KR20100119985A - Sericite exchanged metal ion having anti-bacteria and preparing methods for thereof - Google Patents

Abstract

PURPOSE: Sericite substituted with an antibacterial metal ion, and a manufacturing method thereof are provided to control the transformation of the antibacterial metal ion for extending the lifetime of the sericite, using an antioxidant. CONSTITUTION: Sericite substituted with an antibacterial metal ion is marked with chemical formula 1: KaAlb(SicAld)OeXfYgNah(OH)i. In the chemical formula 1, X and Y are Ag, Fe, Zn, or Cu. A manufacturing method of the sericite comprises the following steps: mixing 0.1~3wt% of natural sericite with 97~99.9wt% of purified water to form a first suspension; inserting 10~200 ppm of antibacterial metal ion to the first suspension, and stirring to make a second suspension; and adding an antioxidant to the second suspension.

Description

Sericite exchanged with antimicrobial metal ions and its preparation method {SERICITE EXCHANGED METAL ION HAVING ANTI-BACTERIA AND PREPARING METHODS FOR THEREOF}

The present invention relates to a sericite exchanged antimicrobial metal ions and a method for manufacturing the same, and relates to an invention for imparting functions such as antibacterial and deodorization to sericite, which is a widely used eco-friendly material.

The term sericite, also called chorus, is derived from the Greek word for silk, belonging to the monoclinic system, and have a pearlescent appearance of white or off-white. Originally referred to as the dominant mineral of crystalline schist, especially chorionic schist, today it refers to clay-like fine muscovite formed by hydrothermal action. The chemical composition is almost the same as that of the mica, but generally potassium is less than the mica and a little more moisture. It is produced as a secondary alteration such as feldspar, cordierite, and hongseokseok, and is the most common constituent mineral of feldspar, slate rock or stony rock subjected to light power metamorphism. The potter's stone is caused by the alteration of volcanic rock, which is composed of quartz (70%) and biotite (30%). Cicada is used as a mixing material in ceramics or firebrick, and has various uses such as paints, electrical insulators, active materials, and cosmetics.

Sericite is called sericite because its surface has silky luster, and it is white or light brown and its chemical composition is K ₂ Al ₄ (Si ₅ Al ₂ ) O ₂₀ Na ₂ (OH) ₄ It has an intermediate property, and dehydrated unit cell is slightly expanded at 600 ~ 700 ℃, and dehydrated unit cell is decomposed at around 1050 ~ 1100 ℃ to produce mullite. Because of its viscosity, the load softening temperature is high.

 In addition, since it plays the role of feldspar that plays the role of a plastic material clay and a flux, when preparing chamomile refractory brick, when crushing about 5% of the clay containing sericite and blending it into the raw material, the firing temperature It can be reduced to about 30 ~ 40 ℃, which is very helpful for saving fuel, sintering is good, and the load softening temperature is hardly lowered. Since sericite is white in color, it can be used in various applications.

Conventionally, the invention using sericite relates to a method for producing a multifunctional inorganic antibacterial product including a photocatalyst and a product thereof, and more specifically to a natural mineral zeolite, bentonite, sericite, diatomaceous earth. Inorganic antimicrobial photocatalyst made of rutile type titanium dioxide composited to improve the antibacterial activity, deodorizing ability and adsorption function by using titanium dioxide having a rutile type crystal structure having good heat resistance and durability through the process. A method of preparing a porous body by a special method is prepared by mixing the agent with an appropriate amount to obtain an inorganic antimicrobial agent in which a slurry photocatalyst is mixed, and then injecting the same into a mold of a desired form.

In addition, the Republic of Korea Patent No. 0428248 relates to a method for producing a ceramic filter and a ceramic filter produced by the same, in detail, the ganban stone, sericite and zeolite powder having an appropriately controlled weight% is mixed with water to prepare a ring The present invention relates to a method for producing a ceramic filter, which is more improved in pharmacological effects and disease prevention, together with an effective water purification function, by heat-treating and sintering the prepared ring at a predetermined temperature, and a ceramic filter manufactured accordingly.

However, the Patent No. 0255570 relates to a method for preparing a porous body by using a natural mineral and appropriately mixing a photocatalyst having an antimicrobial function, but the porous body may have antibacterial properties, but the natural mineral and the photocatalyst are mixed. However, it has a limit of exhibiting antimicrobial properties only when there is a light source.

