EP2964337A2

EP2964337A2 - Eggshell compositions, preparations and uses

Info

Publication number: EP2964337A2
Application number: EP14712218.8A
Authority: EP
Inventors: Elzbieta Ewa Brand-Garnys
Original assignee: Beckman Lapre Beheer BV; JAO Beheer BV
Current assignee: Beckman Lapre Beheer BV; JAO Beheer BV
Priority date: 2013-03-05
Filing date: 2014-03-05
Publication date: 2016-01-13
Also published as: WO2014135598A2; EP2774655A1; WO2014135598A3

Abstract

The present invention relates to composition comprising chicken egg shell particles. We have surprisingly found that chicken egg particles can be advantageously used in treatment of the skin. Other applications include hard surface cleaning. The invention relates to compositions, as well as methods of preparing and applications of the chicken egg particles.

Description

Eggshell compositions, preparations and uses

Technical field

The present invention relates to compositions, to a method of preparing a composition, to a method of treating the skin, to a method of preparing particles, to a method of preparing a composition, and to the use of particles.

Background to the invention

Various types of particulate material have been used for scrub and abrasive compositions including polyethylene particles. Recently, however, it has been concluded that these plastic particles accumulate in the environment and represent a significant aquatic health hazard. Alternative scrub compositions have been proposed and are used, such as formulations comprising bamboo fibres, crushed almond and walnut shells, coral & sea lichen, loofah, and other hard particles from vegetable origin. These alternatives may, however, be associated with difficulties of sourcing, difficulties in processing, dermatological limitations and complications in creating stable products. Products containing these substances are often unstable. Particles may be sharp to the skin, potentially even leading to skin injuries. The resulting products may not have customer preferred properties for instance with particles that are too hard, too soft, too large or too small or sometimes with particles that have undesired changing character during storage or usage.

US2005/0170979 (Unilever) discloses liquid detergent compositions that are internally structured using lamellar droplets of surfactant material and have an acidic pH. US2003/0133900 (McLaughlin) refers to powdered eggshell and discloses pastes and creams containing them. CN 101191047 discloses egg shells generally with particle size of 1 to lOOmicrons as friction agent in toothpaste or skin products. Chicken eggshell is mentioned in a list of options. The skin product shown in the example is a highly viscous soap bar without any polymer and with high anionic surfactant levels. KR 2001 0036526 discloses a mouth wash composition that may comprise particles of 100 to 300 micrometer for waste and plaque removal by a toothbrush. Egg shells are only generally mentioned along with sand and shells in a list of possible particles. US6344217 discloses the preparation of solid tablet formulations with ground, washed and dried chicken egg shell for formulations comprising putamen ovi (a certain plant species) for oral administration, for instance in bone fracture prevention or for treatment of calcium deficiency. CN101665619 discloses the use of general egg shell particles as filler for plastic composites based on polylactic acid. CN102871003 discloses an animal nutrient soup comprising dry general egg shell powder of 50-100 meshes. GB 1474389 discloses compositions comprising ground general egg shells and pH of at least 8 which is achieved by use of alkaline metal silicates and phosphates. The compositions are preferably solid concentrates that are diluted before usage as hard surface cleaners. JP-H-04187615 discloses the use of inner eggshell membrane for frictional action of the skin. The outer egg shell is dissolved in lactic acid during processing. US2004/0266645 discloses an abrasive thickening formulation comprising synthetic abrasive particles of 75 to 400 micron. EP1674134 discloses cleaning products with abrasive particles of 100 to 500micron with a polyacrylate polymer structurant. The document does not refer to egg shells particles and does not disclose a specific pH, only generally referring to addition of "q.s. NaOH" in the Examples. US2007/0179078 discloses aqueous liquids with cross-linked polymers with pH of from 4 to 10. According to paragraph 20, the polymers may be used in shampoos with pH of 4.75 to 7.0.

Described formulations may show chemically and/or physically instability, represent a significant aquatic health hazard and often provide limited customer benefits, particularly after storage. Summary of the invention

The present invention overcomes one or more of the above mentioned or other problems. Accordingly, the present invention relates to a composition comprising from 1 to 30% by weight of chicken eggshell particles wherein at least 50% by weight of the chicken eggshell particles has a particle size of at least 74μιη and at most 595μπι. Preferably, the pH of the composition is higher than 7.5 and lower than 9 and wherein the composition further comprises a polymer providing an external structure to the composition. Preferably, the composition further comprises from 1-20% by weight of anionic surfactant and from 0.5- 12% by weight of non-ionic surfactant with a ratio of anionic to nonionic surfactant of from 3:1 to 4:1. Preferably, the composition comprises egg shell membrane particles. Preferably, the composition further comprises water at a level of from 2 to 90% by weight of composition. Preferably, the composition further comprises emollient at a level of from 0.2%) to 40% by weight of the composition.

The invention further relates to a method of preparing a composition comprising chicken eggshells and polymer material, wherein the chicken eggshell is ball-milled to particles which are subsequently dispersed in the composition comprising polymer material and wherein the pH is subsequently set at higher than 7.5. Preferably, at least 50% by weight of the chicken eggshell particles has a particle size of at least 74μιη and at most 595μηι.

The invention further relates to a method of treating the skin by removing dead skin cells from the skin surface with chicken eggshell particles. Preferably, the chicken eggshell particles are- first ball-milled. Preferably, the skin treatment comprises the steps of (a) providing a cleaning composition comprising surfactant and chicken eggshell particles; (b) applying the composition to the skin;(c) adding water to wet the skin and develop a lather; and (d) rubbing the lather into the skin to remove dead skin cells from the skin surface. The invention further relates to a method of preparing chicken eggshell particles by washing and ball-milling the eggshells, wind sifting and sterilizing the resulting chicken eggshell particles, and subsequently sieving the chicken eggshell particles into fractions. The invention further relates to a method of preparing a composition comprising chicken eggshell particles dispersed in an aqueous composition comprising polymer, wherein the polymer is mixed with water, the chicken eggshell particles are added under stirring and the pH of the composition is set at higher than 7.5.

