CN117120015A

CN117120015A - Pickering emulsion stabilized by particles

Info

Publication number: CN117120015A
Application number: CN202280024438.6A
Authority: CN
Inventors: W·菲波; P·比乌索布莱
Original assignee: Firmenich SA
Current assignee: Firmenich SA
Priority date: 2021-03-29
Filing date: 2022-03-25
Publication date: 2023-11-24

Abstract

The present application relates to a liquid product in the form of an oil-in-water or water-in-oil emulsion stabilized by organic or inorganic particles, a process for obtaining the emulsion, consumer products and uses thereof.

Description

Pickering emulsion stabilized by particles

Cross Reference to Related Applications

The present application claims priority from U.S. provisional application No.63/167,186 filed on 3 months 29 of 2021 and European application No.21172852.2 filed on 7 months 5 of 2021. The entire contents of these applications are expressly incorporated herein by reference.

Technical Field

The present application relates to a liquid product in the form of an emulsion stabilized by organic or inorganic particles, a process for obtaining the emulsion and its use.

Background

In high quality fragrance (fine fragrance) applications, there is an increasing demand for reduced or no ethanol products. This demand has increased during the post Covid19 period. In the past, such applications have been hindered by skin irritation and the like.

Disclosure of Invention

The present application meets industry recognized needs for an ethanol free form by providing an emulsion stabilized by solid particles.

The present application provides an emulsion comprising: an aqueous phase comprising water, an oil phase comprising a perfume oil and an oil miscible solvent, and a stabilizer selected from the group consisting of inorganic particles, organic particles, and combinations thereof.

The oil miscible solvent according to the present application may be, for example, tributyl O-acetyl citrate, triethyl citrate, caprylic triglyceride, triacetin, coco (and) coco caprylate/caprate, propylene glycol dicaprylate, 1, 3-propanediol caprylate, isopropyl palmitate, isopropyl myristate, ethyl oleate, glyceryl triheptanoate, or mixtures thereof.

In certain forms, the oil-miscible solvent is from 1 wt% to 70 wt% based on the total weight of the emulsion, or from 10 wt% to 60 wt% based on the total weight of the emulsion.

The emulsions of the present application may also comprise an oil miscible co-solvent (co-solvent). The oil miscible co-solvent may be, for example, caprylic/capric glyceride, undecane and tridecane, C15-C19 alkane, squalene, silicone oil, glycol ethers such as tripropylene glycol methyl ether, dipropylene glycol n-propyl ether, DIPG monomethyl ether, dimethyl adipate/glutarate, benzyl benzoate or mixtures thereof.

The oil-miscible co-solvent may be from 1 wt% to 50 wt% based on the total weight of the emulsion, or from 5 wt% to 40 wt% based on the total weight of the emulsion.

The stabilizers of the present application may be, for example, hydrophilic silica, hydrophilic titanium dioxide, zinc oxide, calcium carbonate, nanocrystalline cellulose, microcrystalline cellulose and cellulose derivatives, starch, cereal flour (flower), clay, latex, water insoluble proteins, or combinations thereof.

In aspects of the application, the inorganic particles, organic particles, or a combination thereof comprise from 0.001 to 10%, from 0.001 to 1%, or from 0.001 to 0.5% by weight of the emulsion.

In some aspects of the application, the aqueous phase does not comprise a C1-C4 alcohol.

In some forms, the emulsions of the present application may also include an oil miscible weighting agent (weighting agent) in the oil phase. The oil-miscible weighting agent may be, for example, a gum, an ester gum, a dammar gum, sucrose acetate isobutyrate, or a combination thereof.

In some forms, the oil-miscible weighting agent may be 5 wt% to 50 wt%, or 5 wt% to 30 wt%, based on the total weight of the emulsion.

In aspects of the application, the aqueous phase comprises an oil-miscible tackifier. The oil-miscible tackifier may be, for example, a cellulose derivative such as ethylcellulose, a polyethylmethacrylate polymer, a diisobutylPEG-24/PPG-7/polydimethylsiloxane copolymer, and mixtures thereof. In some forms, the oil-miscible tackifier comprises from 1% to 30% by weight of the oil phase or from 2% to 10% by weight of the oil phase.

In some aspects of the application, the aqueous phase further comprises a water-miscible tackifier. The water-miscible viscosity increasing agent may be, for example, xanthan gum, natural gums (e.g., agar gum, alginic acid, gellan gum, tragacanth gum), guar gum, cellulose derivatives, polyacrylic acid, acrylate copolymers, or combinations thereof.

In certain forms, the water-miscible tackifier comprises from 0.05% to 5%, from 0.05% to 1%, or from 0.05% to 0.3% by weight of the aqueous phase.

The emulsions of the present application may also comprise a water-miscible co-solvent. The water miscible co-solvent may be, for example, 1, 2-propanediol (propylene glycol), 1, 6-hexanediol (hexylene glycol), dipropylene glycol, glycerol, acetonide (isopropylidene glycol), butanediol (1, 3-butanediol), 2, 3-butanediol, 1, 2-pentanediol, 1, 2-hexanediol, 1, 3-propanediol and isopropanol, ethyl lactate, or mixtures thereof. In some forms, the water-miscible co-solvent may comprise from 1% to 50% by weight of the aqueous phase, or from 2% to 20% by weight of the aqueous phase. The water-miscible co-solvent may be of synthetic and/or natural origin.

The emulsions of the present application may be water-in-oil or oil-in-water emulsions.

The emulsions of the present application may comprise droplets of an aqueous phase dispersed in an oil phase and comprise from about 10% to about 80% by weight of the emulsion.

In the form of the emulsion of the present application wherein the oil phase is a dispersion of droplets in the aqueous phase and comprises from about 10% to about 80% by weight of the emulsion.

In aspects of the application, the perfume oil in the oil phase is from 1% to 50% by weight of the emulsion or from 5% to 20% by weight of the emulsion.

According to the present application, the dispersed phase droplets may have a diameter of about 1 micron to about 8 millimeters. In other forms, the diameter of the dispersed phase droplets is from 0.1 to 5mm. In still other aspects, the dispersed phase droplets have a diameter of 0.5 to 5mm.

