Oil dispersion compositions comprising biopolymer complexes

Abstract

To provide a stable dispersion composition containing biopolymer complex particles dispersed in an oil phase at a high concentration.SOLUTION: The present invention relates to a dispersion composition comprising a continuous oil phase and a plurality of biopolymer complexes dispersed in the oil phase, wherein the biopolymer complexes comprise (a) at least one biopolymer, (b) at least one acid having four or more acid groups, and (c) at least one lipophobic material. The composition according to the present invention is very stable for various industries, such as cosmetic applications, pharmaceutical applications, and coating applications.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an oil dispersion composition comprising at least one biopolymer complex, particularly to an oil dispersion composition comprising at least one biopolymer complex for cosmetic use. In addition, the present invention relates to a method for producing the composition and its cosmetic use. [Background technology]

[0002] Eco-friendly cosmetic formulations are designed and developed with environmental concerns in mind and are an important goal in efforts to address global issues. Therefore, it is essential to propose more sustainable compositions, preparation methods and ingredients to meet these environmental challenges.

[0003] In this context, it is important to develop new cosmetic compositions that have a better carbon footprint, in particular by promoting the use of renewable raw materials and / or materials with a good naturalness index and / or materials of natural origin, more particularly materials of plant origin, while reducing the use of compounds of petrochemical origin.

[0004] In recent years, biopolymer composite particles with various functions have been developed. For example, WO2021 / 249974 discloses cross-linked polysaccharide particles containing a certain amount of fucoidan and carrying a certain amount of tissue-type plasminogen activator by adsorption. In this invention, cross-linked polysaccharide particles were obtained and dispersed in an oily phase.

[0005] However, there remains a need to provide a stable dispersion composition in which a natural water-soluble polymer is dispersed in an oily phase at a high concentration. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] WO2021 / 249974 [Patent Document 2] National Patent No. 1492597

Patent document 3

Patent document 4

Patent document 5

Non-licensed literature

[0007]

Non-licensed literature 1

Non-licensed Document 4

Non-licensed Document 5

Non-licensed Document 6

[0008] An object of the present invention is to provide a stable dispersion composition comprising biopolymer complex particles dispersed at high concentrations in an oily phase. [Means for solving the problem]

[0009] The object of the present invention as described above is to provide a dispersion composition comprising a continuous oily phase and a plurality of biopolymer complexes dispersed in the oily phase, wherein the biopolymer complexes are (a) at least one biopolymer; (b) at least one acid having four or more acidic groups, and (c) at least one lipophobe This can be achieved by a dispersion composition comprising:

[0010] (a) The biopolymer may be selected from polyamino acids, cationic polysaccharides, and anionic polysaccharides.

[0011] (a) The biopolymer may be selected from polylysine, collagen, gelatin, chitosan, xanthan gum, and hyaluronic acid and its salts, and combinations thereof.

[0012] (b) The acid having four or more acidic groups may be selected from phosphoric acids and carboxylic acids, preferably phosphoric acids.

[0013] (b) The acid having four or more acidic groups may be selected from inositol pentaphosphate, phytic acid, and combinations thereof.

[0014] (c) The lipophobic substance may be selected from monosaccharides, oligosaccharides, C2-C4 lower polyols, sugar alcohols, inorganic salts, and mixtures thereof.

[0015] The amount of (a) biopolymer may be 0.01% to 5% by weight, preferably 0.05% to 3% by weight, more preferably 0.075% to 1% by weight, relative to the total weight of the composition.

[0016] (b) The amount of the acid having four or more acidic groups may be 0.001% by mass to 0.5% by mass, preferably 0.002% by mass to 0.1% by mass, and more preferably 0.003% by mass to 0.05% by mass, relative to the total mass of the composition.

[0017] The amount of (c) oleophobic substance may be in the range of 0.1% to 5% by mass, preferably 0.2% to 3% by mass, and more preferably 0.3% to 1% by mass, relative to the total mass of the composition.

[0018] The biopolymer composite is in the form of hydrogel particles or xerogel particles.

[0019] The composition is a cosmetic composition, in particular a topical cosmetic composition for caring for and / or conditioning keratinous materials, such as skin.

[0020] The composition is a pharmaceutical composition, particularly a pharmaceutical composition for drug delivery, a coating composition, or an ink composition.

[0021] The present invention also provides a method for preparing a dispersion composition according to the present invention, comprising the steps of: (i) A step of separately preparing an oily phase and an aqueous phase, wherein the aqueous phase is (a) at least one biopolymer; (b) at least one acid having four or more acidic groups, and (c) at least one oleophobic substance and (ii) mixing an aqueous phase and an oily phase to obtain a mixture; (iii) emulsifying the mixture to obtain a dispersion composition comprising a continuous oily phase and a plurality of biopolymer complexes dispersed in the oily phase; The present invention also relates to a method, including:

[0022] The present invention also relates to a cosmetic method for caring for and / or conditioning keratinous materials, such as the skin, which comprises applying a composition according to the invention to the keratinous materials. DETAILED DESCRIPTION OF THE INVENTION

[0023] After extensive investigation, the present inventors have surprisingly discovered that biopolymer complex particles comprising (a) at least one biopolymer, (b) at least one acid having four or more acidic groups, and (c) at least one lipophobic substance (also known as a "lipophobe") can be stably dispersed in an oily phase, thereby providing a stable formulation comprising biopolymer complex particles dispersed in an oily phase at a high concentration.

[0024] Additionally, the present inventors have surprisingly discovered that the dispersion compositions of the present invention can provide additional cosmetic benefits by providing keratinous materials with a less sticky feeling and a less shiny appearance.

[0025] Additionally, when the biopolymer complex is in the format of xerogel particles, the inventors of the present invention have surprisingly discovered that the dispersion composition can exhibit a transparent appearance, which has the added benefit of being appealing to consumers in various industries, such as the cosmetic, pharmaceutical, and coating industries.

[0026] Accordingly, the present invention provides a dispersion composition comprising a continuous oily phase and a plurality of biopolymer complexes dispersed in the oily phase, wherein the biopolymer complexes are (a) at least one biopolymer; (b) at least one acid having four or more acidic groups, and (c) at least one oleophobic substance The present invention relates to a dispersion composition comprising:

[0027] The compositions, preparation methods, and cosmetic methods according to the present invention are described in more detail below.

[0028] [Composition] The dispersion composition according to the present invention comprises a continuous oily phase and a plurality of biopolymer complexes dispersed in the oily phase, the biopolymer complexes comprising (a) at least one biopolymer, (b) at least one acid having four or more acidic groups, and (c) at least one oleophobic material.

[0029] The composition according to the present invention can provide a high concentration of (a) a biopolymer dispersed in an oily phase, which can be dispersed in the form of a biopolymer complex in combination with (b) an acid having four or more acidic groups and (c) an oleophobic material.

[0030] The biopolymer complex can be in the form of hydrogel particles or xerogel particles. The biopolymer dispersed in the oily phase at high concentrations can be obtained in both forms of biopolymer complex particles. Thus, the present application is intended to cover both embodiments in which the biopolymer complex is a hydrogel particle and an xerogel particle.

[0031] When the biopolymer complex forms hydrogel particles, the dispersion composition according to the present invention may be in the form of a miniemulsion, in particular a reverse miniemulsion.

[0032] When the biopolymer complex forms xerogel particles, the dispersion composition according to the present invention can exhibit a transparent appearance, which is preferable for various applications, such as cosmetic applications, pharmaceutical applications, and coating applications.

[0033] The composition according to the present invention can be a cosmetic composition.The inventors of the present invention have surprisingly found that the application of the dispersion composition can provide less stickiness and less greasiness to keratinous materials, such as skin.Therefore, in one embodiment of the present invention, the composition according to the present invention is intended for topical application, particularly application to keratinous materials, such as skin.

[0034] For the purposes of the present invention, "keratinous materials" is intended to mean skin and keratinous fibers. As used herein, the term "skin" includes facial and / or body skin, as well as the scalp. As used herein, the term "keratinous fibers" includes eyelashes, eyebrows, and hair.

[0035] According to certain embodiments of the present invention, the composition is intended for topical application to keratinous materials, such as the scalp, skin, and hair, in particular the skin. In some embodiments, the composition may be a hair care and / or scalp care and / or skin care composition, in particular a skin care composition.

[0036] Furthermore, the present inventors have surprisingly discovered that when the biopolymer complex is in the form of xerogel particles, the dispersion composition of the present invention can exhibit a transparent appearance, which is highly suitable for various applications, such as cosmetic applications, pharmaceutical applications, and coating applications.

[0037] Furthermore, the composition according to the present invention has a unique morphology in which the stable dispersion contains a high concentration of biopolymer complex particles in the oily phase, making the composition useful for, for example, drug delivery in pharmaceutical applications and coating applications. Therefore, the dispersion composition according to the present invention can be a pharmaceutical composition for drug delivery, a coating composition, or an ink composition.

[0038] The components and forms of the compositions are described in detail below.

[0039] {Biopolymer composite} The oil dispersion composition according to the present invention comprises a plurality of biopolymer complexes dispersed in a continuous oily phase, the biopolymer complexes comprising (a) at least one biopolymer, (b) at least one acid having more than four phosphate groups, and (c) at least one oleophobic material.

[0040] The biopolymer complex can take the form of particles, in particular hydrogel or xerogel particles. The biopolymer dispersed in the oily phase at high concentrations can be obtained in the form of biopolymer complex particles in each case. Each case is described in detail below.

[0041] - Hydrogel particles When the biopolymer complex forms hydrogel particles, the dispersion composition according to the present invention can be in the form of an inverse miniemulsion.

[0042] The average particle size of the biopolymer complexes in the miniemulsion can be 30 nm to 100 μm, preferably 40 nm to 10 μm, and more preferably 30 nm to 1 μm. As used herein, the term "average particle size" refers to the volume-average diameter, which may refer to the diameter given by the statistical particle size distribution for half of the population, and is referred to as D50. The volume-average diameter means that the diameter can be measured, for example, by a dynamic light scattering particle size distribution analyzer.

[0043] When the biopolymer composite forms a hydrogel particle, the biopolymer composite contains a large amount of aqueous medium, such as water. For example, the amount of aqueous medium in the biopolymer composite in the form of a hydrogel particle can be more than 70% by weight, preferably 75% by weight or more, more preferably 80% by weight or more, and particularly 85% by weight or more, based on the total weight of the biopolymer composite.

[0044] The upper limit of the content of the aqueous medium in the hydrogel particles is not particularly limited, but it can generally be 95% by mass or less, and preferably 90% by mass or less.

[0045] For purposes of the present invention, aqueous medium herein means water and hydrophilic organic solvents that are miscible with water. In particular, aqueous medium in the present invention comprises water.

[0046] Therefore, the aqueous medium contained in the hydrogel particles can include water.

[0047] Water may be present in the composition according to the invention in an amount of 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, relative to the total weight of the composition.

[0048] Water may be present in the composition according to the invention in an amount of less than or equal to 25% by weight, preferably less than or equal to 20% by weight, more preferably less than or equal to 15% by weight relative to the total weight of the composition.

[0049] Water may be present in the composition according to the invention in an amount ranging from 1% to 25% by weight, preferably from 3% to 20% by weight, more preferably from 5% to 15% by weight, relative to the total weight of the composition.

[0050] In another embodiment, water may be present in the hydrogel particle biopolymer composite in an amount of 70% by weight or more, preferably 75% by weight or more, and more preferably 80% by weight or more, based on the total weight of the biopolymer composite.

[0051] Water may be present in the hydrogel particle biopolymer composite in an amount of 99% by weight or less, preferably 96% by weight or less, and more preferably 93% by weight or less, based on the total weight of the biopolymer composite.

[0052] Water may be present in the hydrogel particle biopolymer complex in an amount ranging from 70% to 99% by weight, preferably from 75% to 96% by weight, and more preferably from 80% to 93% by weight, based on the total weight of the biopolymer complex.

[0053] When the biopolymer complex forms hydrogel particles containing an aqueous medium, the biopolymer complex may be present in the composition according to the present invention in an amount of 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, based on the total weight of the composition.

[0054] When the biopolymer conjugate forms hydrogel particles, the biopolymer conjugate may be present in the composition according to the invention in an amount of 25% by weight or less, preferably 20% by weight or less, more preferably 15% by weight or less, relative to the total weight of the composition.

[0055] When the biopolymer conjugate forms hydrogel particles, the biopolymer conjugate may be present in the composition according to the invention in an amount ranging from 1% to 25% by weight, preferably from 3% to 20% by weight, more preferably from 5% to 15% by weight, relative to the total weight of the composition.

[0056] - Xerogel particles When the biopolymer complex forms xerogel particles, the dispersion composition according to the present invention can exhibit a transparent appearance.