The invention further relates to chicken eggshell particles for use in treatment of skin. Preferably, at least 50% by weight of the chicken eggshell particles has a particle size of at least 74μιη and at most 595μηι.

The present invention surprisingly provides for chemically and physically stable compositions with chicken eggshells that offer preferred properties, even after prolonged storage at elevated temperature and without detrimental effects on the environment. The invention offers a low cost option with abundant supply (in 2011 about 450,000 tonnes) and relatively easy processing.

Surprisingly, we have found that chicken eggshell particles can be chemically and physically stably suspended in compositions of the present invention. The chicken eggshell particles do not accumulate in the environment and are fully biodegradable, are of extreme purity, are compatible with other ingredients present in compositions, absence of undesirable contaminants, are easy to process and provide excellent scrubbing benefits.

According to the invention, chicken eggshell particles are beneficially applied to remove dead skin cells from the skin surface. According to the invention, larger particles of chicken eggshell are preferably used for scrubbing the skin, while smaller particles of chicken eggshell are preferably used for polishing the skin. In a further embodiment, chicken eggshell particles of the invention are preferably used as abrasive in tooth paste. In a further embodiment, chicken eggshell particles of the invention are preferably used as abrasive in hard surface cleaners. In a further embodiment, chicken eggshell particles of the invention are preferably used as abrasive in car polish. In a further embodiment, chicken eggshell particles of the invention are preferably used as filler for surface coatings. In a further embodiment, chicken eggshell particles of the invention are preferably used as tableting aids in pharmaceutical compositions. In a further embodiment, chicken eggshell particles of the invention are preferably used as antacids. Detailed description of the invention

Compositions according to the invention comprise chicken eggshell particles. The I CI monograph ID code 10361 represents egg shell powder obtained from dried, ground egg shell of Gallus gallus domesticus. Chicken eggshell particles are preferably used in personal care products, cosmetic cream products (both scrub and polish), in household products, in chemical technical products and in medical products.

In its non-processed form, a cliicken eggshell consists mostly of calcite, a crystal form of calcium carbonate. It contains substantially no toxins. Generally between 95-97% of chicken eggshells represents calcium carbonate. The structure of the chicken eggshell of the invention is porous yet hard, making chicken eggshell particles particularly suitable for use in the compositions of the present invention. Furthermore, calcium carbonate originating from chicken egg shells have high purity (contains only trace amounts if any), enabling to usefully apply chicken egg shells as food supplement or as food additive to avoid calcium deficiency in adults, which can eventually lead to osteoarthritis and osteoporosis.

We have surprisingly found that compositions of the invention comprising chicken eggshell particles enable removal of dead cells from the stratum corneum. Not being bound by theory, the degree thereof depends on the size and morphology of the particles, and their hardness. Large, rough and hard particles are usually harsh and irritating to the skin, while small and soft particles may not be less effective. The abrasive properties are also determined by the hardness of the chicken eggshell particles. Hardness is typically expressed using the Moh scale. Moh's scale of mineral hardness characterises the scratch resistance of various minerals through the ability of a harder material to scratch a softer material. The scale ranges in order of increasing relative hardness from 1 (softest, e.g. talc) to 10 (hardest, e.g. diamond). Preferably, the Moh hardness of the chicken eggshell particles of the invention is below 5 and preferably at least 3, and best between 3.5 and 4 (absolute hardness 10-20 using a sclerometer).

Chicken eggshell particles are distinct from calcium carbonate particles from other sources, such as mined calcium carbonate, precipitated calcium carbonate and other eggshell particles. In comparison, mined calcium carbonate contains undesirable concentration of elements (sodium, magnesium and heavy metals/transition elements (strontium [ up to 1 % in aragonite], barium, lead, copper, zinc, strontium, uranium, manganese, iron), due to its mineral origin. Precipitated calcium carbonate may contain undesirable sharp edged particles, possibly due to the crystallization step involved. Other sources for eggshells include quail eggshells, ostrich eggshells and in particular emu eggshells which also have abundant supply. However, these eggshells are more difficult to process and do not provide the benefits of the chicken egg particles by the present invention.

Surprisingly, we have found that chicken eggshell particles can be stably incorporated in compositions of the invention, largely eliminating sharp edges, and providing safe products with low or no contamination and with preferred processing and user characteristics even after storage of said compositions.

Further, surprisingly, upon application and use of the compositions of the invention, for instance on the skin, the chicken egg shell particles may further slowly lose their sharp edges, possibly due to their porosity. Consequently, for skin applications the efficacy of I removing dead cells from the skin surface seems to slowly decrease during usage of the chicken eggshell particles in compositions of the invention, presenting a unique benefit, not provided by the other agents mentioned.

According to the invention, the chicken eggshell particle size is subdivided in different fractions using sieves according to ASTM CI 36-06. These sieves have different mesh sizes including the following ΙΟΟΟμιη (mesh 18), 841μιη (mesh 20), 707μιη (mesh 25), 595μιη (mesh 30), 500μηι (mesh 35), 420μιη (mesh 40), 354μιη (mesh 45), 297μηι (mesh 50), 250μιη (mesh 60), 210μηι (mesh 70), 177μιη (mesh 80), 149μπι (mesh 100), 25μιη (mesh 120), 105μιη (mesh 140), 88μιη (mesh 170), 74μηι (mesh 200), 63μιη (mesh 230), 53μιη (mesh 270), 44μιη (mesh 325), and 37μιη (mesh 400). Also smaller fraction sizes are possible. By sieving particles, the preferred particle size can be obtained. According to the invention, the particle size is determined by means of sieve analysis using standardised sieves according to ASTM CI 36-06. In line with the above sieving method, particle size determination according to the invention is based on the smallest diameter (other options in the art include particle size determination based on volume or surface area). Equipment to determine the particle size according to the invention in products, such as dispersions that falls within the scope of the present invention, is available in the art. For instance, Malvern equipment is suitable, but so are similar devices available elsewhere.

