TWI588093B - Method for manufacturing polymer latex particle containing nano silver particles - Google Patents

Description

Preparation method of nano silver particle polymer latex particles

The invention relates to a method for preparing nano-silver particle polymer latex particles, in particular to a method for uniformly and firmly coating nano silver on the surface of latex particles by specific preparation conditions. Thereby, the latex particles prepared by the invention have good antibacterial activity, can not only replace the addition of preservatives in cosmetics, but also solve the problem that tiny nano silver penetrates into the human cells through the skin, and can achieve the silver particles. Nano-dispersion enhances its antibacterial effect.

In recent years, cosmetic care products have become an indispensable daily necessities for beauty lovers. In order to extend the life of cosmetic products, it is necessary to add chemical antibacterials or preservatives to cosmetic products to improve the shelf life. Preservatives most commonly added to cosmetic care products such as parabens, Phenoxyethanol, Benzoic acid, sorbic acid, and other organic chemicals, and It has a good antibacterial effect, but when it accumulates over a certain dose after long-term use, there are still doubts about skin allergies and toxicity.

In addition to chemically synthesized organic antibacterial agents or preservatives, the most widely known inorganic antibacterial agents are nano silver particles, which have excellent deodorizing and bactericidal effects and are resistant to high temperatures. In addition, the nano silver particles can also avoid the need to contact the absence of ultraviolet light when using titanium dioxide photocatalyst for antibacterial. Accordingly, a number of inventions have been made to provide additional antimicrobial activity to the substrate by incorporating the nanoparticles onto different substrates.

For example, the method of manufacturing a substrate-containing surface-bonded metal nanoparticle according to the Patent Publication No. I455778 of the Republic of China, discloses a method for producing a surface-bonded metal nanoparticle of a substrate, comprising the steps of: The substrate is immersed in a salt solution containing a predetermined concentration of metal ions, the metal ions in the salt solution are attached to the substrate, the substrate is taken out, and a reaction solution containing a predetermined reducing agent is added. Adhering to the substrate, and providing an energy to the substrate, causing metal ions attached to the substrate to be reduced to metal nanoparticles, and finally, drying the substrate in a predetermined manner to obtain a bonding metal The base material of the nanoparticle, whereby the product produced is not easy to leave a chemical component harmful to the human body, and does not need to be treated by a complicated separation procedure; the Republic of China Patent Publication No. I495481 "Polyoxime composite particles and The manufacturing method and the cosmetic material disclose a polyfluorene-oxygen composite particle which can be added to the deodorant cosmetic, and is characterized in that 100 parts by mass of the polythene oxide elastomer spherical particles It is coated with 0.5 to 25 parts by mass of a polyoxyxene resin, wherein the polyfluorene oxide spherical particles have an average particle diameter of 0.1 to 100 μm, and the polyfluorene oxide resin has an organic germanium sesquioxane unit as a main component. Ingredients, and inorganic fine particles having an average particle diameter of 100 nm or less; and the Republic of China Patent Publication No. I455718 "Nano-silver particles/clay composites for antibacterial use and a method for producing the same", which disclose a method applicable to biology, medicine, Nano-silver particles/clay composites in the fields of chemistry, chemical engineering, materials, etc. (such as antibacterial and scald medical treatment), which are a powder, including metal particles and flaky inorganic clay, wherein the length and width of the flaky inorganic clay a ratio of 100 to 1000, and as a carrier of the metal particles, so that the metal particles reach nanometer-scale dispersion, the size of the antibacterial nano metal particles/inorganic clay composite is 5 to 100 nm; wherein the sheet-like inorganic When the clay is bentonite or nano-powder, and the flaky inorganic clay is bentonite, the weight ratio of the nano metal particles to the clay is 1:100~1:13.83 or 1:6.944~100:1; the flaky inorganic When the clay is a nano-slice, M clay particles and metal weight ratio of 1: 13.43 to 100: 1; the group consisting of a metal selected from silver.