[0057] The average particle size of the biopolymer complex in the form of xerogel particles can be 1 nm to 500 nm, preferably 2 nm to 250 nm, and more preferably 3 nm to 50 nm. The particle size of the xerogel particles can be measured by methods commonly known in the art, for example, by image analysis using a dynamic light scattering particle size distribution analyzer or a TEM. In one embodiment, the average particle size of the xerogel particles is determined by measuring the particle size of, for example, 50 particles by TEM image analysis and then calculating the average particle size.

[0058] In one embodiment, the dispersion composition containing the biopolymer complex xerogel particles exhibits a low turbidity of 70 NTU or less, preferably 60 NTU or less, and more preferably 50 NTU or less. Turbidity can be measured, for example, using a 2100Q (commercially available from Hach Company) with a round cell (25 mm diameter and 60 mm height) and a tungsten filament bulb capable of emitting visible light (between 400 and 800 nm, preferably 400-500 nm). Measurements can be performed on the undiluted composition. Blanks can be determined using distilled water or the oil used in the oily phase.

[0059] When the biopolymer composite forms a xerogel particle, the biopolymer composite does not contain a large amount of aqueous medium, such as water. For example, the amount of aqueous medium in the biopolymer composite in the form of a xerogel particle can be 70% by weight or less, preferably 50% by weight or less, more preferably 30% by weight or less, and particularly 10% by weight or less, based on the total weight of the biopolymer composite. In another embodiment, the biopolymer composite is water-free.

[0060] In another embodiment of the present invention, when the biopolymer complex forms xerogel particles, the composition according to the present invention does not contain a significant amount of aqueous medium, such as water. For example, the amount of aqueous medium in the composition can be 5% by weight or less, preferably 3% by weight or less, and more preferably 1% by weight or less, based on the total weight of the biopolymer complex. In yet another embodiment, the composition according to the present invention is water-free or anhydrous when the biopolymer complex is in the form of xerogel particles.

[0061] When the biopolymer complex forms xerogel particles, the biopolymer complex may be present in the composition according to the invention in an amount of 0.25% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more, relative to the total weight of the composition.

[0062] When the biopolymer complex forms xerogel particles, the biopolymer complex may be present in the composition according to the invention in an amount of 8% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less, relative to the total weight of the composition.

[0063] When the biopolymer complex forms xerogel particles, the biopolymer complex may be present in the composition according to the invention in an amount ranging from 0.25% to 8% by weight, preferably from 0.5% to 5% by weight, more preferably from 1% to 3% by weight, relative to the total weight of the composition.

[0064] In the context of this specification, any combination of the above upper and lower limits can be used to express a range of preferred amounts.

[0065] (biopolymer) The dispersed biopolymer complexes of the present invention comprise at least one type of (a) biopolymer. Two or more types of biopolymers may be used in combination. Thus, a single type of (a) biopolymer may be used, or different types of (a) biopolymers may be used in combination.

[0066] The term "biopolymer" herein is intended to mean a polymer that can be produced by a living organism, or a derivative thereof. A biopolymer may be obtained synthetically (e.g., through laboratory synthesis) and / or obtained and / or derived from nature (e.g., from living organisms or former living organisms). For example, a biopolymer of the present invention may be a derivative of a polymer produced by a living organism, where the derivative results from the synthetic methods used to obtain or isolate the biopolymer from nature.

[0067] The (a) biopolymer of the present invention may be water-soluble. For purposes of the present invention, the term "water-soluble" herein means that the material is water-soluble at room temperature (25°C) and atmospheric pressure (10 5By "soluble in water," we mean soluble in water at a concentration of at least 1% by weight, such as at least 5% or 10% by weight, based on the total weight of water, in saturation (in Pa).

[0068] (a) The molecular weight of the biopolymer may be in the range of 1,000 to 2,000,000, preferably 2,000 to 1,000,000, more preferably 3,000 to 500,000, and even more preferably 5,000 to 300,000. Unless otherwise specified in the description, "molecular weight" refers to the number average molecular weight. Molecular weight can be measured or determined, for example, by gel permeation chromatography in accordance with ASTM D5296-19.

[0069] (a) The biopolymer may be a homopolymer or a copolymer, and the term "copolymer" herein is understood to mean both copolymers obtained from two types of monomers and copolymers obtained from more than two types of monomers, for example terpolymers obtained from three types of monomers.

[0070] (a) Biopolymers include, but are not limited to, proteins or polyamino acids, and polysaccharides, preferably polysaccharides.

[0071] Examples of proteins or polyamino acids include collagen, gelatin, wheat protein, conchiolin protein, soybean protein, and polylysine.

[0072] Polylysine is well known and is a polyamine. Polylysine can be a natural homopolymer of L-lysine that can be produced by bacterial fermentation. For example, polylysine can be ε-poly-L-lysine, which is typically used as a natural preservative in foods. Polylysine is a polyelectrolyte that is soluble in polar solvents, such as water. Polylysine is commercially available in various forms, such as poly-D-lysine and poly-L-lysine. Polylysine can be in the form of a salt and / or a solution.

[0073] The polysaccharide may be selected from cationic polysaccharides, anionic polysaccharides, nonionic polysaccharides, and combinations thereof. Preferably, the polysaccharide is selected from ionic polysaccharides, cationic and anionic polysaccharides.

[0074] - Cationic polysaccharides The cationic polysaccharide has a positive charge density of 0.01 meq / g to 20 meq / g, preferably 0.05 to 15 meq / g, and more preferably 0.1 to 10 meq / g.

[0075] The cationic polysaccharide may have at least one positively charged and / or positively charged moiety selected from the group consisting of primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanide groups, imidazole groups, imino groups, and pyridyl groups. The term (primary) "amino group" herein means an -NH2 group.

[0076] Preferably, the cationic polysaccharide has at least one quaternary ammonium group, preferably a quaternary trialkylammonium group, more preferably a quaternary trimethylammonium group.

[0077] The quaternary ammonium group has the following chemical formula (I):

[0078] [ka]

[0079] [In the formula, Each of R1 and R2 is C 1~3 represents an alkyl group, preferably a methyl group or an ethyl group, more preferably a methyl group; R3 is C 1~24 represents an alkyl group, preferably a methyl group or an ethyl group, more preferably a methyl group; X- represents an anion, preferably a halide ion, more preferably a chloride ion; n represents an integer of 0 to 30, preferably 0 to 10, and more preferably 0; R4 is C 1~4 represents an alkylene group, preferably an ethylene group or a propylene group. The quaternary ammonium group may be present in a group containing quaternary ammonium groups, which may be represented by:

[0080] The left-most ether bond (-O-) in the above chemical formula (I) can be attached to a sugar ring of a polysaccharide.

[0081] The quaternary ammonium group-containing group is -O-CH2-CH(OH)-CH2-N + It is preferably (CH3)3.

[0082] The cationic polysaccharide may preferably be selected from cationic cellulose polymers.

[0083] According to the present invention, "cationic cellulose polymer" refers to any non-silicinated (does not contain any silicon atoms) cellulose polymer that contains cationic groups and / or groups that can be ionized to cationic groups, and preferably does not contain anionic groups and / or groups that can be ionized to anionic groups.

[0084] The term "cellulose" polymer, according to the present invention, denotes any polysaccharide compound having in its structure at least 20 glucose residue chains connected by β-1,4 bonds. The cellulose polymer may be associative, i.e., having in its structure at least one C8-C 30 It may have a fatty chain.

[0085] Non-limiting examples of cationic cellulose polymers are: (1) Cationic cellulose polymers, such as cellulose ether derivatives containing one or more quaternary ammonium groups, as described, for example, in French Patent No. 1492597, such as the polymers sold by Dow Chemical under the names "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M). These polymers are also defined in the CTFA dictionary as quaternary ammonium hydroxyethyl celluloses reacted with epoxides substituted with trimethylammonium groups. (2) Cationic cellulose polymers, such as cellulose copolymers and derivatives grafted with at least one water-soluble quaternary ammonium monomer, as described, for example, in U.S. Pat. No. 4,131,576, including hydroxyalkyl celluloses grafted with at least one monomer selected from methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium, and dimethyldiallylammonium, such as hydroxymethyl-, hydroxyethyl-, and hydroxypropylcellulose. Commercially available products corresponding to these polymers include those sold by Akzo Novel under the names "Celquat® L 200" and "Celquat® H 100." (3) A cationic cellulose polymer having at least one quaternary ammonium group containing at least one fatty chain.

[0086] The fatty chain of the quaternized cellulose modified by a group containing at least one linear fatty chain may be a linear alkyl, a linear or branched aryl alkyl, a linear alkyl aryl, preferably a linear alkyl (these groups contain at least 8 carbon atoms, in particular 8 to 30 carbon atoms, more preferably 10 to 24 or 10 to 14 carbon atoms), or a mixture thereof.

[0087] Preferred examples include quaternized hydroxyethyl cellulose modified with a group containing at least one linear fatty chain, such as a linear alkyl group, a linear arylalkyl group, a linear alkylaryl group, preferably a linear alkyl group (these groups contain at least 8 carbon atoms, particularly 8 to 30 carbon atoms, more preferably 10 to 24 or 10 to 14 carbon atoms), or a mixture thereof.

[0088] Preferably, the compound of formula (Ib):

[0089] [ka]

[0090] [In the formula, - R is an ammonium group RaRbRcN + -, Q-, where Ra, Rb, and Rc are the same or different and are a hydrogen atom or a linear C1-C 30 alkyl, preferably alkyl; Q represents an anionic counterion, for example a halide, for example a chloride or bromide; - R' is an ammonium group R'aR'bR'cN + -, Q'-, where R'a, R'b, and R'c are the same or different and are a hydrogen atom or a linear C1-C 30 Q'- represents an anionic counterion, such as a halide ion, for example a chloride ion or a bromide ion, preferably an alkyl ion; At least one of the groups Ra, Rb, Rc, R'a, R'b, and R'c is a linear C8-C 30 is understood to represent alkyl, - n, x and y are the same or different and represent integers between 1 and 10000. Examples of hydroxyethyl cellulose include:

[0091] Preferably, in formula (Ib), at least one of the groups Ra, Rb, Rc, R'a, R'b, and R'c is a linear C8-C 30 Alkyl, preferably C 10 ~C 24 or C 10 ~C 14 In particular, the dodecyl group (C 12 Preferably, this or other groups represent linear C1-C4 alkyl, in particular methyl.

[0092] Preferably, in formula (Ib), only one of the groups Ra, Rb, Rc, R'a, R'b, and R'c is a linear C8-C 30 Alkyl, preferably C 10 ~C 24 or C 10 ~C 14 In particular, the dodecyl group (C 12 Preferably, all other groups represent linear C1-C4 alkyl, in particular methyl.

[0093] More preferably, R is -N + (CH3)3, Q' - and -N + (C 12 H 25 )(CH3)2, Q' - , preferably -N + (CH3)3, Q' - It can be a group selected from the group:

[0094] More preferably, R' is -N + (C 12 H 25 )(CH3)2, Q' - It can be a group.

[0095] The percentage of nitrogen can vary from 0.1 to 10% by weight, preferably from 0.2 to 5% by weight, more preferably from 0.5 to 3% by weight, relative to the total weight of the polymer.

[0096] Mention may in particular be made of the polymers with the following INCI names: Polyquaternium-24, such as the product QUATRISOFT LM 200® (sold by AMERCHOL / DOW CHEMICAL), PG-hydroxyethylcellulose cocodimonium chloride, such as the product CRODACEL QM®, - PG-hydroxyethyl cellulose lauryldimonium chloride (C 12 alkyl), such as the product CRODACEL QL®, and - PG-hydroxyethyl cellulose stearyldimonium chloride (C 18 alkyl), such as the product CRODACEL QS® (sold by the company CRODA).

[0097] Formula (Ib) [wherein R represents trimethylammonium halide, R' represents dimethyldodecylammonium halide, preferably R represents trimethylammonium chloride Cl - , (CH3)3N + -, and R' represents dimethyldodecylammonium chloride Cl - ,(CH3)2(C 12 H 25 )N + Polymers of this type are known by the INCI name Polyquaternium-67, and commercial products include SOFTCAT POLYMER SL® polymers from AMERCHOL / DOW CHEMICAL, such as SL-100, SL-60, SL-30, SL-5, and SX-1300X.

[0098] More particularly, the cationic cellulose polymer is chosen from hydroxyethyl cellulose reacted with trimethylammonium epoxide and lauryldimethylammonium epoxide (INCI name Polyquaternium-67), preferably sold under the name Softcat Polymer SL-100 or Softcat Polymer SX-1300X by the company Amerchol.

[0099] It may also be preferred that the cationic polysaccharide is selected from cationic starches.

