WO2019135420A1 - Composite using porous material and polymer, and use thereof - Google Patents

Abstract

The present invention relates to a composite using a porous material and a polymer, and a use thereof. The composite of the present invention includes a bioactive substance supported on the micropores of volcanic soil, which is a porous material, the micropores being capped with an ionic polymer so as to protect the bioactive substance from the external environment, and includes a network formed through Van der Waals bonding between ionic polymer moieties, which are exposed to the surface after capping, and a nonionic polymer so as to prevent self-aggregation, thereby preventing separation, precipitation and discoloration after the composite is prepared and, particularly, providing remarkable water dispersibility, and thus is readily applied to the cosmetics, food or medical field using the same and can implement functionality by the supported bioactive substance.

Description

Composite using porous material and polymer and use thereof

The present invention relates to a composite using a porous material and a polymer and a use thereof. More particularly, the present invention relates to a composite material comprising a porous material, a physiologically active substance supported on the micropores of a volcanic soil and an ionic polymer The present invention relates to a method for protecting a biologically active material from external environment by capping and preventing self aggregation by forming a network due to Van der Waals bonding between an ionic polymer residue exposed on a surface and a nonionic polymer after sealing, Precipitation, and discoloration, and particularly excellent in water dispersibility, and uses thereof.

The physiologically active substance is a trace amount of a substance that greatly affects the function and physiological function of the living body, and includes vitamins, hydroxy acids, unsaturated fatty acids, hormones, enzymes, neurotransmitters and the like.

Physiologically active substances such as vitamins, salicylic acid, hydroxy acids, unsaturated fatty acids and glutathione (GLT) have functions such as antioxidation, acne treatment, skin whitening, exfoliation, starch removal, skin moisturizing and wrinkle prevention However, it is oxidized at light or high temperature and can cause discoloration and irrigation, so that there are many restrictions on practical applications.

Particularly, vitamins including vitamins A (retinol), vitamin C (ascorbic acid), vitamin E (tocopherol) and derivatives thereof are widely used in the field of cosmetics. They are used for preventing skin whitening and pigmentation, promoting collagen synthesis, Prevention of dryness and keratinization of skin, prevention of wrinkles, skin moisturization and so on. Despite these effects, however, it has many limitations in practical applications due to the instability of vitamin, irritation, toxicity, dispersibility and the disadvantage that it is easily destroyed by heat, light, oxygen.

The volcanic soil is a soil formed by the formation of the soil after the high and far ash (ash) is deposited on the ground at the time of the volcanic eruption. It is characterized by porosity and low specific density. Therefore, it shows excellent ability to hold moisture, excellent in pollution treatment and antibacterial action.

For example, in Korean Patent No. 1105343, the excellent water resistance of a volcanic ash composed of a crystal phase of boehmite (Al (OH) ₃ ), quartz and gypsum (calcium sulfate hydrate) And introducing clean water into the stream or groundwater.

According to the report on the ceramic filter media using the black volcanic ash soil from Jeju [The 46th National Science Exhibition Entrance Environment, Jeju Tourism Industry High School Kim Hyong Shin, Kim Chu Sik], the pollutants It is described that the rate of permeability in soil is determined by the size and amount of pores.

For example, in the case of the black volcanic ash soil, the weight of the soil per unit volume is 0.54 g / cm 3, which is significantly lower than 1.2 g / cm 3 of the land area general soil and the porosity is 75%, which is much larger than about 50% Is fast. In addition, it has been reported that the present invention is applied to maintain good water quality by adsorbing power to pesticides of soil using excellent adsorption characteristics of pollutants. That is, the possibility of the ceramic carrier is suggested by using the permeability and adsorption force due to the pores of the clay soil.

Accordingly, the present inventors have made efforts to efficiently carry weakly physiologically active substances against the external environment such as air, light, heat, pH, moisture, and the like. As a result, they have found that volcanic ash as a porous material is selected as an inorganic carrier material, The physiologically active substance is supported on the pores, the micropores are enclosed with the ionic polymer to protect the physiologically active substance from the external environment, and due to van der Waals bonding between the ionic polymer residue exposed on the surface and the nonionic polymer substance, To prevent self-agglomeration. Thus, after the preparation of the composite, there was no dropout, precipitation, discoloration, and in particular, excellent water dispersibility was confirmed, thereby completing the present invention.