Preferably, at least 50% by weight of chicken eggshell particles in the composition of the invention has a particle size of preferably at least 74μηι, more preferably at least 88μιη, most preferably at least 125μηι and in particularly preferred at least 149μιη and preferably at most to 595μιη, more preferably at most 500μπι, most preferably at most 420μιη. More preferably, at least 65% by weight of the chicken eggshell particles has such size, most preferably at least 80%, and in particular preferred at least 95% by weight of the chicken eggshell particles.

Preferably, at least 50% by weight of chicken eggshell particles in compositions for scrubbing has a particle size of preferably at least 149μηι, more preferably at least 177μιη, most preferably at least 210μιη and preferably at most to 595μιη, more preferably at most 500μιη, most preferably at most 420μιη. More preferably, at least 65% by weight of the chicken eggshell particles has such size, most preferably at least 80%, and in particular preferred at least 95% by weight of the chicken eggshell particles.

Preferably, at least 50% by weight of chicken eggshell particles in compositions for polishing and for hard surface cleaning has a particle size of preferably at least 74μηι, more preferably at least 88μιη, most preferably at least 125μιη and in particularly preferred at least 149μηι and preferably at most 354μιη, more preferably at most 297μιη, most preferably at most 210μιη. More preferably, at least 65% by weight of the chicken eggshell particles has such size, most preferably at least 80%, and in particular preferred at least 95% by weight of the chicken eggshell particles.

Preferably, compositions of the invention comprise chicken eggshell particles at a level of at least 1% by weight, more preferably at least 2% by weight, most preferably at least 3% by weight of the composition and preferably at most 30% by weight, more preferably at most 20% by weight, most preferably at most 15% by weight and in particular preferred at most 7% by weight of the composition.

hi a preferred embodiment, personal care scrub compositions and cosmetic cream compositions preferably comprise chicken eggshell particles at a level at least 1% by weight, more preferably at least 2% by weight, most preferably at least 3% by weight of the composition and preferably at most 12% by weight, more preferably at most 8% by weight, most preferably at most 6% by weight and in particular preferred at most 5% by weight of the composition.

In a preferred embodiment, household compositions, and preferably hard surface cleaner compositions, comprise eggshell particles preferably at a level at least 1% by weight, more preferably at least 3% by weight, most preferably at least 4% by weight of the composition and preferably at most 30% by weight, more preferably at most 20% by weight, most preferably at most 15% by weight and in particular preferred at most 7% by weight of the composition.

Chicken eggshell is covered on the inside with a separate membrane, often named the eggshell membrane. For the purpose of this invention, reference to chicken eggshell refers to the outer shell only and does not include this membrane. Chicken eggshell particles of the invention may contain some membrane as well, but preferably comprises at least 90% of calcium carbonate. The eggshell membrane is composed of collagen and mainly consists of collagen type I, and has an l chain (<MW>=130 kDa) and a2 chain (<MW>=116 kDa). The ratio al/cc2 is approximately 1 (Zhao, Chi, Biotechnology 8(2):254-258,2009). Eggshell membrane further contains significant amounts of glucosamine, chondroitin sulphate and hyaluronic acid. We have found that presence of these constituents of the eggshell membrane is beneficial in consumer products such as bath & shower products for skin scrubbing. According to the invention, the eggshell membrane is preferably at least partially separated from the eggshell. This can for instance be accomplished by treatment with hot/boiling water and/or by wind sifting as will be explained below. JP4169513 and JP4187616 describe separating the membrane from the eggshell but dissolve the eggshell in lactic acid. The membrane is subsequently used for cosmetic skin purposes.

In a preferred embodiment of the present invention, eggshell membrane particles are prepared from eggshell membrane. These membrane particles comprise of at least 90% by weight of eggshell membrane. The membrane particles may be added to the composition with the chicken eggshell particles and, this way, a well-defined egg shell fraction is obtained for beneficial application in personal care and/or cosmetic consumer products, and in particular for skin treatment. Thus, the present invention further relates to a composition comprising chicken eggshell particles and eggshell membrane particles.

Preferably, at least 50% of eggshell membrane particles in the composition of the invention has a particle size of at least 149μιη, more preferably at least 177μηι, most preferably at least 210 ιηι and preferably at most to 595μιη, more preferably at most 500μιη, most preferably at most 420μιη. More preferably, at least 65% by weight of the eggshell membrane particles has such size, most preferably at least 80% by weight, and in particular preferred at least 95% by weight of the chicken eggshell particles.

Preferably, the composition of the invention comprises eggshell membrane particles at a level of at least 0.1% by weight and preferably at most 20% by weight of the composition.

Preferably, compositions of the invention comprise one or more surfactants, which are sometimes called surface active agents. In general, surfactant may be chosen from the surfactants described in well-known textbooks like "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, and/or the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch" , H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 and "Surfactant Encyclopaedia, 2^nd edition, by Rieger (Allured Publishing, 1996), and other sources from the open literature. Any type of surfactant, i.e. anionic, cationic, nonionic or amphoteric surfactant, can be used. Preferably, the composition comprises anionic and/or nonionic surfactant.

Preferred anionic surfactants are water-soluble salts of organic sulphuric acid esters and sulphonic acids having in the molecular structure an alkyl group containing 8-22 carbon atoms or an alkylaryl group containing 6-20 C atoms in the alkyl part. Examples of such anionic surfactants are water soluble salts of:

- long chain (i.e. 8-22 carbon atom) alcohol sulphates (hereinafter referred to as PAS), especially those obtained by sulphating the fatty alcohols obtained from vegetable oils by (1) trans-esterification of the triglyceride, and (2) followed by catalytic reduction with hydrogen. The counter-ion may be sodium, potassium, calcium, magnesium, ammonium or zinc ions, or alkanolamines such as but not limited to monoethanolamine, triethanolamine and triisopropanolamine. Suitable vegetable oils are coconut and palm kernel oil;

- secondary alkyl sulphonates derived from unsaturated petrochemical feedstock, using as the counter-ion sodium, potassium, calcium, magnesium, ammonium or zinc, or alkanolamines such as but not limited to monoethanolamine, triethanolamine and triisopropylamine.