[0100] Examples of cationic starches that may be mentioned include starches modified with 2,3-epoxypropyltrimethylammonium salts (e.g. chloride), such as the product known by the INCI name Starch Hydroxypropyltrimonium Chloride and sold by Ondeo under the name SENSOMER Cl-50 or by Ingredion under the name Pencare™ DP 1015.

[0101] It may also be preferred that the cationic polysaccharide is selected from cationic gums, especially cationic galactomannan gums.

[0102] The term "cationic galactomannan gum" refers to any galactomannan gum that contains cationic groups and / or groups that can be ionized to cationic groups.

[0103] Galactomannans are polysaccharides essentially composed of galactose and mannose units, with the mannose units linked together by 1-4 glycosidic bonds and galactose branching to the mannose units by 1-6 crosslinks. Each ring of a galactose or mannose unit (i.e., a sugar unit) has three free hydroxyl groups available for chemical reactions. Galactomannans are commonly found in the endosperm of legumes, such as guar or carob grains.

[0104] Preferred cationic groups are selected from those comprising primary, secondary, tertiary, and / or quaternary amine groups.

[0105] The group of galactomannans suitable for use according to the invention are, for example, gums containing trialkyl(C1-C4)ammonium cationic groups. Preferably, between 2% and 30% of the number of hydroxyl functional groups of these gums contain trialkylammonium cationic groups.

[0106] Among these trialkylammonium groups, mention may be made very particularly of trimethylammonium and triethylammonium groups.

[0107] Even more preferably, these groups represent 5% to 20% by weight of the total weight of the modified galactomannan gum.

[0108] According to the present invention, the cationic galactomannan gum is preferably a guar gum containing hydroxypropyltrialkylammonium groups, more preferably a guar gum containing hydroxypropyltrimethylammonium groups, i.e., a guar gum modified with, for example, 2,3-epoxypropyltrimethylammonium chloride.

[0109] The gum may, for example, be selected from the group consisting of cassia gum, karaya gum, konjac gum, tragacanth gum, tara gum, and acacia gum.

[0110] These galactomannan gums, in particular guar-derived gums modified with cationic groups, are products already known per se and are described, for example, in US Pat. Nos. 3,589,578 and 4,031,307.

[0111] Examples of cationic gums include cationic polygalactomannan derivatives, such as guar gum derivatives and cassia gum derivatives. Such products are sold, inter alia, by Rhodia under the trade names Jaguar EXCEL, Jaguar C13 S, Jaguar C15, Jaguar C17, and Jaguar C162 (guar hydroxypropyltrimonium chloride), by Degussa under the name Amilan® Guar (guar hydroxypropyltrimonium chloride), and by Aqualon under the name N-Hance® 3000 (guar hydroxypropyltrimonium chloride). Hydroxypropyl guar hydroxypropyltrimonium chloride is a hydroxypropyl derivative of guar hydroxypropyltrimonium chloride and is commercially available from Rhodia Inc. under the trade name Jaguar® series. Cassia hydroxypropyltrimonium chloride is commercially available from Lubrizol Advanced Materials, Inc. under the trademarks Sensomer™ CT-250 and Sensomer™ CT-400, or from Ashland Inc. under the trademark ClearHance™.

[0112] It is also preferred that the cationic polysaccharide is selected from polyamines, such as chitosan.

[0113] In one preferred embodiment, the cationic polysaccharide is selected from cationic gums, more preferably cationic galactomannan gums, especially cationic polygalactomannan derivatives, such as guar gum derivatives.

[0114] It may be preferred that the cationic polysaccharide is selected from the group consisting of polyquaternium-4, polyquaternium-10, polyquaternium-24, polyquaternium-67, starch hydroxypropyltrimonium chloride, guar hydroxypropyltrimonium chloride, hydroxypropyl guar hydroxypropyltrimonium chloride, cassia hydroxypropyltrimonium chloride, chitosan, and mixtures thereof, and more preferably selected from guar hydroxypropyltrimonium chloride, hydroxypropyl guar hydroxypropyltrimonium chloride, and mixtures thereof.

[0115] - Anionic polysaccharides Anionic polysaccharides may be water soluble and may have a negative charge in water.

[0116] The anionic polysaccharides may have at least one negatively charged and / or negatively charged moiety selected from the group consisting of carboxylate, e.g., carboxyalkyl, sulfate, sulfonate, e.g., sulfoalkyl, phosphate, and phosphonate groups. The alkyl groups of these moieties are selected from the group consisting of C 1~4 It may also be an alkyl group, for example, methyl, ethyl, and propyl.

[0117] The anionic polysaccharide preferably has at least one carboxylate group, e.g., a carboxyalkyl group. The counterion of the anionic group is usually an alkali metal or alkaline earth metal, preferably sodium, potassium, magnesium, or calcium. The anionic group can also exist in acid form, whereby the corresponding anionic group is formed in an aqueous environment.

[0118] The anionic polysaccharide may contain at least one anionic group derived from carboxylic acid, sulfonic acid, sulfenic acid, phosphoric acid, phosphonic acid, or pyruvic acid. Preferably, the anionic group is a carboxylic acid group. The anionic group may also be in the form of an acid salt, particularly a sodium, calcium, lithium, or potassium salt.

[0119] The anionic polysaccharide may be selected from natural anionic polysaccharides and synthetic anionic polysaccharides.

[0120] Examples of suitable natural anionic polysaccharides of the present invention include polysaccharides containing at least one glucuronic acid as a constituent, such as xanthan gum, gellan gum, gum arabic, alginic acid or alginates, hyaluronic acid and its salts; polysaccharides containing at least one galacturonic acid as a constituent, such as pectin; sulfated polysaccharides, such as carrageenan, ulvan, fucoidan, chondroitin sulfate, dermatan sulfate, agar, and combinations thereof.

[0121] Xanthan is a heteropolysaccharide produced on an industrial scale by aerobic fermentation by the bacterium Xanthomonas campestris. Its structure consists of a β(1,4)-linked β-D-glucose backbone, similar to cellulose. One of the two glucose molecules has a trisaccharide side chain composed of α-D-mannose, β-D-glucuronic acid, and a terminal β-D-mannose. The internal mannose residues are generally acetylated at carbon 6. Approximately 30% of the terminal mannose residues have a pyruvate group attached in a chelate form between carbons 4 and 6. Glucuronic acid and charged pyruvate are ionizable, thus contributing to the anionic nature of xanthan (negative charge up to pH 1). The content of pyruvate and acetate residues varies depending on the strain, fermentation process, post-fermentation conditions, and purification steps.

[0122] Xanthan gum is represented, for example, by products sold under the name Rhodicare by Rhodia Chimie, Satiaxane™ by Cargill Texturizing Solutions (for the food, cosmetics and pharmaceutical industries), Novaxan™ by ADM, and Kelzan® and Keltrol® by CP-Kelco.

[0123] Gellan gum is an anionic linear heteropolysaccharide based on tetrasaccharide oligosaccharide units. D-glucose, L-rhamnose, and D-glucuronic acid are present in gellan gum in the form of monomeric elements in a ratio of 2 / 1 / 1. Gellan gum is sold, for example, by CP Kelco under the name Kelcogel CG LA.

[0124] Gum arabic is a highly branched acidic polysaccharide that exists in the form of a mixture of potassium, magnesium, and calcium salts. The monomeric components of the free acid (arabic acid) are D-galactose, L-arabinose, L-rhamnose, and D-glucuronic acid.

[0125] Alginic acid, a natural substance derived from brown algae or certain bacteria, is a polyuronic acid composed of two uronic acids, β-D-mannuronic (M) acid and α-L-glucuronic (G) acid, linked by a 1,4-glycosidic bond. Alginic acid can form water-soluble salts (alginates) with alkali metals, such as sodium, potassium, or lithium, lower amines, and ammonium-substituted cations, such as methylamine, ethanolamine, diethanolamine, or triethanolamine.

[0126] Hyaluronic acid can be represented by the following chemical formula:

[0127] [ka]

[0128] In the context of the present invention, the term "hyaluronic acid" particularly encompasses the basic unit of hyaluronic acid of the formula:

[0129] [ka]

[0130] This is the smallest fraction of hyaluronic acid that contains the disaccharide dimer, D-glucuronic acid and N-acetylglucosamine.

[0131] The term "hyaluronic acid and its derivatives" in the context of the present invention also includes linear polymers comprising the above polymer units linked together in a chain via alternating β(1,4) and β(1,3) glycosidic bonds, with a molecular weight (MW) that can range between 380 and 1,000,000 daltons, which depends primarily on the source from which the hyaluronic acid is obtained and / or the preparation method.

[0132] In the context of the present invention, the term "hyaluronic acid and its derivatives" also includes hyaluronic acid salts. Examples of salts include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as magnesium salt, ammonium salt, and mixtures thereof. In a preferred embodiment, the hyaluronic acid derivative is sodium hyaluronate.

[0133] According to a preferred embodiment of the present invention, the hyaluronic acid fraction suitable for use in the present invention has a molecular weight of between 50,000 and 5,000,000, in particular between 100,000 and 5,000,000, and especially between 400,000 and 5,000,000 Da, in which case the term used is high molecular weight hyaluronic acid.

[0134] Alternatively, hyaluronic acid fractions that may also be suitable for use within the present invention have a molecular weight between 50,000 and 400,000 Da, in which case the term used is intermediate molecular weight hyaluronic acid.

[0135] Additionally or alternatively, hyaluronic acid fractions that may be suitable for use within the present invention have a molecular weight of less than 50,000 Da, in which case the term used is low molecular weight hyaluronic acid.

[0136] Pectin is a linear polymer of α-D-galacturonic acid (at least 65%), linked to a certain proportion of carboxylic acid groups esterified with methanol groups at positions 1 and 4. Approximately 20% of the sugars constituting a pectin molecule are neutral sugars (L-rhamnose, D-glucose, D-galactose, L-arabinose, and D-xylose). L-rhamnose residues are present in all pectins and are integrated into the backbone at positions 1 and 2. Uronic acid molecules contain a carboxyl functional group. This functional group, when in the COO form, gives pectin the ability to exchange ions. Divalent ions (especially calcium) have the ability to form ionic bridges between the two carboxyl groups of two different pectin molecules.

[0137] Carrageenan is an anionic polysaccharide that constitutes the cell walls of various red algae (Rhodophyceae) belonging to the families Gigartinaceae, Hypneaceae, Furcellariaceae, and Polyideaceae. Carrageenan is generally obtained by hot water extraction from natural strains of these algae. These linear polymers formed by disaccharide units consist of two D-galactopyranose units linked via alternating α(1,3) and β(1,4) bonds. Carrageenan is a highly sulfated polysaccharide (20-50%), and the α-D-galactopyranosyl residues may be in the 3,6-anhydro form. Depending on the number and position of the sulfate ester groups on the repeating disaccharide of the molecule, several types of carrageenan are distinguished: kappa-carrageenan, which has one sulfate ester group, iota-carrageenan, which has two sulfate ester groups, and lambda-carrageenan, which has three sulfate ester groups. Carrageenan is essentially composed of sulfate esters of polysaccharides with potassium, sodium, magnesium, triethanolamine, and / or calcium salts.

[0138] Agar is formed from a polymeric group whose basic backbone is β(1,3) D-galactopyranose and α(1,4) L3-6 anhydrogalactose chains, and these units repeat regularly and alternatingly. Differences within the agar family arise from the presence or absence of solvated methyl or carboxyethyl groups. These hybrid structures are generally present in varying percentages depending on the algae species and harvest time.

[0139] In a preferred embodiment, the anionic polysaccharide is selected from polysaccharides containing at least one glucuronic acid as a constituent, such as xanthan gum, gellan gum, gum arabic, alginic acid or alginates, and hyaluronic acid, in particular xanthan gum.

[0140] Examples of suitable synthetic anionic polysaccharides include anionic cellulose derivatives. The anionic cellulose derivatives include those containing carboxyalkyl groups, particularly C1~4 Carboxyalkyl groups, such as carboxymethyl, carboxyethyl, carboxypropyl, and sulfoalkyl groups, especially C 1~4 Examples of anionic cellulose derivatives include those modified with sulfoalkyl groups, such as sulfomethyl groups. Examples of anionic cellulose derivatives include carboxymethyl cellulose, carboxyethyl cellulose, carboxypropyl cellulose, sulfoethyl carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose ("CM-HEC"), and carboxymethyl cellulose.

[0141] The anionic polysaccharide may preferably be selected from polysaccharides containing at least one glucuronic acid as a constituent, such as xanthan gum, gellan gum, gum arabic, alginic acid or alginates, hyaluronic acid and its salts, more preferably xanthan gum, and hyaluronic acid and its salts, and combinations thereof.

