WO2023109209A1 - Antibacterial microcapsule of bionic structure, preparation method therefor, and use thereof - Google Patents

Abstract

The present invention relates to the technical field of antibacterial products, and in particular to an antibacterial microcapsule of a bionic structure, a preparation method therefor and a use thereof. The solution comprises a core material and a capsule wall material wrapping the surface of the core material. The capsule wall material is provided with a through hole structure. The surface of the capsule wall material is negatively charged. The antibacterial microcapsule is spherical or sphere-like and has a diameter of 0.8 to 10 micrometers. The preparation method comprises: mixing the core material, a silane coupling agent and a monomer to form a first mixture; mixing a composite emulsifier of an aqueous phase with the first mixture to form an O/W emulsion; adjusting the pH value of the O/W emulsion to 2 to 4; and adding an initiator into the O/W emulsion, and forming the antibacterial microcapsule by means of heating and polymerization. The antibacterial microcapsule prepared from the method can provide a composite functional microcapsule having at least two functions, that is, the microcapsule core material provides a function, while the own property of the core material can be released via the through holes on the surface of the microcapsule. Meanwhile, the microcapsule has efficient antibacterial performance.

Description

A kind of antibacterial microcapsule of bionic structure and its preparation method and application technical field

The invention relates to the field of antibacterial products, in particular to an antibacterial microcapsule with a bionic structure and its preparation method and application.

Background technique

Antibacterial agents are generally divided into three types: inorganic antibacterial agents, organic antibacterial agents and natural antibacterial agents. Using the antibacterial ability of metals such as silver, copper, and zinc, metals such as silver, copper, and zinc (or their Ions) are fixed on the surface of porous materials such as fluorspar and silica gel to make antibacterial agents, and then added to corresponding products to obtain materials with antibacterial capabilities. Metals such as mercury, cadmium, and lead also have antibacterial capabilities, but they are harmful to the human body. Harmful; at the same time, copper, nickel, lead and other ions are colored, which will affect the appearance of the product. Zinc has certain antibacterial properties, but its antibacterial strength is only 1/1000 of silver ions;

For example, the prior art Chinese patent CN201910842257 proposes an antibacterial phase-change microcapsule and its formulation technology. This prior art uses the in-situ reduction of silver on the surface of the microcapsule to obtain a phase-change microcapsule with antibacterial function; another example of the prior art Chinese patent CN108686262A provides a pretreated expanded perlite as a carrier, vacuum absorbs a liquid phase change material, and then adsorbs a silver-containing chitosan layer on the surface, and then forms a sodium alginate porous gel layer to obtain a double-wall slow release The method of antibacterial phase-change microcapsules, but the method process is more complicated; the above-mentioned method mostly uses the antibacterial ability of silver itself to carry out antibacterial.

The main varieties of organic antibacterial agents are vanillin or ethyl vanillin compounds, which are often used in polyethylene food packaging films to play an antibacterial role. In addition, there are anilides, imidazoles, thiazoles, isothiazolone derivatives, The safety of organic antibacterial agents such as quaternary ammonium salts, biquats, and phenols is still under study. Most organic antibacterial agents have poor heat resistance, are easily hydrolyzed, and have a short validity period. Such as the prior art Chinese patent CN200880018078.9 proposes a polymer microcapsule containing quaternary ammonium salt and its manufacturing method, the core of the method is to use cetylpyridinium chloride as the representative antibacterial agent as the core material , and then encapsulated with polymers to form microcapsules.

Natural antibacterial agents mainly come from the extraction of natural plants, such as chitin, mustard, castor oil, horseradish, etc., which are easy to use, but have limited antibacterial effect, poor heat resistance, low bactericidal rate, cannot be used for broad-spectrum and long-term use, and the quantity is very large few. For example, the prior art Chinese patent CN201510287717.3 proposes a preparation method of essential oil microcapsules with chitosan as the wall material. At the same time, the essential oil with antibacterial function is selected as the core material to realize the antibacterial function. The antibacterial rate reaches 85%.

Yet above-mentioned prior art, its core technical feature all is, has introduced antibacterial agent by various technical means, comprises above-mentioned inorganic antibacterial agent, organic antibacterial agent or natural antibacterial agent to reach antibacterial effect, and does not introduce antibacterial agent, but There is no prior art report that can realize the antibacterial effect;

For this reason, the present invention proposes a kind of antibacterial microcapsule of bionic structure and its preparation method and application.