An object of the present invention is to provide a composite in which a porous material, which is a porous material, is used as an inorganic carrier and a physiologically active substance is stably supported.

Another object of the present invention is to provide a cosmetic, food or pharmaceutical field using the same, which has no dropout, settling, discoloration and excellent water dispersibility after the production of the composite.

In order to accomplish the above object, the present invention provides a method for preparing a porous material, comprising the steps of supporting a physiologically active substance on micropores of a porous material, encapsulating the micropores into an ionic polymer, and exposing the surface to ionic polymer residues and non- To form a network due to van der Waals bonding and to stabilize the water dispersibility.

More specifically, the complex of the present invention contains 10 to 30 parts by weight of the physiologically active substance per 100 parts by weight of the volcanic ash, 1 to 10 parts by weight of the ionic polymer and 1 to 10 parts by weight of the nonionic polymer, .

The physiologically active substance may be selected from the group consisting of vitamin A, vitamin C, vitamin E, salicylic acid, kojic acid, alpha-lipoic acid, elacydic acid, resveratrol, docohexaenoic acid (DHA), eicosapentaenoic acid (EPA), linoleic acid and glutathione Or a mixed form of them may be applied.

The ionic polymer is any one selected from the group consisting of alginic acid, pectin, carrageenan, xanthan gum, hyaluronic acid, gum Arabic, karaya gum and tragacanth gum.

In addition, the nonionic polymer is selected from the group consisting of starch or cyclotin.

Further, the present invention provides a functional product in which the complex is applied to any one selected from the group consisting of cosmetics, foods, and medicines, and is embodied by a physiologically active substance.

The present invention can provide a physiologically active substance complex using a porous material and a polymer. That is, not only is it possible to effectively support various physiologically active substances in the micropores of the clay soil, but also to increase the stability by enclosing the physiologically active substances carried on micropores of the clayey soil with ionic polymers, It is possible to protect the physiologically active substance enclosed in the micropores from the external environment and prevent coagulation and precipitation between physiologically active substances, thereby maintaining the inherent physiological activity of the substance as it is.

Also, since the residue of the ionic polymer exposed on the surface of the complex is bound to van der Waals by a non-ionic polymer, a network is formed to prevent self-agglomeration, thereby enhancing the dispersion stability of the aqueous solution.

Thus, the complex of the present invention is not only environmentally friendly but also skin-friendly and has high stability to aqueous solution, so that it can be applied not only to raw materials for functional cosmetics but also to industrial fields such as foods and pharmaceuticals, .

Fig. 1 schematically shows a composite structure of the present invention.

Hereinafter, the present invention will be described in detail.

The present invention provides a composite using a porous material and a polymer.

Figure 1 schematically shows the composite structure of the present invention. The composite of the present invention is characterized in that the composite of the present invention is formed by supporting a physiologically active substance in micropores of a porous material, sealing the micropores with an ionic polymer, And forms a network due to Van der Waals bonding between the exposed ionic polymer residue and the nonionic polymer.

At this time, the porous material to be used can be applied as long as it can be used as a conventional inorganic carrier having a micropore. Although volcanic soil has been selected and described in the embodiments of the present invention, it will be understood that silica, zeolite and the like can also be applied.

In the present invention, a complex using a volcanic ash selected as a porous material will be described in detail. In the present invention, 10 to 50 parts by weight of a physiologically active substance is supported on 100 parts by weight of a volcanic ash, 1 to 10 parts by weight of an ionic polymer 1 to 10 parts by weight of a non-ionic polymer is contained and stabilized.

Accordingly, when the physiologically active substances are supported on the micropores of the porous material, which is a porous material, by physically interacting with the micropores of the porous material, the ionic polymer binds to the entrance of the micropores to protect and stabilize the physiologically active substances from the external environment. At this time, the hydrophobic residues of the ionic polymer exposed to the surface of the complex due to not being incorporated into the micropores form a network due to the interaction of non-ionic polymers with Van der Waals, thereby causing self-aggregation between the complexes And to increase the dispersion of the aqueous solution.

The volcanic ash used in the present invention is a stabilized colloidal solution by stirring or ultrasonicating 0.01 to 1% by weight in distilled water at room temperature.