[0142] - Nonionic polysaccharides Nonionic polysaccharides can be selected from those described, for example, in "Encyclopedia of Chemical Technology," Kirk-Othmer, 3rd Edition, 1982, Vol. 3, pp. 896-900, and Vol. 15, pp. 439-458; in "Polymers in Nature," by E.A. MacGregor and C.T. Greenwood, published by John Wiley & Sons, Inc., Chapter 6, pp. 240-328, 1980; and in "Industrial Gums - Polysaccharides and Their Derivatives," edited by Roy L. Whistler, 2nd Edition, published by Academic Press Inc., the contents of which are incorporated by reference in their entirety.

[0143] In particular, the nonionic polysaccharides may be selected from glucans, modified and unmodified starches (e.g., those derived from cereals such as wheat, corn or rice, those derived from vegetables such as yellow pea, and tubers such as potato or cassava), amylose, amylopectin, glycogen, dextran, cellulose and its derivatives (methylcellulose, hydroxyalkylcellulose, ethylhydroxyethylcellulose and carboxymethylcellulose), mannan, xylan, lignin, araban, galactan, galacturonan, chitin, glucuronoxylan, arabinoxylan, xyloglucan, glucomannan, arabinogalactan, tragacanth gum, ghatti gum, karaya gum, locust bean gum or carob gum, galactomannans such as guar gum, and nonionic derivatives thereof (e.g., hydroxypropyl guar), and mixtures thereof, which are different from the cationic and anionic polysaccharides described above.

[0144] Among the starches that can be used, mention can be made, for example, of macromolecules in the form of polymers containing basic units that are anhydroglucose units. Depending on the number of these units and their aggregation, a distinction can be made between amylose (linear polymers) and amylopectin (branched polymers). The relative proportions of amylose and amylopectin, and also their degree of polymerization, can vary depending on the plant origin of the starch.

[0145] The plant origin of the starch molecules used may be cereals or tubers, and the starch may therefore be selected, for example, from maize starch, rice starch, cassava starch, tapioca starch, barley starch, potato starch, wheat starch, sorghum starch, and pea starch.

[0146] Starch is generally in the form of a white powder that is insoluble in cold water and has a primary particle size in the range of 3 to 100 microns.

[0147] The starch may optionally be C1-C6 hydroxyalkylated or C1-C6 acylated (e.g., acetylated). The starch may also be subjected to a heat treatment.

[0148] The guar gum may be modified or unmodified.

[0149] The modified nonionic guar gum is, for example, modified with a C1-C6 hydroxyalkyl group.

[0150] Among the hydroxyalkyl groups, mention may be made, for example, of hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxybutyl groups.

[0151] These guar gums are well known in the prior art and can be prepared, for example, by reacting guar gum with the corresponding alkene oxide, e.g., with propylene oxide to obtain guar gum modified with hydroxypropyl groups.

[0152] The degree of hydroxyalkylation corresponds to the number of alkylene oxide molecules consumed divided by the number of free hydroxyl functions present in the guar gum and may, for example, be in the range of 0.4 to 1.2.

[0153] Such non-ionic guar gums, optionally modified with hydroxyalkyl groups, are sold, for example, by Solvay under the trade names Jaguar HP-8 COS, Jaguar HP-60 and Jaguar HP-120.

[0154] Among the celluloses used are, for example, hydroxyethyl cellulose and hydroxypropyl cellulose. Mention may be made of the products sold under the names Klucel EF, Klucel H, Klucel MF and Klucel G by the company Ashland.

[0155] Alternatively, polysaccharides derived from microorganisms can also be preferably used as the hydrophilic nonionic polysaccharide thickener.

[0156] The polysaccharides derived from microorganisms refer to polysaccharides produced by microorganisms such as bacteria.

[0157] Microbial-derived polysaccharides are not plant-derived polysaccharides, and therefore it may be preferred that the microbial-derived polysaccharides are not cellulose-based.

[0158] Examples of polysaccharides derived from microorganisms include curdlan, gellan gum, dextran, pullulan, sclerotium gum, and mixtures thereof.

[0159] In a preferred embodiment of the present invention, the (a) biopolymer is selected from polyamino acids, such as collagen, gelatin, and polylysine, and polysaccharides, preferably ionic polysaccharides, i.e., cationic and anionic polysaccharides, more preferably polyamines, and polysaccharides containing at least one glucuronic acid as a component, even more preferably chitosan, xanthan gum, and hyaluronic acid and its salts, and combinations thereof.

[0160] (a) The biopolymer may be present in the composition according to the invention in an amount of 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.3% by weight or more, relative to the total weight of the composition.

[0161] (a) The biopolymer may be present in the composition according to the invention in an amount of not more than 7% by weight, preferably not more than 5% by weight, more preferably not more than 3% by weight, relative to the total weight of the composition.

[0162] The (a) biopolymer may be present in the composition according to the invention in an amount ranging from 0.01% to 7% by weight, preferably from 0.05% to 5% by weight, more preferably from 0.075% to 3% by weight, relative to the total weight of the composition.

[0163] In another embodiment, (a) the biopolymer may be present in the biopolymer complex of the hydrogel particle in an amount of 0.1% by weight or more, preferably 0.5% by weight or more, and more preferably 0.75% by weight or more, based on the total weight of the biopolymer complex.

[0164] (a) The biopolymer may be present in the hydrogel particle biopolymer composite in an amount of 30% by weight or less, preferably 20% by weight or less, and more preferably 10% by weight or less, based on the total weight of the biopolymer composite.

[0165] (a) The biopolymer may be present in the hydrogel particle biopolymer complex in an amount ranging from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight, and more preferably from 0.75% to 10% by weight, based on the total weight of the biopolymer complex.

[0166] In another embodiment, (a) the biopolymer may be present in the xylogel particle biopolymer composite in an amount of 10% by weight or more, preferably 20% by weight or more, and more preferably 30% by weight or more, based on the total weight of the biopolymer composite.

[0167] (a) The biopolymer may be present in the xylogel particle biopolymer composite in an amount of 70% by weight or less, preferably 60% by weight or less, and more preferably 50% by weight or less, based on the total weight of the biopolymer composite.

[0168] (a) The biopolymer may be present in the xylogel particle biopolymer composite in an amount ranging from 10% to 70% by weight, preferably from 20% to 60% by weight, and more preferably from 30% to 50% by weight, based on the total weight of the biopolymer composite.

[0169] (acids with four or more acidic groups) The dispersed biopolymer composites of the present invention contain at least one type of (b) acid having four or more acidic groups. Two or more types of acids having four or more acidic groups may be used in combination. Thus, a single type of (b) acid having four or more acidic groups may be used, or different types of (b) acids having four or more acidic groups may be used in combination.

[0170] (b) Acids with four or more acidic groups can act as cross-linking agents to introduce cross-links between (a) biopolymer chains to produce biopolymer composite particles.

[0171] The (b) acid may be an organic acid or an inorganic acid, and preferably, the (b) acid is selected from organic acids.

[0172] The acidic group of the (b) acid can be selected from, for example, a carboxylic acid group, a sulfate group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, a phenolic hydroxyl group, and mixtures thereof, and is preferably a phosphoric acid group. Preferably, the (b) acid is selected from those having four or more phosphoric acid groups or from carboxylic acids, especially those having phosphoric acid groups.

[0173] In one embodiment of the present invention, the (b) acid contains 4 to 8 acidic groups, preferably 4 to 7 acidic groups, and more preferably 5 or 6 acidic groups.

[0174] In one embodiment of the present invention, the (b) acid contains 2 to 12 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms.

[0175] In one embodiment of the present invention, the (b) acid is selected from phosphoric acids and carboxylic acids, preferably phosphoric acids. Non-limiting examples of phosphoric acids having four or more phosphate groups include inositol pentaphosphate, phytic acid, and combinations thereof.

[0176] In one embodiment of the present invention, the (b) acid is selected from carboxylic acids. Non-limiting examples of carboxylic acids having four or more carboxylic acid groups include tetracarboxylic acids such as EDTA, pentacarboxylic acids, and hexacarboxylic acids.

[0177] In another embodiment of the present invention, the (b) acid can be selected from those containing at least one alicyclic group, such as a cycloalkane group, preferably a C5 or C6 cycloalkane group, in particular a cyclohexane group. Examples of the (b) acid containing at least one alicyclic group include inositol pentaphosphate and phytic acid.

[0178] The acid of the present invention may be in the form of a salt. The term "salt" herein refers to a salt formed by adding a suitable base to the acid. Examples of the salt include metal salts, such as salts with alkali metals such as Na and K, salts with alkaline earth metals such as Mg and Ca, and ammonium salts.

[0179] (b) The acid may be present in the composition according to the invention in an amount of 0.001% by weight or more, preferably 0.002% by weight or more, more preferably 0.003% by weight or more, relative to the total weight of the composition.

[0180] (b) The acid may be present in the composition according to the invention in an amount of not more than 0.5% by weight, preferably not more than 0.1% by weight, more preferably not more than 0.05% by weight, relative to the total weight of the composition.

[0181] (b) The acid may be present in the composition according to the present invention in an amount ranging from 0.001% to 0.5% by weight, preferably from 0.002% to 0.1% by weight, and more preferably from 0.003% to 0.05% by weight, relative to the total weight of the composition.

[0182] In another embodiment, (b) the acid may be present in the biopolymer complex of the hydrogel particle in an amount of 0.01% by weight or more, preferably 0.02% by weight or more, and more preferably 0.03% by weight or more, based on the total weight of the biopolymer complex.

[0183] (b) The acid may be present in the biopolymer composite of the hydrogel particle in an amount of 1% by weight or less, preferably 0.5% by weight or less, and more preferably 0.1% by weight or less, based on the total weight of the biopolymer composite.

[0184] (b) The acid may be present in the hydrogel particle biopolymer complex in an amount ranging from 0.01% to 1% by weight, preferably from 0.02% to 0.5% by weight, and more preferably from 0.03% to 0.1% by weight, based on the total weight of the biopolymer complex.

[0185] In another embodiment, (b) the acid may be present in the xylogel particle biopolymer composite in an amount of 0.05% by weight or more, preferably 0.1% by weight or more, and more preferably 0.2% by weight or more, based on the total weight of the biopolymer composite.

[0186] (b) The acid may be present in the xylogel particle biopolymer composite in an amount of 3% by weight or less, preferably 2% by weight or less, and more preferably 1% by weight or less, based on the total weight of the biopolymer composite.

[0187] (b) The acid may be present in the xylogel particle biopolymer composite in an amount ranging from 0.05% to 3% by weight, preferably from 0.1% to 2% by weight, and more preferably from 0.2% to 1% by weight, based on the total weight of the biopolymer composite.

[0188] (oleophobic substance) The dispersed biopolymer composite of the present invention includes at least one (c) oleophobic material. Two or more oleophobic materials may be used in combination. Thus, a single type of (c) oleophobic material may be used, or different types of (c) oleophobic materials may be used in combination.

[0189] The term "oleophobic substance" herein is intended to mean an oleophobic substance that is not soluble or is substantially insoluble in lipids, oils, and / or non-polar solvents, such as isododecane, n-octanol, corn oil, and castor oil, particularly corn oil and / or castor oil.

[0190] For example, in one embodiment of the present invention, (c) the oleophobic material is 5 In another embodiment, the (c) oleophobic substance has a solubility in lipids, oils, and / or other non-polar solvents at a concentration of 0.1% by weight or less, e.g., 0.01% by weight or less, or 0.001% by weight or less, at a pH of 10. In another embodiment, the (c) oleophobic substance is not soluble in isododecane, n-octanol, and / or castor oil, particularly castor oil.

[0191] In another embodiment of the present invention, (c) the lipophobic substance may be a substance that is insoluble in the oily phase, in particular insoluble in oily or fatty substances, such as oil, that are contained in the oily phase as the oily medium.

[0192] The term "oleophobic material" may also be expressed as "oleophobic material."

[0193] In the present invention, the (c) oleophobic substance may be hydrophilic. Specifically, the (c) oleophobic substance may be hydrophilic at room temperature (25° C.) and atmospheric pressure (10 5 Pa), in water at a concentration of at least 5% by weight based on the total weight of water.

[0194] In one embodiment of the present invention, (c) the oleophobic material is at room temperature (25° C.) and atmospheric pressure (10 5 Pa), in water at a concentration of at least 10% by weight, preferably at least 20% by weight, more preferably at least 30% by weight, based on the total weight of water.

[0195] The (c) oleophobic substance used in the present invention can function to prevent or inhibit the exchange of materials between droplets of the dispersed phase (dispersed biopolymer complexes or dispersed aqueous phase), thus reducing or completely preventing the undesirable Ostwald ripening of the dispersed phase droplets, which leads to droplet size growth, resulting in stable particles of biopolymer complexes in the oily phase of the present invention.

[0196] In one embodiment of the present invention, (c) the oleophobic material is not a polymer. In this embodiment, (c) the oleophobic material may not be a polymeric material.

