WO2023128949A1

WO2023128949A1 - Skin care product comprising halloysite nanotubes

Info

Publication number: WO2023128949A1
Application number: PCT/TR2022/050589
Authority: WO
Inventors: Caner ACAR; Şamil Ercan ÖZCAN
Original assignee: Eczacibasi Tuketim Urunleri Sanayi ve Ticaret AS
Current assignee: Eczacibasi Tuketim Urunleri Sanayi ve Ticaret AS
Priority date: 2021-12-27
Filing date: 2022-06-14
Publication date: 2023-07-06
Anticipated expiration: 2024-06-27

Abstract

The subject of the invention relates to a skin product enabling the skin care agents, which provide various actions such as anti-aging, to be released into the skin over an extended period of time at a specified rate, i.e. in a controlled manner, in the presence of halloysite nanotubes, and thus, exhibiting long-lasting care action without irritating the skin. The skin product according to the invention basically comprises the halloysite nanotube carriers on which at least one skin care agent is loaded. In case the skin care agent loaded in the halloysite nanotubes has the anti-aging property, the product exhibits high performance when applied especially in the nights, the most favorable time for the formation of the new healthy skin cells.

Description

SKIN CARE PRODUCT COMPRISING HALLOYSITE NANOTUBES

Subject of the Invention

The subject of the invention relates to a skin product enabling the skin care agents, which provide various actions such as anti-aging, to be released into the skin over an extended period of time at a specified rate, i.e. in a controlled manner, in the presence of halloysite nanotubes, and thus, exhibiting long-lasting care action without irritating the skin.

State of the Art

The skin is an important part of the body, which protects the internal organs from the external mechanical, chemical and biological effects, helps with the regulation of the body temperature, enables its elastic structure and natural flora to be preserved by keeping the water content above 10% owing to the natural moisturizing factors it contains, and is able to repair itself by carrying out the production of collagen and protein. The function of renewal and repair of the skin cells takes place during the sleep in the night. Since the individual is in an enclosed ambience, in an inactive state and in the darkness, the free radical damage is at the lowest level in the night. Therefore, the night is the most suitable time for the elimination of the toxic substances that have accumulated during the day and for the formation of the new healthy skin cells. Accordingly, the anti-aging night creams were developed, which repair the skin damage caused by the water loss and other factors by nourishing the skin while the body is resting during the night. It is desirable that the night creams remain on the skin throughout the night. To be able to achieve this, these creams should not be rapidly absorbed by the skin. In this way, the cream layer will remain for a long time on the skin to prevent the moisture loss from the surface and to enable the water to pass to the bottom layers over time.

In order to achieve longer-lasting action for the conventional anti-aging skin products, the skin repair active ingredients are encapsulated with the synthetic carriers such as Tween 20, polyethylene glycol derivatives, colloidal silica and the like. However, the synthetic carriers cause the irritation of especially the sensitive and vulnerable skin. Thus, while the products comprising these carriers are expected to moisturize the skin, regulate the skin flora and repair the skin, they, to the contrary, irritate the skin due to the carriers they comprise and thus render the skin even more vulnerable to the pathogenic microorganisms. For this reason, the skin care products, which exhibit long- lasting anti-aging action without irritating the skin and are as such suitable for use especially in the night, are needed.

Controlled release is a process whereby an active ingredient is delivered from within a system to a target area over an extended period of time, at a specified rate and at the required quantity and thus the active ingredient is enabled to maintain its action for a long time in said area. The carriers are the systems on the surface of which the active ingredients are bound/loaded and via which the active ingredient is thus able to be released in a controlled manner. While the mineral halloysite, belonging to the kaolin group, having the composition A SizOsfOHj^HzO and having a tubular form, features the same properties on the outer surface as those of negatively charged SiCh in the pH range of 6-7, its inner cylinder core has the same properties as those of the positively charged AI2O3. Since it features, owing to its tubular structure and its surface charges, the ability to simultaneously bind more than one inorganic and/or organic active ingredient required for the skin health, is nontoxic, is biocompatible, is able to be absorbed through the skin, does not irritate the skin, has a long-term thermodynamic stability and has great surface area, halloysite is a mineral quite suitable for use as a carrier for the controlled release. The halloysite nanotubes increase the stability of the active ingredient they carry, reduce the interaction of the active ingredient with the other substances in the ambience, and thus, enable the active ingredient to maintain its activity for a longer time in the environments that would cause the degeneration of the active ingredient when present in the unloaded state.

