WO2025085530A1

WO2025085530A1 - Low color lecithin for personal care applications

Info

Publication number: WO2025085530A1
Application number: PCT/US2024/051598
Authority: WO
Inventors: Cyril Michel Armel Paul LEMOINE; Jean-Noel Ollagnier
Original assignee: Cargill Inc
Current assignee: Cargill Inc
Priority date: 2023-10-17
Filing date: 2024-10-16
Publication date: 2025-04-24
Anticipated expiration: 2026-04-17

Abstract

The present invention relates to the production of specialized lecithins for use in personal care products. Particularly, this disclosure relates to the preparation and use of hydroxylated and de-oiled lecithins of low color and their use in personal care applications where in wherein the hydroxylated and de-oiled lecithin comprises > 90% by weight PL preferably between 90 wt% and 98 wt%; and has an acetyl value between 30 and 38; an oil content < 10% by weight; and a Gardner color value less than 6.

Description

LOW COLOR LECITHIN FOR PERSONAL CARE APPLICATIONS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63/590,836, filed October 17, 2023, and U.S. Provisional Application No. 63/594.531, filed October 31 , 2023, each of which is incorporated by reference herein in its entirety.

FIELD OF INVENTION

[0002] The present invention relates to the production of specialized lecithins for use in personal care products. Particularly, this disclosure relates to the preparation and use of hydroxylated and de-oiled lecithins of low color and their use in personal care applications.

BACKGROUND

[0003] As the number of personal care products and brands continue to grow, manufacturers are striving both for ways to make their products perform better and ways to increase their manufacturing efficiency. Personal care products such as shampoos, conditioners, lotions, body washes, sunscreens are uniquely adapted to the needs of specific consumer and markets. They are highly complex formulas with numerous ingredients added for specific purposes and to achieve specific functionality. Many of these kinds of personal care products are formulated as, or with, oil-in-water emulsions.

[0004] These emulsions are prepared by mixing oil and water in the presence of an emulsifier in order to create a stable emulsion. Many synthetic emulsifiers are known and used but they come with reliance on fossil fuels for their production. These materials are not sustainable and as such are less desirable to an increasingly knowledgeable consumer base. Accordingly, there is a continued drive to create naturally based sustainable alternative emulsifiers. It is critical for naturally based solutions to perform well a have a low color in order to compete successfully with synthetic solutions.

SUMMARY OF INVENTION

[0005] The present disclosure describes novel hydroxylated and de-oiled lecithins of low color value that are useful for the preparation of personal care products. Typical hydroxylated lecithins impart a yellowish beige color to formulated products that is unacceptable to manufacturers and consumers. By contrast the hydroxylated and de-oiled lecithins described herein have much lower color values and allow for formulations that are pleasantly white or off- white.

DETAILED DESCRIPTION

[0006] Explanations of abbreviations and terms used in this disclosure are provided to assist in comprehending and practicing the invention.

[0007] All parameter ranges disclosed include the end-points and all values in between, unless otherwise specified.

[0008] Representative features are set out in the following description, which stand alone or may be combined, in any combination, with one or more features disclosed elsewhere in the description and/or drawings of the specification.

[0009] When used in this specification and claims, the terms "comprises" and "comprising" and variations thereof mean that the specified features, steps or integers are included. The terms are not to be interpreted to exclude the presence of other features, steps, or components. [0010] Unless otherwise indicated, percentages represented in formulations or compositions described herein are understood to be percent by weight of the formulation or composition.

