KR102340022B1 - Method for preparing organic-inorganic hybrid nanocellulose composite - Google Patents

Abstract

Disclosed are a method for producing an organic-inorganic hybrid nanocellulose composite, an organic-inorganic hybrid nanocellulose composite prepared through the same, and a cosmetic composition including the composite.

Description

Manufacturing method of organic-inorganic hybrid nanocellulose composite {METHOD FOR PREPARING ORGANIC-INORGANIC HYBRID NANOCELLULOSE COMPOSITE}

The present invention relates to a method for producing an organic-inorganic hybrid nanocellulose composite, an organic-inorganic hybrid nanocellulose composite prepared through the same, and a cosmetic composition comprising the composite.

Nanocellulose can be obtained from marine organisms, but most are more readily obtained from wood and plant fibers. In addition, it has been developed for numerous innovative applications by giving functionality based on the structural characteristics of cellulose composed of β-1,4-D-glucose, and has established itself as an important research field due to the many positive advantages of nanocellulose.

Due to the improved characteristics of nanocellulose compared to cellulose, which has eco-friendly and economic advantages, interest in nanocellulose research has increased, and it has been studied for application in various fields such as cosmetics, coatings, pharmaceuticals, and textiles. Nanocellulose is a structurally nano-structured material from cellulose, and it is converted by physical, chemical, and biological methods. In addition to many advantages such as high surface area and light weight, research is being conducted to utilize the reactive functional groups of nanocellulose. The preparation of a hybrid composite based on the surface chemical properties of nanocellulose is an applied technology for reactive functional groups of nanocellulose, and it can also exhibit the advantages of regenerating nanocellulose and continuously producing it, as well as the advantages of other materials.

The surface of nanocellulose has the ease of surface modification due to numerous hydroxyl groups, but has a disadvantage in that it has very strong hydrophilicity and thus lacks compatibility with hydrophobic polymers. Therefore, there is a need for the development of a nanocellulose composite that can compensate for the above disadvantages.

Therefore, the present inventors have been researching to solve the above problems, and through the modification of the hydrophilic surface functional group of nanocellulose, the lipophilicity is increased to increase compatibility with other hydrophobic materials, so that the organic-inorganic hybrid nanocellulose composite A manufacturing method was proposed.

In this regard, Korean Patent Registration No. 10-1921612 discloses a hydrogel sheet for a mask pack containing nanocellulose.

The present invention has been devised to solve the above-mentioned problem, and an embodiment of the present invention provides a method for manufacturing an organic-inorganic hybrid nanocellulose composite.

In addition, another embodiment of the present invention provides an organic-inorganic hybrid nanocellulose composite prepared by the method for preparing the organic-inorganic hybrid nanocellulose composite.

In addition, another embodiment of the present invention provides a cosmetic composition comprising the organic-inorganic hybrid nanocellulose composite.

The technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by those of ordinary skill in the art to which the present invention belongs from the description below. There will be.

As a technical means for achieving the above-described technical problem, one aspect of the present invention is,

Preparing nanocellulose; and mixing the surface modifying material with the nanocellulose to prepare an organic-inorganic hybrid nanocellulose composite; it provides a method for producing an organic-inorganic hybrid nanocellulose composite comprising a.

The surface modifying material may include a material selected from the group consisting of metal oxides, noble metals, carbon materials, and combinations thereof.

The metal oxide may include a material selected from the group consisting of titanium oxide, cerium oxide, zinc oxide, aluminum oxide, zirconium oxide, and combinations thereof.

Mixing the metal oxide to prepare an organic-inorganic hybrid nanocellulose composite; may be characterized in that it is carried out at pH 3 to pH 7, preferably performed at pH 5 to pH 6, characterized in that it could be

The noble metal may include a material selected from the group consisting of gold (Au), silver (Ag), platinum (Pt), copper (Cu), and combinations thereof.

Preparing the organic-inorganic hybrid nanocellulose composite by mixing the noble metal; may be characterized in that it is carried out at pH 9 to pH 12, preferably characterized in that it is carried out at pH 10 to pH 11 can

The carbon material may include a material selected from the group consisting of graphene, graphene oxide, reduced graphene, graphite, carbon nanotubes, carbon nanofibers, and combinations thereof.