Contents of the invention

In order to solve the problems in the prior art, the present invention proposes a bionic structure antibacterial microcapsule and its preparation method and application.

In order to achieve the above object, the present invention adopts the following technical solutions:

An antibacterial microcapsule with a bionic structure comprises a core material and a capsule wall material wrapped on the surface of the core material, the capsule wall material has a through-hole structure, and the surface of the capsule wall material is negatively charged.

Further, the antibacterial microcapsules are spherical or spheroidal, with a D50 diameter of 0.8-10 microns.

Further, the inner shell surface of the core material wrapped by the capsule wall material is lipophilic, the outer shell surface of the capsule wall material is hydrophilic, and the core material includes phase change materials, fat-soluble essences, plant essential oils, and fat-soluble vitamins. at least one.

A preparation method of bionic structure antibacterial microcapsules, comprising the steps of:

Mix the core material, silane coupling agent and monomer to form the first mixture, mix the composite emulsifier of the water phase with the first mixture to form an O/W emulsion, adjust the pH of the O/W emulsion to 2-4, and adjust the pH of the O/W emulsion to 2-4. Initiator is added into the W emulsion and the temperature rises to polymerize to form antibacterial microcapsules.

Further, after adjusting the pH of the O/W emulsion to 2-4, the second mixture with the first shell is formed after 4h-8h, and then the temperature of the second mixture is raised to 60-80°C and the initiator is added to keep the temperature constant After 5h-12h, the second layer of shell is formed by polymerization to obtain antibacterial microcapsules.

Further, the core material includes at least one of phase change materials, fat-soluble flavors, plant essential oils, and fat-soluble vitamins;

The silane coupling agent includes aminopropyltrimethoxysilane, aminopropyltriethoxysilane, phenyltriethoxysilane, 3-(methacryloxy)propyltrimethoxysilane, orthosilane At least two of tetraethyl orthosilicate and tetramethyl orthosilicate;

The monomers include at least one of styrene, divinylbenzene, acrylate monomers, acrylic monomers, and diisocyanate prepolymers;

Described composite emulsifier is the composition of anionic surfactant and nonionic surfactant.

Further, the complex emulsifier includes polyethylene-maleic anhydride copolymer or its hydrolyzed salt, polystyrene-maleic anhydride copolymer or its hydrolyzed salt, block copolymer of epoxy resin and polyethylene glycol, Sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sorbitan monooleate polyoxyethylene ether, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty alcohol polyoxypropylene At least one of ether, glycerol monofatty acid ester, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester and/or fatty acid pentaerythritol ester.

Further, the parts by weight of each component include: 25-60 parts of core material, 0.6-8 parts of silane coupling agent, 1.2-10 parts of monomer and 0.19-3 parts of composite emulsifier.

An antibacterial product, which contains the above antibacterial microcapsule with bionic structure or the antibacterial microcapsule prepared by the above preparation method.

Application of antibacterial microcapsules with bionic structure in transportation or storage of food, medicine, textiles or cosmetics, the antibacterial microcapsules are the above antibacterial microcapsules with bionic structure or the antibacterial microcapsules prepared by the above preparation method.

Beneficial effects of the present invention:

1. Without the introduction of other antibacterial agents (i.e. inorganic antibacterial agents, organic antibacterial agents or natural antibacterial agents), the antibacterial microcapsules with a bionic structure provided by the invention possess efficient antibacterial properties;

2. The preparation process of the microcapsules of the present invention is simple, relatively universal, and the core material can be replaced conveniently. It is an excellent carrier of functional substances such as drugs, and can realize microstructure transfer, transportation or controlled release of functional substances;

3. The antimicrobial microcapsules prepared by the method of the present invention can provide composite functional microcapsules with at least two functions, that is, the core material of the microcapsules provides a kind of functionality, and the core material can release the self-performance of the core material through the through holes on the surface of the microcapsules. , At the same time, the microcapsules have high antibacterial properties.

4. The present invention obtains an antibacterial microcapsule with a bionic structure, and the microcapsule has a pore structure that runs through the shell. Staphylococcus, Candida albicans, Escherichia coli, etc. have a diameter of several microns in size, and the surface of the bacteria is negatively charged. At the same time, there will be some fine pore structures on the surface of bacteria, and these pore structures run through the shell. The present invention itself is a beneficial and important attempt in the design and synthesis of micro-nano structural units.