Lecithins

[0011] Phospholipids (PLs) are the major components of biological membranes and are important biochemical intermediates in the growth and functioning of cells, both in plants and in animals. PLs mainly from vegetable origin (vegetable lecithins) are derived commercially from oil-bearing seeds such as soybeans, sunflower kernels, and canola (rapeseed) and are widely used for their emulsifying and structural improvement properties in food matrices. In biochemistry and medicine, the name lecithin is exclusively given to the sn-3 phosphatidylcholine. Here we define lecithin as a mixture of PLs with adherent glycolipids and oil. Vegetable lecithins contain predominantly phosphatidylcholine (PC), phosphatidylethanol amine (PE), phosphatidylinositol (PI), phosphatidic acid (PA), small amounts oflysophosphatidylcholine (LPC), and other glycerol PLs of complex fatty acid composition. Animal lecithins are sourced from egg, dairy⁷, and marine species, including krill. In some aspects, the lecithins are soy, sunflower, or canola lecithins. PL content can be determined by analytical methods known in the art. P³¹ NMR is typically utilized as a method to characterize PL structures and content. LOO 12] Table 1 shows the commonly understood composition of canola, rapeseed, soy, and sunflower lecithin.

Table 1. Phospholipid Composition of Vegetable Lecithins

Canola Soy Lecithin Sunflower

Lecithin (%) Lecithin (%)

(%)

Acetone-insoluble matter

Phospholipids

Phosphatidylcholine 17 15 16

Phosphatidylethanolamine 9 11 8

Phosphatidylinositol 10 10 14

Phosphatidic acid 4 4 3

Other phospholipids 6 7 6

Subtotal: All phospholipids 46 47 47

Glycolipids 11 11 11

Complex carbohydrates 4 4 4

Total: Acetone insoluble 62 62 63

Acetone-soluble matter

Oil + added fatty acid 37 37 36

Moisture <1 <1 <1

Total 100 10 100

Willem van Nieuwenhuyzen Production and Utilization of Natural Phospholipids Lecipro Consulting, 1906 AH Limmen, The Netherlands

[0013] Hydroxylated lecithin is known as a food additive and is regulated in the US under 21 CFR §172.814. Hydroxylation of the double bonds in the unsaturated fatty acids of the PLs may be done in the presence of peroxide and organic acids, resulting in the highest possible lecithin hydrophilicity.

-CH=CH- -CH(OOH)-CH(OOH)- -CH(OH)-CH(OH)-

In this process, the crude lecithin may be mixed with 2-14% hydrogen peroxide and 1 % lactic acid at 50-60°C. The lactic acid reduces the pH and facilitates the reaction. 0014] Naturally extracted lecithins contain approximately 35% residual oil primarily in the form of triglycerides. This oil content may be reduced by methods known in the art. Typically, the lecithin is treated with a solvent and the lecithin filtered. A variety of solvents may be employed in the process. Typically, acetone is utilized in the solvent extraction process for producing oil-free lecithin powders and granules. Triglycerides dissolve in acetone in contrast to the other more polar components of standard lecithin. Deoiling with acetone is executed as an efficient continuous process, in which the crude lecithin is mixed and agitated with acetone. The phospholipids, glycolipids, and adherent carbohydrates precipitate as sediments, which are centrifuged and/or filtered. The extraction process may be repeated a number of times at ambient, below ambient, or above ambient temperature. A careful drying process is required to eliminate the residual acetone. The freshly de-oiled lecithin can be dried under vacuum at ambient or elevated temperature or in combination with high vacuum freeze drying techniques. Accordingly, de-oiled lecithins typically have only 2-5% residual remaining oil.

[0015] By convention, the amber color tones of lecithins are measured on the Gardner color scale or the Iodine color scale. The color range of most clear lecithins is generally in the range of Gardner 11-17. While the hydroxylation process can lower the Gardner color of some lecithins, use in cosmetic and personal care application can be still be limited by residual color that is found unacceptable to customers and consumers. Surprisingly, the de-oiled hydroxylated lecithins described herein have low Gardner color values and appear white or off white in personal care formulations. In some aspects, the hydroxylated and de-oiled lecithin have a Gardner color value of less than 8, less than 6 or between 3 and 6. Gardner color can be assessed by AOCS Ja 9-87.