Mixing the carbon material to prepare an organic-inorganic hybrid nanocellulose composite; may be characterized in that it is carried out at pH 3 to pH 7, preferably performed at pH 5 to pH 6, characterized in that it could be

The method for preparing the organic-inorganic hybrid nano-cellulose composite includes the steps of preparing nano-cellulose; Thereafter, mixing the hydrolyzed silane coupling agent with the nanocellulose; may further include.

The content of the surface modifying material may be 0.25 to 10 parts by weight based on 100 parts by weight of the nanocellulose.

In addition, another aspect of the present invention,

It provides an organic-inorganic hybrid nano-cellulose composite prepared by the above manufacturing method.

According to an embodiment of the present invention, the nanocellulose surface-modified with the surface-modifying material may have increased compatibility with other hydrophobic materials because lipophilicity is increased due to surface modification. That is, when it is prepared as a cosmetic composition, it can be usefully used as a cosmetic composition by increasing the skin oil and water content.

In addition, since the method for producing an organic-inorganic hybrid nanocellulose composite according to the present invention can selectively apply a pH range in which surface modification can be performed smoothly depending on the type of surface modification material, various surface modifying materials are applied to nanocellulose. It may be possible to introduce

Specifically, in the case of nanocellulose surface-modified with a metal oxide according to an embodiment of the present invention, it can be applied as a UV-blocking cosmetic composition, etc., and can exhibit an antibacterial effect.

In addition, in the case of nanocellulose surface-modified with a noble metal according to an embodiment of the present invention, it can be applied as a skin moisturizing cosmetic composition.

In addition, in the case of nanocellulose surface-modified with a carbon material according to an embodiment of the present invention, it has an excellent effect of adsorbing fine dust and can be usefully used as a cleansing cosmetic composition.

It should be understood that the effects of the present invention are not limited to the above-described effects, and include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a schematic diagram showing a method of manufacturing an organic-inorganic hybrid nanocellulose composite according to an embodiment of the present invention.
2 is an FT-IR analysis graph of nanocellulose prepared according to different pH ranges according to an experimental example of the present invention.
3 is an SEM photograph of nanocellulose prepared according to an embodiment of the present invention.
4 is an FT-IR analysis graph of the nanocellulose composite surface-modified with titanium oxide prepared according to different pH ranges according to an experimental example of the present invention.
5a is an FT-IR analysis graph of a nanocellulose composite surface-modified with gold or silver prepared according to different pH ranges according to an experimental example of the present invention.
5B is an FT-IR analysis graph of the surface-modified nanocellulose composite prepared according to the content of gold or silver according to an experimental example of the present invention.
6 is an FT-IR analysis graph of a nanocellulose composite surface-modified with graphene prepared according to different pH ranges according to an experimental example of the present invention.
7 is a graph showing a powder contact angle analysis result of a nanocellulose composite surface-modified with gold or silver according to an experimental example of the present invention.
8 is a graph measuring the skin oil-water balance of a cosmetic composition comprising a nanocellulose composite surface-modified with a carbon material according to an experimental example of the present invention.
9a and 9b are photographs showing antibacterial test results of a cosmetic composition comprising a nanocellulose composite surface-modified with titanium oxide according to an experimental example of the present invention.

Hereinafter, the present invention will be described in more detail. However, the present invention may be embodied in various different forms, and the present invention is not limited by the embodiments described herein, and the present invention is only defined by the claims to be described later.

In addition, the terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the entire specification of the present invention, 'including' any component means that other components may be further included, rather than excluding other components, unless otherwise stated.

The first aspect of the present application is

Preparing nanocellulose; and mixing the surface modifying material with the nanocellulose to prepare an organic-inorganic hybrid nanocellulose composite; it provides a method for producing an organic-inorganic hybrid nanocellulose composite comprising a.

Hereinafter, the method for producing the organic-inorganic hybrid nanocellulose composite according to the first aspect of the present application will be described in detail step by step.

First, in one embodiment of the present application, the method for preparing the organic-inorganic hybrid nanocellulose composite includes preparing nanocellulose; (S100).

