KR20170103628A - Composition containing Cellulose Nanofiber water dispersions - Google Patents

Abstract

The present invention relates to a water-dispersible cellulose nanofiber dispersion which is dispersed in aqueous solutions and in which an alcohol group in cellulose-based raw materials is substituted with a carboxyl group. The water-dispersible cellulose nanofiber dispersion of the present invention is soft and less sticky compared to existing cellulose, and nanofibers formed in skin can improve moisturizing functions and elasticity. In addition, when applied to formulations, the water-dispersible cellulose nanofiber dispersion gets to have viscosity, and thus can be widely applied to development of cosmetic ingredients.

Description

[0001] The present invention relates to a cellulose nanofiber water dispersion composition,

The present invention relates to a cellulose aqueous dispersion composition.

Cellulose used in the human body includes natural cellulose, cellulose derivatives, bio-cellulose and the like. Of these, natural cellulose is a powder of tens of micrometers in size and does not dissolve in water. It is mainly used for scrubbing and peeling gel. The cellulose derivative may be obtained by substituting the hydroxy alcohol group of cellulose, and includes hydroxyethyl cellulose, carboxymethyl cellulose and the like which are substituted for dissolving in water because cellulose itself does not dissolve in water. Such water-soluble cellulose is in the form of a polymer and is mainly used as a thickening agent. Bio cellulose is a cellulose nanofiber synthesized from bacterial cellulose, which has thinner fibers, higher crystallinity, and higher physical strength than cellulose derived from plants, but is used mainly in mask pack sheets because it is synthesized in gel or sheet form. It has a drawback that it is difficult to apply the formulation. Therefore, it is necessary to disperse the cellulose in an aqueous solution so as to be contained in a cosmetic formulation while maintaining the nanofiber form.

Disclosure of the Invention The present invention provides a water-dispersible cellulose nano fiber dispersion for human body, a composition containing the same, and a process for producing the same.

Disclosure of the Invention In order to solve the above problems, the present invention provides a water-dispersible cellulose nano fiber dispersion for a human body, a method for producing the same, and a composition comprising the same.

DISCLOSURE OF THE INVENTION The present inventors have conducted studies to solve the problems of the prior art and found that a cellulose nano fiber dispersion in which an alcohol group of a cellulose raw material is substituted with a carboxyl group is dispersed in an aqueous solution and a dispersion thereof The present inventors have found that the composition of the present invention has a favorable human body characteristic, in particular, a skin mountability, a high moisture holding ability, an increase in elasticity, a decrease in skin friction and an increase in strength. Accordingly, the present invention has been completed on the basis of the application of the water-dispersed cellulose nano fiber dispersion to the human body, for example, the utility as a cosmetic or quasi-drug.

The present inventors have found that the water-dispersed cellulose nano fiber dispersion according to the present invention and the composition containing the water-dispersed cellulose nano fiber dispersion have the following characteristics:

And exhibits excellent skin adhesion. Means that the water-dispersed cellulose nanofiber dispersion is applied to the skin while maintaining the nanofiber structural physicochemical characteristics and / or water dispersibility. The skin is an organs covering the outside of an animal, and from the outside it means three distinct layers of epidermis, dermis and subcutaneous fat layer.

And exhibits a high moisture holding ability. The 'moisture holding ability' means a force or ability to attract moisture around the water-dispersed cellulose nanofiber dispersion and / or a force or ability to maintain the surrounding water. Moisture holding ability and moisture holding ability are in proportion to each other.

It shows the effect of increasing elasticity. The 'elasticity' refers to the resistance to the applied external force, the same as the 'restoring force', and reflects the compactness of the surface structure. It means that the film-forming ability of the water-dispersed cellulose dispersion and the resistance to the external force of the object to which the water-dispersed cellulose dispersion is applied are improved, improved or improved.

Increasing power. The 'incremental force' means a viscosity increasing ability. Means that the water-dispersed cellulose dispersion has the ability to increase the viscosity while maintaining the nanofiber structural and physicochemical characteristics.