Description of drawings

Fig. 1 is the scanning electron microscope (SEM) photo of a kind of bionic structure antibacterial microcapsule described in the embodiment of the present invention 1;

Fig. 2 is the transmission electron microscope (TEM) photo of a kind of bionic structure antibacterial microcapsule described in embodiment 1;

Fig. 3 is the laser particle size test curve of a kind of biomimetic structure antibacterial microcapsule of embodiment 1 gained;

Fig. 4 is the scanning electron microscope (SEM) photograph of a kind of biomimetic structure antibacterial microcapsule of embodiment 2 gained;

Fig. 5 is the transmission electron microscope (TEM) photograph of a kind of biomimetic structure antibacterial microcapsule of embodiment 2 gained;

Fig. 6 is the laser particle size test curve of a kind of biomimetic structure antibacterial microcapsule of embodiment 2 gained;

Fig. 7 is the DSC test curve of a kind of biomimetic structure antibacterial microcapsule of embodiment 2 gained;

Fig. 8 is the scanning electron microscope (SEM) photograph of a kind of biomimetic structure antibacterial microcapsule of embodiment 3 gained;

9 is a scanning electron microscope (SEM) photograph of a partially enlarged shell of a bionic structure antibacterial microcapsule obtained in Example 3.

Detailed ways

The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some, not all, embodiments of the present invention.

The present invention adopts following technical scheme:

A preparation method of bionic structure antibacterial microcapsules, characterized in that the preparation method comprises the following steps:

a. The process of uniformly mixing the core material, silane coupling agent and polymer monomer to form an oil phase;

b. The process of dissolving the compound emulsifier in water to form a water phase;

c. The process of obtaining the O/W emulsion from the above-mentioned oil-water two-phase;

d. The process of silane coupling agent forming the first shell;

e. The process of monomer polymerization to form the second shell.

The core material includes at least one of phase change material, n-docosane, industrial paraffin, n-octadecane, pink rose essential oil, fat-soluble essence, plant essential oil, and fat-soluble vitamin;

In the usual microcapsule structure, the core material is the core component, endowing the material with functionality, such as heat storage, temperature response, release of fragrance or functional substances, etc.;

The core material and the continuous phase are often incompatible. At the interface between the two, a place for the formation of the microcapsule wall material is provided. The core material in this plan is mainly based on various staphylococcus and candida albicans during implementation. , Escherichia coli cell fluid investigation, selected materials with similar physical and chemical properties as the main component of the core material.

Described silane coupling agent comprises aminopropyltrimethoxysilane coupling agent, KH550 silane coupling agent (3-aminopropyltriethoxysilane), phenyltriethoxysilane coupling agent, 3-( At least two of methacryloyloxy)propyltrimethoxysilane coupling agent, tetraethyl orthosilicate, and tetramethyl orthosilicate; the silane coupling agent is used as an inorganic silicon source, and the formed Silica is a part of the wall material. At the same time, the silane coupling agent can effectively modify the interface through the simple and convenient sol-gel process, and the selection range of the silane coupling agent is also relatively large;

The method introduces at least two chemical groups with different properties into the wall material by selecting at least two kinds of silane coupling agents, which can regulate the properties of the microcapsule shell to a certain extent;

The monomers include at least one of styrene, divinylbenzene, acrylate monomers, acrylic monomers, and diisocyanate prepolymers. After the monomer initiates polymerization, it forms a composite shell with the aforementioned inorganic substances. The organic-inorganic composite shell formed under the method of the present invention can exhibit different properties on both sides of the shell, such as facing the core. The inner shell side of the material is more oleophilic, while the outer shell side facing the water phase is more hydrophilic. These two sides are actually two sides of the same shell;

Described compound emulsifier is selected from the block copolymer of polyethylene-maleic anhydride copolymer or its hydrolyzed salt, polystyrene-maleic anhydride copolymer or its hydrolyzed salt, epoxy resin and Polyethylene Glycol, dodecane Sodium Alkyl Sulfate, Sodium Dodecyl Benzene Sulfonate, Fatty Alcohol Polyoxyethylene Ether, Tween 80 (Sorbitan Monooleate Polyoxyethylene Ether), Tween 60 (Polyoxyethylene Sorbitan Stearate ester), triton (polyethylene glycol p-isooctyl phenyl ether), alkylphenol polyoxyethylene ether, fatty alcohol polyoxypropylene ether, glycerin monofatty acid ester, polyoxyethylene sorbitan A composition of at least one anionic surfactant and at least one nonionic surfactant in fatty acid esters, sorbitan fatty acid esters, fatty acid pentaerythritol esters;

