eyeliner creams, anti-wrinkle creams or anti-aging creams, eyeshadows, eyebrow pencils, mascaras, mouthwashes, toothpastes, oral care products, skin cleansing products, textile cleansing products, tableware cleansing products, hair or fur cleansing products, and skin care lotions or moisturizers.

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

15. A method for preparing a non-aqueous based composition for dispersing metal oxide particles, the method comprising mixing an ester and a polyester to form a homogeneous solution, the polydispersity index (PDI) of the polyester being greater than about 2.3, and the ester being selected from the group consisting of the following (i)-(v): (i) A liquid ester of formula I: wherein R and R1 are each a linear, branched or cyclic alkyl group; a linear, branched or cyclic alkenyl group; or a linear, branched or cyclic alkynyl group; provided that if one of R and R1 is a linear alkyl group, the other of R and R1 is a branched or cyclic alkyl group; a linear, branched or cyclic alkenyl group; or a linear, branched or cyclic alkynyl group; (ii) A liquid ester of formula II: wherein R2 is a branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, R3 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group, and R4 is a linear or branched alkyl group, a linear or branched alkenyl group, or a linear or branched alkynyl group; (iii) A liquid ester of formula III: wherein R5 is a branched alkyl, linear or branched olefin, or linear or branched alkyne, R6 is a linear or branched alkyl, linear or branched olefin, or linear or branched alkyne, and R7 is a linear or branched alkyl, linear or branched olefin, or linear or branched alkyne; (iv) a liquid ester of formula IV: wherein R8, R9, and R 10 are each independently selected from C5-C 18 linear, branched, saturated or unsaturated alkyl groups having 5 to 18 carbon atoms; and (v) a combination of the above esters.

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