[0197] (c) The oleophobic material may have a weight average molecular weight of less than 600, preferably less than 500, in particular less than 400. In the context of this specification, average molecular weight denotes number average molecular weight.

[0198] The lipophobic substance (c) in the present invention can be selected from monosaccharides, oligosaccharides, C2 to C4 lower polyols, sugar alcohols, inorganic salts, and mixtures thereof.

[0199] Monosaccharides can include pentoses, hexoses, and heptoses, such as glucose, dextrose, galactose, mannose, and glucuronic acid.

[0200] Oligosaccharides can include disaccharides such as sucrose, lactose, maltose, and trisaccharides such as raffinose.

[0201] An example of a C2 to C4 lower polyol is glycerol.

[0202] Sugar alcohols can include erythritol, lactitol, maltitol, mannitol, and mixtures thereof.

[0203] Inorganic salts can include calcium, potassium, sodium, and magnesium salts of inorganic acids such as hydrochloric acid, nitric acid, carbonic acid, sulfuric acid, and phosphoric acid. Inorganic salts can include NaCl, MgCl, KNO, and mixtures thereof.

[0204] The (c) lipophobic substance may preferably be selected from monosaccharides, oligosaccharides, inorganic salts, and combinations thereof. More preferably, the (c) lipophobic substance may preferably be selected from glucose, sucrose, NaCl, and combinations thereof.

[0205] (c) The oleophobic material may be present in the composition according to the invention in an amount of 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.3% by weight or more, relative to the total weight of the composition.

[0206] (c) The oleophobic material may be present in the composition according to the invention in an amount of not more than 5% by weight, preferably not more than 3% by weight, more preferably not more than 1% by weight, relative to the total weight of the composition.

[0207] (c) The oleophobic substance may be present in the composition according to the invention in an amount ranging from 0.1% to 5% by weight, preferably from 0.2% to 3% by weight, more preferably from 0.3% to 1% by weight, relative to the total weight of the composition.

[0208] In another embodiment, (c) the oleophobic material may be present in the biopolymer composite of the hydrogel particle in an amount of 0.5% by weight or more, preferably 1% by weight or more, and more preferably 2% by weight or more, based on the total weight of the biopolymer composite.

[0209] (c) The oleophobic material may be present in the biopolymer composite of the hydrogel particle in an amount of 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less, based on the total weight of the biopolymer composite.

[0210] (c) The oleophobic material may be present in the hydrogel particle biopolymer composite in an amount ranging from 0.5% to 20% by weight, preferably from 1% to 15% by weight, and more preferably from 2% to 10% by weight, based on the total weight of the biopolymer composite.

[0211] In another embodiment, (c) the oleophobic material may be present in the xylogel particle biopolymer composite in an amount of 10% by weight or more, preferably 20% by weight or more, and more preferably 30% by weight or more, based on the total weight of the biopolymer composite.

[0212] (c) The oleophobic material may be present in the xylogel particle biopolymer composite in an amount of 70% by weight or less, preferably 60% by weight or less, and more preferably 50% by weight or less, based on the total weight of the biopolymer composite.

[0213] (c) The oleophobic material may be present in the xylogel particle biopolymer composite in an amount ranging from 10% to 70% by weight, preferably from 20% to 60% by weight, and more preferably from 30% to 50% by weight, based on the total weight of the biopolymer composite.

[0214] (pH adjuster) The biopolymer composites of the present invention may further comprise at least one pH adjusting agent. A single type of pH adjusting agent may be used, or different types of pH adjusting agents may be used in combination.

[0215] The pH adjuster may be at least one acidifying agent and / or at least one basifying agent (alkaline agent), and is different from (b) an acid having four or more acid groups and (c) an oleophobic substance.

[0216] The acidifying agent can be, for example, a mineral or organic acid, such as hydrochloric acid, phosphoric acid, a carboxylic acid, such as tartaric acid, citric acid, and lactic acid, or a sulfonic acid.

[0217] The basifying agent, i.e., alkaline agent, may be, for example, any inorganic or organic basic agent commonly used in cosmetics, such as ammonia; alkanolamines, such as mono-, di-, and tri-ethanolamine, isopropanolamine; sodium hydroxide and potassium hydroxide; urea, guanidine, and derivatives thereof; basic amino acids, such as lysine or arginine; and diamines, such as 1,3-propanediamine, having the following structure:

[0218] [ka]

[0219] [In the formula, R represents alkylene, such as propylene, optionally substituted with hydroxyl or a C1-C4 alkyl group; and R1, R2, R3, and R4 independently represent a hydrogen atom, an alkyl group, or a C1-C4 hydroxyalkyl group. Arginine, urea, and monoethanolamine may be preferred.

[0220] The acidifying or basifying agent may be present in an amount ranging from 0.1% to 5% by weight, preferably from 0.2% to 1% by weight, relative to the total weight of the composition.

[0221] The acidifying or basifying agent may be present in an amount ranging from 1% to 30% by weight, preferably from 2% to 25% by weight, based on the total weight of the biopolymer composite.

[0222] The pH of the biopolymer complex can be adjusted to, for example, 3.0 to 7.5, preferably 3.50 to 7.0, and more preferably 4.0 to 6.5.

[0223] {oily phase} Dispersion compositions according to the present invention comprise a continuous oily phase in which the biopolymer complexes are dispersed. The oily phase is generally comprised of an oily or fatty substance, such as an oil.

[0224] The oily phase may be composed of lipophilic components. The term "lipophilic" here means that the oily phase is hydrophobic and has a viscosity that is stable at room temperature (25°C) and atmospheric pressure (10 5 The solubility of a lipophilic substance in water can be measured at room temperature (25°C) and atmospheric pressure (10 5 Pa), it can be less than 1% by weight of water, for example less than 0.5% by weight, or less than 0.1% by weight.

[0225] The oily phase may be present in the composition according to the invention in an amount of greater than or equal to 50% by weight, preferably greater than or equal to 65% by weight, more preferably greater than or equal to 80% by weight relative to the total weight of the composition.

[0226] The oily phase may be present in the composition according to the invention in an amount of less than or equal to 99% by weight, preferably less than or equal to 96% by weight, more preferably less than or equal to 93% by weight relative to the total weight of the composition.

[0227] The oily phase may be present in the composition according to the invention in an amount ranging from 50% to 99% by weight, from 65% to 96% by weight, more preferably from 80% to 93% by weight relative to the total weight of the composition.

[0228] The oily phase of the present invention may comprise at least one oil and / or at least one surfactant.

[0229] · Oil The oily phase of the present invention may comprise at least one oil. Two or more oils may be used in combination. Thus, a single type of oil may be used, or different types of oils may be used in combination.

[0230] Here, "oil" is at atmospheric pressure (10 5 The oil used in the present invention preferably has a viscosity of 10 Pa at room temperature (25°C) and is in the form of a liquid, a paste (non-solid), or a solid. 5The oil is in the form of a liquid or paste at room temperature (25°C) under a temperature of 100°C (Pa). As the oil, oils commonly used in cosmetics can be used alone or in combination. These oils can be volatile or non-volatile.

[0231] The term "liquid" refers to a substance in a liquid state, i.e., at 25°C and atmospheric pressure (10°C), as opposed to a "solid" state. 5 Pa), is intended to mean that a material is capable of flowing under its own weight.

[0232] The oil is preferably heated at atmospheric pressure (10 5 The composition contains at least one oil that is in liquid form at room temperature (25°C) under high pressure (H2O).

[0233] Among the oils that can be used in the present invention, mention may be made of volatile or non-volatile oils, which may be hydrocarbon-based oils, especially of animal or vegetable origin, synthetic oils, silicone oils, fatty alcohols, or mixtures thereof.

[0234] For purposes of the present invention, "hydrocarbon-based oil" or "hydrocarbon oil" is intended to refer to an oil containing primarily hydrogen and carbon atoms, and optionally oxygen, nitrogen, sulfur, and / or phosphorus atoms. Hydrocarbon-based oils do not contain any silicon atoms.

[0235] For the purposes of the present invention, "silicone oil" is intended to mean an oil containing at least one silicon atom and in particular at least one Si-O group.

[0236] For purposes of the present invention, a "polar oil" is defined as an oil having a solubility parameter δ a is 0 (J / cm 3 ) 1 / 2 It is intended to mean an oil that is other than

[0237] In particular, "polar oil" is intended to mean an oil whose chemical structure is essentially formed or even consists of carbon and hydrogen atoms and which contains at least one highly electronegative heteroatom, such as an oxygen, nitrogen, silicon or phosphorus atom.

[0238] The definition and calculation of solubility parameters in the Hansen three-dimensional solubility space is described in the article "The three-dimensional solubility parameters" by CM Hansen, J. Paint Technol, Vol. 39, p. 105 (1967).

[0239] According to this Hansen space, - δ D characterizes the London dispersion force resulting from the formation of dipoles induced during molecular collisions, - δ p also characterized the Debye interaction forces between permanent dipoles and the Keesom interaction forces between induced and permanent dipoles, - δ h characterizes the strength of a particular interaction (e.g., hydrogen bonding, acid / base bonding, and donor / acceptor bonding), - δ a is the formula δ a =(δ p 2 +δ h 2 ) 1 / 2 is determined by.

[0240] Parameter δ p , δ h , δ D , and δ a is (J / cm 3 ) 1 / 2 It is expressed as:

[0241] Preferably, the polar oil used according to the invention has a δ between 4 and 9.1 a , preferably δ between 6 and 9.1 a , and even better, δ between 7.3 and 9.1 a It has.

[0242] The oil may be a non-polar oil, such as a hydrocarbon oil, a silicone oil, or the like; a polar oil, such as a vegetable or animal oil, and an ester or ether oil; or a mixture thereof.

[0243] The oil may be selected from the group consisting of oils of vegetable or animal origin, synthetic oils, silicone oils, hydrocarbon oils, and fatty alcohols.

[0244] Examples of vegetable oils include linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, camellia oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil, and mixtures thereof.

[0245] Examples of animal oils include squalene and squalane.

[0246] Examples of synthetic oils include alkane oils such as isododecane and isohexadecane, ester oils, ether oils, and artificial triglycerides.

[0247] The ester oil is preferably a saturated or unsaturated, linear or branched C1-C 26 Aliphatic mono- or polyacids and saturated or unsaturated, linear or branched C1-C 26 They are liquid esters of aliphatic monoalcohols or polyalcohols, the total number of carbon atoms in the ester being 10 or more.

[0248] In one embodiment of the present invention, in the case of esters of monoalcohols, at least one of the alcohol and the acid from which the esters of the present invention are derived is branched.

[0249] Ester oils of monoesters of monoacids and monoalcohols can be represented by the formula R1COOR2, where R1 represents the residue of a linear or branched, preferably linear, fatty acid containing 1 to 40 carbon atoms, preferably 6 to 24 carbon atoms, more preferably 10 to 20 carbon atoms, and R2 represents a hydrocarbon-based chain, especially a branched chain, containing 1 to 40 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, with the proviso that R1+R2 is 10 or more.

[0250] Among the monoesters of monoacids and monoalcohols, mention may be made of ethyl palmitate, ethylhexyl palmitate, isopropyl palmitate, dicaprylyl carbonate, alkyl myristates such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl neopentanoate, and isostearyl neopentanoate.

[0251] The ester oil is preferably selected from fatty acid ester oils.

[0252] C4~C 22 Dicarboxylic or tricarboxylic acids and C1-C 22 Esters with alcohols, and monocarboxylic, dicarboxylic or tricarboxylic acids with non-sugar C4-C 26 Esters with dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols may also be used.

[0253] Among these, mention may be made of diethyl sebacate, diisopropyl sebacate, bis(2-ethylhexyl) sebacate, diisopropyl adipate, di-n-propyl adipate, dioctyl adipate, bis(2-ethylhexyl) adipate, diisostearyl adipate, bis(2-ethylhexyl) maleate, triisopropyl citrate, triisocetyl citrate, triisostearyl citrate, glyceryl trilactate, glyceryl trioctanoate, trioctyldodecyl citrate, trioleyl citrate, neopentyl glycol diheptanoate, and diethylene glycol diisononanoate.

[0254] As ester oil, C6-C 30 , preferably C 12 ~C 22 Sugar esters and diesters of fatty acids can be used. The term "sugar" is recalled to mean an oxygen-carrying hydrocarbon-based compound containing at least four carbon atoms, with or without aldehyde or ketone functional groups, and containing some alcohol functional groups. These sugars can be monosaccharides, oligosaccharides, or polysaccharides.

[0255] Examples of suitable sugars that may be mentioned include sucrose (or sucrose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, as well as derivatives thereof, especially alkyl derivatives, such as methyl derivatives, for example methylglucose.

[0256] Sugar esters of fatty acids are, in particular, those esters of the sugars mentioned above with linear or branched, saturated or unsaturated C6-C 30 , preferably C 12 ~C 22 They can be selected from the group comprising esters or mixtures of esters with fatty acids, which, when unsaturated, can have 1 to 3 conjugated or non-conjugated carbon-carbon double bonds.