- alkylbenzene sulphonates, such as those in which the alkyl group contains from 6 to 20 carbon atoms using as the counter-ion sodium, potassium, calcium, magnesium, ammonium or zinc, or alkanolamines such as but not limited to monoethanolamine, triethanolamine and triisopropylamine;

Also suitable anionics are the salts of:

- sulphates of ethoxylated aliphatic alcohols containing 1-12 alkylene oxide units in which the alkylene group contains from 2 to 14 carbon atoms;

- ethoxylated alkylphenols sulphates with from 1 to 30 alkylene oxide units in which the alkyl group contains from 2 to 14 carbon atoms;

- sarcosinates, preferably as the ammonium or triethanolamine salt;

- taurates, preferably as the sodium salt;

- ester carboxylates derived from di- or tricarboxylic acid such as citric acid & ethercarboxylates derived from ethoxylated fatty alcohols with 2-20 ethylene oxide units and reacted with chloroacetic acid;

- sulfosuccinates derived from maleic acid anhydride, reacted with a suitable fatty alcohol or ethoxylated fatty alcohol, followed by sulphonation and neutralisation with a suitable anion;

- acylamino acids (acylglutamates, as mono- or disodium salts).

As the counter-ion may be used sodium, potassium, calcium, magnesium, ammonium or zinc, or alkanolamines such as -but not limited to- monoethanolamine, triethanolamine and triisopropylamine. Preferably anionic surfactants are used that do not form insoluble salts with divalent metal ions, such as calcium & magnesium.

Suitable nonionic surfactants can be broadly described as compounds produced by the condensation of simple alkylene oxides, which are hydrophilic in nature, with an organic hydrophobic compound which may be aliphatic or alkyl-aromatic in nature. The length of the hydrophilic or polyoxyalkylene chain which is attached to any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired balance between hydrophilic and hydrophobic elements. This enables the choice of nonionic surfactants with the right HLB.

Particular examples include the condensation products of aliphatic alcohols having from 8 to 22 carbon atoms in either straight or branched chain configuration with ethylene oxide, such as a coconut alcohol ethylene oxide condensates having from 2 to 15 moles of ethylene oxide per mole of fatty alcohol; condensates of alkylphenols having C6-C15 alkyl groups with 5 to 25 moles of ethylene oxide per mole of alkylphenol; condensates of the reaction product of ethylenediamine and propylene oxide with ethylene oxide, the condensates containing from 40 to 80% of oxyethylene groups by weight. Petrochemical alcohols with 7-25 carbon atoms, reacted with alkylene oxide (2-20 units), are also suitable nonionic surfactants. These alkoxylated long chain alcohols may also be converted in the corresponding sulphate, neutralised with a suitable counter-ion. Reaction of the alkoxylated alcohol with chloroacetic acid leads to the formation of ethercarboxylic acids that are suitable as anionic surfactant after neutralisation with sodium hydroxide or triethanolamine.

Other examples are: alkyl polyglucosides, which are condensation products of fatty alcohols and polyglucose obtained from corn; tertiary amine oxides of structure RRRNO, where one R is an alkyl group of 8 to 20 carbon atoms and the other R's are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, e.g. dimethyldodecylamine oxide and fatty acid alkanolamides. Ethoxylated aliphatic alcohols are particularly preferred.

Specific nonionic surfactants are block copolymers of ethylene and propylene oxide and are most suitable in low foaming but effective cleansing preparations. Preferred examples are poloxamines and poloxamers (POE)_n-(PPO)_m-(POE)„ wherein n=l 0-200 and m=20-80; a number of poloxamers are fluid (with n=low and m=high) or pasty, some are solid (with n=high and m=moderately low).

Suitable amphoteric surfactants are derivatives of fatty acids having an aliphatic group of from 8 to 18 carbon atoms that have reacted with a suitable diamine such as N,N-dimethyl- 1,3-propylenediamine, subsequently reacted with chloroacetic acid to obtain the corresponding zwitterionic species, also named betaines. Other suitable amphoteric surfactants are sultaines and imidazole-based surfactants.

Preferably, compositions of the present invention comprise compositions containing surfactants preferably at least 1% by weight, more preferably at least 2% by weight, most preferably at least 4% by weight of the composition and preferably at most 30% by weight, more preferably at most 20% by weight, most preferably at most 16% by weight of the composition, and in particular preferred around 12% by weight.

Preferably, compositions of the present invention comprise anionic surfactants and preferably at a level of at least 0.5% by weight, more preferably at least 1% by weight, most preferably at least 2% by weight of the composition and preferably at most 20% by weight, more preferably at most 14% by weight, most preferably at most 10% by weight of the composition.

Preferably, compositions of the present invention comprise nonionic surfactants and preferably at a level of at least 0.5% by weight, more preferably at least 1% by weight, most preferably at least 2.5% by weight of the composition and preferably at most 12% by weight, more preferably at most 10% by weight, most preferably at most 6% by weight of the composition.

Preferably, compositions of the present invention comprise anionic and nonionic surfactants and preferably in a ratio of from 3:1 to 4:1.

We have surprisingly found that chicken eggshell particles may be stably incorporated in compositions of the present invention by using particular polymers that provide an external structure to the composition. Preferably, the polymer has a sufficiently high yield stress value. The yield stress value is best defined using the empirical formula by Herschel & Bulkley:

τ = τ₀ + αχβχρ(-βχθ)

τ is the shear stress (expressed in [Pascal) and τ₀ represents the yield stress value, also expressed in [Pa] seal. The constants a and β are material parameters characteristic for the product. D represents the shear rate, and is the running parameter, and is expressed in s^"1. Preferably, the polymer as rheological additive is selected from different polymer families including (1) acrylic/methacrylic acid homo- & copolymers, (2) polysaccharides obtained from vegetable resources, and mixtures thereof.