In the examples of the present invention, as the physiologically active substance, there may be mentioned retinoic acid, ascorbic acid, vitamin E (tocopherol), salicylic acid, kojic acid, alpha-lipoic acid lipoic acid, ellagic acid, resveratrol, docohexaenoic acid (DHA), eicosapentaenoic acid (EPA), linoleic acid (LA) , Glutathione, or a mixed form thereof. However, the present invention is not limited thereto, and may be changed depending on the application field.

Also, it is preferable that 10 to 30 parts by weight of the physiologically active substance is supported on 100 parts by weight of the volcanic ash. At this time, the more a lot of the content of the physiologically active substance is preferably supported from the functional implementation thereof, because if it exceeds the 30 parts by weight, the amount of increase is not supported, it is not preferable Table 1.

The ionic polymers used in the present invention may be selected from the group consisting of alginic acid, pectin, carrageenans, xanthan gum, hyaluronic acid, Arabic gum, Karaya gum, and Tragacanth gum.

The ionic polymer is used in an amount of 1 to 10 parts by weight, more preferably 2 to 3 parts by weight, based on 100 parts by weight of the volcanic ash. At this time, if the ionic polymer content is less than 1 part by weight, hwasanto to the stabilization after the carry of a biomolecule lack the micro pores and the storage period 4 weeks elapsed time, the precipitation occurs in the third week, or a problem of discoloration Table 2 ]. On the other hand, when the amount is more than 10 parts by weight, precipitation or discoloration is not observed. However, when the excess amount is insufficient, the effect improvement effect is insufficient, and the more the remaining unbonded amount is, the more the nonionic polymer content is increased.

In the complex of the present invention, starch or cyclodextrin is used as the nonionic polymeric substance.

It is preferable to select a natural polymer which has little or no bio-toxicity and which can be skin-friendly and environmentally friendly. In the present invention, a physiologically active substance supported on a volcanic soil is stabilized, So as to have a stable dispersion degree.

The nonionic polymer is preferably used in an amount of 1 to 10 parts by weight, more preferably 1 to 3 parts by weight, based on 100 parts by weight of the volcanic ash. At this time, or the ionic polymer content is less than 1 part by weight, when the weight exceeds 10 parts, the precipitation or color change occurred in the storage period Week 4 [Table 3].

Therefore, it is possible to effectively remove various physiologically active substances from the porous material and to encapsulate them with a polymer and to form a network by using the porous material, which is not observed to be detached, precipitated, or discolored even after 4 weeks from the production of the complex of the present invention. Protected and stabilized complexes can be prepared and the dispersion degree improved over aqueous solutions.

Accordingly, the present invention relates to a method for preparing a stable colloid by stirring or ultrasonically dispersing a volcanic ash, mixing 100 parts by weight of a volcanic ash and 10 to 30 parts by weight of a physiologically active substance to carry a biologically active substance on the micropores of the volcanic ash,

A second step of enclosing the micropores with an ionic polymer to form a stabilized complex of the supported physiologically active substance, and

The present invention provides a method for producing a composite comprising three steps of inhibiting self-aggregation of a complex through a network of a non-ionic polymer and a residue of an anionic polymer exposed on the surface of the composite.

Hereinafter, the method for producing the composite of the present invention will be described in detail for each step.

The step 1 is a step of stably supporting a physiologically active substance on the micropores of a porous material, which is a porous material. The physiologically active substance is mixed with 100 parts by weight of the volatile earth by stirring or ultrasonication at 0 to 4 캜, Separate and wash and re-disperse in distilled water.

At this time, the volcanic ash is mixed with distilled water at a rate of 0.01 to 1 wt% at room temperature or by ultrasonication to produce a stable colloidal solution. At this time, stirring is performed for more than 24 hours for 1 hour or more, and the colloid solution is centrifuged to remove the precipitate, thereby finally obtaining a stable volcanic colloid.

In addition, the physiologically active substance is prepared by dissolving the selected physiologically active substance to 0.1 wt% in distilled water at 4 to 20 ° C. In the case of a physiologically active substance other than ascorbic acid, sodium hydroxide is added in an equivalent ratio of 1: Dissolve.

In step 2, the micropores are sealed with an anionic polymer to protect the supported physiologically active substance from the external environment such as air, light, heat, pH, moisture, and the like, thereby preparing a stabilized complex.

Specifically, 1 to 10 parts by weight of an ionic polymer is added to the redispersed solution in 100 parts by weight of the volcanic ash, and the mixture is stirred or sonicated at 4 to 20 DEG C, followed by centrifugation and washing with distilled water. .