[0016] In some aspects, the lecithin may be hydroxylated and de-oiled. In some aspects, the hydroxylated and de-oiled lecithin has an oil content of less than 30% by weight. In some aspects, the hydroxylated and de-oiled has an oil content of less than 10% by weight. In some aspects, the hydroxylated and de-oiled lecithin has an oil content of less than 5%. In some aspects, the hydroxylated and de-oiled lecithin has an oil content of between 2% and 5% by weight.

[0017] In some aspects, the de-oiled hydroxylated lecithin has an acetyl value between 30 and 38. Acetyl value is a recognized and well understood parameter for hydroxylated lecithins and is specifically identified in 21 CFR §172.814.

[0018] In some aspects, the de-oiled hydroxylated lecithin has a high phospholipid content of greater than 90% by weight. In some aspects, the de-oiled hydroxylated lecithin has a phospholipid content of greater than 95% by weight. In some aspects, the de-oiled hydroxylated lecithin has a high phospholipid content of between 90% and 98% by weight.

Emulsions

[0019] In one aspect, the present disclosure is a oil-in-water emulsion comprising the lecithins described herein. An emulsion may be defined as a mixture containing two immiscible liquids, in which one liquid is dispersed as droplets or globules throughout the other. The dispersed liquid is called the dispersed phase, while the other liquid is called the continuous phase. In an oil- in-water emulsion, as in the present disclosure, the oil is the dispersed phase or oil phase, and water is the continuous phase or aqueous phase.

[0020] The emulsions of the present invention include emulsions with oil phase in the emulsion between 1 wt% to 50%. In some aspects, the amount of oil phase in the emulsion may be between 2 wt% to 45 wt%, between 2 wt% and 35 wt%, or between 2 wt% and 20 wt%.

[0021] The emulsions may have good stability, with little or no separation between the aqueous phase and oil phase over an extended period of time (e.g., 4, 8, or 12 weeks) when measured at room temperature and/or elevated storage temperatures (e.g., 45°C). Therefore, it may be used to make products (e.g., topical formulations) requiring a long shelf life.

1. Aqueous Phase

[0022] The inventive emulsion contains an aqueous phase. The aqueous phase may comprise or consist of water, in particular a demineralized water; a floral water such as cornflower water; a mineral water such as Vittel water, Lucas water or La Roche Posay water; and/or a spring water. Preferably, demineralized water is used as the aqueous phase utilized by the present disclosure.

[0023] The amount of the aqueous phase in the emulsion may be between 50 wt% to 99 wt%. In some aspects, the amount of the aqueous phase in the emulsion may preferably be between 20 wt% to 98 wt%.

[0024] The aqueous phase may also include other components that are soluble or miscible with water such as fragrances, texturizers, colorants, preservatives, and the like.

2. Oil phase

[0024] The emulsion also contains an oil phase dispersed in the aqueous phase. As used herein, the term “dispersion” refers to an oil phase forming droplets inside the aqueous phase. The droplets may have any sizes and shapes. Preferably, the droplets are homogeneously distributed throughout the aqueous phase. The nature of the oil phase of the emulsion is not critical. The oil phase may thus consist of any Patty substance conventionally used in the cosmetic or dermatological fields; in particular the oil phase may comprise at least one oil, i.e.. any fatty substance that is in substantially or completely liquid form at room temperature (20-25°C) or elevated temperate of (40°-70°C) and at atmospheric pressure (760 mmHg).

[0025] The preferred oil phase(s) comprises at least one oil plant based, such as liquid triglycerides of fatty acids comprising from 4 to 22 carbon atoms, examples include, coconut oil, canola oil, rapeseed oil, sunflower oil; maize oil; soybean oil; cucumber oil; grape seed oil; sesame seed oil; hazelnut oil; apricot oil; macadamia oil; arara oil; castor oil; cocoa butter; almond oil; avocado oil; babassu oil; caprylic/capric acid triglycerides, such as those sold by Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by Dynamit Nobel; Simmondsia Chinensis (Jojoba) Seed oil sold under the tradename Jojoba Oil Golden by Desert Whale; Betacarotene sold under the tradename Betatene 30% OLV by Cognis (BASF); Rosa Canina Fruit Oil sold under the tradename Rosehip Seed Oil by Nestle World Trade Co.; shea butter oil; and mixtures thereof. The plant based oils maybe hydrogenated or non-hydrogenated.