Indicating a decrease in frictional force. The 'frictional force' is a force that interferes with the movement of the object contacting the contact surface, and the skin friction is reflected in the skin roughness. Means that the degree of hindrance to the movement of the object contacting the contact surface to which the water-dispersed cellulose dispersion is applied is decreased, which means that the softness is increased, improved or improved, or the roughness is reduced.

The above-mentioned characteristics of the water-dispersed cellulose nano fiber dispersion are also maintained in the composition containing the water-dispersed cellulose nano fiber dispersion.

The water-dispersed cellulose nano fiber dispersion according to the present invention is obtained by replacing an alcohol group of a cellulose raw material with a carboxyl group and dispersed in an aqueous solution.

Examples of the "cellulose-based raw material" used in the present invention include powdery cellulose obtained by crushing various types of wood-derived craft paper or sulfite pulp with a high-pressure homogenizer or mill, Microcrystalline cellulose powder purified by a chemical treatment such as microcrystalline cellulose, bacterial cellulose, and the like. In addition, plants such as kenaf, hemp, rice, bacchus and bamboo may also be used. Of these, the use of bacterial cellulose nanofibers is advantageous in that it does not require pretreatment and can utilize the inherent strengths of the bacterial cellulose nanofibers. In addition, when woody or non-woody cellulosic raw materials are used, a finely divided step is required to produce a water dispersion, while bacterial cellulose nanofibers can be used to make small and constant diameter nanofiber dispersions without splitting There are advantages.

The aqueous solution is a solution obtained by using water as a solvent. The aqueous solution may contain any component that maintains the structural physicochemical characteristics and / or water dispersibility of the aqueous dispersion of cellulose nano fiber dispersion as a nanofiber.

The alcohol group of the cellulose raw material may be replaced with the carboxyl group by a variety of methods in the art, but the oxidizing agent and the cellulose raw material may be added to the distilled water in which the N-oxyl compound is dissolved and stirred. This process will be described later.

The number average diameter of the water-dispersed cellulose nano fiber dispersion according to the present invention is 0.1 to 200 nm, preferably 1 to 150 nm, more preferably 20 to 100 nm, and most preferably 30 to 60 nm. The maximum diameter of the cellulose nano fiber dispersion produced by the present invention is about 0.1 to 200 nm, preferably about 1 to 150 nm, more preferably about 20 to 100 nm, and most preferably about 30 to 60 nm . The cellulose nanofibers may be in the form of a single microfibril or nanofibers intertwined with each other, but are not particularly limited thereto.

And has a number-average diameter and a maximum diameter range, which is advantageous for human application, and is advantageous for use, for example, as a cosmetic composition or a quasi-drug composition.

The method for producing a water dispersed cellulose nano fiber dispersion according to the present invention comprises the following steps:

Dissolving the N-oxyl compound in distilled water;

Adding and agitating the cellulose raw material and the oxidizing agent to the melt; and

And removing the reactants through a washing process.

The 'N-oxyl compound' which can be used in the present invention is a catalyst and is used for promoting the oxidation reaction in the present invention. The N-oxyl compound includes, for example, 2,2,6 , 6-tetramethyl-1-piperidine-oxy radical (TEMPO); The hydroxyl group of the 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine-oxy radical (4-hydroxy TEMPO) is etherified with an alcohol or esterified with a carboxylic acid or sulfonic acid 4-hydroxy TEMPO derivatives imparting suitable hydrophobicity; Or an azadimethan-type nitroxyl radical; , And most preferably 2,2,6,6-tetramethyl-1-piperidine-oxy radical (TEMPO) can be used.

The amount of the N-oxyl compound to be used is not particularly limited as long as it is a catalyst amount capable of converting the cellulose raw material into nanofiber. For example, 0.01 to 100 mmol, preferably 0.01 to 50 mmol, particularly preferably 0.05 to 30 mmol can be used for 1 g of the cellulose-based dry raw material.

