SILICON ION COMPLEX ORGANIZED WITH CARBOXYLIC ACID, METHOD FOR MANUFACTURING COMPLEX, AND PRODUCT USING SAME

Abstract

Proposed is a technology related to the ionization of silicon, and more particularly, to a technology for ionization by organizing silicon using a water-soluble silicate with a tricarboxylic acid or a dicarboxylic acid. This technology enables preparation and use of products containing an organized silicon ion complex in a variety of applications including foods such as water and beverages and medical products, as well as electrochemical applications. In particular, it is expected to treat and prevent various diseases caused by silicon deficiency by providing an organized form of silicon that does not exist as an ion in nature.

Claims

1. A method for preparing a silicon ion complex organized with a carboxylic acid, comprising: (1) dissolving at least one carboxylic acid selected from a dicarboxylic acid and a tricarboxylic acid to prepare an aqueous solution of carboxylic acid; (2) adjusting the pH of the aqueous solution of carboxylic acid to a value ranging from 1.0 to 13.0 to make the aqueous solution acidic or basic; (3) dissolving a water-soluble silicate compound in the pH-adjusted aqueous solution of carboxylic acid; and (3) selectively adding a cation.

2. The method according to claim 1, wherein the dicarboxylic acid in step (1) is an amino acid.

3. The method according to claim 1, wherein adjusting the pH of the aqueous solution to a value ranging from 1.0 to 13.0 to make the solution acidic or basic in step (2) is adding any one of carboxylic acid, sodium carbonate (Na.sub.2CO.sub.3), sodium hydrogen carbonate (NaHCO.sub.3), sodium hydroxide (NaOH), and amino acid.

4. The method according to claim 1, wherein the water-soluble silicate compound dissolved in step (3) is at least one selected from a water-soluble silicate containing sodium, potassium, or calcium in addition to silicon and a water-soluble silicate complex prepared by selectively adding a mineral in the preparation of the water-soluble silicate, the water-soluble silicate including sodium silicate, potassium silicate, or calcium silicate.

5. The method according to claim 4, wherein the water-soluble silicate complex prepared by selectively adding a mineral in the preparation of the water-soluble silicate is a water-soluble silicate complex prepared by adding at least one selected from sodium carbonate, potassium carbonate, sodium triphosphate, sodium pyrophosphate, sea salt, magnesium carbonate, calcium carbonate, magnesium oxide, calcium oxide, iron oxide, or manganese oxide.

6. The method according to claim 1, wherein the cation selectively added in step (4) is selected from the cations of magnesium, potassium, iron, manganese, sodium, zinc, sulfur, calcium, phosphorus, titanium, or zirconium.

7. The method according to claim 6, wherein selectively adding a cation is dissolving a substance containing the cation in an aqueous solution of a dicarboxylic acid or a tricarboxylic acid.

8. The method according to claim 1, further comprising: performing sterilization after step (4) by using at least one method selected from UV sterilization, high-temperature sterilization, chlorination, gaseous dioxide sterilization, or ozone sterilization.

9. A silicon ion complex organized with a carboxylic acid prepared by the method according to claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0161] FIG. 1 shows a silicate precipitated in a gastric acid environment (pH 1.5 or below).

[0162] FIG. 2 is a diagram showing the crystal structure obtained through evaporation of a saturated solution of an organized silicon ion complex prepared with tartaric acid.

[0163] FIG. 3 is a diagram showing the crystal structure in a saturated solution of an organized silicon ion complex prepared with tartaric acid.

[0164] FIG. 4 shows the surface of an accessory product plated with a gold plating solution containing the organized silicon ion complex prepared with tartaric acid in Example 3.

[0165] FIG. 5 shows a substitution reaction test performed using the silicon ion complex organized with tartaric acid as prepared in Example 3 on the surface of a stainless steel product (left: the stainless steel surface before substitution reaction, right: the stainless steel surface after substitution reaction).

[0166] FIG. 6 shows an experimental image showing water repellence on a stainless steel surface after substitution reaction with silicon ions.

DETAILED DESCRIPTION OF THE DISCLOSURE

[0167] Hereinafter, the present invention will be described as follows.

[0168] In order to explain a silicon ion complex organized with a carboxylic acid according to the present invention, there was performed an experiment for ionization through organization of a water-soluble silicate using (1) an organic acid having a tricarboxyl group or a dicarboxyl group, such as citric acid, malic acid, or tartaric acid and (2) glycine as one of amino acids.