[0026] The oil phase may include other components that are not soluble or miscible with water such as emollients, stabilizers, colorants, essential oils, perfumes, long chain alcohols, and the like.

[0027] The emulsion may further comprise at least one further ingredient. The further ingredient may include, without limitation, a preservative, salt, vitamin, emulsifier, texturiser, nutrient, micronutrient, sugar, protein, polysaccharide, polyol, glucose, sucrose, glycerol, sorbitol, pH adjusters, emollients, dyes, pigments, skin actives, waxes, or silicones.

Emulsifiers

[0028] Emulsions are stabilized by use of emulsifiers. Emulsifiers are well known in the art of personal care formulations. An emulsifier is a substance that stabilizes an emulsion by reducing the oil-water interfacial tension. Emulsifiers are ty pically amphiphilic, meaning they have a polar or hydrophilic (i.e., water-soluble) part and a non-polar (i.e., hydrophobic or lipophilic) part. Emulsifiers that are more soluble in water (and, conversely, less soluble in oil) will generally form oil-in-water emulsions. Emulsifiers utilized in personal care applications are well known to the skilled applications scientist in personal care industry. Any emulsifier or mixture of emulsifiers that result in the particle size and/or particle size distribution mentioned herein may be employed to manufacture the emulsifier system for the compositions of the present disclosure.

[0029] In some aspects, the emulsifier system comprises hydroxylated and de-oiled lecithin. In some aspects, the emulsifier system is naturally based in whole or in part. In some aspects, the emulsifier system is not petroleum based, or synthesized from petroleum products in whole or in part.

[0030] In some aspects, the naturally based emulsifier system further comprises emulsifiers selected from the group consisting of lecithin (oiled or de-oiled), hydroxylated lecithin (oiled or de-oiled). sorbitan esters (such as SPAN products), SPAN 20, alkyl glycerides (such as Monomuls®), and mixtures thereof. In some aspects, the emulsifier system is a mixture of emulsifiers. The mixture of emulsifiers may be in any ratio desired to create the effect desired for the application. In some aspects, the emulsifier system is a mixture of a hydroxylated and de-oiled lecithin and an alkyl glyceride.

[0031] The term '‘alkylglyceride” as used herein mean a glycerol backbone with one or two C8-C22 fatty acid chains attached thereto. Alkyglycerides are typically derived from vegetable oil sources through enzymatic treatment. They may be substantially pure mono or diglycerides or mixtures thereof. They are widely available in a variety of commercial grades and are typically sold predominately in either the mono or di fatty acid form. But most often as some form of mixture of the two.

[0032] The emulsions disclosed herein comprise a functional amount of the emulsifier system. In some aspects, the emulsions contain an amount of the emulsifier system selected from the group consisting of; 1-20%, 2-10%, 2-7%, or 3-5% by weight. In some aspects, the emulsions contain 2-7% by weight of the emulsifier system. In some aspects, the emulsions contain 3-5% by w eight of the emulsifier system.

[0033] Emulsions may be prepared by methods know n in the art. The water phase may be added to the oil phase with mixing or visa versa. The mixing may be done with a conventional stirring apparatus, a homogenizer, a sonicator. or other high shear mixing implements or a through a combination of these techniques. The emulsifier may be included in one phase or the other and mixing may be done at an elevated temperature to ease handling of materials. The skilled artisan will adapt the techniques and temperatures for the particularities of their applications. Topical formulation

[0034] The emulsion provided herein is useful in the manufacture of topical formulations such as personal care products or cosmetics. Emulsions of the present disclosure are useful in creating personal care products with improved performance. Use of the emulsions of the present disclose creates products with lighter color, greater stability, better foaming performance, improved conditioning, and a less greasy sensory experience, that with conventional lecithins.