Examples of the 'oxidizing agent' used in the oxidation reaction of the cellulose raw material include halogen, hypohalogen acids, halogenated acids, perhalogen acids or their salts, halogen oxides, halogen peroxides and the like, And chlorine, hypochlorous acid, chlorous acid, perchloric acid or salts thereof, chlorine oxide, and chlorine peroxide are preferable, and sodium hypochlorite is most preferably used. Sodium hypochlorite is particularly advantageous because it is economical in terms of nanofiber production costs and is the most commonly used low cost and environmentally friendly current industrial process.

The amount of the oxidizing agent to be used can be selected within a range capable of promoting the oxidation reaction. For example, 0.5 to 500 mmol, preferably 0.5 to 50 mmol, particularly preferably 2.5 to 25 mmol can be used for 1 g of the cellulose-based dry raw material.

In the method for producing the cellulose nano fiber dispersion according to the present invention, bromide is not substantially used.

The substantially not used means to use 0.1 mmol or less, preferably 0.01 mmol or less, more preferably 0.001 mmol or less, based on 1 g of the cellulose-based dry stock.

Bromide, for example, bromine chloride, may cause toxicity problems in the trachea or lungs, and may not be used in the present invention because of safety problems during handling and environmental pollution due to heavy metals during disposal.

According to the present invention, it is possible to produce a water-dispersed cellulose nanofiber dispersion having excellent efficacy without using bromide.

The method for preparing a water-dispersed cellulose dispersion according to the present invention is characterized in that the oxidation reaction can proceed smoothly even at a mild condition at room temperature of about 15 to 30 ° C. Since the carboxyl group is generated in the cellulose structure as the oxidation reaction progresses, the pH of the reaction solution lowers. Therefore, for efficient oxidation reaction, the pH of the reaction solution should be maintained at about 8 to 12, more preferably about 10 to 11, by continuously adding an alkaline solution. The reaction time of the oxidation reaction can be suitably set and is not particularly limited, but is, for example, about 0.5 to 60 hours, preferably about 1 to 50 hours, particularly preferably about 24 to 48 hours.

In another aspect, the present invention provides a cosmetic composition comprising a water-dispersed cellulose nano fiber dispersion characterized by dispersing the cellulosic raw material in an aqueous solution as a cellulose nano fiber dispersion wherein the alcohol group of the cellulose raw material is substituted with a carboxyl group.

The cosmetic composition of the present invention can be used as an adjuvant commonly used in the cosmetics field, for example, a lipid material, an organic solvent, a solubilizing agent, a thickening agent, a gelling agent, a softening agent, an antioxidant, a suspending agent, a stabilizer, a foaming agent, Preservatives, vitamins, blockers, wetting agents, essential oils, dyes, pigments, hydrophilic or lipophilic active agents, lipid vesicles, as well as cosmetics, cosmetics, As well as any other ingredients commonly used in cosmetics or dermatology, such as cosmetics or dermatological sciences.

The water dispersed cellulose nano fiber dispersion for human body according to the present invention may contain 0.0001 to 10, preferably 0.0005 to 5,% by dry weight based on the total weight of the cosmetic composition.

In the present invention, the term "cosmedical, cosmeceutical" means a product having a specialized function which is emphasized on physiologically active effects and effects, unlike general cosmetics, , Products that help to whiten skin, products that help to improve skin wrinkles, and products that help protect skin from UV rays or skin lightly.

The cosmetic composition containing the cosmetic composition according to the present invention may be prepared in any form conventionally produced in the art and may be in the form of a solution, a suspension, an emulsion, a paste, a gel, a cream, a lotion, a powder, But are not limited to, surfactant-containing cleansing, oils, powder foundations, emulsion foundations, wax foundations and sprays. More specifically, the present invention relates to a cosmetic lotion composition comprising a lotion, a cosmetic lotion, a nourishing lotion, a nutritive cream, a massage cream, a moisture cream, a moisture gel cream, a lotion, a gel, Packs, ointments, sticks, patches, sprays or powders.