In order to enable the skin care agents with actions such as anti-aging and/or repair and/or moisturizing to be released into the skin at a specified quantity and at a specified rate over an extended period of time, i.e. in a controlled manner, and thus enable the same to provide long-lasting action on the skin, a skin care product, which comprises the halloysite carriers loaded with at least one skin care agent, preferably with anti-aging feature, has been developed within the scope of the invention. Owing to comprising the non-synthetic halloysite carriers, the product, unlike the conventional anti-aging products, does not irritate the skin. The halloysite nanotubes, owing to having different surface charges and featuring the ability to bind the substances with different properties, may simultaneously contain the agents having different properties and thus the users may obtain many benefits from the use of a single product.

Object of the Invention

An object of the invention is to develop a skin care product, which enables the skin care agents to be released into the skin at a specified rate over an extended period of time, i.e. in a controlled manner, and thus provides a long-lasting skin care action on the skin.

Another object of the invention is to enable the halloysite nanotubes to be used in the skin products; in other words, to provide a new field of use for the halloysite tubes.

Another object of the invention is to develop a skin care product, which, owing to comprising the halloysite nanotubes with the ability to simultaneously deliver many agents with different properties, exhibits many actions alone.

Another object of the invention is to develop a skin care product, which, owing to comprising as the carrier the nanotubes of the halloysite being a skin-compatible and natural mineral, exhibits the skin care action without irritating the skin.

Another object of the invention is to develop a night cream, which exhibits long-lasting anti-aging action without irritating the skin.

Description of the Invention

The subject of the invention relates to a skin product enabling the skin care agents, which provide various actions such as anti-aging, to be released into the skin over an extended period of time at a specified rate, i.e. in a controlled manner, in the presence of halloysite nanotubes, and thus, exhibiting long-lasting care action without irritating the skin. The product according to the invention basically comprises the halloysite nanotube carriers on which at least one skin care agent is loaded. The skin care agent loaded on the halloysite nanotubes is preferably an agent with the anti-aging property, preferably ellagic acid.

Ellagic acid which is available in the pomegranate peels has antioxidant, antimutagen and anticancer properties. Ellagic acid reduces the skin damage caused by the sun, inhibits the free radicals, slows down the aging and prevents the formation of brown spots on the skin. Besides all these properties, ellagic acid also has the skin-whitening effect.

In a preferred embodiment of the product according to the invention, the halloysite nanotubes contain the skin care agent at a ratio of 10% based on their weight.

The product according to the invention comprises the halloysite nanotubes, loaded with the skin care agent, preferably at a ratio of 5-10% by weight.

The product according to the invention additionally comprises an oil phase containing the oil-soluble ingredients and a water phase containing the water-soluble ingredients. The oil phase basically contains at least one type of oil, at least one surfactant enabling the water phase to be homogeneously dispersed in the oil phase and at least one skin care agent. The water phase basically contains water, at least one skin care agent and at least one surfactant.

The skin product according to the invention comprises, in the oil phase, 0.5-2% by weight oil, 3.5-11% by weight surfactant and 6.5-17% by weight skin care agent; and in the water phase, 40-50% by weight water, 0.1-0.5% by weight surfactant and 2.6-8.5% by weight skin care agent.

The oil/s contained in the product according to the invention is/are selected from, but not limited to, squalene, coconut oil, olive oil, sunflower oil, sweet almond oil, jojoba oil, apricot kernel oil, avocado oil, sesame oil, macadamia oil, corn oil, wheat germ oil, safflower oil, borage oil and willow thorn oil.

In a preferred embodiment, the product according to the invention comprises squalene as the oil in the oil phase. The surfactant/s contained in the product according to the invention may be selected from, but are not limited to, the compounds xanthan gum, glyceryl oleate, sodium stearoyl lactylate, glyceryl stearate citrate, glyceryl stearate, cetearyl alcohol, polyglyceryl-2 dipolyhydroxystearate, polyglyceryl-3 diisostearate, polyglyceryl-2 sesquiisostearate and polyglyceryl-3 polyricinoleate.