In addition, the ring formed using the elvan and the sericite and zeolite powder of the Patent No. 0428248 can act as a ceramic filter, but there is a disadvantage that there is no antibacterial.

Therefore, there is a need for a natural inorganic material that is simple in manufacturing and yet has a sustained antibacterial and deodorizing power.

In order to solve the above problems, the present invention is to provide a natural inorganic antimicrobial material and a method for preparing the same by a simple immersion process, easy to combine the antimicrobial metal components to natural minerals, and having a continuous antibacterial and deodorizing power by the combined antimicrobial metal. do.

In order to achieve the above object, the present invention provides a sericite represented by the following formula (1) in which antibacterial metal ions are exchanged.

K _a Al _b (Si _c Al _d ) O _e X _f Y _g Na _h (OH) _i

(X and Y are any one of Ag, Fe, Zn and Cu, and 1≤a, d, h, i≥10, 1≤b, c, g, f≥20, 1≤e≥40.)

The use of sericite is diverse, but typical uses include cosmetics, soap, toothpaste, clothing, feed, fertilizer, environment, construction, health products, broadcasting, satellite, aerospace, ceramics, welding, and other It is widely used for pigments, paints, medicine, food additives, and the like.

In the present invention, to give an additional function by mixing with the antimicrobial material to the sericite, an antimicrobial material can be added. The antimicrobial material may be used without limitation as long as it is a material that can be used in the art, and preferably a metal having antibacterial property, and more preferably Ag, Fe, Zn, Cu, or the like may be added. The metal may exert a function of inhibiting the metabolism of strains that cause disease and strains that cause odors, thereby sterilizing. In this case, the method of introducing the antimicrobial metal ions into the sericite may be introduced by exchanging a part of potassium or sodium present in the sericite with the antimicrobial metal ions. Specifically, potassium or sodium is ionized in sericite and separated from sericite, and instead the antimicrobial metal ions are bonded to sericite, thereby allowing ion exchange to be performed.

In addition, in the present invention, the exchange of metal ions and the combination of metal ions should be interpreted in the same sense.

In addition, the present invention provides a method for producing sericite in which metal ions are exchanged: 1) a primary suspension in which natural sericite is dispersed in purified water by mixing and stirring 0.1 to 3% by weight of natural sericite and 97 to 99.9% by weight of purified water. Preparing a; 2) preparing a secondary suspension by adding antimicrobial metal ions to the primary suspension with a final concentration of 10 to 200 ppm and stirring; And 3) adding an antioxidant to the secondary suspension.

In addition, the present invention may further comprise the step of centrifuging the final product of step 3), and drying it.

Firstly, step 1) is to prepare a primary suspension in suspension using sericite.

Although the said sericite is not specifically limited, Preferably what is 25-1000 mesh powder can be used. The mesh is a unit representing the particle size of the abrasive or abrasive. The lower the mesh value, the larger the particle size. The higher the mesh value, the smaller the particle size. When the sericite is less than 25 mesh, the particle size is large, making it difficult to prepare the sericite in a suspension state, and the bond with the metal ions is decreased. The binding rate of no longer increases.

The purified water used in this step is not particularly limited, and distilled water may be preferably used. The amount of sericite added to the purified water is not particularly limited, and preferably, 0.1 to 3% by weight of sericite and 97 to 99.9% by weight of purified water can be mixed. In this case, when less than 0.1% by weight of sericite is used, it is difficult to obtain sufficient sericite due to the small amount used, and when it exceeds 3% by weight, adhesion between the sericites occurs, thereby decreasing the permeability of the metal ions. It becomes difficult to produce sericite that is ion exchanged. Reactivity can be reduced.

In addition, when the sericite is dissolved in purified water, pH 5.0 ~ 8.2, it is necessary to adjust to a neutral pH of 6.5 ~ 7.5 for a constant reactivity. The step of neutralizing the sericite is not particularly limited. In this step, sericite may be manufactured and used for various purposes, for example, cosmetic materials, antibacterial balls for beverages, and the like. In order to be used as the material, it is necessary to manufacture the neutral region for biocompatibility.