[0169] The water-soluble silicate used to explain the present invention is Na.sub.2SiO.sub.3.9H.sub.2O, but is not limited thereto. It may also be Na.sub.2SiO.sub.3, Na.sub.2SiO.sub.3.5H.sub.2O, Na.sub.2SiO.sub.3.10H.sub.2O, and mineral-containing water-soluble silicate complexes produced in the preparation of a water-soluble silicate. Hydrates containing water molecules in the molecule have some potential to form insoluble precipitates, but they can exist as ions without any specific problems when dissolved at a low temperature. In general, water-soluble silicate complexes containing various mineral components are produced in the preparation process for water-soluble silicates, and the mineral components chiefly available in the process may include magnesium (Mg), potassium (K), iron (Fe), manganese (Mn), sodium (Na), zinc (Zn), sulfur (S), calcium (Ca), and phosphorus (P).

[0170] These mineral components are used by way of adding substances such as sodium carbonate, potassium carbonate, sodium triphosphate, sodium pyrophosphate, sea salt, magnesium carbonate, calcium carbonate, magnesium oxide, calcium oxide, iron oxide, or manganese oxide.

[0171] Hereinafter, the present invention will be described in detail with reference to the specific examples as follows.

[Comparative Example 1] Experiment 1 for Metasilicate Dissolution

[0172] A dissolution experiment was performed using sodium metasilicate nonahydrate (Na.sub.2SiO.sub.3.9H.sub.2O).

[0173] The procedures were performed as follows.

[0174] (1) 1 g of metasilicate nonahydrate (Na.sub.2SiO.sub.3.9H.sub.2O) was dissolved in 500 ml of pure water to prepare a solution, which was clear and had a pH of 12.23 (with a measurement deviation of a digital pH meter).

[0175] (2) The pH of the solution was lowered to pH 1.5 using 37% hydrochloric acid and measured again.

[0176] (3) The dissolved silicate gelled while agglomerating.

[Comparative Example 2] Experiment 2 for Metasilicate Dissolution (Gastric Acid Conditions)

[0177] (1) 150 ml of water was added in a 250 ml beaker, adjusted in pH to a value of 1.5 with 37% hydrochloric acid to meet the standards for gastric acid of the human body, and combined with another water to a volume of 250 ml.

[0178] (2) 1 g of metasilicate nonahydrate (Na.sub.2SiO.sub.3.9H.sub.2O) was added to the solution of step (1).

[0179] (3) The silicate got partly loose, but precipitated rather than dissolved.

[0180] Through the comparative examples, it was confirmed that the metasilicate was unable to exist in an ionic state alone in the gastric acid (FIG. 1).

[0181] Even though the metasilicate was reduced to a nano-scale size, it was in the form of silica gel, which was difficult to digest and absorb.

[0182] The precipitated substance was unable to re-ionize in the same solution.

[Example 1] Experiment for Preparation of Organized Metasilicate Ion Complex using Citric Acid

[0183] An organic ionization testing was performed using metasilicate nonahydrate (Na2SiO3.9H2O).

[0184] The procedures were performed as follows.

[0185] (1) 20 g of citric anhydride was added into a 500 ml beaker.

[0186] (2) Sodium carbonate was used to adjust the pH to a value of 8.0 (alkaline); this pH adjustment was conducted to prevent insoluble impurities from produced by pH shock, due to the metasilicate dissolving easily under neutral-to-alkali conditions without pH shock.

[0187] (3) 20 g of silicate nonahydrate (Na.sub.2SiO.sub.3.9H.sub.2O) was slowly dissolved under mechanical agitation; water absorption and endothermic reaction occurred during the dissolution process.

[0188] (4) The organized silicon ion complex thus obtained was stabilized in the form of a clear solution. 20 g of the complex was sufficiently dissolved in 500 ml of the solution and maintained in an ionic state; when reduced to the amount of pure silicon ions, the silicon ion content amounted to about 3.954 g/L.

[0189] (5) 100 ml of the organized silicon ion complex thus obtained was transferred to a 250 ml beaker and then adjusted in pH to a lower value (≤1.5) with 37% hydrochloric acid to determine its stability. In about 20 days of observation, the organized silicon ion complex was maintained in a stable state. This testing was to determine whether the organized silicon ion complex was able to exist as ions in the environment similar to the human gastric acid.