In some forms of the application, the oil phase further comprises a non-polar cosmetically acceptable solvent, emollient, or combinations thereof.

In aspects of the application, the emulsion comprises a surface modifying agent such as, for example, a surfactant, an amino acid, lecithin, an acid, an alcohol, a salt, and combinations thereof. The surface modifying agents of the present application may include, for example, arginine, lysine, oleic acid, stearic acid, SDS, caCl ₂ Or a combination thereof.

The emulsions of the present application may further comprise a cyclodextrin, such as an alpha cyclodextrin, a beta cyclodextrin, a gamma cyclodextrin, a hydroxypropyl modified cyclodextrin, a methyl modified cyclodextrin, or a combination thereof.

In one aspect of the application, the perfume oil comprises from 0.01% to 50% of ingredients having a log p of less than 2.5. In another form, the perfume oil comprises from 0.01% to 50% of ingredients having a log p of less than 2.0. In another form, the perfume oil comprises from 0.01% to 50% of ingredients having a log p of less than 1.5.

The present application encompasses consumer products comprising the emulsions of the present application. The consumer product may be, for example, a high quality fragrance product, a body care product or an air care product.

The application also includes the use of the application for stabilizing water and oil emulsions.

Detailed Description

The present application meets industry recognized needs for reduced or no ethanol forms by providing oil-in-water emulsions and water-in-oil emulsions. The emulsions of the present application are stabilized by solid particles. The emulsions of the present application may optionally be free of surfactants or emulsifiers. By careful selection of the particles according to the application, which may be inorganic or organic in nature, a stable two-phase high quality fragrance system is provided.

In one form of the application, the oil droplets are stabilised in the aqueous phase by particles (solid stabilised "Pickering" emulsion). In another aspect of the application, the water droplets are stabilized in the oil phase.

The solid-stabilized emulsions of the present application:

optionally free of surfactants;

may be free of C1-C4 alcohols, such as ethanol;

up to 80% by weight of the emulsion of a dispersed phase; and

up to 50% by weight of perfume may be present.

The O/W emulsion stabilized by solid particles according to the application allows up to 5mm of oil droplets to be dispersed in water. Droplets of this size provide an attractive visual effect to the solution for consumers of high quality fragrances, body care products and air care products.

Surprisingly, according to the present application large oil droplets in water can be obtained. For example, it has been found that large oil droplets in water are stable with silica, calcium carbonate, clay or cereal flour (e.g., amaranth flour).

Unless otherwise indicated, the terms "particles", "solid particles" and their plural forms refer to solid materials that are dispersible but insoluble in an oil or water phase. As used in this disclosure, solid particles act as stabilizers that accumulate at the interface between two immiscible liquids (commonly denoted as oil and water phases) and stabilize the droplets during formation of the pickering emulsion to prevent coalescence. As used herein, the terms "particle," "solid particle," and their plural forms do not include core-shell structures.

"perfume oil" or "fragrance oil" according to the present application encompasses any synthetic or natural oil suitable for fragrance use.

"LogP" is the logarithm of the octanol-water partition coefficient and is known as a measure of lipophilicity.

Oil miscible solvent: the emulsion composition of the present application comprises an oil miscible solvent which may be, for example, tributyl O-acetyl citrate, triethyl citrate, caprylic triglyceride, glyceryl triacetate, coco (and) coco caprylate/caprate, propylene glycol dicaprylate, 1, 3-propanediol caprylate, isopropyl palmitate, isopropyl myristate, ethyl oleate, glyceryl triheptanoate, caprylic/caprate, and mixtures thereof. In one embodiment, the oil miscible solvent is triethyl citrate, tributyl O-acetyl citrate, and mixtures thereof. When present, the oil miscible solvent is used in an amount of 5 wt% to 70 wt%, or 10 wt% to 60 wt%, based on the total weight of the emulsion.

Oil miscible co-solvent: according to the application, the oil phase in the emulsion according to the application may comprise cosolvents, for example undecane and tridecane (CETIOL ULTIMATE), C15-C19 alkanes, squalene, silicone oils, glycol ethers such as tripropylene glycol methyl ether (Dowanol) ^TM TPM), dipropylene glycol n-propyl ether (Dowanol) ^TM DPnP), DIPG monomethyl ether, dimethyl adipate/dimethyl glutarateLVP esters), benzyl benzoate, and mixtures thereof. In one embodiment, the oil miscible co-solvent is undecane and tridecane (CETIOL ULTIMATE), tripropylene glycol methyl ether (Dowanol) ^TM TPM), dipropylene glycol n-propyl ether (Dowanol) ^TM DPnP), benzyl benzoate, and mixtures thereof. When present, the oil-miscible co-solvent is used in an amount of 1 wt% to 50 wt%, or 5 wt% to 40 wt%, based on the total weight of the emulsion.

Oil-miscible weighting agents: according to the present application, the oil phase in the emulsion of the present application may comprise weighting agents, such as gums (e.g., ester gums, dammar gums) and/or Sucrose Acetate Isobutyrate (SAIB). In some forms, the weighting agent in the oil phase is an ester gum or a dammar gum. When present, the oil-miscible weighting agent is used in an amount of 5 wt% to 50 wt%, or 5 wt% to 30 wt%, based on the total weight of the emulsion.

Oil miscible tackifier: according to the application, the oil phase in the emulsion of the application may comprise a viscosity increasing agent, for example cellulose derivatives such as ethylcellulose, polyethylmethacrylate polymers, diisobutylPEG-24/PPG-7/polydimethylsiloxane copolymers and mixtures thereof. In some forms, the oil tackifier is ethylcellulose. When present, the oil-miscible tackifier is present in an amount of 1% to 30%, or 2% to 10% by weight of the oil phase.

Water-miscible co-solvent: according to the present application, the emulsion composition of the present application may contain a water-miscible co-solvent, such as a mono-solvent and a multi-solvent. Non-limiting examples of such solvents include 1, 2-propanediol, 1, 6-hexanediol, dipropylene glycol, glycerol, acetonylglycerol, butanediol (1, 3-butanediol), 1, 2-pentanediol, 1, 2-hexanediol, 1, 3-propanediol and isopropanol, ethyl lactate, and mixtures thereof. In some forms, the water-miscible co-solvent is glycerol, 1, 2-hexanediol, and mixtures thereof. When present, the water-miscible co-solvent is used in an amount of 1% to 50%, or 2% to 20% by weight of the aqueous phase.