In another aspect, the present invention provides a quasi-drug composition comprising a water-dispersed cellulose nano fiber dispersion characterized by dispersing the cellulosic raw material in an aqueous solution as a cellulose nano fiber dispersion wherein the alcohol group of the cellulose raw material is substituted with a carboxyl group.

In the present invention, " quasi-drugs " are used for the purpose of treating, alleviating, treating or preventing diseases of humans or animals, those which are weak to the human body or do not act directly on the human body, A product which is one of the products used for sterilization, insecticide and similar uses for the prevention of infection and which is used for diagnosis, treatment, alleviation, treatment or prevention of diseases of human or animal, Means an article, not an apparatus, not an apparatus, a machine or an apparatus, used for the purpose of giving a pharmacological effect to the structure and function of a person or an animal, and includes external preparations for skin and personal hygiene products.

In the present invention, the term "external preparation for skin" means a solid, semi-solid or liquid external preparation which can be easily applied to skin by mixing drugs with various bases such as oils, petrolatum, lanolin, glycerol and the like. External formulations are not particularly limited, but may include, for example, powders, gels, ointments, creams, liquids or aerosol formulations.

The water dispersed cellulose nano fiber dispersion for human body according to the present invention may contain 0.0001 to 10, preferably 0.0005 to 5,% by dry weight, based on the total weight of the quasi-drug composition.

The water-dispersed cellulose nano fiber dispersion of the present invention is not only soft and sticky as in the conventional cellulose, but also has the ability to increase the elasticity and moisturizing power of the nanofibers formed on the skin and to increase the strength when applied to a formulation. Can be usefully used.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate exemplary embodiments of the invention and, together with the description of the invention, It should not be construed as limited.
Fig. 1 is a photograph of (a) a cellulose nanofiber of Comparative Example 1, and (b) a photograph of a water-dispersed cellulose nanofiber dispersion after chemical treatment of Example 1. Fig.
2 is a SEM photograph of pig skin before and after applying Example 1. Fig.
3 is a graph showing changes in the contact angle of water with time in (a) porcine skin coated with cellulose according to Examples and Comparative Examples, and (b) micrographs of initial contact angles.
4 is a graph showing frictional force data measured after applying Example 1 to the skin.
5 is a graph showing viscosity data of the essence formulations (Comparative Example 4, Examples 2 and 3).
FIG. 6 is a graph showing changes in water contact angle with time in pig skin applied with Comparative Examples 4 and 2. FIG.

Hereinafter, embodiments of the present invention will be described in detail to facilitate understanding of the present invention. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the following embodiments. Embodiments of the invention are provided to more fully describe the present invention to those skilled in the art.

Example  1: Chemical treatment of cellulose

A certain amount of bacterial cellulose sheet and sodium hypochlorite and 2,2,6,6-tetramethyl-1-piperidine-N-oxy radical (hereinafter referred to as TEMPO) catalyst were used for the chemical treatment of cellulose. After the TEMPO catalyst was dissolved in the distilled water, the cellulose sheet was added, sodium hypochlorite was added thereto, and the mixture was stirred while maintaining the pH at 10 or higher to prepare a cellulose sheet in the form of a nanofiber in which the cellulose sheet was dispersed in water (FIG. The prepared aqueous dispersion of cellulose nano fiber dispersion was prepared through purification and washing, and then stored at room temperature. The cellulose nanofiber dispersion thus obtained had a maximum diameter of 60 nm and a number average of 30-50 nm.

In order to confirm whether the synthesized Example 1 retained the original nanofiber structure, it was confirmed by using a scanning electron microscope (SEM). As a result, it was confirmed that the water-dispersed cellulose retained the nanofiber form (lower part of b in Fig. 1).

Comparative Example 1 was prepared by adding a cellulose sheet to distilled water and stirring. (Fig. 1 (a)). SEM photographs are shown at the bottom of Fig.