In one embodiment of the present application, the nanocellulose is carboxymethylation or tempo (TEMPO) treatment of at least one cellulose selected from red algae fiber, wood fiber, cotton, abaca, jute, bamboo, flax, kenaf and reed. It may be prepared by mechanical treatment after oxidation pretreatment, preferably by tempo treatment. Specifically, the carboxyl group may be efficiently introduced to the surface of cellulose nanofibril (CNF) when the nanocellulose is prepared by using the tempo treatment. That is, conventional nanocellulose includes only a hydroxyl group (-OH) on the surface, but the nanocellulose prepared according to the present invention may include a large amount of hydrophilic groups such as a hydroxyl group (-OH) and a carboxyl group (-COOH).

In one embodiment of the present application, the width of the nanocellulose may be 2 nm to 500 nm, preferably 2 nm to 100 nm, and more preferably 20 nm to 50 nm. Meanwhile, the length of the nanocellulose may be 20 nm to 10 μm.

Next, in one embodiment of the present application, the method for producing the organic-inorganic hybrid nanocellulose composite includes the steps of: preparing an organic-inorganic hybrid nanocellulose composite by mixing a surface modifying material with the nanocellulose; (S200) do.

In one embodiment of the present application, the surface modifying material may include a material selected from the group consisting of metal oxides, noble metals, carbon materials, and combinations thereof. In this case, the metal oxide may include a material selected from the group consisting of titanium oxide, cerium oxide, zinc oxide, aluminum oxide, zirconium oxide, and combinations thereof, and may preferably include titanium oxide. . In addition, the noble metal may include a material selected from the group consisting of gold (Au), silver (Ag), platinum (Pt), copper (Cu), and combinations thereof, preferably gold (Au) Alternatively, it may include silver (Ag). On the other hand, the carbon material may include a material selected from the group consisting of graphene, graphene oxide, reduced graphene, graphite, carbon nanotubes, carbon nanofibers, and combinations thereof, preferably graphene may include.

In one embodiment of the present application, when the surface modifying material is a metal oxide, the step of preparing the organic-inorganic hybrid nanocellulose composite; may be characterized in that it is carried out at pH 3 to pH 5. That is, by performing the surface modification reaction in the pH range as described above, the metal oxide may be surface-modified to a high content in the nanocellulose.

On the other hand, the metal oxide may be preferably mixed in the form of a nano-sol, for example, when the metal oxide is titanium oxide, the titanium oxide nano-sol is titanium ethoxide, titanium propoxide, titanium butoxide, a material selected from the group consisting of titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, titanium chloride, titanium dichloride, titanium trichloride, titanium tetrachloride, titanium bromide, titanium sulfide, and combinations thereof may include.

In one embodiment of the present application, when the surface modifying material is a noble metal, the step of preparing the organic-inorganic hybrid nanocellulose composite; may be characterized in that it is carried out at pH 9 to pH 12. That is, by performing the surface modification reaction in the pH range as described above, the noble metal may be surface-modified to a high content in the nanocellulose.

In one embodiment of the present application, when the surface modifying material is a carbon material, the step of preparing the organic-inorganic hybrid nanocellulose composite; may be characterized in that it is carried out at pH 3 to pH 5. That is, by performing the surface modification reaction in the pH range as described above, the carbon material may be surface-modified to a high content in nanocellulose.

In one embodiment of the present application, the organic-inorganic hybrid nanocellulose composite manufacturing method comprises the steps of: preparing nanocellulose; Thereafter, mixing the hydrolyzed silane coupling agent with the nanocellulose; may further include.

In one embodiment of the present application, an amine group appears as a functional group on the surface of the nanocellulose by mixing the hydrolyzed silane coupling agent with the nanocellulose. The amine group appearing on the surface of the nanocellulose may be combined with the surface modifying material, so that the surface modification can be performed more effectively. Meanwhile, the mixing of the silane coupling agent may be preferably applied when gold (Au) or silver (Au) is used as a surface modifying material.