Water-miscible tackifier: according to the application, the aqueous phase of the emulsion according to the application may comprise a viscosity increasing agent, such as xanthan gum, natural gums (e.g. agar gum, alginic acid, gellan gum, tragacanth gum), guar gum, cellulose derivatives, polyacrylic acid and/or acrylate copolymers. In some forms, the tackifier in water is xanthan gum, gellan gum, polyacrylic acid, acrylate copolymer, or mixtures thereof. When present, the tackifier is present in the water in an amount of from 0.05% to 5%, from 0.05% to 1%, or from 0.05% to 0.3% by weight of the aqueous phase.

The optional ingredients are: according to the present application, the emulsion composition may further comprise optional ingredients such as colorants, preservatives, opacifiers, emollients, moisturizers, antioxidants, free radical scavengers, POV restoratives, coolants, vitamins, insect repellents, fragrance fixatives, cosmetic benefit agents, chelators, functional polymers, electrolytes and pH adjusters.

Suitable cooling agents include, for example, menthol; menthone; isopulegol; n-ethyl-p-menthane carboxamide; n,2, 3-trimethyl-2-isopropylbutanamide; ethyl N- [ [ 5-methyl-2- (isopropyl) cyclohexyl ] carbonyl ] glycinate; menthyl lactate; menthone glycerol acetal; a monomenthyl succinate; a monomenthyl glutarate; o-menthyl glycerol; 2-sec-butylcyclohexanone; menthane; camphor; menthol of the species Mentha spicata; eucalyptol; peppermint oil; peppermint oil; spearmint oil; eucalyptus oil; 3-l-menthoxypropane-1, 2-diol; 3-l-menthoxy-2-methylpropane-1, 2-diol; p-menthane-3, 8-diol; 2-l-menthoxyethane-1-ol; 3-l-menthoxypropane-1-ol; 4-L-menthoxybutan-1-ol, N-ethyl-p-menthyl-3-carboxamide, isopulegol, piperonyl alcohol, L-menthol, 3- (L-menthoxy) propane-1, 2-diol, cis/trans-p-menthane-3, 8-diol, 3- (L-menthoxy) -2-methylpropane-1, 2-diol, 2- [2- (p-menthan-3-yloxy) ethoxy ] ethanol, menthoxyethanol, (1R, 2R, 4R) -1- (2-hydroxy-4-methylcyclohexyl) ketene, (1R, 2R, 5R) -N-ethyl-5-methyl-2- (prop-1-en-2-yl) cyclohexanecarboxamide, N- (3-hydroxy-4-methoxyphenyl) -2-isopropyl-5, 5-dimethyl-cyclohexanecarboxamide, N- [4- (cyanomethyl) phenyl ] -2-isopropyl-5, 5-dimethyl-cyclohexanecarboxamide, N- (2-hydroxy-2-phenyl) -2-isopropyl-5, 5-dimethyl-cyclohexanecarboxamide, (-) -glycerol-1-menthyl carbonate, (-) -menthyl-1-carbonate, (-) -menthyl-L-menthyl-carbonate, (-) D/L-menthone 1, 2-glycerol ketal, (-) -menthyl 1-propanediol carbonate, (-) -menthyl 2-propanediol carbonate, D/L-menthyl 1-propanediol carbonate, D/L-menthyl 2-propanediol carbonate, (1R, 2S, 5R) -N- (4-methoxyphenyl) -5-methyl-2- (1-methylethyl) cyclohexane carboxamide, menthylethylamino oxalate, (E) -3-benzo [1,3] dioxolan-5-yl-N, N-diphenyl-2-acrylamide, 3, 4-methylenedioxycinnamic acid, N, N-diphenylamide, N-dimethyl (-) -menthylsuccinimide, (1R, 2S, 5R) -N- (4- (cyanomethyl) phenyl) -menthylcarboxamide, (-) -menthopyrrolidinone formate, (-) -phenylephrine p-menthanecarboxamide, (1R, 2S, 5R) -N- (4- (cyanomethyl) -phenyl) menthylcarboxamide, (1R, 2S, 5R) -N- (2- (pyridin-2-yl) ethyl) menthylcarboxamide, 6-isopropyl-3, 9-dimethyl-1, 4-dioxaspiro [4.5] decan-2-one, (1R, 2R, 4S) -dihydro umbrella Liu Chun, N-ethyl-p-menthane-3-carboxamide, 2-isopropyl-N, 2, 3-trimethylbutyramide, ethyl 3- (p-menthane-3-carboxamide) acetate, N-ethyl-2, 2-diisopropylbutyramide, N- (1, 1-dimethyl-2-hydroxyethyl) -2, 2-dimethylbutyramide, N-cyclopropyl-5-methyl-2-isopropyl-cyclohexanecarboxamide, acetoacetate (-) -menthyl, succinic acid (-) -menthyl, (S) -3-hydroxybutyrate (-) -menthyl, glutaric acid (-) -menthyl, 1- [ 2-hydroxyphenyl ] -4- [ 2-nitrophenyl ] -1,2,3, 6-tetrahydropyrimidin-2-one, glutaric acid di- (-) -menthyl and N- (2-hydroxyethyl) -2, 3-dimethyl-2-isopropylbutyramide.

Suitable perfume fixatives (fish) include, for example, octyl alcohol (capryl alcohol), octyl alcohol (octotanol), butyl octanol, isotridecyl alcohol, hexyl decyl alcohol, isocetyl alcohol, isostearyl alcohol, octyl decyl alcohol, octyl dodecyl alcohol, decyl tetradecyl alcohol, tetradecyl octadecyl alcohol, neopentyl glycol diethyl hexanoate, PPG-3 myristyl alcohol ether, and PPG-20 methyl glucose ether.

Non-limiting examples of suitable insect repellents include citronella, dimethyl phthalate, and n, n-dimethyl-m-toluidine.