Suitable polymers from the group of acrylic/methacrylic acid homo- and copolymers are low cross-linked homopolymers of acrylic acid, better known as carbomer 941 types such as commercially available from Lubrizol, RITA Corporation, Evonik Industries, 3-V Chemical, Guangzhou Tinci Materials Technology Sumitomo Seika Chemicals Co., Nihon Junyaku, and others. Copolymers of acrylic & methacrylic acid are known as acrylates/ClO- 30 alkyl acrylate copolymer, commercially available from Evonik Industries, Lubrizol, Rita Corporation, Sumitomo Seika Chemicals Co., Guangzhou Tinci Materials Technology, and others. Other suitable acrylates comprise acrylates/steareth-20 methacrylate copolymers such as made available by DOW Chemical (Aculyn) and homopolymers of acrylamide such as made available by Seppic & copolymers of acrylic acid, acrylamide and methacrylic acid esters, such as made available from Grain Processing, BASF, DOW Chemical, Lubrizol, AKZO Nobel, Goo Chemical, and others.

Polysaccharides that exhibit sufficient yield stress value are preferably selected from xanthan gum, various forms of carrageenan (preferably in combination with xanthan gum) and/or locust bean gum.

Synergy of the polymer with a clay material allows formulation of compositions with a yield stress value of at least 50 Pa that lead to a stable dispersion of chicken eggshells. Thus, in a preferred embodiment, the polymer is combined with mineral clay, preferably selected from sodium magnesium silicates, magnesium aluminium silicates and/or aluminium silicates. The boundary condition for choosing the desired polymer is the yield stress value: the yield stress value shall be at least 50 Pa to obtain a stable product. In practice, the yield stress value is preferably lower than 150Pa.

Preferably, compositions of the present invention comprise a polymer and preferably at a level of at least 0.1% by weight, more preferably at least 0.2% by weight, most preferably at least 0.5% by weight of the composition and preferably at most 4% by weight, more preferably at most 2.5% by weight, most preferably at most 1.4% by weight of the composition.

Preferably, the composition of the present invention comprises one or more solvents. The solvent is preferably liquid and preferably selected from water, lower (C1-C4) alcohols and ketones, diols and triols. Examples include methanol, ethanol, propanol, isopropanol, butanol, isobutanol and glycerol, and water. Compositions of the present invention preferably comprise solvent at a level of at least 2% by weight, more preferably at least 10% by weight, most preferably at least 20% by weight and preferably at most 90% by weight of composition, more preferably at most 60% by weight of composition, most preferably at most 40% by weight of the composition.

Preferably, the composition of the present invention is aqueous. Preferably, the compositions of the present invention comprises water at a level of at least 2% by weight of composition, more preferably at least 10% by weight of composition, most preferably at least 20% by weight of the composition and preferably at most 90% by weight of composition, more preferably at most 60% by weight of composition, most preferably at most 40% by weight of the composition.

The pH of the composition comprising chicken eggshell particles may change over time and may drift towards higher pH values possibly due to dissolution of calcium carbonate. Preferably, according to the present invention, pH drifting of the compositions of the present invention is at least somewhat prevented as that may affect the chicken eggshell particles, in shape and/or level which might negatively affect the composition, particularly upon storage.

Compositions of the present invention preferably have a pH of higher than 7.5, more preferably of higher than 7.6, most preferably of higher than 7.7. For skin compositions, the pH of the composition is preferably lower than 9, more preferably lower than 8.7, most preferably lower than 8.5. Prior art skin products typically have a pH of between 5 and 7 corresponding to the skin pH.

Preferably, hard surface cleaning compositions have a pH of lower than 11, more preferably lower than 10, most preferably lower than 9.5.

In an embodiment, compositions of the present invention comprise a buffer to maintain the pH of the composition over time within the pH ranges indicated and prevent pH drift. Preferably, the compositions according to the invention comprise a phosphoric acid pH buffer. A preferred example is the combination of potassium dihydrogen phosphate and sodium hydroxide. For pharmacy application, the combination of phthalic acid and NaOH is preferred as buffer.

According to the invention, preferably, a drift in pH upon storage may be minimized, leading to compositions with chicken eggshell particles that are chemically and physically stably suspended in the composition over time.

Preferably, the composition of the invention, and in particular cream compositions, comprises one or more emollients. Emollients are oily substances that may be used in personal care & cosmetic creams. Preferably, the emollient is selected from:

- hydrocarbons (linear, branched, alicyclic) and/or aliphatic alcohols (linear, branched, alicyclic) that may originate from petrochemical origin, and preferably mixtures thereof;

- esters of vegetable fatty acids with a chain length of 6-24 carbon atoms, linear or branched, saturated or (polyunsaturated, esterified with a suitable alcohol with a chain length of 1-24 carbon atoms, linear or branched, saturated or unsaturated;

- esters of polyhydric alcohols with vegetable fatty acid with a chain length of 6-24 carbon atoms, linear or branched, saturated or (poly)unsaturated;

- vegetable oils;

- waxes; and

- mixtures thereof.

Preferably, the emollient is present at a level of at least 1% by weight and preferably at most 20% by weight of the composition.

The composition of the present invention may further include optional ingredients such as one or more emulsifiers, foam boosters & stabilisers, refatting agents, irritation quenchers, fragrance, preservatives and water-soluble dyes. Preferably, the compositions of the present invention are chemically and/or physically stable. We have found that use of the pH, as indicated, surprisingly contributes to the stability of the composition. Chicken eggshell particles are preferably used in personal care products, cosmetic cream products (both scrub and polish), in household products, in chemical technical products and in medical products and the following preferred ranges can be indicated for the various applications.

The chicken eggshell particles of the invention may preferably be used for treatment of skin, preferably by exfoliating action. Exfoliating means removal of dead skin cells from the skin surface. Exfoliation can be accomplished by scrubbing the skin or by polishing the skin, polishing being the milder version of scrubbing and generally using smaller particle sizes in comparison.

The composition is preferably used as personal care scrub composition, for instance as bath and shower product. The chicken eggshell particles in such compositions are used for skin treatment, in particular to remove dead skin cells from the skin surface. The compositions preferably comprise from 3 to 6% by weight of chicken eggshells. Preferably, at least 50% by weight of the particle size of the chicken eggshell particles is preferably at least 297μηι and preferably at most 595 μηι. Preferably, the composition comprises surfactant at a concentration of from 10 to 14%, preferably around 12%. Preferably, the pH of the composition is higher than 7.5 and lower than 8.5, more preferably around 8.0.