Surfactants provide the key guarantee for stabilizing the oil-water interface while creating sites for shell formation. The specific phase behavior of surfactants at the oil-water interface can be adjusted by two or more different types of surfactants to achieve different effects;

These effects include interfacial stabilization, fusion of two phases or spreading of one phase on another, i.e. induction of phase separation, on the other hand through the adjustment of the amount of one of the surfactants, a pore structure can be produced, through the adjustment of the type and amount , the pore structure that runs through the shell can be obtained, and we know that there are pore structures that can transmit energy or substances on the cell membranes of Staphylococcus and Escherichia coli. This feature is one of the structural features imitated by the present invention. The microcapsules of the present invention The through-hole structure can be used to release the core material's own performance;

The sum of the consumption of the core material, silane coupling agent and polymer monomer is 10.0%-59.0%wt of the final microcapsule suspension; the nonionic surfactant consumption is no more than 0.8% of the final microcapsule suspension. %wt;

Preferably, the sum of the amount of the core material, silane coupling agent, and polymer monomer is 15.0%-49.0%wt of the final microcapsule suspension, and the amount of the nonionic surfactant is the final microcapsule suspension 0.1%-0.67%wt;

More preferably, the sum of the amount of the core material, silane coupling agent, and polymer monomer is 25.0%-39.0%wt of the final microcapsule suspension, and the amount of the nonionic surfactant is the final microcapsule suspension 0.2%-0.45%wt of liquid.

The start time of step d is earlier than the start time of step e. In the present invention, step d represents the sol-gel process, and step e represents the polymerization process of organic monomers. In actual operation, the two processes can be passed. Conditions such as temperature, pH, initiator ultraviolet light, etc. control the successive start respectively, or start at the same time;

It is found through experiments that the sol-gel process is started first, and then the organic monomer polymerization is started, which is more conducive to the formation of the biomimetic structure described in the present invention. The hydrophilic outer shell structure is more conducive to the formation of the through-hole structure.

The microcapsules are spherical or spheroidal, with a D50 diameter of 0.8 microns to 10 microns; the surface of the microcapsules is negatively charged; the microcapsules have a pore structure that runs through the shell;

Staphylococcus, Candida albicans, Escherichia coli, etc. have a diameter of several microns in size, and the surface of the bacteria is negatively charged. At the same time, there are some small pore structures on the surface of the bacteria. These pore structures run through the shell, and the bacteria pass through these negatively charged membrane structures, or pores. structure for nutrition. The biomimetic structure microcapsule of the present invention performs very well in antibacterial aspect, and its reason includes as follows, when the microcapsule of the present invention and bacterium are in the same condition together, this type of biomimetic structure microcapsule can produce competition with some bacteria Food effect, the possibility of bacteria obtaining nutrition is greatly reduced, which hinders bacteria from obtaining nutrition and multiplying, thus achieving antibacterial effect;

At the same time, in the bactericidal test, the biomimetic structure microcapsules performed poorly, because the structure biomimetic microcapsules did not contain any of the above three antibacterial agents, and could not actively kill bacteria, but in the antibacterial test Among them, it can reduce the chance of bacterial survival by competing for food.

The above-mentioned experimental demonstration of the present invention has only studied staphylococcus, Candida albicans, the antibacterial effect of escherichia coli, but reasonable extrapolation under the method of the present invention and design spirit situation all should be regarded as not departing from the technology of the present invention The extension or modification of the scheme belongs to the protection scope determined by the claims of the present invention.

Of course, in order to enhance the bactericidal effect, the above-mentioned three antibacterial agents, namely inorganic antibacterial agents, organic antibacterial agents or natural antibacterial agents, can also be introduced into the structural biomimetic microcapsule process of the present invention. According to the specific situation of process implementation and application scenarios, various fillers will be used during processing, such as catalysts, accelerators, covering agents, whitening agents, pigments, thinners, thickeners, curing agents, etc., and some functions will also be used Sexual fillers, etc., these should be regarded as extensions or deformations that do not deviate from the technical solutions of the present invention, and fall within the scope of protection determined by the claims of the present invention.