In a preferred embodiment, the product according to the invention comprises xanthan gum as the surfactant in the water phase.

In a preferred embodiment, the product according to the invention comprises glyceryl stearate citrate preferably at a ratio of 1-4% by weight, sodium stearoyl lactylate preferably at a ratio of 0.5-1% by weight, cetearyl alcohol (50%) preferably at a ratio of 1-3% by weight and glyceryl stearate preferably at a ratio of 1-3% by weight as the surfactants in the oil phase.

The skin care agent/s contained in the product according to the invention may be selected from, but are not limited to, the agents moisturizing the skin and/or repairing the skin and/or tightening the skin and/or regulating the skin flora, preferably from the polyhydric alcohols such as glycerin, galactoarabinan, propylene glycol, pentylene glycol and caprylyl glycol, or the vitamins such as retinol (vitamin A), riboflavin (vitamin B2), niacinamide (vitamin B3), panthenol (provitamin B5), biotin, folic acid and tocopheryl acetate (vitamin E), or the extracts such as bisabolol, allantoin, lanolin, urea, sodium hyaluronate, PEG-75 lanolin, sodium lactate, sodium gluconate, sodium PCA, olive oil PEG-7 ester, saccharide isomerate, sugar leaf (stevia rebaudiana) extract, coconut (cocos nucifera) fruit extract and aloe barbadensis leaf extract, or the sugars such as fructose, maltose, glucose, sorbitol, maltodextrin, trehalose and lactose, or the proteins such as collagen, keratin and milk protein, or the probiotic-prebiotic additives such as bifida ferment lysate, alpha-glucan oligosaccharide, lactobacillus and inulin, or the amino acids available in the natural skin structure such as arginine, aspartic acid, glycine, alanine, serine, valine, proline, threonine, isoleucine, histidine and phenylalanine, or the skin softeners such as ethylhexyl palmitate, isopropyl myristate, isopropyl palmitate, caprylic/capric triglyceride and coco caprylate/caprate, or the silicones such as dimethicon, or the vegetable oils such as jojoba oil, almond oil and avocado oil, or the hydrocarbon oils such as vaseline, squalene, paraffin and mineral oil, or the fatty acids or the fatty alcohols or the esters or the peptides or the vegetable waxes or the phospholipids or the sterols.

In a preferred embodiment, the product according to the invention comprises coco caprylate/caprate preferably at a ratio of 3-8% by weight, caprylic/capric triglyceride preferably at a ratio of 3-8% by weight and vitamin E preferably at a ratio of 0.5-1% by weight as the skin care agents in the oil phase.

In a preferred embodiment, the product according to the invention comprises glycerin preferably at a ratio of 1-4% by weight, panthenol preferably at a ratio of 1-3% by weight, aloe barbadensis leaf extract preferably at a ratio of 0.1-0.5% by weight and galactoarabinan preferably at a ratio of 0.5-1% by weight as the skin care agents in the water phase.

In a preferred embodiment, the product according to the invention comprises, in addition to the main ingredients, at least one pH regulating agent, of type and quantity suitable for adjusting the pH of the product to a value in the range of 5-5.5, preferably at a ratio of 0.1-0.5% by weight. The pH regulating agent is preferably citric acid (20%).

In a preferred embodiment, the product according to the invention comprises, in addition to the main ingredients, at least one preservative agent preferably at a ratio of 0.2-1% by weight.

For the choice of the preservative agents to be used in the product, the properties of these agents such as their effects on the skin, whether they are natural or of natural origin, their water solubility, the pH values at which they exhibit activity, their odors and whether they cause color change in the finished product are determining. For this reason, the preservative agent/s contained in the product according to the invention may be selected preferably from, but are not limited to, the compounds sodium benzoate, benzoic acid, levulinic acid, benzyl alcohol, pentylene glycol, potassium sorbate and sodium levulinate, which are natural or of natural origin, have high water solubility, are odorless or pleasant-smelling and cause no color change in the finished product. In a preferred embodiment, the product according to the invention comprises sodium benzoate preferably at a ratio of 0.1-0.5% by weight and potassium sorbate preferably at a ratio of 0.1-0.5% by weight as the preservative agents.