Comparative Example 2 was prepared by adding carboxymethylcellulose, which is a water-soluble cellulose commonly used as a cosmetic, into distilled water and stirring.

Comparative Example 3 was prepared by adding hydroxyethyl cellulose, which is a water-soluble cellulose conventionally used as a cosmetic, into distilled water and stirring.

Comparative Example 4 is an essence dosage form containing no Example 1.

Example 2 is an essence formulation containing 0.015% by dry weight of the aqueous dispersion of cellulose nanofibers of Example 1.

Example 3 is an essence formulation containing 0.03% by dry weight of the aqueous dispersion of cellulose nanofibers of Example 1.

Experimental Example  One: Water dispersion  Cellulose nanofibers Dispersion  Confirm skin seating

0.03 dry weight% of Example 1 was applied to skin (2 cm x 2 cm) to check whether it was adhered to skin when applied to skin, dried, and confirmed by SEM. As can be seen from FIG. 2, it was confirmed that the cellulose nanofiber dispersion was stably coated on the surface of the pig skin, and through this, it was proved that the nanofiber was formed on the surface of the skin to settle.

Experimental Example  2: Water dispersion  Cellulose nanofibers Dispersion  moisture Possession  Confirm

In order to confirm the water holding ability, Comparative Examples 1, 2, 3 and Example 1 were applied to pig skin at 0.5% dry weight%, dried, dropped water, and contact angle was measured. The initial contact angle was in the order of Comparative Example 3> Comparative Example 1> Comparative Example 2> Example 1, and a smaller contact angle means hydrophilic property.

In addition, the change in the contact angle with time is shown in Fig. In the case of Example 1, the contact angle was drastically decreased, which means that the water-dispersed cellulose nanofibers rapidly attracted water, and thus it was confirmed that the water-dispersible cellulose nanofiber increased moisture retention by moisture retention.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Contact angle 70.8 64.1 76.5 19.6

Experimental Example  3: Water dispersion  Cellulose nanofibers Dispersion  Check skin friction

0.015% by dry weight Water 30 minutes after application of the dispersed cellulose dispersion to the skin, skin friction was measured using a fraction meter. As a result, it was confirmed that the skin friction was reduced by 10% as compared to that before application (FIG. 4), and the cellulose nanofiber dispersion remaining on the skin softened the skin.

Experimental Example  4: Water dispersion  Cellulose nanofibers Dispersant  Containing formulation Increasing power  Confirm

The essence formulation was prepared and evaluated by the formulation shown in Table 2 (unit: wt%). As a result of measuring the viscosity of the skin cosmetic obtained after the preparation, the viscosity increased as the ratio of Example 1 was increased (FIG. 5). This confirms that the structure of the nanofibers is maintained, but the cellulosic grains are seen together.

Raw material Comparative Example 4 Example 2 Example 3 One Dimethicone 1.00 1.00 1.00 2 Pentaerythritol tetrahexyl hexanoate 3.00 3.00 3.00 3 Hydrogenated polydecene 1.00 1.00 1.00 4 Dipropylene glycol 7.00 7.00 7.00 5 glycerin 7.00 7.00 7.00 6 Methylglucose sesquistearate 0.40 0.40 0.40 7 Cyclopentasiloxane 3.00 3.00 3.00 8 Purified water Up to 100 Up to 100 Up to 100 9 Example 1 - 0.015 0.03 10 Xanthan gum 4.00 4.00 4.00 11 Carbomer 12.00 12.00 12.00 12 antiseptic 1.50 1.50 1.50 13 Sorbitol 1.50 1.50 1.50 14 Chelating agent 0.40 0.40 0.40 15 Anti-inflammatory agent 2.00 2.00 2.00 16 pH adjusting agent 2.00 2.00 2.00

Experimental Example  5: Water dispersion  Cellulose nanofibers Dispersant  The moisture content of the formulation retention  Confirm

In order to confirm the water retentivity of the water-dispersed cellulose nano fiber dispersion formulation, an essence formulation (Comparative Example 4 and Example 2) according to the presence or absence of the cellulose nano fiber dispersion was prepared (weight% is as shown in Table 2) The contact angle was measured by applying water to pig skin and drying. As a result, it was confirmed that the decrease in contact angle in the formulation containing Example 1 was large over time (FIG. 6). This is because cellulose nanofibers retain the property of absorbing water even though they are contained in the formulation.