[0035] In one aspect, the present invention is a topical formulation comprising an emulsion as described herein. As used herein, the term “topical formulation” refers to a formulation that may be applied directly to a part of the body. The term “formulation” is used herein to denote compositions of various ingredients in various weight ranges, in accordance with the present invention.

[0036] The formulations manufactured with the microemulsions described herein are suitable for use on hair, scalp, nails, and skin, for delivering cosmetic or actives to the skin or hair for providing cleansing, conditioning, moisturizing, minimizing, or treating skin imperfections, reducing skin oiliness, providing fragrances to the hair or skin and the like.

[0037] “Personal care” means and comprises any cosmetic, hygienic, toiletry and topical care products including, without limitation, leave-on products (i.e., products that are left on keratinous substrates after application); rinse-off products (i.e., products that are washed or rinsed from keratinous substrates during or within a few minutes of application); shampoos; hair curling and hair straightening products; hair style maintaining and hair conditioning products; lotions and creams for nails, hands, feet, face, scalp and/or body; hair dye; face and body makeup; nail care products; astringents; deodorants; antiperspirants; anti-acne; antiaging; depilatories; colognes and perfumes; skin protective creams and lotions (such as sunscreens); skin and body cleansers; skin conditioners; skin toners; skin firming compositions; skin tanning and lightening compositions; liquid soaps; bar soaps; bath products; shaving products; and oral hygiene products (such as toothpastes, oral suspensions, and mouth care products).

[0038] The texture of such personal care formulations is not limited and may be. without limitation, a liquid, gel, spray, lotion, cream, shampoo, pomade, foam, tablet, stick (such as lip care products), makeup, suppositories, among others, any of which can be applied to the skin or hair or hale and which typically are designed to remain in contact therewith until removed, such as by rinsing with water or washing with shampoo or soap. Other forms could be gels that can be soft, stiff, or squeezable. Sprays can be non-pressurized aerosols delivered from manually pumped finger-actuated sprayers or can be pressurized aerosols such as mousse, spray, or foam forming formulation, where a chemical or gaseous propellant is used.

[0039] The topical formulation comprising the microemulsion disclosed herein may be a shampoo, conditioner, body wash, cream, or lotion. In some aspects, the topical formulation is a shampoo.

[0040] Formulations prepared using the emulsion disclosed herein have a white or pale white color that is generally considered to be aesthetically appealing. In some cases, the formulations of the invention may be further processed to make a colored end product. In such cases, the white color is beneficial because it will show up the additional pigment without influencing the final color.

[0041] Furthermore, formulations prepared using the emulsions of the present invention have a good spreadability with powdery and less greasy residual feeling on the skin. Even with high oil content, the ingredient absorbs the fatty film at the skin surface. The use of the ingredients of the present invention improves creaminess. body, and formula gloss. The texture feels pleasant to touch and apply.

[0042] Formulations may optionally contain at least one further ingredient chosen from the group consisting of preservative, salt, vitamin, emulsifier, texturiser, nutrient, micronutrient, sugar, protein, polysaccharide, polyol, glucose, sucrose, glycerol, sorbitol, pH adjusters, emollients, dyes, pigments, skin actives, waxes, or silicones.

[0043] The emulsions of the present disclosure are useful in sunscreen applications. Sunscreens contain ingredients intended to block UV radiation from reaching the skin. UV blockers can be physical such as or chemical salts like ZnO or TiO2 or chemical (max authorized level indicated) such as Butyl Methoxydibenzoylmethane (5%); Octocrylene (10%); Titanium dioxide (25%); Ethylhexyl Salicylate (5%); Ethylhexyl Methoxycinnamate (10%); Bis- ethylhexyloxyphenol Methoxyphenyl Triazine (10%); Emulsions of the present disclosure can be used with any type of UV blocker know in the art or mixtures of UV blockers.