A biomimetic structure antibacterial microcapsule of the present invention is used in textile processing technology including at least one of finishing, coating, padding, printing or spinning, and the biomimetic structure antibacterial microcapsule can be mixed with additives In the form of finishing paste, or printing paste, padding bath, through further related processing, it is attached to the fabric or similar layered structure, thereby endowing the product with antibacterial properties, similar, In wet spinning, by adding the microcapsules of the present invention to the spinning solution, it can also be injected before spinning to obtain the fiber material containing the antibacterial microcapsules of the bionic structure of the present invention. An antibacterial product claimed in the present invention includes textiles with antibacterial function prepared in the above process;

In addition to the field of textiles, the antibacterial microcapsule with a bionic structure and its method described in the present invention can also be used in the fields of medical care, transportation or storage of food and medicine, cosmetics, and the like.

Example 1

Provide a kind of biomimetic structure antibacterial silicon dioxide-polystyrene microcapsule in this example, its preparation method comprises the following steps:

a. Mix 25g pink rose essential oil with 3g tetraethyl silicate, 1.2g KH550 silane coupling agent (3-aminopropyltriethoxysilane), 5g styrene, 5g divinylbenzene, stir for 30min, and form a uniform oil phase process;

b. 30g, 10%wt styrene-maleic anhydride hydrolyzed sodium salt solution and 0.19g Tween 80 (sorbitan monooleate polyoxyethylene ether) were dissolved in 100g water, stirred to make it evenly mixed;

c. The above-mentioned oil-water two-phase is subjected to 6000rpm-12000rpm, and the homogenizer is processed for 5 minutes to obtain an O/W emulsion (oil-in-water emulsion);

d. At room temperature, adjust the pH of the aforementioned emulsion to 2-4, and form the first layer of shell after 4h-8h;

e. The temperature of the emulsion is raised to 60-80°C, the initiator AIBN (azobisisobutyronitrile) is added, and the temperature is kept for 5h-12h to make it polymerize to form the second shell.

That is to obtain the antibacterial microcapsules with a biomimetic structure whose shell layer is silicon dioxide-polystyrene.

The SEM photo of the obtained biomimetic structure microcapsule is shown in accompanying drawing 1. It can be seen from Figure 1 that there are several holes on the surface of the microcapsules.

Figure 2 is a TEM photo of the obtained microcapsules. The TEM photos show that the pores on the surface of the microcapsules penetrate the shell and form larger cavities inside the capsules. The hole can be used to load functional substances such as essential oils.

The Zeta potential test showed that the Zeta potential of the microcapsules was -30.4mV, indicating that the surface of the microcapsules was negatively charged. This is because a kind of surfactant styrene-maleic anhydride hydrolyzed sodium salt used in this example is an anionic surfactant.

Figure 3 is the laser particle size analysis curve of the obtained microcapsules, it can be seen that the D50 diameter is 0.85 microns.

It can be seen that we have obtained a biomimetic structure microcapsule with a negatively charged surface, a D50 of 0.85 microns, and several micropores on the surface. And did not introduce any aforementioned 3 kinds of antibacterial agents in this example.

The microcapsules obtained in this example are used for the after-finishing of fabrics, and the treated fabrics are tested for antibacterial performance. The test method refers to FZ/T 73023-2006 antibacterial knitwear, and the results in Table 1 are obtained: the antibacterial rate of Candida albicans is 86% , The antibacterial rate of Escherichia coli is 86%, and the antibacterial rate of Staphylococcus aureus is 88%.

Table 1 antibacterial performance test

Example 2

Provide a kind of antibacterial silicon dioxide-polyacrylate microcapsule of biomimetic structure in this example, its preparation method comprises the following steps:

a. 50g n-octadecane and 8g tetraethyl silicate, 0.6g aminopropyltrimethoxysilane coupling agent, 1.2g phenyltriethoxysilane coupling agent, 5g dimethacrylic acid 1,4 -butanediol ester, stirring for 20min, the process of uniformly forming an oil phase;

B. 10g, 10%wt ethylene-maleic anhydride hydrolysis sodium salt aqueous solution and 0.62g Tween 60 (polyoxyethylene sorbitan stearate) are dissolved in 110g water, stir and make it mix homogeneously;

c. Process the above-mentioned oil-water two-phase through 6000rpm-12000rpm and homogenizer for 5min to obtain O/W emulsion;

d. At room temperature, adjust the pH of the aforementioned emulsion to 2-4, and form the first layer of shell after 4h-8h;

e. The temperature of the emulsion is raised to 50-80°C, the initiator APS (ammonium persulfate) is added, and the temperature is kept for 5h-12h, so that the organic monomers are polymerized to form the second shell.