In a preferred embodiment, the product according to the invention comprises, in the water phase, water preferably at a ratio of 40-50% by weight, at least one surfactant preferably at a ratio of 0.1-0.5% by weight and at least one skin care agent preferably at a ratio of 2.6-8.5% by weight; in the oil phase, at least one type of oil preferably at a ratio of 0.5-2% by weight, at least one surfactant preferably at a ratio of 3.5-11% by weight and at least one skin care agent preferably at a ratio of 6.5-17% by weight; and in addition to these phases, the halloysite nanotubes, loaded with at least one anti-aging agent, preferably at a ratio of 5-10% by weight, at least one preservative agent preferably at a ratio of 0.2-1% by weight and at least one pH regulating agent preferably at a ratio of 0.1-0.5% by weight.

In said embodiment, the product comprises the xanthan gum as the surfactant in the water phase, glycerin preferably at a ratio of 1-4% by weight, panthenol preferably at a ratio of 1-3% by weight, aloe barbadensis leaf extract preferably at a ratio of 0.1-0.5% by weight and galactoarabinan preferably at a ratio of 0.5-1% by weight as the skin care agents in the water phase, squalene as the oil in the oil phase, glyceryl stearate citrate preferably at a ratio of 1-4% by weight, sodium stearoyl lactylatepreferably at a ratio of 0.5-1% by weight, cetearyl alcohol (50%) preferably at a ratio of 1-3% by weight and glyceryl stearate preferably at a ratio of 1-3% by weight as the surfactants in the oil phase, coco caprylate/ca prate preferably at a ratio of 3-8% by weight, caprylic/capric triglyceride preferably at a ratio of 3-8% by weight and vitamin E preferably at a ratio of 0.5-1% by weight as the skin care agents in the oil phase, sodium benzoate preferably at a ratio of 0.1-0.5% by weight and potassium sorbate preferably at a ratio of 0.1-0.5% by weight as the preservative agents and citric acid (20%) as the pH regulating agent.

The skin product according to the invention is preferably a cream particularly suitable for use in the night.

The subject of the invention further relates to a method for obtaining the skin product according to the invention, which skin product comprises the halloysite nanotubes loaded with at least one skin care agent and enables the skin care agent to be released into the skin in a controlled manner, said method comprising the steps of

• preparing the water phase and heating the same to 75-80 °C,

• preparing the oil phase and heating the same to 75-80 °C,

• slowly adding the oil phase to the water phase being stirred at 5000 rpm,

• stirring the mixture of water and oil phases for 5 minutes,

• after stirring, cooling the mixture of water and oil phases to 30-35 °C, and

• adding the halloysite nanotubes loaded preferably with at least one skin care agent with anti-aging property to the mixture being stirred at 500 rpm

The method according to the invention comprises the step of adding at least one preservative agent to the mixture after the addition of halloysite nanotubes loaded with the skin care agent.

The method according to the invention comprises the step of adding at least one pH regulating agent to the mixture after the addition of all the ingredients. A pH regulating agent of type and quantity suitable for adjusting the pH to a value preferably in the range of 5-5.5 is added.

In the method according to the invention, in case the product comprises glycerin as the skin care agent in the water phase, the water phase is prepared by dispersing the surfactant into glycerin, then adding water to these ingredients, stirring the phase for at least 5 minutes at 3500 rpm and adding the other skin care agents to the phase after the stirring.

Owing to the described product, a specified quantity of the skin care agents is released into the skin at a specified rate for an extended period of time, i.e. in a controlled manner, thereby providing a long-lasting action on the skin, and since the halloysite nanotubes are used instead of a synthetic carrier, no irritation is caused in the skin. In case the skin care agent is an anti-aging agent, the product exhibits high performance when applied to the skin especially in the nights, the most favorable time for the formation of the new healthy skin cells.

Claims

1. A skin product, which enables the skin care agents to be released into the skin in a controlled manner and thus exhibits a long-lasting care action without irritating the skin, characterized in that the skin product comprises the halloysite nanotubes loaded with at least one skin care agent.