Then, in step 3, 1 to 10 parts by weight of a nonionic polymer is added to the redispersed composite solution in step 2, and the mixture is stirred or ultrasonicated at 4 to 20 ° C, followed by centrifugation and washing with distilled water. .

The polymer selected in the second and third steps is used in distilled water in an amount of 0.01 to 1% by weight. When the weight ratio of the polymer to water is too high, the viscosity of the solution is excessively increased or difficult to be dissolved by the polymer, so that the preparation of the complex is not easy. Conversely, when the weight ratio of the polymer to the distilled water is too low, Lowering the effect of enclosing the physiologically active substance and the stability of the egg / insoluble complex.

The average molecular weight of the polymer is preferably 1,000 to 100,000. The temperature of the polymer solution is preferably 20 to 80 DEG C, and the pH of the solution is preferably 5 to 8.

Through the above-described method for producing a complex, not only can various physiologically active substances be effectively supported on the micro pores of the clay soil, but also the physiologically active substance supported on the micro pores of the clay soil is sealed with the ionic polymer to improve the stability, The encapsulated physiologically active substance is protected from the external environment and coagulation and precipitation of the physiologically active substance are prevented so that the inherent physiological activity of the substance can be maintained.

Also, since the residue of the ionic polymer exposed on the surface of the complex is bound to van der Waals by a non-ionic polymer, a network is formed to prevent self-agglomeration, thereby enhancing the dispersion stability of the aqueous solution.

Thus, the complex of the present invention is not only environmentally friendly but also skin-friendly and highly stable to an aqueous solution, so that it can be applied to foods and medicines which are required to stabilize a target substance as well as a raw material for functional cosmetics.

Further, the present invention provides a functional cosmetic comprising the above-mentioned complex and having a functional property by the supported physiologically active substance.

The present invention also provides functional foods or medicines based on physiologically active substances including the complex.

Hereinafter, the present invention will be described in more detail with reference to Examples.

The present invention is intended to more specifically illustrate the present invention, and the scope of the present invention is not limited to these embodiments.

≪ Preparation Examples 1 to 5 > Determination of loading amount of physiologically active substance on volcanic soil

A solution of 0.1% vitamin C in 100 g of a 0.1% volcanic acid dispersion was mixed in the amounts shown in Table 1 below. Thereafter, the mixture was stirred at 4 ° C for 24 hours, centrifuged and washed, lyophilized, and the mass of the powder was measured. The amount of physiologically active substance loaded on the volcanic soil was calculated by the following equation.

From the results shown in Table 1, it was confirmed that about 30% of the physiologically active substance per 1 g of the volcanic soil can be supported at the maximum when the vitamin C was carried on the volcanic soil for 24 hours.

<Examples 1 to 6> Confirmation of stabilization and dispersion of physiologically active substance by polymer

Based on the above preparation example, 100 g of the 0.1% volcanic earth dispersion and 30 g of the 0.1% vitamin C solution were stirred at 4 캜 for 24 hours, centrifuged and washed, and redispersed in 100 g of distilled water. At this time, vitamin C was selected in order to easily determine the deformation of the physiologically active substance due to discoloration.

Thereafter, the reaction is carried out by stirring the redispersed physiologically active substance / volcanic acid solution and the anionic polymer solution at 4 ° C for 24 hours, centrifuging and washing, and adding the nonionic polymer solution to 100 g of the prepared composite dispersion solution Followed by stirring at 4 ° C for 24 hours for centrifugation and washing. The final product was dispersed in 100 g of distilled water.

At this time, a complex was prepared as shown in Table 2 below using 0.1% hyaluronic acid as an anionic polymer and 0.1% starch as a nonionic polymer. The composites prepared in each Example were stored at 50 &lt; 0 &gt; C and observed for sedimentation and discoloration.

From the results shown in the above Table 2, it can be seen that when an anionic polymer is used in an amount of 2 g or more and 100 g of a nonionic polymer is used in an amount of 1 g or more, Respectively. In addition, the optimum range in which sedimentation and discoloration of vitamin C were not observed even after 4 weeks of storage were found.

The stabilization of the complex supports that the anionic polymer and the non-ionic polymer form a network to improve the stability of the egg / insoluble substance in the aqueous solution.