According to the literature search results, although there are many applications for bonding nano silver particles to different substrates, how to achieve uniform bonding of nano silver particles to a substrate depends on different preparation methods. Therefore, how to develop and produce better nano-silver particle polystyrene latex particles as an antibacterial agent is an urgent need for the inventors in related fields to break through.

SUMMARY OF THE INVENTION The main object of the present invention is to provide a method for uniformly and firmly adhering and distributing nano silver to the surface of latex particles by specific preparation conditions. Thereby, the latex particles obtained by the present invention have good antibacterial activity and can be added to the cosmetic as a preservative.

In order to achieve the above-mentioned object, the present invention comprises a method for preparing nano-silver particle polymer latex particles, which comprises the first step: adding a polymer latex particle suspension and a silver nitrate (AgNO ₃ ) aqueous solution in a weight percentage of 10:1~1. : 10 uniformly mixed to form a mixed solution, and the temperature is 50 ° C ~ 90 ° C for 10 ~ 120 minutes; and step 2: the mixed solution is cooled to 50 ° C ~ 85 ° C, then add sodium citrate aqueous solution in the mixed solution For 10 to 240 minutes (preferably for 20 to 130 minutes), to obtain polymer latex particles coated with nano silver particles; wherein the diameter of the polymer latex particles is greater than 50 nm, and the diameter of the nano silver particles is 1~500nm.

In one embodiment of the invention, the polymer latex-containing particle suspension is composed of 3.8 wt% polymer latex particles and residual weight percent water.

In one embodiment of the present invention, the polymer latex particles may be, for example, polystyrene latex particles, polymethylmethacrylate latex particles or poly-n-butyl methacrylate. Latex particles, latex particles of styrene and methyl methacrylate copolymer, latex particles of styrene and butyl methacrylate copolymer, latex particles of methyl methacrylate and butyl methacrylate copolymer, etc. . If the polymer latex particles are polystyrene latex particles, The preparation method may, for example, comprise (a) mixing styrene, polyetherimide (PEI), methanol and deionized water and heating to 50 ° C to 90 ° C; (b) adding an initiator azo The diisobutyronitrile (AIBN) methanol solution is subjected to a reaction for 3 to 12 hours; and (c) is purified by centrifugation to obtain purified polystyrene latex particles.

In one embodiment of the invention, the aqueous silver nitrate solution consists of 1.96 wt% silver nitrate and the remaining weight percent water; and the aqueous sodium citrate solution consists of 16.2 wt% sodium citrate and the remaining weight percent water.

In one embodiment of the invention, the nanosilver-containing polystyrene latex particles are used to inhibit the growth of Gram-positive bacteria, Gram-negative bacteria, and fungi.

In one embodiment of the present invention, the nano silver-containing particle polystyrene latex particles are used as a cosmetic raw material composition and a pharmaceutical composition as a bacteriostatic agent or a preservative.

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(S2)‧‧‧Step 2

First Figure: Flow chart of the steps of a preferred embodiment of the present invention.

Fig. 2 is a view showing the appearance of a nano-silver particle-containing polystyrene latex particle obtained by a specific embodiment of the present invention.

Fig. 3 is a view showing the appearance of a nano-silver particle-containing polystyrene latex particle obtained by the second embodiment of the present invention.

Fig. 4 is a view showing the appearance of a nano-silver particle-containing polystyrene latex particle obtained by the three specific embodiments of the present invention.

Fig. 5 is a view showing the appearance of a nano-silver particle-containing polystyrene latex particle obtained by four specific embodiments of the present invention.

Fig. 6 is a view showing the appearance of a nano-silver particle-containing polystyrene latex particle obtained by the fifth embodiment of the present invention.

Figure 7 is a graph showing the inhibition concentration of the nano-silver particle polystyrene latex particles of the present invention.

The object of the present invention and its structural and functional advantages will be explained in conjunction with the specific embodiments according to the structure shown in the following drawings, so that the reviewing committee can have a more in-depth and specific understanding of the present invention.