In one embodiment of the present application, the silane coupling agent is 3-aminopropyltriethoxysilane (3-Aminopropyltriethoxysilane), vinyltrimethoxysilane (Vinyltrimethoxysilane), vinyltriethoxysilane (Vinyltriethoxysilane), 2-(3, 4 Epoxycyclohexyl)ethyltrimethoxysilane (2-(3,4 epoxycyclohexyl)ethyltrimethoxysilane), 3-Glycidoxypropyl trimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane ( 3-Glycidoxypropyl methyldiethoxysilane, 3-Glycidoxypropyl triethoxysilane, 3-Acryloxypropyl trimethoxysilane, N-2-(aminoethyl)-3- Aminopropylmethyldimethoxysilane (N-2-(Aminoethyl)-3-aminopropylmethyldimethoxysilane), 3-Aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3 dimethyl moiety) Partially hydrolysates of 3-Triethoxysilyl-N-(1,3 dimethyl-butylidene)propylamine, N-Phenyl-3-aminopropyltrimethoxysilane ), N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride (N-(Vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride), N-(vinylbenzyl)-2- Hydrolyzate of aminoethyl-3-aminopropyltrimethoxysilane hydrochloride (N-(Vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, hydrolysate), 3-ureidopropyltriethoxysilane, 3-Isocyanatepropyltriethoxysilane, and combinations thereof may include a material selected from the group consisting of and preferably 3-aminopropyltriethoxysilane.

In one embodiment of the present application, the ?t amount of the silane coupling agent may be 0.1 parts by weight to 0.5 parts by weight based on 100 parts by weight of the nanocellulose. When the ?t amount of the silane coupling agent is less than the above parts by weight, the content of the silane coupling agent is relatively small, so that the surface modification of the surface modifying material may not be effectively performed in a later step. ) may be formed and the reaction may not proceed. In addition, since the content of the silane coupling agent is relatively high compared to the content of the nanocellulose, the effect of the cosmetic composition that can be achieved by using the nanocellulose may be reduced.

The concentration of the silane coupling agent may be 1 to 10%. When the silane coupling agent in a concentration higher than the above range is used, bonding to the metal may be reduced.

In one embodiment of the present application, the content of the surface modifying material may be 0.25 to 10 parts by weight based on 100 parts by weight of the nanocellulose. Specifically, when the surface modifying material is a metal oxide, the content of the metal oxide may be 0.25 to 1 part by weight based on 100 parts by weight of the nanocellulose. In addition, in the case of a noble metal, the content of the noble metal may be 1 part by weight to 10 parts by weight based on 100 parts by weight of nanocellulose, and when the surface modifying material is graphene, the content of the carbon material is 1 part by weight based on 100 parts by weight of nanocellulose It may be in an amount of parts to 5 parts by weight. That is, the high content of metal oxide, noble metal, and carbon material as described above may be because the reaction is performed in a pH range suitable for each surface modifying material as described above, and the pH suitable for the reaction according to the type of surface modifying material The range may be selectable.

On the other hand, when the content of the surface modifying material is less than 0.25 parts by weight compared to 100 parts by weight of the nanocellulose, the surface modification of the nanocellulose is not sufficiently performed, and the content of the nanocellulose is relatively high. The compatibility may be lowered, and if it exceeds 10 parts by weight, since the content of the nanocellulose is relatively small, there may be a problem in that the function as a cosmetic composition that can be achieved by using the nanocellulose is lowered.

The second aspect of the present application is

It provides an organic-inorganic hybrid nanocellulose composite prepared by the manufacturing method of the first aspect of the present application.

Although a detailed description of the overlapping parts of the first aspect of the present application is omitted, the description of the first aspect of the present application may be equally applied even if the description thereof is omitted in the second aspect.

Hereinafter, the organic-inorganic hybrid nanocellulose composite according to the second aspect of the present application will be described in detail.

In one embodiment of the present application, the size of the organic-inorganic hybrid nanocellulose composite may be 2 nm to 500 nm, and the shape is not particularly limited, but, for example, to have a shape such as a linear, spherical, or needle-like shape. can

In one embodiment of the present application, the organic-inorganic hybrid nanocellulose composite has a high lipophilicity because it is surface-modified, and thus may have a large contact angle with respect to water. Specifically, the contact angle of the organic-inorganic hybrid nanocellulose composite to water may be 70° or more, preferably 80° or more, and more preferably 85° or more.

The third aspect of the present application is

It provides a cosmetic composition comprising the organic-inorganic hybrid nanocellulose composite according to the second aspect of the present application.

Although detailed descriptions of parts overlapping with the first and second aspects of the present application are omitted, the descriptions of the first and second aspects of the present application may be equally applied even if the description is omitted in the third aspect. .

Hereinafter, the cosmetic composition according to the third aspect of the present application will be described in detail.

In one embodiment of the present application, the cosmetic composition may further include an organic solvent, silicone oil, fiber, emulsifier, moisturizer, plasticizer or purified water in addition to the organic-inorganic hybrid nanocellulose composite.