[0257] The esters according to this variant may also be chosen from monoesters, diesters, triesters, tetraesters and polyesters, and mixtures thereof.

[0258] These esters may be, for example, oleate, laurate, palmitate, myristate, behenate, coconut, stearate, linoleate, linolenate, caprate and arachidonic acid esters, or mixtures thereof, such as, inter alia, mixed esters of oleopalmitate, oleostearate and palmitostearate, and pentaerythrityl tetraethylhexanoate.

[0259] Examples of preferred ester oils include diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2-ethylhexyl octanoate, 2-ethylhexyl (caprylic / capric acid), methyl palmitate, ethyl palmitate, isopropyl palmitate, dicaprylyl carbonate, isononyl isononanoate, ethylhexyl palmitate, isohexyl laurate, hexyl laurate, isocetyl stearate, isopropyl isostearate, isopropyl myristate, isodecyl oleate, glyceryl tri(2-ethylhexanoate), pentaerythrityl tetra(2-ethylhexanoate), 2-ethylhexyl succinate, diethyl sebacate, and mixtures thereof.

[0260] Ether oils include dialkyl ethers, such as those represented by the formula: R 1 -OR 2 [In the formula, R 1 and R 2 each independently being a linear, branched or cyclic C4-C 24Alkyl groups, preferably C6 to C 18 Alkyl groups, more preferably C8 to C 12 indicates an alkyl group]. R 1 and R 2 It may be preferable that

[0261] Examples of the linear alkyl group include a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a behenyl group, a docosyl group, a tricosyl group, and a tetracosyl group.

[0262] Branched alkyl groups include 1-methylpropyl, 2-methylpropyl, t-butyl, 1,1-dimethylpropyl, 3-methylhexyl, 5-methylhexyl, 1-ethylhexyl, 2-ethylhexyl, 1-butylpentyl, 5-methyloctyl, 1-ethylhexyl, 2-ethylhexyl, 1-butylpentyl, 5-methyloctyl, 2-butyloctyl, isotridecyl, 2-pentylnonyl, and 2-hexyldecyl. Examples of the alkyl groups include methyl methyl esters, isostearyl groups, 2-heptylundecyl groups, 2-octyldodecyl groups, 1,3-dimethylbutyl groups, 1-(1-methylethyl)-2-methylpropyl groups, 1,1,3,3-tetramethylbutyl groups, 3,5,5-trimethylhexyl groups, 1-(2-methylpropyl)-3-methylbutyl groups, 3,7-dimethyloctyyl groups, and 2-(1,3,3-trimethylbutyl)-5,7,7-trimethyloctyl groups.

[0263] Examples of the cyclic alkyl group include a cyclohexyl group, a 3-methylcyclohexyl group, and a 3,3,5-trimethylcyclohexyl group.

[0264] Examples of artificial triglycerides include caprylic / caprylyl glyceride, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, capric / caprylic triglyceride, and capric / caprylic / linolenic triglyceride.

[0265] Examples of silicone oils include linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane; cyclic organopolysiloxanes such as cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; and mixtures thereof.

[0266] Preferably, the silicone oil is chosen from polydialkylsiloxane fluids, especially polydimethylsiloxane fluids (PDMS) and polyorganosiloxane fluids containing at least one aryl group.

[0267] These silicone oils can also be organically modified.The organically modified silicone that can be used according to the present invention is the silicone oil as defined above, and in its structure, contains one or more organic functional groups bonded via hydrocarbon-based groups.Organopolysiloxane is more fully defined in Walter Noll, Chemistry and Technology of Silicones (1968), Academic Press.Organopolysiloxane can be volatile or non-volatile.

[0268] If volatile, the silicones are more particularly chosen from those having a boiling point between 60°C and 260°C, and even more particularly from:

[0269] (i) Cyclic polydialkylsiloxanes containing 3 to 7, preferably 4 to 5, silicon atoms, such as octamethylcyclotetrasiloxane, sold in particular under the names Volatile Silicone® 7207 by Union Carbide or Silbione® 70045 V2 by Rhodia, decamethylcyclopentasiloxane, sold in particular under the names Volatile Silicone® 7158 by Union Carbide and Silbione® 70045 V5 by Rhodia, and dodecamethylcyclopentasiloxane, sold in particular under the name Silsoft 1217 by Momentive Performance Materials, and mixtures thereof. Cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type, such as those of the formula:

[0270] [ka]

[0271] Mention may also be made of Silicone Volatile® FZ 3109 sold by Union Carbide, of the company AB.

[0272] Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as a 50 / 50 mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol, and a mixture of octamethylcyclotetrasiloxane and oxy-1,1'-bis(2,2,2',2',3,3'-hexatrimethylsilyloxy)neopentane.

[0273] (ii) Contains 2 to 9 silicon atoms and has a density of 5 × 10 at 25 °C -6 m 2Linear volatile polydialkylsiloxanes with a viscosity of 0.1 / s or less. An example is decamethyltetrasiloxane, sold in particular by Toray Silicone under the name SH 200. Silicones belonging to this category are also described in the article published by Todd & Byers, Volatile Silicone Fluids for Cosmetics, Vol. 91, January 1976, pp. 27-32. The viscosity of silicones is measured at 25°C according to ASTM Standard 445, Appendix C.

[0274] Non-volatile polydialkylsiloxanes can also be used, these being more particularly chosen from polydialkylsiloxanes, among which mention can be made mainly of polydimethylsiloxanes containing trimethylsilyl end groups.

[0275] Among these polydialkylsiloxanes, mention may be made, but is not limited to, the following commercially available products: Silbione® oils of the 47 and 70 047 series or Mirasil® oils sold by the company Rhodia, for example 70 047 V 500 000 oil, oils of the Mirasil® series sold by the company Rhodia; - Dow Corning 200 series oils, e.g. 60000mm 2 DC200 having a viscosity of 1 / s, and Viscasil® oils manufactured by General Electric and certain oils of the SF series manufactured by General Electric (SF 96, SF 18).

[0276] Mention may also be made of polydimethylsiloxanes containing dimethylsilanol end groups, known under the name dimethiconol (CTFA), such as the 48 series oils from Rhodia.

[0277] Among the silicones containing aryl groups, mention may be made of polydiarylsiloxanes, especially polydiphenylsiloxanes, and polyalkylarylsiloxanes, such as phenylsilicone oils.

[0278] Phenylsilicone oils have the following formula:

[0279] [ka]

[0280] [In the formula, R1~R 10 are, independently of one another, saturated or unsaturated, linear, cyclic or branched C1-C 30 Hydrocarbon groups, preferably C1-C 12 a hydrocarbon group, more preferably a C1 to C6 hydrocarbon group, in particular a methyl, ethyl, propyl or butyl group; m, n, p, and q are each independently an integer of 0 to 900 inclusive, preferably 0 to 500 inclusive, and more preferably 0 to 100 inclusive; However, the sum n+m+q is non-zero. The phenyl silicones may be selected from the following:

[0281] Examples that may be mentioned include products sold under the following names: - Silbione® oils from Rhodia, 70 641 series; Rhodorsil® 70 633 and 763 series oils from Rhodia; - Dow Corning 556 Cosmetic Grade Fluid oil, manufactured by Dow Corning; - PK series silicones from Bayer, e.g. product PK20, - Certain oils of the SF series manufactured by General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.

[0282] Phenyl silicone oils include phenyl trimethicone (wherein R to R 10 is methyl, p, q and n=0, and m=1).

[0283] The organically modified silicone fluids may contain, inter alia, polyethyleneoxy and / or polypropyleneoxy groups. Mention may thus be made of silicone KF-6017 proposed by Shin-Etsu Chemical Co., Ltd., and oils Silwet® L722 and L77 from Union Carbide.

[0284] The hydrocarbon oil may be selected from: - Linear or branched, optionally cyclic C6-C 16 Lower alkanes. Examples that may be mentioned include hexane, undecane, dodecane, tridecane, and isoparaffins such as isohexadecane, isododecane and isodecane. - linear or branched hydrocarbons containing more than 16 carbon atoms, such as liquid paraffin, liquid petroleum jelly, polydecene and hydrogenated polyisobutenes, such as Parleam®, and squalane. - Alkanes, for example mixtures of C9-12 alkanes, C10-13 alkanes, C13-14 alkanes, C13-15 alkanes, C14-17 alkanes, C14-19 alkanes, C15-19 alkanes, C15-23 alkanes, C18-21 alkanes, C8-9 alkanes / cycloalkanes, C9-10 alkanes / cycloalkanes, C9-11 alkanes / cycloalkanes, C9-16 alkanes / cycloalkanes, C10-12 alkanes / cycloalkanes, C11-14 alkanes / cycloalkanes, C11-15 alkanes / cycloalkanes, and C12-13 alkanes / cycloalkanes.

[0285] Preferred examples of hydrocarbon oils include linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oils (e.g., liquid paraffin), paraffin, petrolatum or petroleum, naphthalene, etc.; hydrogenated polyisobutene, isoeicosane, and decene / butene copolymers; and mixtures thereof.

[0286] The term "aliphatic" in aliphatic alcohols means containing a relatively large number of carbon atoms. Thus, alcohols having 4 or more, preferably 6 or more, and more preferably 12 or more carbon atoms are included within the scope of aliphatic alcohols. Fatty alcohols can be saturated or unsaturated. Fatty alcohols can be linear or branched.

[0287] The aliphatic alcohol may have the structure R-OH, where R is selected from saturated and unsaturated, linear and branched groups containing from 4 to 40 carbon atoms, preferably from 6 to 30 carbon atoms, and more preferably from 12 to 20 carbon atoms. In at least one embodiment, R is selected from C 12 ~C 20 Alkyl groups, and C 12 ~C 20 R may be selected from the group consisting of alkyl, aryl ...

[0288] The aliphatic alcohols can have the structure R-OH, where R is a saturated or unsaturated linear group containing from 4 to 40 carbon atoms, preferably from 6 to 30 carbon atoms, and more preferably from 12 to 20 carbon atoms.

[0289] The aliphatic alcohols can have the structure R-OH, where R is a saturated or unsaturated branched group containing from 4 to 40 carbon atoms, preferably from 6 to 30 carbon atoms, and more preferably from 12 to 24 carbon atoms.

[0290] Examples of fatty alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, oleyl alcohol, linoleyl alcohol, palmitoleyl alcohol, arachidonyl alcohol, erucyl alcohol, and mixtures thereof.

[0291] The aliphatic alcohol is preferably a saturated aliphatic alcohol. Thus, the aliphatic alcohol may be a linear or branched, saturated or unsaturated C6-C 30 Alcohols, preferably linear or branched, saturated C6-C 30 Alcohols, more preferably linear or branched saturated C 12 ~C 20 The alcohol may be selected from:

[0292] The term "saturated fatty alcohol" as used herein means an alcohol having a long, saturated aliphatic carbon chain. A saturated fatty alcohol is any linear or branched, saturated C-C 30 Preferably, the alcohol is selected from linear or branched saturated C6-C aliphatic alcohols. 30 Among fatty alcohols, linear or branched saturated C 12 ~C 20 Fatty alcohols may be preferably used. Any linear or branched saturated C 16 ~C 20 Fatty alcohols are more preferably used. 16 ~C 20 Aliphatic alcohols are even more preferably used.

[0293] Examples of saturated fatty alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof. In one embodiment, cetyl alcohol, stearyl alcohol, octyldodecanol, hexyldecanol, or mixtures thereof (e.g., cetearyl alcohol), and behenyl alcohol can be used as saturated fatty alcohols.

[0294] It is also preferred that the oil is chosen from oils having a molecular weight of less than 600 g / mol.

[0295] Preferably, the oil has a low molecular weight, such as less than 600 g / mol, and is composed of short chain hydrocarbons (C1 to C 12 ), ester oils (e.g., isopropyl myristate, isopropyl palmitate, isononyl isononanoate, and ethylhexyl palmitate), silicone oils (e.g., volatile silicones such as cyclohexasiloxane), hydrocarbon oils (e.g., isododecane, isohexadecane, and squalane), branched and / or unsaturated fatty alcohols (C 12 ~C 30 ) type oils, such as octyldodecanol and oleyl alcohol, and ether oils such as dicaprylyl ether.

[0296] The oil is preferably selected from polar oils, more preferably from ester oils, fatty alcohols, and combinations thereof. It is further preferred that the oil comprises both ester oils and fatty alcohols, in particular monoesters of monoacids and monoalcohols represented by the formula R1COOR2, where R1 represents a residue of a linear fatty acid containing 10 to 20 carbon atoms and R2 represents a branched hydrocarbon chain containing 2 to 8 carbon atoms, and fatty alcohols having the structure R—OH, where R is selected from saturated branched groups containing 4 to 40 carbon atoms, preferably 6 to 30 carbon atoms, more preferably 12 to 20 carbon atoms.