Referring to the first figure, a method for preparing nano silver particle-containing polymer latex particles of the present invention comprises: Step 1 (S1): adding a polymer latex particle suspension and a silver nitrate (AgNO ₃ ) aqueous solution in weight percentage 10:1~1:10 are uniformly mixed to form a mixed solution, and the temperature is applied at a temperature of 50 ° C to 90 ° C for 10 to 120 minutes, wherein the polymer latex particle-containing suspension can be, for example, 3.85 wt% of polymer latex particles and residual weight. a percentage of water, and the aqueous silver nitrate solution may, for example, consist of 1.96 wt% silver nitrate and the remaining weight percent water; and the aqueous sodium citrate solution consists of 16.2 wt% sodium citrate and the remaining weight percent water; and step two (S2): Step 2: After the mixed solution is cooled to 50 ° C ~ 85 ° C, add sodium citrate aqueous solution in the mixed solution for 10 to 240 minutes (preferably for 20 to 130 minutes) to obtain surface coating A polymer latex particle having nano silver particles, which has the characteristics of inhibiting the growth of Gram-positive bacteria, Gram-negative bacteria and fungi, and thus can be applied to a cosmetic raw material composition and a pharmaceutical composition. The material is used as a preservative; wherein the diameter of the polymer latex particles is greater than 50 nm, and the diameter of the nano silver particles is 1 to 500 nm.

The above polymer latex particles are polystyrene latex particles, polymethylmethacrylate latex particles or poly-n-butyl methacrylate latex particles, styrene and methacrylic acid. Latex particles of methyl ester copolymer, latex particles of styrene and butyl methacrylate copolymer, latex particles of methyl methacrylate and butyl methacrylate copolymer, etc.; if polystyrene latex particles can be, for example Prepared by the following method, including (a) mixing styrene, polyetherimide (PEI), methanol and deionized water Combined heating to 50 ° C ~ 90 ° C; (b) adding the initiator azobisisobutyronitrile (AIBN) methanol solution for 3-12 hours; and (c) purification by centrifugation to obtain purified polyphenyl Ethylene latex particles.

It is worth noting here that the inventor of the present invention applied for another application "a polymer latex particle composition containing nano silver particles" on the same day, which is not described in detail herein, and all contents thereof are hereby incorporated by reference. .

In addition, the scope of the invention may be further exemplified by the following specific examples, which are not intended to limit the scope of the invention.

Example 1: Preparation of polystyrene latex particles

The steps of synthesizing the polystyrene latex particles are as follows: (1) first mixing 1.9 g of polyethylenimine (PEI), 30 g of methanol and 1 g of deionized water, and then placing them in a reaction tank (low speed stirring); (2) taking 0.3 g of the initiator AIBN (Azobisisobutyronitrile) was dissolved in 15 g of methanol to prepare AIBN methanol solution; (3) 10 g of styrene was added to the reaction tank and stirred with the solution of step (1), and heated to 70 °C about 15 minutes; (4) quickly dissolve the AIBN methanol solution uniformly dissolved in step (2) into the reaction tank, and maintain the temperature at 70 ° C for 8 hours to obtain a latex solution containing polystyrene latex particles (PS latex emulsion). And (5) purifying the polystyrene latex particles by centrifugation with an average particle diameter of more than 100 nm (about 100 to 2000 nm).

Embodiment 2

Referring to Table 1, the synthesis steps of the nano silver particle-containing polystyrene latex particles in the present embodiment are as follows: (1) 1 g of polystyrene latex particles (PS latex particles) obtained in the first embodiment are uniformly mixed with 25 g of deionized water. To form a polystyrene latex particle suspension; (2) placing a uniformly mixed polystyrene latex particle suspension into the reaction tank, raising the temperature to 90 ° C without stirring the condenser and flowing nitrogen; and continuously stirring; (3) 0.1 g of silver nitrate (AgNO ₃ ) is mixed with 5 g of deionized water to prepare an aqueous solution of silver nitrate; (4) adding a silver nitrate aqueous solution to the reaction tank at a temperature of 90 ° C (the reaction tank solution gradually becomes a goose yellow solution). ), to form a mixed solution, and for 1 hour; (5) after the mixed solution is cooled to 85 ° C, then add sodium citrate aqueous solution (1.94 grams of sodium citrate dissolved in 10 grams of deionized water), continue the reaction for 10 minutes The solution is slowly turned into a black state, that is, a polystyrene latex particle having a surface coated with nano silver particles, wherein the average particle diameter of the polystyrene latex particles is 390 to 990 nm, and the average particle diameter of the nano silver particles is 5 ~100nm. For the results observed by Transmission Electron Microscopy (TEM), please refer to the second figure. After adding sodium citrate, the reaction is only 10 minutes, and the reaction time is too short, so that the amount of silver particles synthesized is too small. And the silver particles are not enough to be adsorbed on the PS latex particles, so the surface of the entire PS latex particles cannot be covered, and the surface of some PS latex particles is bare.