In one embodiment of the present application, when the surface modifying material is a metal oxide, it may have an excellent UV blocking effect, in the case of a noble metal, it may have an excellent skin moisturizing effect, and in the case of a carbon material, it has an excellent fine dust adsorption effect it could be Therefore, the organic-inorganic hybrid nanocellulose composite surface-modified according to each surface-modifying material can be used as a functional cosmetic according to each function.

In one embodiment of the present application, the organic solvent may be alcohol, glycol, silicone oil, natural oil, vegetable oil, nut oil or mineral oil. The organic solvent serves as a solvent for dispersing the surface-modified nanocellulose composite. In addition, the organic solvent can disperse the surface-modified nanocellulose composite, and any organic solvent suitable for preparing a cosmetic composition having a good spreadability can be used without any particular limitation.

In one embodiment of the present application, the silicone oil may be dimethicone, cetyldimethicone, cyclopentasiloxane, cyclohexasiloxane or stearyldimethicone. The silicone oil can form an oil phase in emulsifying a cosmetic, and serves to improve the feeling of use.

In one embodiment of the present application, the textile material may be VGL silk or the like. The textile agent serves to improve the feeling of use of the cosmetic composition.

In one embodiment of the present application, the emulsifier may be a PEG silicone emulsifier, a nonionic W / O emulsifier, a cationic emulsifier or an anionic emulsifier. The emulsifier allows each component of the cosmetic composition according to the present invention to be emulsified. In addition, it serves to improve the stability of the formulation by trapping the complex in the emulsion particles of the oil phase.

In one embodiment of the present application, the moisturizing agent is a natural moisturizing agent such as 1,2-hexanediol, glycerin, propylene glycol, butylene glycol, polyethylene glycol, sorbitol or polyol such as trehalose, amino acids, urea, lactate or PCA-Na A high molecular weight moisturizer such as factor (NMF), hyaluronate, chondroitin sulfate, or hydrolyzed collagen may be used. The moisturizer may increase the moisturizing power of the cosmetic composition according to the present invention and at the same time serve as a preservative.

In one embodiment of the present application, the plasticizer may be DPG (Dipropylene glycol) or the like.

In one embodiment of the present application, in addition to the above ingredients, the cosmetic composition includes oils and fats, waxes, surfactants, thickeners, pigments, cosmetic additives, powders, sugars, antioxidants, buffers, various Components commonly formulated in cosmetic compositions, such as extracts, stabilizers, preservatives, and fragrances, can be appropriately blended.

In one embodiment of the present application, the fats and oils include vegetable oil, such as colostrum oil, rosehip oil, castor oil or olive oil, animal oil such as mink oil or squalene, mineral oil such as liquid paraffin or vaseline, silicone oil or myristine Synthetic oils, such as acid isopropyl, etc. can be used.

In one embodiment of the present application, as the waxes, vegetable waxes such as carnauba wax, candelilla wax or jojoba oil, animal waxes such as beeswax or lanolin may be used.

In one embodiment of the present application, as the surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or a nonionic surfactant may be used.

In one embodiment of the present application, the thickener may be, for example, a water-soluble polymer.

In one embodiment of the present application, as the water-soluble polymer, plant-based (polysaccharide-based) natural polymers such as guar gum, locast bean gum, quince seed, carrageenan, galactan, gum arabic, tragacanth, pectin, mannan or starch , Xanthan gum, textlan, succinol glucan, cadran or hyaluronic acid, etc. Microbial (polysaccharide) Natural polymer, Gelatin, Casein, Albumin or Collagen, etc. Animal (protein) Natural polymer, methyl cellulose, ethyl cellulose , hydroxy, ethyl cellulose, hydroxypropyl cellulose, cellulose-based semi-synthetic polymers such as carboxymethyl cellulose or methyl hydroxypropyl cellulose, starch-based semi-synthetic polymers such as soluble starch, carboxymethyl starch or methyl starch, alginic acid propylene glycol ester or alginic acid Alginic acid-based semi-synthetic polymers such as salts, other polysaccharide derivatives semi-synthetic polymers, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer or vinyl-based synthetic polymers such as sodium polyacrylate, polyethylene oxide, ethylene oxide Alternatively, other synthetic polymers such as propylene oxide block copolymers, and inorganic materials such as bettnite, laponite, micro-dispersed silicon oxide, colloidal alumina, etc. may be used.