Experimental Example  6: Water dispersion  Cellulose nanofibers Dispersion  Elasticity increase efficacy evaluation

In order to confirm the efficacy of the synthesized Example 1, the elasticity measurement experiment was carried out. Gelatin was dissolved in a well plate at a certain concentration, and then the gel was hardened. Then, a water dispersed cellulose nanofiber dispersion was applied, and elasticity was measured using a Texture Analyzer. In the universal physical property analyzer, a specimen smaller than the area of the gelatin gel was attached, and the gelatin gel was pressed down at a constant speed to measure the pressure. When the elasticity is increased, the structure of the surface is dense, so that the principle is used that the resistance force is strengthened when pressed with a constant force. When Example 1 of Comparative Example 1 and 0.03% by dry weight were measured through the following in-vitro elasticity evaluation method, the case of treating Example 1 showed an increase of about 20% more elasticity than that of Comparative Example 1 Respectively.

 It was found that the applied cellulose nanofibers increase the elastic effect by forming a film.

In addition, the improvement of elasticity was observed in 10 people in general, and it was confirmed that there was a significant increase.

Claims (11)

A cellulose nano fiber dispersion wherein an alcohol group of a cellulose raw material is substituted with a carboxyl group, wherein the cellulose nano fiber dispersion is dispersed in an aqueous solution. The water-dispersed cellulose nano fiber dispersion of claim 1, wherein the cellulose-based material is a cellulose-derived cellulose nanofiber. The water-dispersed cellulose nano fiber dispersion of claim 1, wherein the water-dispersed cellulose nano fiber dispersion has a diameter of 30-60 nm. A cellulose nano fiber dispersion in which an alcohol group of a cellulose-based raw material is substituted with a carboxyl group, wherein the cellulose nano fiber dispersion is dispersed in an aqueous solution.
Dissolving the N-oxyl compound in distilled water; and
Adding and agitating the cellulose raw material and the oxidizing agent to the melt; and
And removing the reactants through a washing process. 5. The method of claim 4 wherein said N-oxyl compound is selected from the group consisting of 2,2,6,6-tetramethyl-1-piperidine-oxy radical (TEMPO), 4-hydroxy-2,2,6,6- 1-piperidino-oxy radical (4-hydroxy TEMPO) and azadamantan-type nitroxyl radical. The method according to claim 4, wherein the oxidizing agent is at least one selected from the group consisting of halogens, hypohalogen acids, halogenated acids, perhalogen acids or salts thereof, halogen oxides and peroxides. The method according to claim 4, wherein the oxidizing agent is at least one selected from the group consisting of chlorine, hypochlorous acid, chloric acid, perchloric acid or salts thereof, chlorine oxide and perchloric acid. A cellulose nano fiber dispersion in which an alcohol group of a cellulose raw material is substituted with a carboxyl group, wherein the cellulose nano fiber dispersion is dispersed in an aqueous solution. A cellulose nano fiber dispersion in which an alcohol group of a cellulose raw material is substituted with a carboxyl group, wherein the cellulose nano fiber dispersion is dispersed in an aqueous solution. The cosmetic composition according to claim 8, wherein the content of the water-dispersed cellulose nano fiber dispersion in terms of the total weight of the cosmetic composition is 0.0001 to 10% by dry weight. The quasi-drug composition according to claim 9, wherein the content of the aqueous cellulose nanofiber dispersion is 0.0001 to 10% by dry weight based on the total weight of the quasi-drug composition.

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