[0297] The oil may be preferably selected from oils of vegetable or animal origin.In another embodiment, the oil is preferably selected from vegetable oils, such as linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, camellia oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil, and mixtures thereof.

[0298] The amount of oil in the composition according to the invention may be greater than or equal to 50% by weight, preferably greater than or equal to 65% by weight, more preferably greater than or equal to 75% by weight relative to the total weight of the composition.

[0299] The amount of oil in the composition according to the invention may be up to 98% by weight, preferably up to 95% by weight, more preferably up to 93% by weight, relative to the total weight of the composition.

[0300] The amount of oil in the composition according to the invention may range from 50% to 98% by weight, preferably from 65% to 95% by weight, more preferably from 75% to 93% by weight, relative to the total weight of the composition.

[0301] Surfactants The oily phase of the present invention may contain at least one surfactant. Two or more surfactants may be used in combination. Thus, a single type of surfactant may be used, or different types of surfactants may be used in combination.

[0302] The surfactants may be selected from amphoteric, anionic, cationic, or nonionic surfactants, used alone or in mixtures. Preferably, the oily phase comprises at least one nonionic surfactant.

[0303] The surfactants are preferably derived from natural sources.

[0304] Examples of nonionic surfactants that can be used in the compositions according to the invention include polyethoxylated or polyglycerolated fatty alcohols, such as adducts of ethylene oxide on lauryl alcohol, especially those containing from 9 to 50 oxyethylene units (INCI names Laureth-9 to Laureth-50), in particular Laureth-9; esters of polyols with fatty acids having a saturated or unsaturated chain, for example containing from 8 to 24 carbon atoms, and their oxyalkylenated derivatives, i.e. derivatives containing oxyethylene and / or oxypropylene units, such as esters of glycerol with C8-C 24 Esters of fatty acids and their oxyalkylenated derivatives, in particular polyoxyethylenated glyceryl stearates (mono-, di-, and / or tri-stearates), for example, PEG-20 glyceryl triisostearate; esters of sugars and C8-C 24 Esters with fatty acids and their oxyalkylenated derivatives, e.g., C8-C 24 Polyethoxylated sorbitol esters of fatty acids, in particular polysorbate 80, for example the product sold under the name "TWEEN 80" by Croda; sugars and C8-C 24 Ethers with fatty alcohols, such as caprylyl / capryl glucoside; hydrophobized polysaccharides; polyoxyethylene alkyl ethers; polyoxyethyleneoxypropylene alkyl ethers; fatty acid alkanolamides; alkylamine oxides; alkyl polyglycosides and silicone surfactants, such as polydimethylsiloxanes containing oxyethylene and / or oxypropylene groups, for example, PEG-10 dimethicone, bis-PEG / PPG-14 / 14 dimethicone, bis-PEG / PPG-20 / 20 dimethicone, and PEG / PPG-20 / 6 dimethicone; and polyglyceryl fatty acid esters, such as polyglyceryl-4 caprate, polyglyceryl-10 laurate, polyglyceryl-6 dicaprate, polyglyceryl-6 dicaprate, polyglyceryl-6 dioleate, polyglyceryl-6 caprylate, polyglyceryl-2 oleate, and polyglyceryl-6 polyricinoleate; and mixtures thereof.

[0305] In addition, as a nonionic surfactant, a compound represented by the following general formula (1): RO-(G) x (1) wherein R represents a branched and / or unsaturated alkyl group containing 14 to 24 carbon atoms, G represents a reducing sugar containing 5 or 6 carbon atoms, x represents a value in the range of 1 to 10, preferably 1 to 4, and G represents, in particular, glucose, fructose, or galactose. Examples of this type of alkyl polyglycoside include alkyl polyglucosides (G=glucose in formula (I)), particularly alkyl polyglycosides represented by formula (I) [wherein R is more particularly an oleyl group (an unsaturated C 18 group) or isostearyl group (saturated C 18 Group), G represents glucose, and x is a value in the range of 1 to 2, particularly isostearyl glucoside, oleyl glucoside, and mixtures thereof. The alkyl polyglucosides can be used in mixtures with co-emulsifiers, more particularly with fatty alcohols, in particular fatty alcohols having the same fatty chain as that of the alkyl polyglucoside, i.e., fatty alcohols containing 14 to 24 carbon atoms and having a branched and / or unsaturated chain, such as isostearyl alcohol when the alkyl polyglucoside is isostearyl glucoside, or oleyl alcohol when the alkyl polyglucoside is oleyl glucoside.

[0306] In addition, according to the invention, it is particularly advantageous to use aliphatic alcohols together with alkyl polyglycosides whose alkyl moiety is identical to that of the selected aliphatic alcohol. Among particularly preferred aliphatic alcohol / alkyl polyglycoside mixtures, mention may be made of the products sold under the name Montanov® by the company SEPPIC, such as the following mixture: Cetylstearyl alcohol / cocoyl glucoside (Montanov 82®), arachidyl alcohol and behenyl alcohol / arachidyl glucoside (Montanov 802®), myristyl alcohol / myristyl glucoside (Montanov 14®), cetearyl alcohol / cetearyl glucoside (Montanov 68®), -C 14 ~C 22 Alcohol / C 12 ~C 20 Alkyl glucoside (Montanov L®), cocoyl alcohol / cocoyl glucoside (Montanov S®), and - Isostearyl alcohol / isostearyl glucoside (Montanov WO 18®).

[0307] In the hydrophobized polysaccharide, the polysaccharide may be selected from polyglucose or polyfructose. Preferred polyglucoses are selected from cellulose, methylcellulose, hydroxyethylcellulose, amylose, amylopectin, and dextrin. Preferred polyfructose is inulin. In a preferred embodiment of the present invention, the hydrophobized polysaccharide as a nonionic surfactant is hydrophobized inulin.

[0308] In the hydrophobized polysaccharides, the hydrophobic chains that can be attached or grafted to the polysaccharide backbone can be, in particular, linear or branched, saturated or unsaturated hydrocarbon chains having 1 to 50 carbon atoms, such as alkyl, arylalkyl, alkylaryl and alkylene groups, divalent cycloaliphatic groups, or organopolysiloxane chains. These hydrocarbon or organopolysiloxane chains may, in particular, contain one or more ester, amide, urethane, carbamate, thiocarbamate, urea, thiourea, and / or sulfonamide functional groups. In particular, illustrative but non-limiting examples of hydrophobized inulin that can be used in the compositions according to the invention include stearoyl inulin, such as that sold under the name Lifidrem INST by Engelhard and under the name Rheopearl INS by Ciba, palmitoyl inulin, undecylenoyl inulin, such as that sold under the name Lifidrem INUK and Lifidrem INUM by Engelhard, and inulin lauryl carbamate, such as that sold under the name Inutec SP1 by Orafti.

[0309] In one embodiment of the present invention, the surfactants useful in the present invention have an HLB value of 8.0 or less. The term HLB ("hydrophilic-lipophilic balance") is well known to those skilled in the art and describes the ratio between the hydrophilic and lipophilic portions of a molecule.

[0310] In one preferred embodiment, the surfactants useful in the present invention are selected from polyglyceryl fatty acid esters, especially polyglyceryl fatty acid esters having an HLB value of 8 or less.

[0311] The polyglyceryl fatty acid esters may be selected from mono-, di-, tri- and higher esters of saturated or unsaturated fatty acids.

[0312] The fatty acid portion of the polyglyceryl fatty acid ester may contain 10 or more carbon atoms, preferably 12 or more carbon atoms, more preferably 14 or more carbon atoms, even more preferably 16 or more carbon atoms, and may contain 26 or fewer carbon atoms, preferably 24 or fewer carbon atoms, more preferably 22 or fewer carbon atoms, even more preferably 20 or fewer carbon atoms.

[0313] The fatty acids for the fatty acid portion of the polyglyceryl fatty acid ester may be saturated or unsaturated and may be selected from lauric acid, myristic acid, stearic acid, isostearic acid, and oleic acid.

[0314] Preferably, the polyglyceryl fatty acid ester contains 10 or fewer glycerol units, preferably 8 or fewer glycerol units, more preferably 6 or fewer glycerol units, and even more preferably 4 or fewer glycerol units. Preferably, the polyglyceryl fatty acid ester contains 2 glycerol units.

[0315] Polyglyceryl fatty acid esters include PG2 stearate (HLB: 5.0), PG2 distearate (HLB: 4), PG2 isostearate (HLB: 4.7), PG2 diisostearate (HLB: 3.2), PG2 triisostearate (HLB: 3), PG2 sesquiisostearate (HLB: approx. 4), PG2 oleate (HLB: 5.5), PG2 sesquioleate (HLB: 5.3), PG3 distearate (HLB: 5), and diisostearate. It may be selected from the group consisting of PG3 stearate (HLB: 5), PG3 dicoconut fatty acid (HLB: 7), PG5 hexastearate (HLB: 4.0), PG5 trioleate (HLB: 7.0), PG10 pentaoleate (HLB: 6.4), PG2 sesquicaprylate (HLB: about 8), PG6 distearate (HLB: 8), PG10 tristearate (HLB: 8), PG10 triisostearate (HLB: 8), and mixtures thereof.

[0316] Alternatively, the fatty acid portion of the polyglyceryl fatty acid ester may be a polymer of saturated or unsaturated fatty acid.When the fatty acid has a carboxylic acid group and a hydroxyl group, the polymer may be a polycondensate of fatty acid, which can be formed by the reaction of the carboxylic acid group or the hydroxyl group of one fatty acid with the hydroxyl group and the carboxylic acid group of another fatty acid, respectively.Therefore, the fatty acid portion of the polyglyceryl fatty acid ester may be a polycondensate of saturated or unsaturated hydroxy acid.In other words, the polyglyceryl fatty acid ester may be a polyglyceryl ester, preferably a polyglyceryl monoester, of the polycondensate of saturated or unsaturated hydroxy acid.

[0317] When the fatty acid portion of the polyglyceryl fatty acid ester is polymeric, the fatty acid portion of the polyglyceryl fatty acid ester may contain 25 or more carbon atoms, preferably 30 or more carbon atoms, more preferably 35 or more carbon atoms, and may contain 90 or less carbon atoms, preferably 72 or less carbon atoms, more preferably 54 or less carbon atoms.

[0318] Ricinoleic acid is an example of a hydroxyl acid, particularly an unsaturated hydroxyl acid, and has a carboxylic acid group and a hydroxyl group. Therefore, the fatty acid portion of the polyglyceryl fatty acid ester can be formed by polycondensation of ricinoleic acid to produce polyricinoleate. Therefore, the polyglyceryl fatty acid ester can be polyglycerol polyricinoleate (PGPR), i.e., a polyglyceryl ester of polyricinoleate, preferably a polyglyceryl monoester.

[0319] The polyglyceryl fatty acid ester may be selected from the group consisting of PG3 polyricinoleate, PG4 polyricinoleate, PG5 polyricinoleate, PG6 polyricinoleate (HLB: 3.5), and mixtures thereof.

[0320] The surfactant may be present in the composition according to the invention in an amount of at least 0.1% by weight, preferably at least 1% by weight, more preferably at least 3% by weight relative to the total weight of the composition.

[0321] The surfactant may be present in the composition according to the invention in an amount of up to 20% by weight, preferably up to 15% by weight, more preferably up to 10% by weight relative to the total weight of the composition.

[0322] The surfactant may be present in the composition according to the invention in an amount ranging from 0.1% to 20% by weight, preferably from 1% to 15% by weight, more preferably from 3% to 10% by weight, relative to the total weight of the composition.

[0323] Adjuvants The compositions according to the invention may further comprise one or more adjuvants common in the fields of cosmetics and dermatology chosen from a physiologically acceptable medium, in particular a water-soluble organic solvent; a cationic, anionic, nonionic, amphoteric or zwitterionic polymer, or mixtures thereof; a gelling agent; a thickening agent; a penetrating agent; an antidandruff agent; an antioxidant; a moisturizing agent; an emollient; a free radical scavenger; a suspending agent; a sequestering agent; a buffer; a fragrance; an emollient; a dispersing agent; a dye and / or pigment; a film-forming agent; a stabilizer; a preservative; a co-preservative; an opacifier; an essential oil; an agent capable of causing a cooling sensation; and mixtures thereof.

[0324] Naturally, the skilled person will carefully select the optional adjuvants to be added to the compositions according to the invention so that the advantageous properties inherently associated with the compositions according to the invention are not or substantially not adversely affected by the envisaged addition.

[0325] The adjuvant may be present in the composition of the present invention in an amount preferably in the range of 0.01% to 20% by weight, preferably 0.1% to 10% by weight, more preferably 0.2% to 5% by weight, relative to the total weight of the composition.