In one embodiment of the present application, the dye may be, for example, a synthetic dye or a natural dye, and the synthetic dye is a water-soluble/oil-soluble dye such as FD&C Yellow No 6 or FD&C Red No 4, iron oxide or ultramarine. Inorganic pigments, organic pigments such as D&C Red No 30 or D&C Red No 36, lakes such as FD&C Yellow No 6 Al lake, etc. can be used, and the natural pigments are β-carotene, β-apo-8-carotene, lilo. Carotenoid pigments such as pin, capxanthin, vixin, crosine or candaxanthin, flavonoid pigments such as sisonin, lamanin, ninocyanine, carsamine, saprole yellow, rutin, guelcetin, or cacao pigment; Flavin-based pigments such as riboflavin, quinone-based pigments such as laccaic acid, carminic acid (cochinyl), kermesic acid, arizarin, cycorin, arkanine or nicinochrome, porphyrin-based pigments such as chlorophyll or hemoglobin; Diketone-based pigments such as krkmin (dameric), betacyanidin-based pigments such as betanin, and the like may be used.

In one embodiment of the present application, the cosmetic additive, for example, vitamin, plant extract or animal extract may be used, and the vitamin is retinol (vitamin A), tocopherol (vitamin E) or ascorbic acid (vitamin X), etc. Can be used, and the plant extract is menthol (mint), azulene (chamomile), allantoin (wheat), caffeine (coffee), licorice extract, cinnamon extract, green tea extract, lavender extract or lemon extract, etc. may be used, and the As the animal extract, placenta (cow placenta), royal jelly (bee secretion), snail extract (mucus secretion), etc. may be used.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.

Preparation Example 1. Preparation of surface-modified nano-cellulose composite with titanium oxide

Step 1: Preparation of nanocellulose

Pulp was added to a high-concentration NaOH solution and ball milled (or pulverized). After washing with distilled water, cellulose nanofibril (CNF) was prepared using 1 g of cellulose and TEMPO/NaBr/NaClO, and pH 10 was maintained with 0.5M NaOH. After that, when there was no change in pH, the reaction was considered to have been completed, and ethanol was added to terminate the reaction.

Thereafter, the cellulose nanofibrils were added to a 1M HCl solution and washed after 2 hours of reaction to obtain a nanocellulose composite.

Step 2: Preparation of surface-modified nanocellulose composite with titanium oxide

A titanium oxide nanosol was mixed with the nanocellulose obtained in step 1 to adjust the pH to pH 3, pH 5, pH 7, pH 8, and pH 12 to prepare a nanocellulose composite surface-modified with titanium oxide.

On the other hand, the weight mixing ratio of the nano-cellulose and titanium oxide nano-sol obtained in step 1 may be 100: 0.1 to 5.

As the titanium oxide nanosol, one of titanium isopropoxide, titanium ethoxide, and titanium tetrachloride was used, and a combination of isopropyl alcohol, ethanol, and water was used as the solvent.

Preparation Example 2. Preparation of surface-modified nanocellulose composite with gold (Au) or silver (Ag)

For the preparation of the organic-inorganic hybrid nanocellulose composite according to the present invention, a nanocellulose composite surface-modified with gold or silver was prepared.

Step 1: Preparation of nanocellulose

It was prepared in the same manner as in Step 1 of Preparation Example 1.

Step 2: Preparation of surface-modified nanocellulose composite with gold or silver

Using aminopropyl triethoxysilane as a silane coupling agent, it was hydrolyzed by reacting at room temperature for two hours at a molar ratio of water and ethanol of 4:6. Thereafter, the hydrolyzed silane coupling agent was mixed with the nanocellulose obtained in step 1, the pH was adjusted to pH 2, pH 7, and pH 10 to react and wash. Next, a colloidal gold solution or a colloidal silver solution was added to the nanocellulose to which the hydrolyzed silane coupling agent was bound, and curled at 80 degrees to prepare a nanocellulose composite surface-modified with gold or silver.

Preparation Example 3. Preparation of surface-modified nanocellulose composite with graphene

For the preparation of the organic-inorganic hybrid nanocellulose composite according to the present invention, a nanocellulose composite surface-modified with graphene was prepared.

Step 1: Preparation of nanocellulose

It was prepared in the same manner as in Step 1 of Preparation Example 1.