As used herein, the term "peroxide value" or "POV" refers to the amount of equivalents of oxidation potential per 1 kg of material. Without being bound to any particular theory, the POV of a material may be determined by analysis. The term "POV" does not refer to a chemical compound or group of compounds, but is generally used interchangeably with the product of autoxidation in a sample that causes a response during a POV test. These autoxidation products vary depending on the particular material tested. During the POV test, many classes of compounds respond, including but not limited to organic and inorganic hydroperoxides, organic and inorganic peroxides, peroxyhemiacetals, peroxyhemiketals, and hydrogen peroxide itself.

By way of illustration, one POV test is the iodometric redox titration method. All compounds sensitive to POV have the property of oxidizing iodide ions to molecular iodine within the time specified by the test. In fact, the oxidation reaction of iodide is the basis of the test. Thus, "POV" is a value representing the molar sum of all iodide oxidizing species in a particular sample. See U.S. patent No. 10,456,339; U.S. patent publication No. 20200289388; WO 2020089440.

The "POV repair agent" according to the present application is an agent that reduces POV in a sample.

The POV repair agent may be an alpha-oxocarboxylic acid such as, for example, alpha-ketoglutaric acid, pyruvic acid, 2-oxovaleric acid, phenylglyoxylic acid, 2-oxobutyric acid, 2-oxo-2-furanacetic acid, oxaloacetic acid, alpha-ketoglutaric acid, 2-oxoglutaric acid (2-oxoglutarate), indole-3-pyruvic acid, 2-thiophenglyoxylic acid, trimethylpyruvic acid, 2-oxoadipic acid, 4-hydroxyphenylpyruvic acid, phenylpyruvic acid, 2-oxooctanoic acid, or a combination thereof. The POV repair agent may be a 2-hydroxyketone such as, for example, alpha-ketoglutarate dimethyldodecamine, acetoin, erythrulose, dihydroxyacetone, 2-keto-D-gluconic acid hemicalcium salt hydrate, (1 s,2s,5 s) - (-) -2-hydroxy-2-pinone, benzoin, p-anisoin, benzil, 2-hydroxy-3-oxo-hexadecane, or a combination thereof.

The emulsion according to the present application may comprise a weighting agent. Weighting agents increase the density of the oil phase and reduce the emulsification of oil droplets or sedimentation of water droplets in solution. Weighting agents according to the present application may be, for example, gums (e.g., ester gums, dammar gums) and/or Sucrose Acetate Isobutyrate (SAIB).

Thus, for example, the emulsions of the present application may comprise from 1% to 50% by weight of the emulsion of a weighting agent (e.g., dammar gum), or from 3% to 25% by weight of the emulsion of a weighting agent (e.g., dammar gum).

The emulsions according to the present application may comprise a humectant, such as, for example, glycerin. In another form, the emulsion according to the application may comprise a texturizer, such as, for example, xanthan gum, natural gums (such as agar, alginic acid, gellan gum, tragacanth gum), polyacrylic acid and/or acrylate copolymers. The emulsions according to the application may also comprise a modifying agent such as, for example, lysine.

The particles of the present application may be, for example, hydrophilic silica, hydrophilic titanium dioxide, zinc oxide, calcium carbonate, cellulose nanocrystals and crystallites, as well as cellulose derivatives, starches, cereal flour (e.g., amaranth), clays (e.g., laponite, talc, mica, zeolites, and derivatives thereof), latex, and water insoluble proteins. The water insoluble protein may be natural or chemically modified. Exemplary water insoluble proteins include, but are not limited to, gliadins and glutenins.

The oil component may be added to the oil phase prior to emulsification to improve the feel of the emulsion on the skin (high quality fragrance and body care applications).

Humectants such as glycerin may be added to the water prior to emulsification to increase the viscosity of the aqueous phase (enhance stability) and provide moisturizing effects to the skin at the time of application (high quality fragrance and body care applications). Thus, for example, glycerol may comprise from 3% to 40% by weight of the emulsion, or from 3% to 20% by weight of the emulsion.

After emulsification, a viscosity enhancing agent such as xanthan gum may be added to the water to reduce creaming (or sedimentation) of the oil droplets in the emulsion. For example, the tackifier may comprise from 0.05% to 5% by weight of the emulsion, or from 0.1% to 2% by weight of the emulsion.

Optionally a modifier such as lysine is used to adsorb to the particle surface and impart greater affinity to the particle for the oil/water interface. The terms "modifier" and "surface modifier" are used interchangeably and refer to an agent that modifies the surface of a particle, unless otherwise specified. The surface of the particles may be modified to adjust the surface polarity and thus the adsorption characteristics at the oil/water interface.

In some forms, the emulsion comprises an amount of surfactant equal to or less than 1% relative to the amount of stabilizing particles. In other forms, the emulsion is free of surfactant.

According to the application, water represents 10% to 90% w/w of the emulsion. In one form, the water comprises from 10% to 60% w/w of the emulsion.

According to the application, the oil comprises from 10% to 90% w/w of the emulsion. In one form, the oil comprises 20% to 80% w/w of the emulsion.

The fragrance oil comprises from 1% to 50% w/w of the emulsion. In one form of the application, the fragrance oil comprises from 5% to 20% w/w of the emulsion.

According to the application, the particles comprise from 0.01% to 5% w/w of the emulsion. In one form, the particles comprise from 0.01% to 2% w/w of the emulsion.

According to the application, the weighting agent comprises 1% to 70% w/w of the emulsion. In one form, the weighting agent comprises 1% to 55% w/w of the emulsion.

The optional oil component may comprise 1% to 50% w/w of the emulsion. In one form of the application, the optional oil component comprises 3% to 25% w/w of the emulsion.

The method comprises the following steps:

the particles were dispersed in the aqueous phase using strong shear (UltraTurrax 24000rpm or ultrasonic probe for 30 seconds). The oil phase components are mixed together separately. The oil phase is then added to the water phase and if the target is small size droplets, the emulsion is obtained under strong shear (UltraTurrax 24000rpm for 2 minutes or ultrasonic probe for 30 seconds). Giant oil droplets (> 0.5 mm) were suspended in the aqueous phase using low shear (manual shaking or vortexing for 1 min). The emulsion thus obtained may be the final product according to the application. Alternatively, a concentrated aqueous gel of a viscosity enhancing agent (e.g., xanthan gum) is prepared separately and the emulsion is diluted in the concentrated gel to produce the final product according to the application.