[0190] (6) The pH level of the solution of step (5) was changed back to a value of 13.0 using ammonia. The solution remained stable.

[0191] A step of filtration is necessary in the process of preparing a silicon ion complex organized with a carboxylic acid. The filtration is to filter out the impurities produced by the pH shock possibly occurring during the dissolution and those remaining in the substances. The filtration as used herein may include precipitate filtration using the supernatant after precipitation, or filter filtration.

[0192] In addition, sterilization may be necessary in the preparation process. The sterilization as use herein may include at least one sterilization method selected from UV sterilization, high-temperature sterilization, chlorination, gaseous dioxide sterilization, and ozone sterilization.

[0193] In order to adjust the pH of the organized silicon ion complex composed of citric acid to weak acid or weak alkali, carboxylic acids, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, or amino acids was used, and the adjusted pH value ranged from 1 to 13.

[0194] This process made the organized silicon ion complex available for use in water, beverages, or the like. But, the organized silicon ion complex was less stable than that using tartaric acid.

[Example 2] Experiment for Preparation of Organized Metasilicate Ion Complex using Malic Acid

[0195] An organic ionization testing was performed using metasilicate nonahydrate (Na.sub.2SiO.sub.3.9H.sub.2O).

[0196] The procedures were performed as follows.

[0197] (1) 20 g of malic acid was added into a 500 ml beaker.

[0198] (2) Sodium carbonate was used to adjust the pH to a value of 8.0 (alkaline); this pH adjustment was to prevent insoluble impurities from produced by a pH shock, due to the metasilicate dissolving easily under neutral-to-alkali conditions without pH shock.

[0199] (3) 20 g of silicate nonahydrate (Na.sub.2SiO.sub.3.9H.sub.2O) was slowly dissolved under mechanical agitation; water absorption and endothermic reaction occurred during the dissolution process. The dissolution rate of the silicate increases with an increase in the dissolution temperature. It was considered more desirable to slowly dissolve the silicate at a low temperature in order to increase the binding force to the organic acid.

[0200] (4) The organized silicon ion complex thus obtained was stabilized in the form of a clear solution. 20 g of the complex was sufficiently dissolved in 500 ml of the solution and maintained in an ionic state; when reduced to the amount of pure silicon ions, the silicon ion content amounted to about 3.954 g/L.

[0201] (5) 100 ml of the organized silicon ion complex thus obtained was transferred to a 250 ml beaker and then adjusted in pH to a lower value (≤1.5) with 37% hydrochloric acid to determine its stability. In about 20 days of observation, the organized silicon ion complex was maintained in a stable state.

[0202] (6) The pH level of the solution of step (5) was changed back to pH 13.0 using ammonia. The solution was maintained stable.

[0203] The organized silicon ion complex of Example 2 was also less stable than that using tartaric acid.

[Example 3] Experiment 1 for Preparation of Organized Metasilicate Ion Complex using Tartaric Acid

[0204] An organic ionization testing was performed using metasilicate nonahydrate (Na.sub.2SiO.sub.3.9H.sub.2O).

[0205] The procedures were performed as follows.

[0206] (1) 40 g of tartaric acid was added into a 500 ml beaker.

[0207] (2) The procedure of pH adjustment was omitted.

[0208] (3) 40 g of silicate nonahydrate (Na.sub.2SiO.sub.3.9H.sub.2O) was slowly dissolved under mechanical agitation.

[0209] (4) The organized silicon ion complex thus obtained was stabilized in the form of a clear solution. 40 g of the complex was sufficiently dissolved in 500 ml of the solution and maintained in the ionic state; when reduced to the amount of pure silicon ions, the silicon ion content amounted to about 7.908 g/L. Further research is needed as to why such a large amount of silicate was able to dissolve when using tartaric acid.

[0210] (5) 100 ml of the organized silicon ion complex thus obtained was transferred to a 250 ml beaker and then adjusted in pH to a lower value (≤1.5) with 37% hydrochloric acid to determine its stability. In about 20 days of observation, the organized silicon ion complex was maintained in a stable state.

[0211] (6) The pH level of the solution of step (5) was changed back to pH 13.0 using ammonia. The solution was maintained stable.