That is to say, a kind of shell layer is a biomimetic structure antibacterial microcapsule of silicon dioxide-polyacrylate;

The SEM photo of the obtained biomimetic structure microcapsules is shown in accompanying drawing 4, and it can be seen that there are several holes on the surface of the microcapsules;

Figure 5 is a TEM photo of the obtained microcapsules. TEM photos show that the pores on the surface of the microcapsules penetrate the shell;

The Zeta potential test showed that the Zeta potential of the microcapsules was -16.9mV, indicating that the surface of the microcapsules was negatively charged. This is because a kind of surfactant ethylene-maleic anhydride copolymer hydrolysis salt used in this example is a kind of anionic surfactant;

Figure 6 is the laser particle size analysis curve of the obtained microcapsules, it can be seen that the D50 diameter is 3.023 microns.

The DSC curve obtained by differential scanning calorimetry is shown in Figure 7. It can be seen that the phase change melting point of the phase change microcapsules in this example is 29.91°C, and the corresponding phase change enthalpy is 185.5 J/g.

Table 2 Antibacterial Test

It can be seen that this example has obtained a biomimetic structure microcapsule with a negatively charged surface, a D50 of 3.023 microns, and several micropores on the surface. And did not introduce any aforementioned 3 kinds of antibacterial agents in this example;

The microcapsules obtained in this example are used for the finishing of fabrics, and the treated fabrics are tested for antibacterial properties. The test method refers to GB/T20944.2 Appendix B, and the results in Table 2 are obtained as follows: 99.9% antibacterial rate against Candida albicans, washed with water The antibacterial rate after 50 times is 84.9%; the antibacterial rate against Escherichia coli is 99.9%, and the antibacterial rate after washing 50 times is 92.9%; the antibacterial rate against Staphylococcus aureus is 99.9%, and the antibacterial rate after washing 50 times is 96.4%;

Each component in this example is analyzed, and each component is listed in the following table 3, and each comparative sample S2-0 etc. has expressed that only corresponding oil phase or water phase components are used, corresponding to other parts in this example 2 with etc. Measure water instead, and the operation steps are the same as in Example 2. After finishing the operation, carry out the antibacterial test respectively. The results showed that none of the formulations had antibacterial properties.

The antibacterial property test of the control group microcapsule of table 3

This control experiment proves that each component in the present invention alone, and the combination of several components, have no obvious antibacterial effect. And the obtained microcapsule of biomimetic structure has excellent antibacterial effect.

Example 3

This example provides a kind of antibacterial silicon dioxide-polystyrene-polyacrylate composite microcapsule of bionic structure, and its preparation method comprises the following steps:

a. Mix 60g of 44# industrial paraffin with 2g of tetramethyl silicate, 0.8g of KH570 silane coupling agent, 10g of ethylene glycol dimethacrylate, and 2g of divinylbenzene, and stir for 30 minutes to form an oil phase uniformly;

b. 1g sodium lauryl sulfate, 5g, 10%wt styrene-maleic anhydride hydrolyzed sodium salt solution and 1.1g Tween 80 were dissolved in 100g water, stirred to make it evenly mixed;

c. Process the above-mentioned oil-water two-phase at 5000rpm-9000rpm in a homogenizer for 5min to obtain an O/W emulsion;

d. At room temperature, adjust the pH of the aforementioned emulsion to 2-4, and form the first layer of shell after 4h-8h;

e. The temperature of the emulsion is raised to 60-80°C, benzoyl peroxide is added, and the temperature is kept for 5h-12h to allow it to polymerize to form a second shell.

That is, the described shell layer is silicon dioxide-polystyrene-polyacrylate composite microcapsules;

Accompanying drawing 8 and accompanying drawing 9 are the SEM photos of the obtained microcapsules of this example. Accompanying drawing 9 is the partial enlargement of capsule shell, and it can be seen that there are some tiny holes therein;

The Zeta potential test showed that the Zeta potential of the microcapsules was -22.8mV, indicating that the surface of the microcapsules was negatively charged. This is due to the use of 2 anionic surfactants in this example;

Laser particle size analysis shows that the D50 diameter of the microcapsules in this example is 7.536 microns;

The differential scanning calorimetry method obtained the phase change melting point of the phase change microcapsules in this example as 43.95°C, and the corresponding phase change enthalpy value was 140.1J/g;

It can be seen that we have obtained a biomimetic structure microcapsule with a negatively charged surface, a D50 of 7.536 microns, and several micropores on the surface. And did not introduce any aforementioned 3 kinds of antibacterial agents in this example;

The microcapsules obtained in this example are used for the finishing of fabrics, and the treated fabrics are tested for antibacterial performance. The test method refers to FZ/T 73023-2006 antibacterial knitwear. The test shows that the antibacterial rate of Candida albicans is 88%, and that of Escherichia coli The antibacterial rate is 85%, and the antibacterial rate for Staphylococcus aureus is 89%.