Step 2: Preparation of surface-modified nanocellulose composite with graphene

The nanocellulose obtained in step 1 was reacted with graphene oxide by adjusting the pH to pH 1, pH 3, pH 5, pH 7, pH 10, and pH 14, and mixed at the pH for 12 hours to surface-modify the graphene A nanocellulose composite was prepared.

Example 1. Preparation of a cosmetic composition comprising a nano-cellulose composite surface-modified with titanium oxide

As an oil phase, 3 g of Monta wax 68 and 3 g of olive wax were heated to 80° C., and 1 g of cetyl alcohol as an emulsifying aid was mixed. When the mixture is completely dissolved. 10 mL of green tea seed oil was added.

As a water phase, 45 mL of purified water and 10 mL of glycerol were mixed and used.

After slowly mixing the oil phase and the aqueous phase at 80° C., when an emulsion form was seen, 5 mL of hyaluronic acid and 2 g of the nanocellulose composite surface-modified with the titanium oxide were added to the mixture to prepare a cosmetic composition.

Example 2. Preparation of a cosmetic composition comprising a nanocellulose composite surface-modified with gold or silver

It was prepared in the same manner as in Example 1, except that the surface-modified nano-cellulose composite was used as the surface-modified nano-cellulose composite with gold or silver.

Example 3. Preparation of a cosmetic composition comprising a nanocellulose composite surface-modified with graphene

It was prepared in the same manner as in Example 1, except that the surface-modified nano-cellulose composite was used as the surface-modified nano-cellulose composite with graphene.

Experimental Example 1. Analysis of reaction change according to pH in the preparation of nanocellulose

In order to analyze the reaction change according to pH in the preparation of nanocellulose of Preparation Example 1, the pH of the reaction conditions was changed and nanocellulose was prepared by TEMPO-catalyzed oxidation method. This was analyzed by FT-IR spectra and is shown in FIG. 2 .

As shown in FIG. 2, it was confirmed that the reaction was best performed at pH 10.

Experimental Example 2. SEM analysis of the prepared nanocellulose

The shape of the nanocellulose prepared according to Preparation Example 1 was analyzed using a scanning electron microscope (SEM), which is shown in FIG. 3 .

As shown in FIG. 3 , as a result of confirming the shape of the prepared nanocellulose using a scanning electron microscope (SEM), it was confirmed that the nanocellulose had a width in the range of 20 nm to 50 nm.

Experimental Example 3. FT-IR analysis of nanocellulose composite surface-modified with titanium oxide according to pH

The nanocellulose composite surface-modified with titanium oxide according to Preparation Example 1 of the present invention was observed by Fouriertransfer infrared spectroscopy (FT-IR) at different pHs, which is shown in FIG. 4 . As shown in FIG. 4, it was confirmed that the peaks of the hydroxyl group (-OH) and the carboxylate group (-COO) of the FT-IR data were reduced at pH 5, and Ti-OC and Ti, which are peaks related to titanium It was confirmed that the peak of -O increased. It was determined that this is because the hydrophilic nanocellulose is surface-modified with titanium oxide and has lipophilic characteristics.

Experimental Example 4. FT-IR analysis of nanocellulose composites surface-modified with gold or silver according to pH

The nanocellulose composite surface-modified with gold or silver according to Preparation Example 2 of the present invention was observed by Fouriertransfer infrared spectroscopy (FT-IR) at different pHs, which is shown in FIG. 5A . As shown in FIG. 5a, it was confirmed that the peaks of the hydroxyl group (-OH) and the amine group (-NH-) of the FT-IR data of the FT-IR data at pH 10 most distinctly bifurcated, which indicates that the hydrophilic nanocellulose is gold or silver. It was judged that this was because the surface was modified with a lipophilic property.

In addition, the nanocellulose composite surface-modified with gold or silver according to Preparation Example 2 of the present invention was observed by Fouriertransfer infrared spectroscopy (FT-IR) with different gold or silver content, which is shown in FIG. 5B . As shown in FIG. 5B , it can be seen that the peaks of the hydroxyl group (-OH) and the amine group (-NH-) become clear as the content of gold or silver increases. It was determined that this is because the hydrophilic nanocellulose is surface-modified with gold or silver and has lipophilic characteristics.