[0212] (7) The silicon ion complex solution prepared using tartaric acid was made into a saturated solution at room temperature and observed to determine whether it was subjected to gelation. The solution did not form a silica gel, but produced a precipitate having a new needle-shaped structure (Refer to FIG. 2).

[Example 4] Experiment 2 for Preparation of Organized Metasilicate Ion Complex using Tartaric Acid

[0213] An organic ionization testing was performed using metasilicate nonahydrate (Na.sub.2SiO.sub.3.9H.sub.2O).

[0214] This experiment has an object to determine whether gelation occurs in a saturated solution of the organized metasilicate ion complex and to identify the crystal structure of the complex in the saturated solution.

[0215] The procedures were performed as follows.

[0216] (1) 60 g of tartaric acid was added into a 500 ml beaker; its complete dissolution was confirmed by observation with naked eye.

[0217] (2) The procedure of pH adjustment was omitted.

[0218] (3) 60 g of silicate nonahydrate (Na.sub.2SiO.sub.3.9H.sub.2O) was slowly dissolved under mechanical agitation; water absorption and endothermic reaction occurred during the dissolution process.

[0219] (4) The silicate was completely dissolved and partly precipitated in the saturated solution. The precipitate thus obtained had a needle-shaped structure rather than the form of not-dissolved silicate. It was a structure that looked like a fibrous substance possibly found in vegetable fibers. This precipitate was able to re-dissolve (Refer to FIG. 3).

[Example 5] Experiment for Preparation of Organized Metasilicate Ion Complex using Glycine

[0220] An organic ionization testing was performed using metasilicate nonahydrate (Na.sub.2SiO.sub.3.9H.sub.2O) as follows.

[0221] (1) 20 g of glycine was added into a 500 ml beaker; its complete dissolution was confirmed by observation with naked eye.

[0222] (2) Sodium carbonate was used for adjusting the pH to a value of 8.0. Glycine, which is neutral, can be easily changed into alkali by adding a small amount of sodium carbonate.

[0223] (3) 20 g of silicate nonahydrate (Na.sub.2SiO.sub.3.9H.sub.2O) was slowly dissolved under mechanical agitation; water absorption and endothermic reaction occurred during the dissolution process.

[0224] (4) The silicate was completely dissolved to have a pH value of 12.25. This pH level can be lowered with citric acid, malic acid, or tartaric acid to make the solution into a slightly alkaline drinking water.

[0225] In the preparation of the organized silicon ion complex using a carboxylic acid, it is possible to add minerals such as cations of magnesium, potassium, iron, manganese, sodium, zinc, sulfur, calcium, phosphorus, or titanium or zirconium. In this regard, titanium and zirconium are preferably added in the form of organized ions that are stable against pH changes in an aqueous solution.

[0226] Other mineral components as used herein are substances susceptible to ionization in an aqueous solution; cations obtained by dissolution of substances, such as calcium oxide (CaO), calcium hydroxide (Ca(OH).sub.2), calcium ascorbate (Ca(C.sub.6H.sub.7O.sub.6).sub.2), calcium carbonate (CaCO.sub.3), calcium chloride (CaC.sub.12), calcium magnesium acetate, calcium acetate (C.sub.4H.sub.6CaO.sub.4), magnesium acetate (C.sub.4H.sub.6MgO.sub.4), magnesium carbonate-magnesium hydroxide-5 hydrate ((MgCO.sub.3).sub.4.Mg(OH).sub.2.5H.sub.2O), magnesium chloride (MgCl.sub.2), magnesium citrate, magnesium hydroxide (Mg(OH).sub.2), magnesium oxide (MgO), potassium acetate (CH.sub.3COOK), potassium chloride (KCl), potassium citrate, potassium hydroxide (KOH), potassium carbonate (K.sub.2CO.sub.3), potassium hydrogen carbonate (KHCO.sub.3), sodium hydroxide (NaOH), sodium carbonate (Na.sub.2CO.sub.3), sodium hydrogen carbonate (NaHCO.sub.3), sodium acetate (CH.sub.3COONa), sodium citrate, iron oxide, iron chloride, zinc chloride, manganese oxide, sodium phosphate, and trisodium phosphate. A variety of other water-soluble substances can also be used to obtain the cations.