Embodiment 3

Referring to Table 2, the synthesis steps of the nano silver particle-containing polystyrene latex particles in this embodiment are as follows: (1) 1 g of polystyrene latex particles (PS latex particles) obtained in the first embodiment are uniformly mixed with 25 g of deionized water. To form a suspension of polystyrene latex particles; (2) placing a uniformly mixed suspension of polystyrene latex particles in a reaction tank, raising the temperature to 90 ° C to 95 ° C without a condenser and nitrogen gas Continuous stirring; (3) 0.1 g of silver nitrate (AgNO ₃ ) is mixed with 5 g of deionized water to prepare an aqueous solution of silver nitrate; (4) adding a silver nitrate aqueous solution to the reaction tank at a temperature of 90 ° C to 95 ° C (at this time, the reaction tank solution) Will gradually become a goose yellow solution) to form a mixed solution and act for 1 hour; (5) after the mixed solution is cooled to 80 ° C, then add sodium citrate aqueous solution (1.94 g of sodium citrate dissolved in 10 g of deionized water) ), the reaction is continued for 20 minutes to slowly turn the solution into a black state, that is, a polystyrene latex particle having a surface coated with nano silver particles, wherein the average particle diameter of the polystyrene latex particles is 390 to 990 nm, and the nano silver particles are obtained. The average particle size is 5 to 100 nm. For the results observed by a transmission electron microscope (TEM), please refer to the third figure. After adding sodium citrate, it only reacts for 20 minutes, and the reaction time is too short, so that the amount of silver particles synthesized is too small; on the other hand, Since the reaction temperature is too high, the silver particles are rapidly formed, so that the silver particles are not adsorbed on the PS latex particles, so that the surface of the entire PS latex particles cannot be covered, and the surface of some of the PS latex particles is bare. Further testing, if the reaction time after adding the sodium citrate to the step (5) was extended to 30 minutes, similar results were obtained (not shown). Therefore, it is necessary to test different conditions.

Embodiment 4

Referring to Table 3, the synthesis steps of the nano silver particle-containing polystyrene latex particles in this embodiment are as follows: (1) 1 g of polystyrene latex particles (PS latex particles) obtained in the first embodiment are uniformly mixed with 25 g of deionized water. To form a polystyrene latex particle suspension; (2) placing a uniformly mixed polystyrene latex particle suspension into the reaction tank, raising the temperature to 90 ° C without stirring the condenser and flowing nitrogen; and continuously stirring; (3) mixing 0.3 g of silver nitrate (AgNO ₃ ) with 15 g of deionized water to prepare an aqueous solution of silver nitrate; (4) adding a silver nitrate aqueous solution to the reaction tank at a temperature of 90 ° C (the reaction tank solution gradually becomes a goose yellow solution) ) to form a mixed solution and act for 1.5 hours; (5) after the mixed solution is cooled to 80 ° C, then add sodium citrate aqueous solution (5.82 g of sodium citrate dissolved in 30 g of deionized water), continue the reaction for 30 minutes The solution was slowly turned into a black state, that is, a polystyrene latex particle having a surface coated with nano silver particles was obtained. For the results observed by a transmission electron microscope (TEM), please refer to the fourth figure. Since the amount of silver nitrate and sodium citrate is too much, and the reaction is carried out for 1.5 hours after adding silver nitrate, the reaction takes a long time, so the reaction produces too much silver. So many silvers are gathered together.