Therefore, the neutralizing of the sericite may be performed after the antimicrobial metal ions are exchanged with the sericite. Preferably it may be carried out in the step of dissolving sericite in purified water. In order to adjust the pH of the purified water in which the sericite is dissolved, the pH may be adjusted using an acidic solution or a basic solution. The acidic solution may use both strong and weak acids, and the basic solution may use both strong and weak bases.

Next, step 2) is a step of reacting by adding antimicrobial metal ions.

The antimicrobial metal may be used without limitation so long as it is a metal that can be used in the art, and preferably Ag, Fe, Zn, Cu, or the like may be used. The metal is preferably added in the form of ions, and more preferably, the antimicrobial metal may use metal ions prepared by electrolysis. At this time, the method of adding the antimicrobial metal ions can be used by adding a metal to the primary mixed solution in an ionic state, and after the addition, so that the concentration of metal ions in the solution is 10 to 200 ppm. When the concentration of the metal ion is less than 10 ppm, it is difficult to exhibit the antibacterial and deodorizing effect, when it exceeds 200 ppm compared to the addition amount, it is difficult to expect improved antibacterial and deodorizing effect.

In addition, the present invention is to add the antimicrobial metal in the ionic state, when the antimicrobial metal is added to the powder, the size of the metal particles is large, the bonding strength is lowered to the sericite, there may be a disadvantage that the combined metal is less reactive. In addition, there is a disadvantage that the amount of metal added to the sericite in order to increase the expected effect of antibacterial and deodorizing power. However, when the antimicrobial metal is added, when added in the form of ions, there is an advantage that a small amount of the added metal can be used.

In this case, the method of introducing the antimicrobial metal ions into the sericite may be introduced by exchanging a part of potassium or sodium present in the sericite with the antimicrobial metal ions. Specifically, potassium or sodium is ionized in sericite and separated from sericite, and instead the antimicrobial metal ions are bonded to sericite, thereby allowing ion exchange to be performed. The antimicrobial metal ions ion-exchanged with the sericite may be bound by 0.05 to 2% with respect to sericite. At this time, the combined percentage of the antimicrobial metal ions is the most preferred range that can allow the sericite to have a sufficient antimicrobial activity.

Next, step 3) is a step of adding an antioxidant to maintain the reactivity of the sericite of the present invention.

The antioxidant can be used without limitation so long as it is a material for preventing oxidation of the antibacterial metal. Preferably, phenyl-β-naphthylamine, tocopherol, propyl gallate, thioether and the like can be used. In this case, the antioxidant may be added to the secondary mixture to be used at a concentration of 4 ~ 200 ppm. The antioxidant may be administered and stirred to make the reaction easy to produce the final product. If the amount of the antioxidant is less than 4 ppm it is difficult to expect a sufficient antioxidant effect, if it exceeds 200 ppm there is a disadvantage that the antioxidant effect is no longer increased compared to the amount of the antioxidant is added, the utility is inferior .

The final product is a form in which the antibacterial metal and the antioxidant are combined with sericite and form a suspension state. Since the sericite is a large size in which the particles cannot be completely dissolved in water, the sericite in suspension can be obtained by a general method in the art. As a preferred method of obtaining, sericite can be obtained by rotating at 200-3000 g by centrifugation.

Sericite exchanged with antimicrobial metal ions according to the present invention may exhibit antimicrobial activity against pathogenic strains well known in the art and strains that can cause odors. Preferably, E. coli, E. coli O-157, Salmonella, Bacillus subtilus, Staphylococcus aureus, Vibrio bacteria, dysentery, pneumococci, typhoid fever and the like can exhibit antimicrobial activity.

Sericite exchanged antibacterial metal ions according to the present invention can be used as a disinfectant, water purifier, odor and toxic gas adsorbents, deodorants, building materials, paint additives and the like.

The fungicide refers to a substance added with the sericite of the present invention to sterilize a strain which may cause pathogenic or odor.

The water purifying agent refers to a substance to which the sericite is added to remove impurities contained in water and to filter strains.

The malodorous and toxic gas adsorbent refers to a substance to which the sericite of the present invention is added to absorb odor causing factors or toxic gases present in the air.

The deodorant refers to a substance to which the sericite of the present invention is added so as to absorb odor causing factors present in the air.