Prior to the addition of the oil, the particles are dispersed in the aqueous phase under strong shear and emulsified to facilitate the direct formation of the O/W emulsion. The oil phase is prepared separately before the aqueous phase is added for emulsification treatment.

The average size of the particles used is in the range of 20nm to 5 μm. More particularly, the average size of the particles used may be in the range of 100nm to 5 μm. More particularly, the average size of the particles used may be in the range of 300nm to 3 μm. Even more particularly, according to the definition of europe, the particles used do not belong to nanomaterials.

The average size of the oil droplets obtained in the final product may be in the range of 1 μm to 8 mm. More particularly, the average size of the oil droplets in the final product is in the range of 0.2mm to 5mm. In one form of the application, the oil droplets in the final product are visible to the naked eye.

The emulsions of the present application can be prepared under low shear (manual or mechanical shear) to quickly obtain large size droplets.

Alternatively, the tackifier is dissolved in water or aqueous phase, after which the emulsion is added thereto under low shear to produce the final product.

Examples

Example 1: compositions and methods according to the application

a) Composition of the composition

Composition of the components	Content (wt.%)	Function of
			Silica dioxide ¹⁾	0.2	Stabilizing agent
Phenethyl alcohol ²⁾	30	Spice
			Deionized water (acidification)	69.8	Continuous phase

1)SiO ₂ 1.93 μm (5% suspension); the source is as follows: microparticles GmbH

2) Phenethyl alcohol; the source is as follows: firmenich

b) Method of

In a 20ml glass bottle, 0.2g of 1.93 μm silica (5% suspension) was added to 3g of deionized water. The pH of the solution was adjusted to 3.5 using HCl (0.1%) and made up to 3.5g with water, then 1.5g of phenethyl alcohol was added. The mixture was vigorously shaken manually for 30 seconds and then allowed to stand at room temperature.

c) Results

An emulsion having oil droplets of about 5mm in size was obtained. The droplets deposit at the bottom of the sample, obtaining an attractive visual effect. The emulsion can be directly sprayed, or can be manually shaken up before use, and the initial state can be restored after shaking up.

Example 2: compositions and methods according to the application

a) Composition of the composition

Composition of the components	Content (wt.%)	Function of
			Silica dioxide ¹⁾	0.1	Stabilizing agent
Phenethyl alcohol ²⁾	50	Spice
			L-lysine ³⁾	0.05	Surface modifying agent
Deionized water	49.85	Continuous phase

1)SiO ₂ 0.403 μm (5% suspension); the source is as follows: microparticles GmbH

2) Phenethyl alcohol; the source is as follows: firmenich

3) L-lysine; the source is as follows: ACROS Organics ^TM

b) Method of

0.2g of 0.403 μm silica (5% suspension) was weighed into a 20ml glass bottle. 0.1g lysine (0.1%) was added followed by 3g deionized water. The pH of the solution was adjusted to 7 using NaOH (0.1%) and made up to 5g with water, then 5g of phenethyl alcohol was added. The mixture was vortexed for 30 seconds and allowed to stand at room temperature.

c) Results

An emulsion having oil droplets of about 1mm in size was obtained. The droplets deposit at the bottom of the sample, obtaining an attractive visual effect. The emulsion can be directly sprayed, or can be manually shaken up before use, and the initial state can be restored after shaking up.

Example 3: compositions and methods according to the application

a) Composition of the composition

Composition of the components	Content of%Weight percent (S)	Function of
			Silica dioxide ¹⁾	0.2	Stabilizing agent
Phenethyl alcohol ²⁾	50	Spice
			Lecithin ³⁾	0.001	Surface modifying agent
Deionized water	49.799	Continuous phase

2) Phenethyl alcohol; the source is as follows: firmenich

3) Lecithin PC100; the source is as follows: firmenich

b) Method of

0.2g of 0.403 μm silica (5% suspension) was weighed into a 20ml glass bottle. 0.05g lecithin PC100 (0.1%) was added followed by 2g deionized water. The pH of the solution was adjusted to 7 using NaOH (0.1%) and made up to 2.5g with water, then 2.5g of phenethyl alcohol was added. The mixture was vortexed for 30 seconds and allowed to stand at room temperature.

c) Results

Example 4: compositions and methods according to the application

a) Composition of the composition

Composition of the components	Content (wt.%)	Function of
			Silica dioxide ¹⁾	0.2	Stabilizing agent
Aromatic A ²⁾	50	Spice
			Lecithin ³⁾	0.001	Surface modifying agent
Deionized water	49.799	Continuous phase

2) A fragrance A; the source is as follows: firmenich

3) Lecithin PC100; the source is as follows: firmenich

b) Method of

0.2g of 0.403 μm silica (5% suspension) was weighed into a 20ml glass bottle. 0.05g lecithin PC100 (0.1%) was added followed by 2g deionized water. The pH of the solution was adjusted to 7 using NaOH (0.1%) and made up to 2.5g with water, then 2.5g fragrance A was added. The mixture was vortexed for 30 seconds and allowed to stand at room temperature.

c) Results

An emulsion having oil droplets of about 2mm in size was obtained. The droplets are creamy at the top of the sample, and an attractive visual effect is obtained. The emulsion can be directly sprayed, or can be manually shaken up before use, and the initial state can be restored after shaking up.

Example 5: compositions and methods according to the application

a) Composition of the components

Composition of the components	Content (wt.%)	Function of
			Silica dioxide ¹⁾	0.2	Stabilizing agent
Aromatic A ²⁾	25	Spice
			Citric acid triethyl ester ³⁾	25	Oil miscible solvent
Lecithin ⁴⁾	0.001	Surface modifying agent
			Deionized water	49.799	Continuous phase

2) A fragrance A; the source is as follows: firmenich

3) Triethyl citrate; the source is as follows: firmenich

4) Lecithin PC100; the source is as follows: firmenich

b) Method of

0.2g of 0.403 μm silica (5% suspension) was weighed into a 20ml glass bottle. 0.05g lecithin PC100 (0.1%) was added followed by 2g deionized water. The pH of the solution was adjusted to 7 using NaOH (0.1%) and made up to 2.5g with water, then 2.5g of the mixture of fragrance a/triethyl citrate=50/50 was added. The mixture was vortexed for 30 seconds and allowed to stand at room temperature.

c) Results

An emulsion having oil droplets of about 2mm in size was obtained. The droplets slowly settle to the bottom of the sample, obtaining an attractive visual effect. The emulsion can be directly sprayed, or can be manually shaken up before use, and the initial state can be restored after shaking up.