The composition is preferably used as cosmetic polishing cream composition. The chicken eggshell particles in such compositions are used for skin treatment, in particular to remove dead skin cells from the skin surface. Since these polishing cream compositions are gentler, they are preferably used to remove dead skin cells and treat the skin surface and can in particularly be used for treatment of the skin of the face. The cream is an oil-in-water or a water-in oil emulsion, preferably with a viscosity of 800-100,000 cPs Brookfield viscosity. Preferably, the composition comprises from 2 to 4% chicken eggshell particles. Preferably at least 50% by weight of the chicken egg particles have a particle size of preferably at least 88μιη and preferably at most 297μηι. Preferably, the composition has a pH of higher than 7.5 and lower than 8.5, more preferably around 8.0.

The composition is preferably used as cosmetic scrub cream composition. The chicken eggshell particles in such compositions are used for skin treatment, in particular to remove dead skin cells from the skin surface. Thus, these compositions are used to remove dead skin cells and treat the skin surface. The cream is an oil-in-water or a water-in oil emulsions, preferably with a viscosity of 800-100,000 cPs Brookfield viscosity. Preferably, the composition comprises from 2 to 4% chicken eggshell particles. Preferably, at least 50% by weight of the chicken egg particles has a particle size of preferably at least 297 μηι and preferably at most 595μιη. Preferably, the composition has a pH of higher than 7.5 and lower than 8.5, more preferably around 8.0.

The composition is preferably as household product, more preferably a hard surface cleaner. The chicken eggshell particles can be used as abrasive for cleaning hard surfaces. Preferably, the composition comprises from 4 to 10% by weight of chicken eggshell particles. Preferably, at least 50% by weight of the chicken egg particles has a particle size of preferably at least 88μιη and preferably at most 354 μηι. Preferably, the composition comprises surfactant at a concentration of from 10 to 14% by weight, preferably around 12% by weight. The composition preferably has a pH of higher than 7.5 and preferably lower than 11, more preferably lower than 10, most preferably lower than 9.5.

The composition is preferably used as toothpaste. Chicken eggshell particles are used as abrasive for cleaning the teeth. The toothpaste is preferably a gel preparation with a preferred viscosity of 800-100,000 cPs Brookfield viscosity. The toothpaste preferably comprises from 3 to 7% chicken eggshell particles. Preferably, at least 50% by weight of the chicken egg particles have a particle size of preferably at least 88μιη and preferably at most 354μιη. The composition has a pH of preferably higher than 7.5 and preferably lower than 8.5, more preferably around 8.0. Preferably, the toothpaste has a pleasant mouth feel and sweetener such as glycerol, sorbitol.

The composition is preferably used as car polish. The chicken eggshell particles are used as abrasive. The car polish is preferably an oil-in-water or a water-in oil emulsion with a preferred viscosity of 800-100,000 cPs Brookfield viscosity. The car polish preferably comprises from 2 to 4% chicken eggshell particles. Preferably, at least 50% by weight of the chicken egg particles have a particle size of preferably at least 88μιη to preferably at most 297μιη. The composition has a pH of preferably higher than 7.5 and preferably lower than 8.5, for instance around 8.0.

Other applications of chicken eggshells include a tablet aid (preferably a filler) for (pharmaceutical) tablets (with a preferred particle size of at least 50% by weight of from 100 to 300 μηι), antacids to restore (and increase) the pH in the stomach (with a preferred particle size of at least 50% by weight of from 88 to 297μιη) and in paint (with a preferred particle size of 50% by weight of from 88 to 210μηι).

Preferably, chicken eggshells of the invention may be prepared as follows. The chicken egg content is separated from the chicken eggshell. The eggshell membrane may still be present on the surface of the chicken eggshells at this stage. The crude eggshells are washed with water, and subsequently dried in a stream of hot air, lowing the water content, for instance to a water content of less than 1%. This results in a water activity of less than 0.60 whereby micro-organisms are disabled to exhibit growth. The crude chicken eggshells are subsequently milled using a ball mill, hammer mill, disk mill or colloid mill (according to the invention a ball mill is preferred). The obtained granulate still contains eggshell membrane particles, that are removed by wind sifting. Wind sifting also enables to separate different fractions chicken eggshells. The equipment for wind sifting has been used elsewhere in industry, as for instance described in WO1998048950A1 (Metso Panelboard GmbH). Particular large fractions may be fed again into the milling equipment to further reduce the particle size. The present invention takes advantage of the difference in specific gravity of grinded chicken eggshell (density 2400-2800 kg/m3) and chicken eggshell membrane (1400 kg/m³, the bulk weight is 400 kg/m³).

After completion of the milling process and fractionation of the different chicken eggshell fractions, microbiological decontamination may be pursued using a suitable sterilisation agent, more particularly ozone, or eventually formaldehyde gas, whereby residual formaldehyde shall be less than 50 ppb.

Preferably, the chicken eggshells are sieved to ensure use of the desired particle size fraction for use in the composition of the invention. Preferably, standard sieves with US mesh are used according to ASTM C1360-06. Preferably, the resulting chicken eggshell fraction is subsequently free from dust and then packed.

Preferably, the composition of the present invention is prepared as follows:

The polymer material is preferably dispersed in the water under strong agitation, preferably with a propeller mixer. Subsequently, surfactant, chicken eggshell particles, preservative, and/or solvent are added under stirring until a homogeneous dispersion is obtained.

The second step applies to the preparation of an emulsion and involves heating up the water phase (preferably to higher than 60°C and preferably lower than 80°C). Subsequently, the oil phase is mixed and may be heated, preferably to higher than 60°C and preferably lower than 80°C. The oil phase is preferably added to the water phase under mixing (preferably with a planetary mixer) and spontaneous emulsification will be observed. The pre-emulsion is subjected to mixing treatment, preferably with a rotor-stator mixer. The emulsion is cooled while stirring slowly, preferably with a planetary mixer. Any addition ingredients (such as fragrances, etc) may be added at 25°C. The pH may be adjusted to 7.5 to 8.0 with a 10% sodium hydroxide solution.