The building material is a material used to impart additional functions to the building material, for example, the sericite of the present invention can be added so that the general building material has antibacterial or deodorizing power.

The paint additive is a material added to impart an additional function to the paint. For example, after applying the paint, the sericite of the present invention may be added to have antibacterial or deodorizing power while suppressing the release of a substance harmful to the human body.

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

However, the following examples are illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

Example  1: silver ions exchanged Serisite  Produce

 1 g of sericite was stirred in 30 ml of distilled water to sufficiently disperse the suspension, and the suspension was neutralized to pH 7.0 using sodium hydroxide solution or nitric acid at a concentration of 0.1-3.0 normal. Silver ionic liquid was added to 100 ml of the said neutralized suspension so that silver ion concentration might be 100 ppm, and it stirred at room temperature for 10 hours.

The silver ionic liquid used was prepared by electrolysis. This step yielded a sericite suspension with silver ions exchanged and centrifuged at 500 g to give a sericite precipitate. The obtained sericite was dried in air at 100 ° C. for 2 hours to prepare sericite having 0.25% exchanged silver ions.

Example  2: iron ions exchanged Serisite  Produce

Except for using iron ions in the same manner as in Example 1 to prepare a sericite 0.25% exchanged iron ions.

Example  3: zinc ion exchanged Serisite  Produce

Except for using zinc ions in the same manner as in Example 1 to prepare a sericite 0.25% exchanged zinc ions.

Example  4: copper ions exchanged Serisite  Produce

A sericite having 0.25% exchanged copper ions was prepared in the same manner as in Example 1, except that copper ions were used.

Comparative example  1: silver ions exchanged Illite  Produce

An illite having 0.25% exchanged silver ions was prepared in the same manner as in Example 1, except that illite was used instead of sericite.

Comparative example  2: Preparation of Zeolites with Silver Ions Exchanged

Except for using zeolite instead of sericite, zeolite in which 0.25% of silver ions were exchanged was prepared in the same manner as in Example 1.

Experimental Example  1: silver ions exchanged Serisite  X-ray diffraction  analysis

In order to confirm that silver ions were exchanged in the sericite of Example 1, X-ray diffraction analysis was performed using an X-ray diffraction analyzer (Gaigerflex 201, Ewha Electric Co., Ltd.). The results are shown in FIG.

As shown in FIG. 1, sericite has a crystalline form of about 10 μm and exhibits representative X-ray diffraction peaks of 2θ = 12.3, 19.9, and 24.8, but 2θ = 21.2 when silver ions are exchanged in the sericite. , An X-ray diffraction peak of 26.5 can be seen.

Therefore, X-ray diffraction analysis showed that silver ions were bound to sericite in this experiment.

Experimental Example  2: silver ions exchanged Serisite  Antimicrobial experiment

Dioxide chorate medium was placed in two pan-neck flasks and kept warm at 48 ° C. in a thermostat. E. coli was added to the pan-neck flask so as to be 1 × 10 ⁶ (microbial count / ml), followed by stirring. One flask was used as a control by adding 3 mg of sericite exchanged with silver ions and another flask with distilled water. After stirring for a predetermined time, 1 ml of the medium was collected at 10 minute intervals from the pan-neck flask to which sericite was added. The results are shown in FIG.

As shown in Figure 2, the sericite of Example 1 was found to be able to kill E. coli after at least 40 minutes. Therefore, it was found that sericite exchanged with silver ions according to the present invention has high antibacterial activity.

Experimental Example  3: antimicrobial activity comparison experiment

Dioxide chorate medium was placed in four pan-neck flasks and kept warm at 48 ° C. in a thermostat. E. coli was added to the pan-neck flask so as to be 1 × 10 ⁶ (microbial count / ml), followed by stirring. 3 mg of Example 1, Comparative Examples 1, and 2 were added to each flask. After stirring for a predetermined time, 1 ml of the medium was collected from each flask at 10 minute intervals, and suspended in distilled water, and the number of bacteria was measured using a spectrophotometer. The results are shown in Fig.

As shown in Figure 3, Example 1 according to the present invention was found to exhibit an excellent E. coli antibacterial activity than Comparative Examples 1 and 2.

From this, it can be seen that sericite having 0.25% exchanged silver ions according to the present invention shows excellent antibacterial activity.