Example 6: compositions and methods according to the application

a) Composition of the composition

Composition of the components	Content (wt.%)	Function of
			Silica dioxide ¹⁾	0.2	Stabilizing agent
Aromatic A ²⁾	17.5	Spice
			Citric acid triethyl ester ³⁾	7.5	Oil miscible solvent
Arginine (Arg) ⁴⁾	0.1	Surface modifying agent
			Deionized water	74.7	Continuous phase

2) A fragrance A; the source is as follows: firmenich

3) Triethyl citrate; the source is as follows: firmenich

4) Arginine; the source is as follows: ACROS Organics

b) Method of

0.2g of 0.403 μm silica (5% suspension) was weighed into a 20ml glass bottle. 0.5g arginine (1%) was added followed by 1.5g deionized water. The pH of the solution was adjusted to 5.7 using HCl (0.1%) and NaOH (0.1%) and made up to 2.5g with water, then 2.5g of the mixture of fragrance a/triethyl citrate=35/15 was added. The mixture was vortexed for 30 seconds and allowed to stand at room temperature.

c) Results

An emulsion having oil droplets of about 1mm in size was obtained. The droplets slowly settle to the bottom of the sample, obtaining an attractive visual effect. The emulsion can be directly sprayed, or can be manually shaken up before use, and the initial state can be restored after shaking up.

Example 7: compositions and methods according to the application

a) Composition of the composition

Composition of the components	Content (wt.%)	Function of
			Mica (stearate modified) ¹⁾	0.2	Stabilizing agent
Aromatic A ²⁾	15.65	Spice
			O-acetyl tributyl citrate ³⁾	31.25	Oil miscible solvent
Undecane and tridecane ⁴⁾	3.1	Oil miscible co-solvents
			Deionized water	49.8	Continuous phase

1) SMS1 mica S; the source is as follows: daito Kasei

2) A fragrance A; the source is as follows: firmenich

3) Tributyl O-acetyl citrate; the source is as follows: aldrich

4) Cetiol Ultimate; the source is as follows: BASF (base station architecture)

b) Method of

0.02g of mica particles are weighed into a 20ml glass bottle and made up to 5g with water. 5g of the mixture of fragrance a/Cetiol Ultimate/O-acetyl tributyl citrate=10/2/20 was added to the aqueous phase and the mixture was shaken manually for 30 seconds and allowed to stand at room temperature.

c) Results

An emulsion having oil droplets of about 3mm in size was obtained. The droplets are creamy at the top of the sample, and an attractive visual effect is obtained. The emulsion can be directly sprayed, or can be manually shaken up before use, and the initial state can be restored after shaking up.

Example 8: compositions and methods according to the application

a) Composition of the composition

1)RD; the source is as follows: rockwood Additives

2) A fragrance B; the source is as follows: firmenich

3) Triethyl citrate; the source is as follows: firmenich

4) Tributyl O-acetyl citrate; the source is as follows: aldrich

5)Ultimate; the source is as follows: BASF (base station architecture)

b) Method of

0.003g was weighed into a 20ml glass bottleRD. The weight was made up to 2.5g with deionized water. The pH of the solution was adjusted to 7 using HCl (0.1%). The aqueous phase was sonicated for 5 seconds, then the fragrance B/triethyl citrate/O-acetyl tributyl citrate/>Ultimate= 26/30/34/10, 7.5g of the mixture. The mixture was vortexed for 30 seconds and allowed to stand at room temperature. />

c) Results

An emulsion having oil droplets of about 3mm in size was obtained. The droplets slowly settle to the bottom of the sample, obtaining an attractive visual effect. The emulsion can be directly sprayed, or can be manually shaken up before use, and the initial state can be restored after shaking up.

Example 9: compositions and methods according to the application

a) Composition of the composition

1)RD; the source is as follows: rockwood Additives

2) A fragrance B; the source is as follows: firmenich

3) Triethyl citrate; the source is as follows: firmenich

4)Ultimate; the source is as follows: BASF (base station architecture)

b) Method of

0.002g was weighed into a 20ml glass bottleRD. The weight was made up to 2.5g with deionized water. The pH of the solution was adjusted to 7 using HCl (0.1%). The aqueous phase was sonicated for 5 seconds, then fragrance B/triethyl citrate +.Ultimate=7.5 g of mixture 26/64/10. The mixture was vortexed for 30 seconds and allowed to stand at room temperature.

c) Results

Example 10: compositions and methods according to the application

a) Composition of the composition

1)RD; the source is as follows: rockwood Additives

2) A fragrance B; the source is as follows: firmenich

3) Triethyl citrate; the source is as follows: firmenich

4) Tributyl O-acetyl citrate; the source is as follows: aldrich

5)Ultimate; the source is as follows: BASF (base station architecture)

b) Method of

0.05g was weighed into a 20ml glass bottleRD. The weight was made up to 2.5g with deionized water. The pH of the solution was adjusted to 7 using HCl (0.1%). The aqueous phase was sonicated for 5 seconds, then fragrance B/triethyl citrate/tributyl citrate/L was added>Ultimate= 26/44/20/10, 7.5g of the mixture. The solution was sonicated for 30 seconds using an ultrasonic probe (Hielscher UP 400S) and then allowed to stand at room temperature.

c) Results

An emulsion having oil droplets of about 10mm in size was obtained. The emulsion may be sprayed directly.