Chicken eggshell particles as used in the invention are particularly useful in view of the unique porosity and high purity. Without wishing to be bound by any theory, we believe that possibly upon storage of the compositions of the invention, the chicken egg shell particles may lose their sharp edges and become milder while maintaining the quality of the exfoliation activity. Although calcium carbonate is poorly soluble (the solubility product is 4,8xl0^"9, equivalent to a solubility of 0,3% in water), the solubility may be more pronounced on the sharp edges of the shells, and therefore the harslmess of the chicken egg shells is greatly reduced and not noticeable anymore after 1-2 weeks. Consequently, compositions of the invention are preferably stored for at least 2 weeks after production.

The present invention further relates to a method of treating the skin with the composition of the invention comprising the steps of:

a. providing a cleaning composition comprising surfactant (preferably anionic and/or nonionic) and chicken eggshell particles;

b. applying the composition to the skin;

c. adding water to wet the skin and develop a lather; and

d. rubbing the lather into the skin to remove dead skin cells from the skin surface.

As indicated, chicken eggshell particles exhibit unique porosity and high purity. Without wishing to be bound by any theory, we believe that upon application and using of the compositions of the invention on the skin, the chicken egg shell particles may slowly lose their sharp edges, possibly due to their porosity. Consequently, the efficacy of removing dead cells from the skin surface seems to slowly decrease during usage of the chicken eggshell particles in compositions of the invention, presenting a surprising and unique benefit, not provided by other agents. Examples

Example 1

A personal care scrub composition for bath and shower with the following ingredients was prepared:

Ingredients level by weighf) INCI function

Demineralized water ad 100%

Texapon N70 12.5 Sodium Laureth Sulfate, Aqua surfactant

Dehyton K 10.5 Aqua, Cocamidopropyl Betaine surfactant

Chicken eggshell * 3.0 Calcium Carbonate exfoliating agent

Amidet N 2.0 PEG-4 Rapeseedamide, Aqua foam stabiliser

Carbopol ETD2050 0.8 Carbomer flow control polymer

Preservative qs

Perfume qs (solubilised in Polysorbate 20)

Colouring Agent qs

Sodium Hydroxide, 10% to pH=8.0

* with particle size of 354-420 μηι, separated by sieving

The composition was prepared as follows: Carbopol ETD2050 is dispersed in water by adding the powdered polymer to water while strongly agitating with a propeller mixer. As soon as the polymer has been properly dispersed the surfactants are added and the mixture is stirred until homogeneous; Texapon N70 requires strong agitation. The viscosity will markedly increase. Subsequently chicken eggshells are added and mixed until homogeneous. Finally the preservative system, the dyes (optional) and the solubilised fragrance are added. The pH is adjusted to 7,5-8,0 while using a 10% sodium hydroxide solution. pH drift of the composition may be prevented by preferred inclusion of a pH buffer at a pH of 8.0.

The viscosity of the composition was 1,800 cPs (Brookfield viscosity,S4,20 rpm); the yield stress value was 65 Pa. The shower scrub composition was chemically and physically stable after 3 months at 40°C and, upon subsequently use, the composition provided excellent properties for removal of dead skin cells. Example 2

A cosmetic polish cream composition with the following ingredients was prepared:

Ingredients level f% bv weight) INCI function

Demineralized water ad 100 Aqua solvent Mineral oil, high viscous 8.0 Paraffmum Liquidum emollient

Estol 1514 3.0 Isopropyl Myristate emollient

Brij 72 2.5 Steareth-2 nonionic emulsifier

Brij 721 2.5 Steareth-21 nonionic emulsifier

Lanette O 3.0 Cetearyl Alcohol rheological additive

Chicken eggshells* 1,8 Calcium Carbonate exfoliating agent

Rhodicare D 0.6 Xanthan Gum flow control polymer

Perfume qs

Preservative qs

Sodium hydroxide, 10% to pH=8.0

* with particle size of 149- 177pm, separated by sieving

The composition was prepared as follows: Rhodicare D is dispersed in water by adding the powdered polymer to water while strongly agitating with a propeller mixer. As soon as the polymer has been properly dispersed the chicken eggshell particles and the preservative system are added, and stirring is continued until a homogeneous dispersion has been obtained. The water phase of the emulsion is heated to 65-70°C. The oil phase is made by mixing the ingredients to 65-70°C, The oil phase is added to the water phase while stirring with a planetary mixer; spontaneous emulsification will be observed. The pre-emulsion is subjected to treatment with a rotor-stator mixer. The emulsion is cooled while stirring slowly with a planetary mixer. At 25°C the fragrance is added; solubilisation is not required, The pH is adjusted to 7,5-8,0 while using a 10% sodium hydroxide solution. pH drift of the composition may be prevented by preferred inclusion of a pH buffer in the water phase at a pH of 8.0.

The viscosity of the composition was 6,400 cPs (Brookfield viscosity,S4,20 rpm); the yield stress value was 55 Pa. The cream polish composition was chemically and physically stable after 3 months at 40°C and, upon subsequently use, the composition provided excellent properties for removal of dead skin cells. Example 3

A cosmetic body scrub cream with the following ingredients was prepared:

Ingredients level (% by weight) INCI function

Demineralized water ad 100 Aqua solvent

Emulgade SE 6.0 mixed emulsifier* nonionic emulsifier

Sweet almond oil 4.5 Prunus Amygdalus

Dulcis Oil emollient

Pricerine 9099 3.0 Glycerin humectant Lanette O 3.0 Cetearyl Alcohol flow control

Cetiol V 2.0 Decyl Oleate emollient

Cetiol 868 1.8 Ethylhexyl Stearate emollient Chicken eggshell particles** 1.8 Calcium Carbonate exfoliating a;

Rhodicare D 0.5 Xanthan Gum flow control polymer Perfume qs

Preservative qs

Sodium Hydroxide, 10% to pH=8.0

* INCI: Glyceryl Stearate, Ceteareth-12, Ceteareth-20, Cetaryl Alcohol, Cetyl Palmitate ** with particle size of 297-354 μπι, separated by sieving

The composition was prepared as follows: Rhodicare D was dispersed in water by adding the powdered polymer to water while strongly agitating with a propeller mixer. As soon as the polymer has been properly dispersed glycerine, the chicken eggshell particles and the preservative system are added, and stirring is continued until a homogeneous dispersion has been obtained. The water phase of the emulsion is heated to 70-75°C. The oil phase is made by mixing the ingredients to 70-75°C, The oil phase is added to the water phase while stirring with a planetary mixer; spontaneous emulsification will be observed. The pre- emulsion is subjected to treatment with a rotor-stator mixer. The emulsion is cooled while stirring slowly with a planetary mixer. At 25°C the fragrance is added; solubilisation is not required, The pH is adjusted to 7,5-8,0 while using a 10% sodium hydroxide solution. pH drift of the composition may be prevented by preferred inclusion of a pH buffer at a pH of 8.0.