&Lt; Examples 7 to 20 > Preparation of complexes by anionic polymer type and evaluation of physical properties

Based on the results shown in Table 2, when 30 g of vitamin C was supported on 100 g of the volcanic earth dispersion, the content of the anionic polymer was fixed to 2 g and the content of the nonionic polymer was fixed to 1 g, and the amount of the anionic polymer and the nonionic polymer Except that the kind of the catalyst was changed.

Specifically, 100 g of a 0.1% volcanic earth dispersion and 30 g of a 0.1% vitamin C solution were stirred at 4 캜 for 24 hours, centrifuged and washed, and redispersed in 100 g of distilled water.

The anionic polymer shown in the following Table 3 was added to the redispersed solution, stirred at 4 DEG C for 24 hours, centrifuged and washed, and redispersed in 100 g of distilled water. The non-ionic polymer was added to 100 g of the redispersed composite redispersion solution, followed by centrifugation and washing at 4 DEG C for 24 hours with stirring. The final product was dispersed in 100 g of distilled water and stored at 50 ° C to observe sedimentation and discoloration. The results are shown in Table 3 below.

As shown in the results of Table 3, when a composite in which vitamin C was stably supported on a volcanic soil prepared using various anionic polymers at an optimum content ratio was used, precipitation or discoloration of vitamin C even after 4 weeks of storage No precipitation stability and discoloration stability were observed.

&Lt; Examples 21 to 30 > Preparation of composites by physiologically active substance type and evaluation of physical properties

Based on the optimum content ratio in Table 2 and the anionic polymer type in Table 3, when 30 g of the physiologically active substance was supported on 100 g of the volcanic ash dispersion, 2 g of hyaluronic acid as an anion polymer and 1 g of starch as a nonionic polymer were fixed , And the kinds of various physiologically active substances were changed. The final product was dispersed in 100 g of distilled water and stored at 50 ° C to observe sedimentation and discoloration. The results are shown in Table 4 below.

From the results of Table 4, it can be seen that the sedimentation stability and the discoloration stability were improved because the various physiologically active substances in the volcanic soil reacted with the optimal contents of the anionic polymer and the nonionic polymer, Respectively.

These results support that various physiologically active substances can be applied as complexes having sedimentation stability and discoloration stability according to the method of the present invention.

As described above, according to the present invention, when physiologically active substances are supported by physical interaction with micropores of a porous material, which is a porous material, the ionic polymer is bound to the entrance of micropores to protect and stabilize physiologically active substances from the external environment. Lt; / RTI &gt;

In addition, the hydrophobic residues of the ionic polymer exposed on the surface of the composite of the present invention form a network by interaction of non-ionic polymers with Van der Waals, thereby suppressing self-agglomeration between the complexes and enhancing water dispersibility, Since it is not only environmentally friendly but also skin-friendly and highly stable to aqueous solution, it can be applied not only to raw materials for functional cosmetics but also to industrial fields such as foods and medicines that require stabilization of the target substance.

While the invention has been shown and described with reference to certain exemplary embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (6)

1. The physiologically active substance is supported on the micropores of the porous material which is the porous material, the micropores are encapsulated by the ionic polymer, and the water dispersibility is stabilized by van der Waals bonding between the ionic polymer residue exposed on the surface after the sealing and the nonionic polymer Complex.
2. The method of claim 1, wherein 10 to 30 parts by weight of the physiologically active substance is supported on 100 parts by weight of the volcanic ash, 1 to 10 parts by weight of the ionic polymer is contained, and 1 to 10 parts by weight of the nonionic polymer is stabilized &Lt; / RTI &gt;
3. The method of claim 1, wherein the physiologically active substance is selected from the group consisting of vitamin A, vitamin C, vitamin E, salicylic acid, kojic acid, alpha-lipoic acid, elastic acid, resveratrol, docohexaenoic acid (DHA), eicosapentaenoic acid (EPA) Linoleic acid, and glutathione, or a mixed form thereof.
4. The complex according to claim 1, wherein the ionic polymer is any one selected from the group consisting of alginic acid, pectin, carrageenan, xanthan gum, hyaluronic acid, gum Arabic, karaya gum and tragacanth gum.
5. The complex according to claim 1, wherein the nonionic polymer is selected from starch or cyclotin.
6. The functional product according to any one of claims 1 to 5, which is applied to any one selected from the group consisting of cosmetics, foods and medicines, and is embodied by a physiologically active substance.

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