2. A skin product according to Claim 1 characterized in that the skin care agent is an anti-aging agent.

3. A skin product according to Claim 1 or Claim 2 characterized in that the skin product comprises ellagic acid as the skin care agent.

4. A skin product according to any one of Claims 1-3 characterized in that the halloysite nanotubes contain the skin care agent at a ratio of 10% based on their weight.

5. A skin product according to any one of Claims 1-4 characterized in that the skin product comprises the halloysite nanotubes, loaded with the skin care agent, preferably at a ratio of 5-10% by weight.

6. A skin product according to any one of the preceding claims characterized in that the skin product comprises

• an oil phase containing at least one type of oil, at least one surfactant enabling the water phase to be homogeneously dispersed in the oil phase and at least one skin care agent,

• a water phase containing water, at least one skin care agent and at least one surfactant.

7. A skin product according to Claim 6 characterized in that the skin product comprises the oil in the oil phase at a ratio of 0.5-2% by weight.

8. A skin product according to Claim 6 or Claim 7 characterized in that the skin product comprises squalene as the oil.

9. A skin product according to Claim 6 characterized in that the skin product comprises the surfactant in the oil phase at a ratio of 3.5-11% by weight.

10. A skin product according to Claim 6 or Claim 9 characterized in that the skin product comprises glyceryl stearate citrate and/or sodium stearoyl

9 lactylateand/or glyceryl stearate and/or 50% cetearyl alcohol as the surfactant in the oil phase.

11. A skin product according to Claim 10 characterized in that the skin product comprises glyceryl stearate citrate at a ratio of 1-4% by weight, sodium stearoyl lactylate at a ratio of 0.5-1% by weight, 50% cetearyl alcohol at a ratio of 1-3% by weight and glyceryl stearate at a ratio of 1-3% by weight.

12. A skin product according to any one of Claims 6-12 characterized in that the skin product comprises the skin care agent in the oil phase at a ratio of 6.5-17% by weight.

13. A skin product according to Claim 6 or Claim 12 characterized in that the skin product comprises coco caprylate/caprate and/or caprylic/capric triglyceride and/or vitamin E as the skin care agent in the oil phase.

14. A skin product according to Claim 13 characterized in that the skin product comprises coco caprylate/caprate at a ratio of 3-8% by weight, caprylic/capric triglyceride at a ratio of 3-8% by weight and vitamin E at a ratio of 0.5-1% by weight.

15. A skin product according to any one of Claims 6-14 characterized in that the skin product comprises the water in the water phase at a ratio of 40-50% by weight.

16. A skin product according to any one of Claims 6-15 characterized in that the skin product comprises the surfactant in the water phase at a ratio of 0.1-0.5% by weight.

17. A skin product according to Claim 6 or Claim 16 characterized in that the skin product comprises xanthan gum as the surfactant in the water phase.

18. A skin product according to any one of Claims 6-17 characterized in that the skin product comprises the skin care agent in the water phase at a ratio of 2.6-8.5% by weight.

19. A skin product according to Claim 6 or Claim 18 characterized in that the skin product comprises glycerin and/or panthenol and/or aloe barbadensis leaf extract and/or galactoarabinan as the skin care agent in the water phase.

20. A skin product according to Claim 19 characterized in that the skin product comprises glycerin at a ratio of 1-4% by weight, panthenol at a ratio of 1-3% by weight, aloe barbadensis leaf extract at a ratio of 0.1-0.5% by weight and galactoarabinan at a ratio of 0.5-1% by weight.

21. A skin product according to any one of the preceding claims characterized in that the skin product comprises at least one preservative agent.

22. A skin product according to Claim 21 characterized in that the skin product comprises the preservative agent/agents at a ratio of 0.2-1% by weight.

23. A skin product according to Claim 21 or Claim 22 characterized in that the skin product comprises sodium benzoate and/or potassium sorbate as preservative agents.

24. A skin product according to Claim 23 characterized in that the skin product comprises sodium benzoate at a ratio of 0.1-0.5% by weight and potassium sorbate at a ratio of 0.1-0.5% by weight.