Experimental Example  4: Deodorizing power  Comparative experiment

1 g of sericite of Example 1 was placed in a desiccator (6140 mL) and ammonia solution adjusted to an initial concentration of 500 mg / L using a syringe at room temperature attached to the sample inlet of the desiccator at room temperature. Was added dropwise. For air circulation inside the desiccator, the agitator was rotated to diffuse the internal air. After a certain time, the remaining ammonia concentration was measured using a detector tube (Gastack Co., Ltd.). Experiments were carried out in Comparative Examples 1 and 2 in the same manner as above. The results are shown in FIG.

As shown in FIG. 4, Comparative Example 1 exhibited 100% deodorizing power after 50 minutes of experiment time, and Comparative Example 2 exhibited 80% of deodorizing power after 60 minutes of experiment time. On the other hand, Example 1 exhibited 100% deodorizing power after 40 minutes of experiment time.

As a result, it was found that the sericite exchanged with silver ions according to the present invention may exhibit excellent deodorizing ability against ammonia, and the sericite exchanged with antimicrobial metal ions according to the present invention may also have excellent deodorizing power. Could.

Sericite according to the present invention can be used as a disinfectant, water purifier, odor and toxic gas adsorbent, deodorization, building materials, paint additives and the like. In addition, by using the antioxidant, there is also an effect of suppressing the degeneration of the antimicrobial metal ions and extending the life of the sericite in which the antimicrobial metal ions are exchanged. In addition, since the production method of sericite is simple and can be easily produced in large quantities, there is great industrial applicability.

1 is an X-ray diffraction analysis of sericite exchanged with silver ions prepared according to the present invention.

Figure 2 is the result of measuring the antibacterial activity of E. coli of the sericite exchanged silver prepared according to the present invention.

Figure 3 is the result of measuring the antimicrobial activity of E. coli of the sericite exchanged silver and zeolite prepared in accordance with the present invention.

4 is a result of comparing and measuring the deodorizing power of sericite and lide and zeolite exchanged with silver ions prepared according to the present invention.

Claims (15)

Sericite represented by the following formula (1) in which antimicrobial metal ions are exchanged. [Formula 1] K _a Al _b (Si _c Al _d ) O _e X _f Y _g Na _h (OH) _i (X and Y are any one of Ag, Fe, Zn and Cu, and 1≤a, d, h, i≥10, 1≤b, c, g, f≥20, 1≤e≥40.) In the sericite manufacturing method in which metal ions are exchanged, 1) mixing and stirring 0.1 to 3% by weight of natural sericite and 97 to 99.9% by weight of purified water to prepare a primary suspension in which natural sericite is dispersed in purified water; 2) preparing a secondary suspension by adding antimicrobial metal ions to the primary suspension with a final concentration of 10 to 200 ppm and stirring; And 3) adding an antioxidant to the secondary suspension; antimicrobial metal ion exchanged sericite manufacturing method comprising a. The method of claim 2, further comprising the step of centrifuging the final product of step 3) and drying it. The method of claim 2, wherein the sericite is a powder of 25-1000 mesh in step 1). The method of claim 2, wherein the antimicrobial metal ion of step 2) is at least one member selected from the group consisting of Ag, Fe, Zn, and Cu. The method of claim 2, wherein the antimicrobial metal ions of step 2) are metal ions prepared by electrolysis. The method of claim 2, wherein the antioxidant of step 3) is characterized in that 4 to 200 ppm of at least one selected from the group consisting of phenyl-β-naphthylamine, tocopherol, propyl gallate and thioether is added. Serisite manufacturing method. 4. The method of claim 3, wherein the centrifugation is performed at 200-3000 g. The method of claim 2, wherein the sericite prepared in the step is pH 6.5 ~ 7.5 method. A fungicide comprising sericite prepared by the method of any one of claims 2 to 9. A water purification agent comprising sericite prepared by the method of any one of claims 2 to 9. Odor and toxic gas adsorbent comprising a sericite produced by the method of any one of claims 2 to 9. A deodorant comprising sericite prepared by the method of any one of claims 2 to 9. A building material comprising a sericite produced by the method of any one of claims 2 to 9. A paint additive comprising sericite prepared by the method of claim 2.

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