[0326] [Preparation] The dispersion composition according to the present invention can be prepared by mixing the above-described components by any type of preparation method known to those skilled in the art. Preferably, the dispersion composition according to the present invention can be obtained by a preparation method for preparing an inverse mini-emulsion.

[0327] Therefore, the present invention also relates to a method for preparing a dispersion composition comprising a continuous oily phase and a plurality of biopolymer complexes dispersed in the oily phase, the biopolymer complexes comprising (a) at least one biopolymer, (b) at least one acid having four or more acidic groups, and (c) at least one oleophobic substance, by a reverse miniemulsion method.

[0328] In one embodiment, a method for preparing a dispersion composition comprising hydrogel particles of biopolymer conjugates according to the present invention comprises: (i) separately preparing an oily phase and an aqueous phase, wherein the aqueous phase comprises: (a) at least one biopolymer; (b) at least one acid having four or more acidic groups, and (c) at least one oleophobic substance and (ii) mixing an aqueous phase and an oily phase to obtain a mixture; (iii) emulsifying the mixture to obtain a dispersion composition comprising a continuous oily phase and a plurality of biopolymer complexes dispersed in the oily phase; may include:

[0329] Components (a) to (c), the oily phase, and the biopolymer complex are as described above.

[0330] The aqueous phase may further comprise an aqueous medium, such as water, and / or a pH adjuster, as described above.

[0331] The emulsifying step in step (iii) may be carried out by stirring and / or sonication.

[0332] The stirring method is not particularly limited as long as it can provide a strong shear force. For example, a magnetic stirrer, a homogenizer, or a high-pressure homogenizer can be used. In one embodiment, stirring is performed at 500 to 6,000 rpm for 5 to 180 minutes at room temperature (25°C) and atmospheric pressure (10 5 It is carried out in (Pa).

[0333] The conditions for sonication were room temperature (25°C) and atmospheric pressure (10 5 The sonication magnitude can be in the range of 1,000 W / L to 20,000 W / L (at 1000 W / L / s).

[0334] In one embodiment, the emulsifying step in step (iii) is carried out by both stirring and sonication. In a preferred embodiment, the emulsifying step in step (iii) is carried out by stirring followed by sonication.

[0335] After the biopolymer composite in the form of hydrogel particles is obtained, the method according to the present invention may further comprise the step of (iv) evaporating the aqueous medium, e.g., water, from the hydrogel particles to produce the biopolymer composite in the form of xylogel particles.

[0336] Thus, a method for preparing a dispersion composition comprising xerogel particles of biopolymer composites according to the present invention comprises: (i) separately preparing an oily phase and an aqueous phase, wherein the aqueous phase comprises: (a) at least one biopolymer; (b) at least one acid having four or more acidic groups, and (c) at least one oleophobic substance and (ii) mixing an aqueous phase and an oily phase to obtain a mixture; (iii) emulsifying the mixture and then sonicating the mixture to obtain a dispersion composition comprising a continuous oily phase and a plurality of biopolymer complexes dispersed in the oily phase; (iv) evaporating the aqueous phase from the biopolymer complex to obtain a dispersion composition comprising the biopolymer complex in the form of xylogel particles; may include:

[0337] Evaporation can be used to remove the dispersion composition, e.g., 10 3 Pa~10 5 The reaction can be carried out by placing the mixture under a temperature of 10°C to 100°C under a pressure of 10 Pa for 5 to 120 minutes.

[0338] According to a preferred embodiment, the dispersion composition comprises a continuous oily phase and a plurality of biopolymer complexes dispersed in the oily phase, the biopolymer complexes comprising, based on the total weight of the composition: (a) 0.01% by mass to 5% by mass of at least one biopolymer selected from polyamino acids, cationic polysaccharides, and anionic polysaccharides; (b) 0.001% by mass to 0.5% by mass of at least one acid having four or more acidic groups selected from phosphoric acids and carboxylic acids, preferably phosphoric acids; and (c) 0.1% to 5% by mass of at least one lipophobic substance selected from monosaccharides, oligosaccharides, C2 to C4 lower polyols, sugar alcohols, inorganic salts, and mixtures thereof Includes:

[0339] According to another preferred embodiment, the dispersion composition comprises a continuous oily phase and a plurality of biopolymer complexes dispersed in the oily phase, the biopolymer complexes comprising, based on the total weight of the composition: (a) 0.075% to 1% by weight of at least one biopolymer selected from polylysine, collagen, gelatin, chitosan, xanthan gum, and hyaluronic acid and its salts, and combinations thereof; (b) 0.003% to 0.05% by weight of at least one acid having four or more acidic groups selected from inositol pentaphosphate, phytic acid, and combinations thereof; and (c) 0.3% to 1% by weight of at least one lipophobic substance selected from monosaccharides, oligosaccharides, inorganic salts, and combinations thereof Includes:

[0340] [Cosmetic methods and use] The present invention relates to a cosmetic method for caring for and / or conditioning keratinous materials, such as hair, scalp and / or skin, preferably hair, comprising the step of applying a composition according to the present invention to the keratinous materials.

[0341] By cosmetic method is meant here a non-therapeutic cosmetic method for caring for and / or conditioning keratinous materials.

[0342] The applying step can be carried out by any conventional means, for example, by hand, by applicators such as sprays and brushes, etc. The applying step can also be a topical application step.

[0343] The composition according to the present invention is intended to be used as a leave-on cosmetic composition.Therefore, the cosmetic method according to the present invention does not include a step of rinsing or washing off the applied composition from keratinous materials after the application step.In one embodiment of the present invention, the cosmetic method according to the present invention does not include a step of rinsing or washing off the applied composition within 1 hour, preferably within 2 hours, more preferably within 4 hours, and even more preferably within 8 hours after the application step.

[0344] Furthermore, the present invention also relates to the use of the composition according to the invention in the cosmetics field, in particular for caring for and / or conditioning keratinous materials. [Example]

[0345] The present invention will now be described in more detail by way of examples, which should not be construed as limiting the scope of the present invention.

[0346] (Compositions according to Examples 1 and 2 and Comparative Examples 1 to 6) Each of the compositions according to Examples 1 and 2 and Comparative Examples 1 to 6 was prepared using the ingredients listed in Tables 1 and 2 below. First, corn oil and polyglycerol polyricinoleate were mixed to prepare an oily phase. An aqueous phase was prepared separately by mixing the ingredients listed as "aqueous phase" in Tables 1 and 2, and then added to the oily phase. The resulting mixture was stirred at 1,000 rpm for 1 hour at room temperature and then sonicated for 10 minutes at 6,000 W / L in an ice bath to obtain a dispersion composition containing a biopolymer complex dispersed in a continuous oily phase. All numerical values ​​for the amounts of ingredients listed in Tables 1 and 2 are based on the "mass %" of the raw materials relative to the total mass of the composition.

[0347] The dispersion composition according to Example 1 was then heated at 50°C for 70 minutes under a reduced pressure of 36,000 Pa to obtain a composition containing xerogel particles of a biopolymer matrix dispersed in an oily phase. The composition had a transparent appearance. TEM images showed that the average size of the xerogel particles was 154±98 nm. The estimated water content in the resulting composition containing xerogel particles was approximately 0% by mass. The water content was estimated by infrared spectroscopy.

[0348] [evaluation] (stability) The compositions of Examples 1 and 2 and Comparative Examples 1 to 6 were each heated at room temperature (25°C) under atmospheric pressure (10 5 The compositions were left to stand under a constant temperature of 100°C (Pa) for one week, and the appearance was visually evaluated. "Stable" here means that the dispersed biopolymer composite maintained its shape and / or form after one week. The stability of the compositions was ranked according to the following criteria: Good: The composition maintained its shape and / or form after one week. Poor: A small number of particle agglomerations were observed. Very poor: particle settling was observed.

[0349] (sensory evaluation) 50 mg of each of the compositions of Examples 1 and 2 and Comparative Examples 1 to 6 was applied to the inner forearms of eight experts in the laboratory. Sensory evaluation was performed by the eight experts on the following five-point scale for "stickiness on the skin" and "shininess on the skin" (stickiness: 1: very sticky to 5: not very sticky, shininess: 1; shiny to 5: not very shiny). The scores thus obtained were averaged.

[0350] The results are shown in Tables 1 and 2 below.

[0351] [Table 1]

[0352] [Table 2]

[0353] As can be seen from the results shown in the table above, the compositions according to Examples 1 and 2, which comprise a dispersed biopolymer composition comprising a combination of (a) biopolymer, i.e., chitosan or sodium hyaluronate, (b) acid having four or more acidic groups, i.e., phytic acid, and (c) an oleophobic substance, were able to exhibit a very stable dispersion form despite containing a high concentration of (a) biopolymer. In addition, these compositions were able to provide the skin with a less sticky feeling and a less shiny appearance.

[0354] Additionally, although the results are not shown in the table, the composition containing xerogel particles according to Example 1 also exhibited good stability.

[0355] In contrast, the compositions of Comparative Examples 1 to 3, which did not contain any of components (a) to (c), caused a sticky feel and a shiny appearance on the skin. In addition, these compositions exhibited extremely poor stability. Furthermore, the compositions of Comparative Examples 4 to 6, which contained an acid having three or fewer acidic groups instead of the (b) acid of the present invention, also exhibited poor stability. In addition, they failed to provide an improved sticky feel or a less shiny appearance to the skin.

[0356] Therefore, it can be concluded that the composition according to the present invention is very stable for various applications, such as cosmetic, pharmaceutical and coating applications.

Claims

1. 1. A dispersion composition comprising a continuous oily phase and a plurality of biopolymer complexes dispersed in the oily phase, the biopolymer complexes comprising: (a) at least one biopolymer; (b) at least one acid having four or more acidic groups, and (c) at least one oleophobic substance 1. A dispersion composition comprising:

2. 2. The composition of claim 1, wherein the (a) biopolymer is selected from polyamino acids, cationic polysaccharides, and anionic polysaccharides.

3. 3. The composition of claim 1, wherein the (a) biopolymer is selected from polylysine, collagen, gelatin, chitosan, xanthan gum, and hyaluronic acid and its salts, and combinations thereof.

4. 4. The composition according to claim 1, wherein the acid having four or more acidic groups is selected from phosphoric acids and carboxylic acids, preferably phosphoric acids.

5. 5. The composition of claim 1, wherein (b) the acid having four or more acidic groups is selected from inositol pentaphosphate, phytic acid, and combinations thereof.

6. (c) The lipophobic substance is a monosaccharide, an oligosaccharide, or a C 2 ~C 4 6. The composition of claim 1, wherein the additive is selected from lower polyols, sugar alcohols, inorganic salts, and mixtures thereof.

7. 7. The composition of claim 1, wherein (c) the lipophobic substance is selected from monosaccharides, oligosaccharides, inorganic salts, and combinations thereof.

8. 8. The composition according to any one of claims 1 to 7, wherein the (a) biopolymer is present in an amount ranging from 0.01% to 5% by weight, preferably from 0.05% to 3% by weight, more preferably from 0.075% to 1% by weight, relative to the total weight of the composition.

9. 9. The composition of claim 8, wherein (b) the acid having four or more acidic groups is present in an amount ranging from 0.001% to 0.5% by weight, preferably from 0.002% to 0.1% by weight, and more preferably from 0.003% to 0.05% by weight, relative to the total weight of the composition.

10. 10. The composition according to any one of claims 1 to 9, wherein (c) the oleophobic substance is present in an amount ranging from 0.1% to 5% by weight, preferably from 0.2% to 3% by weight, more preferably from 0.3% to 1% by weight, relative to the total weight of the composition.

11. 11. The composition of claim 1, wherein the biopolymer complex is in the form of hydrogel particles or xerogel particles.

12. 12. The composition according to any one of claims 1 to 11, which is a cosmetic composition, in particular a topical cosmetic composition for caring for and / or conditioning keratinous materials, such as the skin.

13. 12. The composition according to any one of claims 1 to 11, which is a pharmaceutical composition, in particular a pharmaceutical composition for drug delivery, a coating composition, or an ink composition.

14. 14. A method for preparing the dispersion composition of any one of claims 1 to 13, comprising: (i) A step of separately preparing an oily phase and an aqueous phase, wherein the aqueous phase is (a) at least one biopolymer; (b) at least one acid having four or more acidic groups, and (c) at least one oleophobic substance and (ii) mixing an aqueous phase and an oily phase to obtain a mixture; (iii) emulsifying the mixture to obtain a dispersion composition comprising a continuous oily phase and a plurality of biopolymer complexes dispersed in the oily phase; A method comprising:

15. A cosmetic method for caring for and / or conditioning keratinous materials, such as skin, comprising the step of applying a composition according to any one of claims 1 to 13 to the keratinous materials.

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