Embodiment 5

Referring to Table 4, the synthetic steps of the nano silver particle-containing polystyrene latex particles in the present embodiment are as follows: (1) 1 g of polystyrene latex particles (PS latex particles) obtained in the first embodiment are uniformly mixed with 25 g of deionized water. To form a polystyrene latex particle suspension; (2) placing a uniformly mixed polystyrene latex particle suspension into the reaction tank, raising the temperature to 90 ° C without stirring the condenser and flowing nitrogen; and continuously stirring; (3) mixing 0.3 g of silver nitrate (AgNO ₃ ) with 15 g of deionized water to prepare an aqueous solution of silver nitrate; (4) adding a silver nitrate aqueous solution to the reaction tank at a temperature of 90 ° C (the reaction tank solution gradually becomes a goose yellow solution) ), to form a mixed solution, and for 1 hour; (5) after the mixed solution is cooled to 80 ° C, then add sodium citrate aqueous solution (5.82 grams of sodium citrate dissolved in 30 grams of deionized water), continue the reaction for 30 minutes The solution was slowly turned into a black state, that is, a polystyrene latex particle having a surface coated with nano silver particles was obtained. The results of observation by a transmission electron microscope (TEM) are shown in the fifth figure. Since the amount of silver nitrate and sodium citrate is excessively added, the reaction produces too much silver, so that many silver are aggregated.

Embodiment 6

Referring to Table 5, the synthetic steps of the nano silver particle-containing polystyrene latex particles in the present embodiment are as follows: (1) 1 g of polystyrene latex particles (PS latex particles) obtained in the first embodiment are uniformly mixed with 25 g of deionized water. To form a polystyrene latex particle suspension; (2) placing a uniformly mixed polystyrene latex particle suspension into the reaction tank, raising the temperature to 90 ° C without stirring the condenser and flowing nitrogen; and continuously stirring; (3) 0.1g of silver nitrate (AgNO ₃ ) is mixed with 5g of deionized water to prepare an aqueous solution of silver nitrate; (4) adding a silver nitrate aqueous solution to the reaction tank at a temperature of 95 ° C (the reaction tank solution gradually becomes a goose yellow solution). ) to form a mixed solution and act for 1 hour; (5) after cooling the mixed solution to 85 ° C, then add an aqueous solution of sodium citrate (1.94 g of sodium citrate dissolved in 10 g of deionized water), continue the reaction for 30 minutes The solution is slowly turned into a black state, that is, a polystyrene latex particle having a surface coated with nano silver particles, wherein the average particle diameter of the polystyrene latex particles is 390 to 990 nm, and the average particle diameter of the nano silver particles is 5 ~100nm. The results of observation by a transmission electron microscope (TEM) are shown in the sixth figure, because the appropriate amount of silver nitrate is added during the synthesis, and the reaction time is appropriate, so that an appropriate amount of silver is formed, and because the reaction time is long, Therefore, the silver particles can have sufficient time to adsorb on the PS latex particles, so that the surface of the generated PS latex particles is uniformly covered with silver particles.

Table 5

Example 7: Minimum inhibitory concentration (MIC) test

The nano-silver particle-containing polystyrene latex particles prepared in Example 6 were subjected to a bacteriostatic test to find the minimum inhibitory concentration (MIC) of the nano-silver particle-containing polystyrene latex particles. The "minimum inhibitory concentration" is the minimum sample concentration value that can inhibit the growth of quantitative test strains in 90% of the medium. The lower the MIC value, the better the bacteriostatic effect of the sample. In this example, Gram-positive bacteria Staphylococcus aureus and Gram-negative bacteria Escherichia coli were used for experiments. Add different concentrations (0~0.020%) of antibacterial samples (including nano silver particle polystyrene latex particles) to the sterile culture tube, and then add 1c.c. Nutrient broth or TSB medium and known strains. The bacterial liquid was uniformly mixed; then, it was shaken and cultured in an incubator at 37 ° C for one day. After culturing, the suspension of the cultivating tube is clarified, and the appropriate ten-fold dilution method is applied to the agar vegetable plate medium for uniform coating. After culturing according to the appropriate growth conditions, the number of colony production is observed and calculated. MIC value.