Example 11: compositions and methods according to the application

a) Composition of the composition

Composition of the components	Content (wt.%)	Function of
			CaCO ₃ ¹⁾	0.25	Stabilizing agent
Aromatic B ²⁾	20.8	Spice
			Citric acid triethyl ester ³⁾	59.2	Oil miscible solvent
Deionized water	19.75	Continuous phase

1)U is provided; the source is as follows: specialty Minerals

2) A fragrance B; the source is as follows: firmenich

3) Triethyl citrate; the source is as follows: firmenich

b) Method of

0.025g was weighed into a 20ml glass bottleU, U. The weight was made up to 2g with deionized water. The aqueous phase was sonicated for 5 seconds and then 8g of a mixture of fragrance B/triethyl citrate=26/74 was added. The mixture was vortexed for 30 seconds and allowed to stand at room temperature.

c) Results

Example 12: compositions and methods according to the application

a) Composition of the composition

Composition of the components	Content (wt.%)	Function of
			Amaranth food ¹⁾	0.2	Stabilizing agent
Aromatic B ²⁾	18.2	Spice
			O-acetyl tributyl citrate ³⁾	51.8	Oil miscible solvent
Deionized water	29.8	Continuous phase

1) Amaranth powder M200; the source is as follows: AS-Biotec

2) A fragrance B; the source is as follows: firmenich

3) Tributyl O-acetyl citrate; the source is as follows: aldrich

b) Method of

0.02g amaranth powder was weighed into a 20ml glass bottle. The weight was made up to 3g with deionized water. The aqueous phase was sonicated for 5 seconds and then 7g of the mixture of fragrance B/O-acetyl tributyl citrate=26/74 was added. The mixture was vortexed for 30 seconds and allowed to stand at room temperature.

c) Results

Example 13: compositions and methods according to the application

a) Composition of the composition

Composition of the components	Content (wt.%)	Function of
			Amaranth food ¹⁾	0.4	Stabilizing agent
Aromatic B ²⁾	20.8	Spice
			Citric acid triethyl ester ³⁾	24.0	Oil miscible solvent
Tripropylene glycol methyl ether ⁴⁾	35.2	Oil miscible co-solvents
			Deionized water	19.6	Continuous phase

1) Amaranth powder M200; the source is as follows: AS-Biotec

2) A fragrance B; the source is as follows: firmenich

3) Triethyl citrate; the source is as follows: firmenich

4)Dowanol ^TM TPM; the source is as follows: dow Chemicals

b) Method of

0.04g amaranth powder was weighed into a 20ml glass bottle. The weight was made up to 2g with deionized water. The aqueous phase was sonicated for 5 seconds and then gradually added with fragrance B/triethyl citrate/Dowanol ^TM TPM = 8g mixture of 26/30/44. The mixture was vortexed for 30 seconds and allowed to stand at room temperature.

c) Results

Example 14: compositions and methods according to the application

a) Composition of the composition

Composition of the components	Content (wt.%)	Function of
			CaCO ₃ ¹⁾	1.0	Stabilizing agent
Aromatic B ²⁾	10.0	Spice
			O-acetyl tributyl citrate ³⁾	10.0	Oil miscible solvent
Polyacrylate crosslinked Polymer-6 ⁴⁾	0.2	Hardening and tempering agent
			Deionized water	78.8	Continuous phase

1)U is provided; the source is as follows: specialty Minerals

2) A fragrance B; the source is as follows: firmenich

3) Tributyl O-acetyl citrate; the source is as follows: aldrich

4)Sepimax ^TM ZEN; the source is as follows: seppic (Seppic)

b) Method of

1g of the mixture was weighed into a 100ml glass bottleU, U. The weight was made up to 30g with deionized water. The aqueous phase was sonicated for 5 seconds and then 20g of the mixture of fragrance B/O-acetyl tributyl citrate=50/50 was added. Again sonicated for 30 seconds, manually shaken for 10 seconds, and sonicated again at maximum frequency for 30 seconds (H14 probe, hielscher UP 400S). The emulsion was then gently added to 50g of 0.4% Sepimax with slow mechanical stirring ^TM In the gel. />

c) Results

An emulsion having oil droplets of about 10 μm in size was obtained. The milk emulsion obtained may be used as an emulsion or a balm, or may even be sprayed.

Publications cited throughout this document are incorporated herein by reference in their entirety. While various forms of the present application have been described above with reference to examples and preferred embodiments, it should be understood that the scope of the application is not limited by the foregoing description, but is defined by the appended claims as appropriately interpreted in accordance with the principles of patent law.

Claims

1. An emulsion, comprising:

(a) An aqueous phase comprising water and a water-containing phase,

(b) An oil phase comprising a perfume oil and an oil miscible solvent, and

(c) A stabilizer selected from the group consisting of inorganic particles, organic particles, and combinations thereof.

2. The emulsion according to claim 1, wherein the oil miscible solvent is selected from the group consisting of: tributyl O-acetyl citrate, triethyl citrate, caprylic triglyceride, glyceryl triacetate, coco caprylate/caprate, propylene glycol dicaprylate, 1, 3-propanediol caprylate, isopropyl palmitate, isopropyl myristate, ethyl oleate, glyceryl triheptanoate, caprylic/capric glyceride, and mixtures thereof.

3. Emulsion according to claim 1 or 2, wherein the oil miscible solvent is from 1 to 70 wt%, based on the total weight of the emulsion.

4. An emulsion according to claim 3, wherein the oil miscible solvent is from 10 wt% to 60 wt%, based on the total weight of the emulsion.

5. The emulsion of any one of claims 1 to 4, further comprising an oil-miscible co-solvent.

6. The emulsion according to claim 5, wherein the oil-miscible co-solvent is selected from the group consisting of: undecane and tridecane, C15-C19 alkanes, squalene, silicone oils, glycol ethers such as tripropylene glycol methyl ether, dipropylene glycol n-propyl ether, DIPG monomethyl ether, dimethyl adipate/dimethyl glutarate, benzyl benzoate, and mixtures thereof.

7. The emulsion of claim 5, wherein the oil-miscible co-solvent is from 1 wt% to 50 wt%, based on the total weight of the emulsion.

8. The emulsion according to claim 7, wherein the oil-miscible co-solvent is from 5 wt% to 40 wt%, based on the total weight of the emulsion.

9. Emulsion according to any one of claims 1 to 8, wherein the stabilizer is selected from the group consisting of: hydrophilic silica, hydrophilic titanium dioxide, zinc oxide, calcium carbonate, nanocrystalline cellulose, microcrystalline cellulose and cellulose derivatives, starches, cereal flour, clays, latex, water insoluble proteins, and combinations thereof.