The viscosity of the composition was 8,200cPs (Brookfield viscosity, S5, 20rpm). The composition was chemically and physically stable after 3 months at 40°C and, upon subsequently use, the resulting body scrub composition provided excellent dead skin removing properties.

Example 4

A liquid abrasive hard surface cleaner, with the following ingredients was prepared:

Ingredients level ( % by weight) function

Water 80.0 % solvent

Fatty Alcohol Ethoxylate

(n=3; Bio-Soft N61-6) 10.0 % nonionic

Ethanol 4.0 % solvent

Chicken eggshell particles* 3.2 % abrasive

Propylene Glycol n-Butyl Ether

(Dowanol PnB) 2.0 % solvent

Sodium Magnesium Silicate

(Laponite XLS) 1.6 % clay

Acrylates/Steareth-20

Methacrylate Crosspolymer

(Aculyn 88) 0.8 % polymer

Preservative qs

Colorant qs

Fragrance (solubilised with

POE-20 oleyl alcohol) qs

Sodium hydroxide solution to pH 9.1

* with particle size of 149-210μιη, separated by sieving

The composition was prepared as follows: Laponite XLS is dispersed in water by adding the powdered clay to water while strongly agitating with a propeller mixer. As soon as the clay has been properly dispersed the surfactant is added and the mixture is stirred until homogeneous and viscous. Aculyn 88 is subsequently added, developing good yield stress value. Subsequently, chicken eggshells are added and mixed until homogeneous. Finally the preservative system, the dyes (optional) and the solubilized fragrance are added. The pH is adjusted to 9.1 using a 10% sodium hydroxide solution. The pH of the composition was 9.1; the viscosity of the composition was 2,200 cPs (Brookfield viscosity, S4, 20 rpm); the yield stress value was 71 Pa. The liquid abrasive cleaner composition was chemically and physically stable after 3 months at 40°C and, upon subsequently use, the composition provided excellent cleaning properties.

Claims

1. Aqueous liquid composition comprising from 1 to 30% by weight of chicken eggshell particles wherein at least 50% by weight of the chicken eggshell particles has a particle size of at least 74μιη and at most 595μιη, wherein the composition comprises a polymer providing an external structure to the composition, and wherein the pH of the composition is higher than 7.5 and lower than 9.

2. Composition according to claim 1, wherein at least 65% by weight of the chicken egg particle has a size of at least 210μιη and at most 420μιη.

3. Composition according to claims 1-2, wherein the pH is lower than 8.5.

4. Composition according to claims 1-3, further comprising from 1-20%) by weight of anionic surfactant.

5. Composition according to claims 1-4, further comprising from 0.5-12% by weight of non-ionic surfactant.

6. Composition according to claims 1-5, further comprising egg shell membrane particles.

7. Composition according to claims 1 -6, wherein the composition further comprising a buffer to maintain the pH of the composition over time within the pH ranges.

8. Composition according to claims 1-7, wherein the composition further comprises emollient at a level of from 0.2% to 40% by weight of the composition.

9. Method of preparing an aqueous composition comprising from 1 to 30% by weight of chicken eggshell particles wherein at least 50% by weight of the chicken eggshell particles has a particle size of at least 74μιη and at most 595μιη, wherein the composition comprises a polymer providing an external structure to the composition, and wherein the pH of the composition is higher than 7.5 and lower than 9, by ball-milling chicken eggshells to particles, subsequently dispersing the particles in a composition comprising the polymer material and subsequently setting the pH at higher than 7.5.

10. Method according to claim 9, further characterised by washing the chicken eggshell particles, ball-milling the chicken eggshell particles, wind sifting chicken eggshell particles, sterilizing the chicken eggshell particles, and subsequently sieving the chicken eggshell particles into fractions.

11. Method according to claims 9-10, wherein at least 65% by weight of the chicken eggshell particles has a particle size of at least 210μιη and at most 420μιη.

12. Method according to claims 9-11, wherein the composition is subsequently stored for at least 2 weeks after production.

13. Method of preparing chicken eggshell particles wherein at least 50% by weight of the chicken eggshell particles has a particle size of at least 74μιη and at most 595μιη, by washing and ball-milling the eggshells, wind sifting and sterilizing the resulting chicken eggshell particles, and subsequently sieving the chicken eggshell particles into fractions.

14. Method of treating the skin by removing dead skin cells from the skin surface with chicken eggshell particles, wherein the skin treatment comprises the steps of:

a. providing an aqueous liquid composition comprising from 1 to 30% by weight of chicken eggshell particles wherein at least 50% by weight of the chicken eggshell particles has a particle size of at least 74μηι and at most 595μιη, wherein the composition comprises a polymer providing an external structure to the composition, wherein the pH of the composition is higher than 7.5 and lower than 9, and wherein the composition comprises surfactant;

b. applying the composition to the skin;

c. adding water to wet the skin and develop a lather; and

15. Aqueous liquid composition comprising chicken eggshell particles for use in treatment of skin, wherein at least 65% by weight of the chicken eggshell particles has a particle size of at least 210μιη and at most 420μηι, wherein the composition comprises a polymer providing an external structure to the composition, and wherein the pH of the composition is higher than 7.5 and lower than 8.5.