It can be seen that the microcapsules in this example have good antibacterial effect.

Example 4

This example provides a kind of biomimetic structure antibacterial silicon dioxide-polyurea composite microcapsule, and its preparation method comprises the following steps:

a. Stir 45g of n-docosane, 4g of tetraethyl silicate, 1.6g of KH550 silane coupling agent, and 10g of isophorone diisocyanate for 30 minutes to form an oil phase uniformly;

b. 20g, 10% wt of styrene-maleic anhydride hydrolyzed sodium salt solution and 0.65g OP-10 were dissolved in 100g of water, and stirred to make them evenly mixed;

c. Process the above-mentioned oil-water two-phase at 5000rpm-9000rpm in a homogenizer for 5min to obtain an O/W emulsion;

d. At room temperature, adjust the pH of the aforementioned emulsion to 2-4, and form the first layer of shell after 4h-8h;

e. The temperature of the emulsion is raised to 50-80°C, and 1,6-hexanediamine is added dropwise, and kept for 2h-8h to make it polymerize to form a second shell.

That is, the described shell layer is a silica-polyurea composite microcapsule;

Scanning electron microscopy showed that the surface of the microcapsules also had some micropores;

The Zeta potential test shows that the Zeta potential of the microcapsules is -31.5mV, indicating that the surface of the microcapsules is negatively charged;

Laser particle size analysis shows that the D50 diameter of the microcapsules in this example is 4.316 microns;

It can be seen that we have obtained a biomimetic structure microcapsule with a negatively charged surface, a D50 of 4.316 microns, and several micropores on the surface. And did not introduce any aforementioned 3 kinds of antibacterial agents in this example.

The microcapsules obtained in this example are used for the finishing of fabrics, and the treated fabrics are tested for antibacterial properties. The test method refers to FZ/T 73023-2006 antibacterial knitwear. The test shows that the bacteriostatic rate of Candida albicans is 87%, and that of Escherichia coli The antibacterial rate is 85%, and the antibacterial rate for Staphylococcus aureus is 91%.

It can be seen that the microcapsules in this example have good antibacterial effect.

Example 5

Provide a kind of antibacterial silicon dioxide-polyacrylate microcapsule of biomimetic structure in this example, its preparation method comprises the following steps:

a. Combine 25g vitamin E, 8g tetraethyl silicate, 0.6g aminopropyltrimethoxysilane coupling agent, 1.2g phenyltriethoxysilane coupling agent, 5g 1,6-hexyl dimethacrylate Glycol ester, stirring for 20 minutes, the process of uniformly forming an oil phase;

b. 15g, 10%wt styrene-maleic anhydride hydrolyzed sodium salt solution and 0.82g Triton (polyethylene glycol p-isooctyl phenyl ether) 100 were dissolved in 110g water, stirred to make it evenly mixed;

c. Process the above-mentioned oil-water two-phase through 6000rpm-12000rpm and homogenizer for 5min to obtain O/W emulsion;

d. At room temperature, adjust the pH of the aforementioned emulsion to 2-4, and form the first layer of shell after 4h-8h;

e. The temperature of the emulsion is raised to 50-80°C, the initiator APS is added, and the temperature is kept for 5h-12h, so that the organic monomers are polymerized to form the second shell.

That is to say, a kind of shell layer is a biomimetic structure antibacterial microcapsule of silicon dioxide-polyacrylate;

It can be seen by TEM that there are several micropores penetrating the shell on the surface of the microcapsules in this example;

The Zeta potential test shows that the Zeta potential of the microcapsules is -11.4mV, indicating that the surface of the microcapsules is negatively charged;

Laser particle size analysis shows that the D50 diameter is 1.99 microns;

From this we can know that this example has obtained a kind of surface negatively charged, and D50 is 1.99 microns, and the biomimetic structure microcapsule of some micropores is arranged on the surface. And did not introduce any aforementioned 3 kinds of antibacterial agents in this example.