[0227] Before addition, these cations are preferably dissolved in an aqueous solution of a dicarboxylic acid or a tricarboxylic acid, more preferably in an aqueous solution of a tricarboxylic acid.

[0228] The silicon ion complex organized with a carboxylic acid thus obtained is available for various use purposes. For example, it can be used for various applications, including drinking water suitable for drinking water quality standards, amino acid beverages, mineral beverages, amino acid-mineral composite beverages, pharmaceutical compositions for oral administration or injection to supply silicon minerals to animal and human bodies, breads, confections, fertilizers for plant growth, cleaning agents, cosmetics, and medical ointments.

[0229] The cleaning agents can be prepared by adding a certain portion of the silicon ion complex organized with a carboxylic acid according to the present invention to shampoos, conditioners, face cleansing solutions, soaps, dish detergents, laundry detergents, toothpaste, etc. and used as cleansing agents for humans and other animals.

[Example 6] Plating Experiment

[0230] The silicon ion complex using a tartaric acid as prepared in Example 3 was diluted with 1 L of water to lower the sodium silicate concentration per liter by 50%, and then analyzed in regards to the electrochemical ion behavior.

[0231] The conventional titanium or zirconium, even though organized (chelated) and made into ions, was available for electrochemical use.

[0232] 1 L of water was added to the solution of Example 3 (ingredient 1) to make 2 L of a diluted solution. 0.1 g of potassium gold cyanide (ingredient 2) and a trace amount (0.01 g or less) of sodium lauryl sulfate (ingredient 3) were added to 250 ml of the diluted solution to prepare 1 L of a gold plating solution.

[0233] With an iridium-coated titanium electrode used as an anode, 1.5V DC current was applied to perform a gold plating on a metallic accessory part, of which the surface was inspected. If insufficient, gold was supplemented in small portions, and the changes in color and texture were measured.

[0234] This experiment was to determine from the texture and color of the surface whether silicon had an ion behavior, although the thickness of silicon was not measurable with a plating thickness measuring device. The measurement results are presented in FIG. 4.

[0235] The gold-plated surface had a slight blue sensation, expressing the texture as if it was coated with a glass film, and the yellow color of gold was slightly darker.

[0236] This result confirmed that the silicon ion complex could be used for a plating solution, such as a gold plating solution. This phenomenon appeared similarly in most of electroplating solutions. Therefore, the silicon ion complex of the present invention can be used in the process of metal reduction and deposition in the electrochemical field, plating, to add the texture of glass, so it is expected to be used for various applications.

[Example 7] Substitution Experiment

[0237] In addition, a substitution experiment was performed to determine whether the silicon ion complex prepared according to the present invention and present as an ion had a substitution ability.

[0238] The reason of this experiment was that it was needed to confirm whether silicon as a metalloid caused a substitution reaction like other metals while in an ionic state.

[0239] In the substitution experiment, 1 L of water was added to the solution prepared in Example 3 to make 2 L of a diluted solution, and various metals were immerged in 250 ml of the diluted solution. As a result, the stainless steel surface exhibited surface purification ability and texture like a glass film coating (Refer to FIG. 5). When the surface was viewed from various angles in the sunlight, it had a light scattering like the pieces of broken glass and a little texture of glass. In addition, the surface was hydrophobic and impervious to water (Refer to FIG. 6).

[0240] It was therefore confirmed that the present invention is not only performing the function of a mineral, but also available as metalloid ions in various applications including electrochemistry (plating), as the metals of titanium and zirconium organized into ions were electrochemically available.

[0241] The terminology used herein is for the purpose of describing an embodiment only and is not intended to be limiting of an exemplary embodiment. As used herein, the singular forms are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising” when used in this specification, specify the presence of stated form, numeral, step, operation, member, element, and/or a combination thereof but do not preclude the presence or addition of one or more other forms, numerals, steps, operations, members, elements, and/or combinations thereof.

[0242] For example, the organic acid, amino acid, or carboxylic acid used in the present invention is not necessarily limited to only the organic acid, amino acid, or carboxylic acid, but may include sodium compounds, potassium compounds, or ammonium compounds containing such components.

[0243] Although the exemplary embodiments of the present invention have been described, it is understood that the present invention should not be limited to these exemplary embodiments but various modifications can be made within the scope of the present invention as hereinafter claimed.