25. A skin product according to any one of the preceding claims characterized in that the skin product comprises at least one pH regulating agent.

26. A skin product according to Claim 25 characterized in that the skin product comprises the pH regulating agent at a ratio of 0.1-0.5% by weight.

27. A skin product according to Claim 25 or Claim 26 characterized in that the skin product comprises 20% citric acid as the pH regulating agent.

28. A skin product according to any one of Claims 1-5 characterized in that the skin product comprises

• a water phase containing water, at least one skin care agent and at least one surfactant,

• at least one preservative agent,

• at least one pH regulating agent.

29. A skin product according to Claim 28 characterized in that the skin product comprises

• in the oil phase, the oil at a ratio of 0.5-2% by weight, the surfactant at a ratio of 3.5-11% by weight and the skin care agent at a ratio of 6.5-17% by weight,

11 • in the water phase, the water at a ratio of 40-50% by weight, the surfactant at a ratio of 0.1-0.5% by weight and the skin care agent at a ratio of 2.6-8.5% by weight,

• the preservative agent at a ratio of 0.2-1% by weight,

• the pH regulating agent at a ratio of 0.1-0.5% by weight. A skin product according to Claim 28 or Claim 29 characterized in that the skin product comprises

• in the oil phase, squalene as the oil, glyceryl stearate citrate, sodium stearoyl lactylate, glyceryl stearate and 50% cetearyl alcohol as the surfactants, and coco caprylate/caprate, caprylic/capric triglyceride and vitamin E as the skin care agents,

• in the water phase, xanthan gum as the surfactant and glycerin, panthenol, aloe barbadensis leaf extract and galactoarabinan as the skin care agents,

• sodium benzoate and potassium sorbate as the preservative agents,

• citric acid 20% by weight as the pH regulating agent. A skin product according to Claim 30 characterized in that the skin product comprises

• in the oil phase, glyceryl stearate citrate at a ratio of 1-4% by weight, sodium stearoyl lactylate at a ratio of 0.5-1% by weight, 50% cetearyl alcohol at a ratio of 1-3% by weight, glyceryl stearate at a ratio of 1-3% by weight, coco caprylate/caprate at a ratio of 3-8% by weight, caprylic/capric triglyceride at a ratio of 3-8% by weight and vitamin E at a ratio of 0.5-1% by weight,

• in the water phase, glycerin at a ratio of 1-4% by weight, panthenol at a ratio of 1-3% by weight, aloe barbadensis leaf extract at a ratio of 0.1- 0.5% by weight and galactoarabinan at a ratio of 0.5-1% by weight,

• sodium benzoate at a ratio of 0.1-0.5% by weight and potassium sorbate at a ratio of 0.1-0.5% by weight as the preservative agents.

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32. A skin product according to any one of the preceding claims characterized in that the skin product is a cream.

33. A method for obtaining a skin product according to any one of the preceding claims characterized in that the method comprises the steps of

• preparing the water phase and heating the same to 75-80 °C,

• preparing the oil phase and heating the same to 75-80 °C,

• slowly adding the oil phase to the water phase being stirred at 5000 rpm,

• stirring the mixture of water and oil phases for 5 minutes,

• after stirring, cooling the mixture of water and oil phases to 30-35 °C,

• adding the halloysite nanotubes loaded with at least one skin care agent to the mixture being stirred at 500 rpm.

34. A method according to Claim 33 characterized in that in case the product comprises glycerin as the skin care agent in the water phase, the water phase is prepared by dispersing the surfactant into glycerin, then adding water to these ingredients, stirring the phase for at least 5 minutes at 3500 rpm and adding the other skin care agents to the phase after the stirring.

35. A method according to Claim 33 or Claim 34 characterized in that the method comprises the step of adding at least one preservative agent to the mixture after the addition of the halloysite nanotubes loaded with at least one skin care agent.

36. A method according to any one of Claims 33-35 characterized in that the method comprises the step of adding at least one pH regulating agent to the product after the addition of all the ingredients, said pH regulating agent being of the type and quantity suitable for adjusting the pH of the product to a value preferably in the range of 5-5.5.

37. A method according to any one of Claims 33-36 characterized in that the skin care agent has the anti-aging property.

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