The microcapsules obtained in this example are used for fabric finishing, and the treated fabric is tested for antibacterial performance. The test method refers to FZ/T 73023-2006 antibacterial knitwear. The test shows that the antibacterial rate of Candida albicans is 85%, and that of Escherichia coli The antibacterial rate is 86%, and the antibacterial rate for Staphylococcus aureus is 94%.

It can be seen that the microcapsules in this example have good antibacterial effect.

The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, any person familiar with the technical field within the technical scope disclosed in the present invention, according to the technical solution of the present invention Any equivalent replacement or change of the inventive concepts thereof shall fall within the protection scope of the present invention.

Claims (10)

1. An antibacterial microcapsule with a bionic structure is characterized in that it includes a core material and a capsule wall material wrapped on the surface of the core material, the capsule wall material has a through-hole structure, and the surface of the capsule wall material is negatively charged.
2. The antibacterial microcapsule with bionic structure according to claim 1, characterized in that, the antibacterial microcapsule is spherical or spherical in shape, and the D50 diameter is 0.8-10 microns.
3. A kind of antibacterial microcapsule of bionic structure according to claim 1, it is characterized in that, the inner shell surface of described capsule wall material wrapping core material is lipophilic, the outer shell surface of described capsule wall material is hydrophilic, and described core material comprises At least one of phase change materials, fat-soluble flavors, plant essential oils, and fat-soluble vitamins.
4. A preparation method of bionic structure antibacterial microcapsules, characterized in that it comprises the steps of:

   Mix the core material, silane coupling agent and monomer to form the first mixture, mix the composite emulsifier of the water phase with the first mixture to form an O/W emulsion, adjust the pH of the O/W emulsion to 2-4, and adjust the pH of the O/W emulsion to 2-4. Initiator is added into the W emulsion and the temperature rises to polymerize to form antibacterial microcapsules.
5. The preparation method of a kind of biomimetic structure antibacterial microcapsule according to claim 4, is characterized in that, after adjusting the pH of O/W emulsion to be 2-4, first forms the second shell with first layer through 4h-8h the mixture, and then raise the temperature of the second mixture to 60-80°C, add an initiator, keep the temperature constant for 5h-12h, polymerize to form a second layer of shell, and obtain antibacterial microcapsules.
6. A method for preparing antibacterial microcapsules with a bionic structure according to claim 4, wherein the core material includes at least one of phase change materials, fat-soluble essences, plant essential oils, and fat-soluble vitamins;

   The silane coupling agent includes aminopropyltrimethoxysilane, aminopropyltriethoxysilane, phenyltriethoxysilane, 3-(methacryloxy)propyltrimethoxysilane, orthosilane At least two of tetraethyl orthosilicate and tetramethyl orthosilicate;

   The monomers include at least one of styrene, divinylbenzene, acrylate monomers, acrylic monomers, and diisocyanate prepolymers;

   The compound emulsifier is a combination of anionic surfactant and nonionic surfactant.
7. The preparation method of a kind of bionic structure antibacterial microcapsule according to claim 6, is characterized in that, described composite emulsifier comprises polyethylene-maleic anhydride copolymer or its hydrolyzed salt, polystyrene-maleic anhydride copolymer or its hydrolyzed salt, block copolymer of epoxy resin and polyethylene glycol, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sorbitan monooleate polyoxyethylene ether, fatty alcohol Polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, fatty alcohol polyoxypropylene ethers, glycerol monofatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitan fatty acid esters and/or fatty acid pentaerythritol at least one of esters.
8. The preparation method of a kind of bionic structure antibacterial microcapsule according to claim 7, is characterized in that, the weight portion of each component comprises: core material 25-60 parts, silane coupling agent 0.6-8 part, monomer 1.2- 10 parts and 0.19-3 parts of compound emulsifier.
9. An antibacterial product, characterized in that it contains the biomimetic structure antibacterial microcapsules as described in any one of claims 1-4 or contains the preparation method as described in any one of claims 5-9. antibacterial microcapsules.
10. Application of bionic structure antibacterial microcapsules in transportation or storage of food, medicine, textiles or cosmetics, the antibacterial microcapsules are the bionic structure antibacterial microcapsules described in any one of claims 1-4 or claim 5-9 The antibacterial microcapsule prepared by the preparation method described in any claim.

Images