The results are shown in the seventh figure. The nano-silver-containing polystyrene latex particles prepared in Example 6 have a bacteriostatic effect, and the minimum inhibitory concentrations for Staphylococcus aureus and Escherichia coli are 0.0075% and 0.011%, respectively.

Since the polystyrene latex particles obtained by the present invention have silver particles uniformly coated on the surface of the polystyrene latex particles, they have a good bacteriostatic effect, and since the silver particles are firmly attached to the polystyrene latex particles The surface will not be arbitrarily separated. Therefore, adding nano-silver particle polystyrene latex particles to cosmetics can not only Instead of adding traditional preservatives, it can also solve the problem of tiny nano silver entering the human cells through the skin, and can achieve the nano-scale dispersion of the silver particles and enhance their antibacterial effect.

In summary, the preparation method of the nano-silver particle-containing polymer latex particles of the present invention can achieve the intended use efficiency by the above-disclosed examples, and the present invention has not been disclosed before the application. It has fully complied with the requirements and requirements of the Patent Law.爰Issuing an application for a patent for invention in accordance with the law, and asking for a review, and granting a patent, is truly sensible.

The illustrations and descriptions of the present invention are merely preferred embodiments of the present invention, and are not intended to limit the scope of the present invention; those skilled in the art, which are characterized by the scope of the present invention, Equivalent variations or modifications are considered to be within the scope of the design of the invention.

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Claims (8)

A method for preparing nano-silver particle polymer latex particles, comprising: step 1: uniformly mixing a polymer latex particle suspension with an aqueous solution of silver nitrate (AgNO ₃ ) at a weight percentage of 10:1 to 1:10 to form a mixture. The solution is applied at a temperature of 50 ° C to 90 ° C for 10 to 120 minutes; and step 2: after the mixed solution is cooled to 50 ° C to 85 ° C, an aqueous solution of sodium citrate is added to the mixed solution for 10 to 240 minutes. a polymer latex particle having a surface coated with nano silver particles; wherein the polymer latex particle has a diameter of more than 50 nm, the nano silver particle has a diameter of 1 to 500 nm; and the polymer latex particle is a polyether Polyetherimide (PEI) is prepared as a dispersing agent. The preparation method according to claim 1, wherein the polymer latex particle-containing suspension is composed of 3.85 wt% of polymer latex particles and a remaining weight percentage of water. The preparation method according to claim 1, wherein the polymer latex particles are polystyrene latex particles, polymethylmethacrylate latex particles or polybutyl methacrylate (poly-). N-butyl methacrylate) latex particles, styrene and methacrylic acid Latex particles of an ester copolymer, latex particles of a styrene and butyl methacrylate copolymer, latex particles of a copolymer of methyl methacrylate and butyl methacrylate. The preparation method according to claim 3, wherein the polymer latex particles are polystyrene latex particles, and the preparation method of the polystyrene latex particles comprises (a) styrene, polyether oxime Mixing polyetherimide (PEI), methanol and deionized water and heating to 50 ° C ~ 90 ° C; (b) adding the initiator azobisisobutyronitrile (AIBN) methanol solution for 3-12 hours; c) Purification by centrifugation to obtain purified polystyrene latex particles. The preparation method according to claim 1, wherein the aqueous silver nitrate solution is composed of 1.96 wt% silver nitrate and the remaining weight percentage of water; and the aqueous sodium citrate solution is composed of 16.2 wt% sodium citrate and the remaining weight percentage. Made up of water. The preparation method according to claim 1, wherein the second step is for 20 to 130 minutes. The preparation method according to claim 1 or 4, wherein the nano silver particle-containing polymer latex particles are used for inhibiting growth of Gram-positive bacteria, Gram-negative bacteria, and fungi. The preparation method according to claim 1 or 4, wherein the nano silver-containing polymer latex particles are used for a cosmetic raw material composition and a pharmaceutical composition.