10. Emulsion according to any of claims 1 or 9, wherein the inorganic particles, organic particles or a combination thereof comprise from 0.001% to 10% by weight of the total emulsion.

11. The emulsion according to any one of claims 1 to 10, wherein the inorganic particles, organic particles, or a combination thereof comprise from 0.001% to 1% by weight of the emulsion.

12. The emulsion according to claim 11, wherein the inorganic particles, organic particles, or a combination thereof comprise from 0.001% to 0.5% by weight of the emulsion.

13. The emulsion according to any one of claims 1 to 12, wherein the aqueous phase does not comprise a C1-C4 alcohol.

14. The emulsion according to any one of claims 1 to 13, further comprising an oil miscible weighting agent in the oil phase.

15. The emulsion according to claim 14, wherein the oil-miscible weighting agent is selected from the group consisting of: gums, ester gums, dammar gums, sucrose acetate isobutyrate, and combinations thereof.

16. The emulsion of claim 15, wherein the oil-miscible weighting agent is 5 wt% to 50 wt%, based on the total weight of the emulsion.

17. The emulsion of claim 16, wherein the oil-miscible weighting agent is 5 wt% to 30 wt%, based on the total weight of the emulsion.

18. The emulsion according to any one of claims 1 to 17, wherein the aqueous phase further comprises an oil-miscible tackifier.

19. The emulsion according to claim 18, wherein the oil-miscible tackifier is selected from the group consisting of: cellulose derivatives such as ethylcellulose, polyethylmethacrylate polymers, diisobutylPEG-24/PPG-7/polydimethylsiloxane copolymers and mixtures thereof.

20. The emulsion of claim 18, wherein the oil-miscible tackifier comprises from 1% to 30% by weight of the oil phase.

21. The emulsion of claim 20, wherein the oil-miscible tackifier comprises from 2% to 10% by weight of the oil phase.

22. The emulsion according to any one of claims 1 to 21, wherein the aqueous phase further comprises a water-miscible tackifier.

23. The emulsion according to claim 22, wherein the water-miscible tackifier is selected from the group consisting of: xanthan gum, natural gums (e.g., agar gum, alginic acid, gellan gum, tragacanth gum), guar gum, cellulose derivatives, polyacrylic acid, acrylate copolymers, and combinations thereof.

24. The emulsion of claim 22, wherein the water-miscible tackifier comprises from 0.05% to 5%, from 0.05% to 1% by weight of the aqueous phase.

25. The emulsion of claim 24, wherein the water-miscible tackifier comprises from 0.05% to 1% by weight of the aqueous phase.

26. The emulsion of claim 25, wherein the water-miscible tackifier comprises from 0.05% to 0.3% by weight of the aqueous phase.

27. The emulsion of any one of claims 1 to 26, further comprising a water-miscible co-solvent.

28. The emulsion according to claim 27, wherein the water-miscible co-solvent is selected from the group consisting of: 1, 2-propanediol, 1, 6-hexanediol, dipropylene glycol, glycerol acetonide, butanediol (1, 3-butanediol), 1, 2-pentanediol, 1, 2-hexanediol, 1, 3-propanediol and isopropanol, ethyl lactate, and mixtures thereof.

29. The emulsion of claim 27, wherein the water-miscible co-solvent comprises from 1% to 50% by weight of the aqueous phase.

30. The emulsion of claim 29, wherein the water-miscible co-solvent comprises 2% to 20% by weight of the aqueous phase.

31. The emulsion according to any one of claims 1 to 30, wherein the emulsion is a water-in-oil or oil-in-water emulsion.

32. The emulsion of claim 31, wherein the aqueous phase is droplets dispersed in the oil phase and comprises from about 10% to about 80% by weight of the emulsion.

33. The emulsion of claim 31, wherein the oil phase is droplets dispersed in the aqueous phase and comprises from about 10% to about 80% by weight of the emulsion.

34. The emulsion according to any one of claims 1 to 33, wherein the perfume oil in the oil phase comprises from 1% to 50% by weight of the emulsion.

35. The emulsion of claim 34, wherein the perfume oil in the oil phase comprises from 5% to 20% by weight of the emulsion.

36. The emulsion of any one of claims 1 to 35, wherein the dispersed phase droplets have a diameter of about 1 micron to about 8 millimeters.

37. An emulsion according to claim 36, wherein the diameter of the dispersed phase droplets is from 0.1 to 5mm.

38. An emulsion according to claim 37, wherein the diameter of the dispersed phase droplets is from 0.5 to 5mm.

39. The emulsion of any one of claims 1 to 38, wherein the oil phase further comprises a non-polar cosmetically acceptable solvent, emollient, or combination thereof.

40. The emulsion of any one of claims 1 to 39, further comprising a surface modifier selected from the group consisting of: surfactants, amino acids, lecithins, acids, alcohols, salts, and combinations thereof.

41. The emulsion of claim 40, wherein the surface modifier is arginine, lysine, oleic acid, stearic acid, SDS, caCl ₂ Or a combination thereof.

42. The emulsion of any one of claims 1 to 41, further comprising a cyclodextrin.

43. The emulsion of claim 42, wherein the cyclodextrin is selected from the group consisting of: alpha cyclodextrin, beta cyclodextrin, gamma cyclodextrin, hydroxypropyl modified cyclodextrin, methyl modified cyclodextrin, and combinations thereof.

44. An emulsion according to any one of claims 1 to 43 wherein the perfume oil comprises from 0.01% to 50% of ingredients having a log p of less than 2.5.

45. The emulsion of claim 44 wherein the perfume oil comprises from 0.01% to 50% of ingredients having a log P less than 2.0.

46. The emulsion of claim 45 wherein the perfume oil comprises from 0.01% to 50% of ingredients having a log P less than 1.5.

47. The emulsion of any one of claims 1 to 46, wherein the emulsion comprises a surfactant in an amount equal to or less than 1% relative to the amount of stabilizing particles.

48. The emulsion of any one of claims 1 to 46, wherein the emulsion is surfactant-free.

49. A consumer product comprising the emulsion of any one of claims 1 to 48, wherein the consumer product is a high quality fragrance product, a body care product, or an air care product.

50. Use of an emulsion according to any one of claims 1 to 49 for stabilizing a water and oil emulsion.