Experimental Example 5. FT-IR analysis of nanocellulose composite surface-modified with graphene according to pH

The nanocellulose composite surface-modified with graphene according to Preparation Example 3 of the present invention was observed by Fouriertransfer infrared spectroscopy (FT-IR) at different pHs, which is shown in FIG. 6 . _{As shown in FIG. 6 , it was confirmed that the peak of CH 2 and} the peak of CO of the FT-IR data of the FT-IR data increased at pH 5, which is thought to be because the hydrophilic nanocellulose is surface-modified with graphene and has a lipophilic characteristic. became

Experimental Example 6. Analysis of the contact angle of the surface-modified nanocellulose composite

The nanocellulose composite surface-modified with silver according to Preparation Example 2 of the present invention was measured as a powder contact angle, and this is shown in FIG. 7 . As shown in FIG. 7 , it was confirmed that the nanocellulose composite surface-modified with silver exhibited a contact angle with respect to water of about 85 degrees, which was judged to be due to the increase in lipophilic properties due to the surface modification of silver.

Experimental Example 7. Measurement of skin oil-water balance of cosmetic composition containing surface-modified nanocellulose composite

The skin oil-water balance of the cosmetic composition comprising the nanocellulose composite surface-modified with graphene according to Example 3 of the present invention was measured, and this is shown in FIG. 8 . As shown in FIG. 8 , it was confirmed that the moisture content and oil content increased as the content of the cosmetic composition including the nanocellulose composite surface-modified with graphene increased. Could know.

Experimental Example 8. Antibacterial test of cosmetic composition containing surface-modified nanocellulose composite

In order to measure the antibacterial effect of the surface-modified nanocellulose prepared according to the present invention, the cosmetic composition comprising the nanocellulose composite surface-modified with titanium oxide according to Example 1 was smeared on an agar medium, and the degree of bacterial propagation was confirmed. . The cosmetic composition was smeared on an agar medium in FIG. 9a, and the change was observed after 10 days at room temperature and shown in FIG. 9b (a: agar / b: 0.5 wt% nanocellulose / c: 1.0 wt% nano Cellulose/TiO ₂ composite / d: 0.5 wt% nanocellulose/TiO ₂ composite / e: 0.2 wt% nanocellulose/TiO ₂ composite).

As shown in Figures 9a and 9b, it was confirmed that the least bacterial propagation appeared when the weight of titanium oxide was 0.25 wt% compared to 100 wt% of nanocellulose, which was maintained by the influence of inorganic metals in the cosmetic composition. was judged to be

Claims (11)

Preparing nanocellulose;
introducing a carboxyl group to the nanocellulose by tempo treatment;
mixing a hydrolyzed silane coupling agent with the nanocellulose; and
Including; mixing the surface modifying material with the nanocellulose to prepare an organic-inorganic hybrid nanocellulose composite;
The width of the nanocellulose is in the range of 2 nm to 500 nm, and the length of the nanocellulose is in the range of 20 nm to 10 μm,
When the surface modifying material is a metal oxide or a carbon material, mixing the surface modifying material with the nanocellulose to prepare an organic-inorganic hybrid nanocellulose composite is characterized in that it is performed at pH3 to pH7, and the surface modifying material In the case of this noble metal, the step of preparing an organic-inorganic hybrid nanocellulose composite by mixing the surface modifying material with the nanocellulose is performed at pH9 to pH12. Method for producing an organic-inorganic hybrid nanocellulose composite.
delete According to claim 1,
The metal oxide is titanium oxide, cerium oxide, zinc oxide, aluminum oxide, zirconium oxide, and a method for producing an organic-inorganic hybrid nanocellulose composite comprising a material selected from the group consisting of combinations thereof.

delete According to claim 1,
The noble metal includes a material selected from the group consisting of gold (Au), silver (Ag), platinum (Pt), copper (Cu), and combinations thereof - Method for producing an organic-inorganic hybrid nanocellulose composite.
delete According to claim 1,
The carbon material includes a material selected from the group consisting of graphene, graphene oxide, reduced graphene, graphite, carbon nanotubes, carbon nanofibers, and combinations thereof - Method for producing an organic-inorganic hybrid nanocellulose composite .
delete delete According to claim 1,
The content of the surface modifying material is 0.25 parts by weight to 10 parts by weight based on 100 parts by weight of the nanocellulose organic-inorganic hybrid nanocellulose composite manufacturing method.
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