EXAMPLES

[0044] Example 1 : Hydroxylated lecithin (Emulfluid H33, Cargill Incorporated - Gardner color of 12.0) 202.19g was heated to 55°C and slowly added to 800g of acetone stirred (lowest speed of UltraTurrax mixer) at 11 °C. The mixture was stirred for a minute and filtered. The filter cake is added to a fresh 880g of acetone stirred in the same manner and filtered. The filter cake is dried in a vacuum oven for 1.5 hours at 45°C and overnight in a freeze drying apparatus to yield 111.6g of a pale white powder. Gardner color of 5.0. Gardner Color measured with 0: 0,1 g/ml sample resolved in toluene.

[0045] Example 2: Example 1 was repeated with 149.24g of Emulfluid H33 to yield 82.6g. Gardner color of 5.1.

[0046] Example 3: Example 1 was repeated with 111.1g of Emulfluid H66, (Cargill Incorporated, Gardner color of 11 .4) to yield 11 1.1g of a pale white powder. Gardner color was 4.8.

[0047] Example 4: Example 1 was repeated with 83g of Emulfluid H66 to yield 83.0g. Gardner color of 4.9.

[0048] Example 5 & 6:

[0049] Examples 5&6 were prepared in the following manner. The water phase was weighted and the Actigum added. The mixture was stirred for 5min at 8000 rpm with Silverson mixer using a (small head). The de-oiled hydroxylated lecithin (or commercially available full oil hydroxylated lecithin Emulfluid HL33) was added and mixing with the Silverson continued or 4 min at 10,000 rpm to entirely disperse the lecithin. The Florasun was added slowly while mixing with the Silverson for an additional 5 min at 10,000 rpm. The tocopherol and Euxyl K712 preservative were added and mixed until homogenous. The pH was adjusted with citric acid solution to between 5-5.5.

[0050] The emulsion of Example 6 had ayellowish color and an unacceptably strong odor. Conversely the emulsion of Example 5 utilizing the de-oiled hydroxylated lecithin had a white or slightly beige color and acceptable odor. Example 5 would perform well as a chassis for use in personal care product formulations where Example 6 would not.

[0051] Example 5A and 6A: Examples 5 A and 6A were prepared in the same manner as for Examples 5 & 6 except that 4% of the material from Example 1 and 4% of Emulfluid 33 were utilized in the formulation. Even at this higher concentration, the Example 5A comprising the material from Example 1 still had an acceptable pale beige color. Sample 5A was compared to Samples 6 and 6A by subjecting them to three freeze/thaw cycles. The sample emulsions were frozen for 8 hours at -18C and thawed for 18 hours at ambient temperature. This was performed 3 times. The emulsions from Example 6 and 6A exhibited a dramatic darkening of the already unacceptable yellowish color with liberated oil collecting on top of the samples. Example 5A, however, surprisingly did not experience any significant color change. Once again demonstrating how the de-oiled hydroxylated lecithin described herein is much better for use in personal care applications.

Claims

CLAIMS We Claim:

1. A hydroxylated and de-oiled lecithin comprising; > 90% by weight PL preferably between 90 wt% and 98 wt%; and wherein the hydroxylated and de-oiled lecithin has an acetyl value between 30 and 38; an oil content < 10% by weight; and a Gardner color value less than 6.

2. A personal care product comprising a hydroxylated and de-oiled lecithin of claim 1.

3. An emulsion comprising an oil phase, an aqueous phase, and an emulsifier system wherein: a. the oil phase comprises 1-50% by weight (preferably 2-25%) of the emulsion; b. the emulsifier system comprises 2-10% by weight of the emulsion; and the emulsifier system comprises a hydroxylated de-oiled lecithin; wherein the hydroxylated de-oiled lecithin comprises greater than 90% by weight PL; and wherein the hydroxylated de-oiled lecithin has an acetyl value between 30 and 38; an oil content < 10% by weight; and a Gardner color value less than 6.

4. A personal care product comprising the emulsion of Claim 3.

5. The personal care product of Claim 4 selected from the group consisting of a shampoo, conditioner, body wash, cream, or lotion.