阅读说明：本技术 一种异质结构抑菌剂 (Heterostructure bacteriostatic agent ) 是由 叶勤政 竹内栄治 朱宁 彭开美 谭邵早 熊军 陈新颖 李正锋 方俊山 姚明泽 梁 于 2021-09-29 设计创作，主要内容包括：本发明提供一种异质结构抑菌剂,按质量百分比计算,包括以下原料：聚硅氧烷微球10～30％和水性溶剂30～80％,聚硅氧烷微球包括Cu-(2)O-AO异质结构和聚硅氧烷外壳,Cu-(2)O-AO异质结构被包裹于聚硅氧烷外壳之中,在Cu-(2)O-AO异质结构中,AO表示带隙宽度不低于3eV的n型半导体。本发明利用具有宽带隙的n型半导体与具有窄带隙的Cu-(2)O形成p-n结异质结构,不仅拓宽了宽带隙半导体的波长范围,还提高了材料的光催化性能。利用聚硅氧烷外壳包裹含有Cu-(2)O的异质结构,有效地延缓了Cu-(2)O的氧化。基于上述理由,本发明所提供的抑制结构抑菌剂能够在可见光的激发下,能够对多种有害菌发挥有效的抑制、杀灭作用。(The invention provides a heterostructure bacteriostatic agent which comprises the following raw materials in percentage by mass: 10-30% of polysiloxane microspheres and 30-80% of aqueous solvent, wherein the polysiloxane microspheres comprise Cu 2 O-AO heterostructure and polysiloxane shell, Cu 2 The O-AO heterostructure is encapsulated in a polysiloxane shell in Cu 2 In the O-AO heterostructure, AO represents an n-type semiconductor having a band gap width of not less than 3 eV. The present invention utilizes n-type semiconductor with wide band gap and Cu with narrow band gap 2 O forms a p-n junction heterostructure, which not only widens the wavelength range of the wide band gap semiconductor, but also improves the photocatalytic performance of the material. Wrapping Cu-containing material with a silicone shell 2 O heterostructure effectively postpones Cu 2 And (4) oxidizing O. Based on the above reasons, the bacteriostatic agent with an inhibiting structure provided by the invention can effectively inhibit and kill various harmful bacteria under the excitation of visible light.)

1. A heterostructure bacteriostatic agent is characterized by comprising the following raw materials in percentage by mass: 10-30% of polysiloxane microspheres and 30-80% of aqueous solvent, wherein the polysiloxane microspheres comprise Cu₂O-AO heterostructure and polysiloxane shell, said Cu₂O-AO heterostructures are encapsulated in the polysiloxane shell in the Cu₂In the O-AO heterostructure, AO represents an n-type semiconductor having a band gap width of not less than 3 eV.

2. The heterostructure bacteriostatic agent of claim 1, wherein: the AO is ZnO and the Cu is₂O-AO heterostructure of Cu₂An O-ZnO heterostructure.

3. The heterostructure bacteriostatic agent of claim 2, wherein:

the Cu₂The O-ZnO heterostructure is prepared by a hydrothermal method, and the hydrothermal reaction condition is that the O-ZnO heterostructure reacts for 2.5-4 hours at 70-100 ℃;

the reaction solution for carrying out the hydrothermal reaction is prepared according to the following steps:

s1, according to Zn²⁺:Cu²⁺Weighing water-soluble zinc salt and water-soluble copper salt according to the molar ratio of 2: 0.3-0.6, and mixing the water-soluble zinc salt and the water-soluble copper salt with water to form an aqueous solution;

s2, dropwise adding the water solution prepared in the step S1 into an alcoholic solution of sodium bis- (2-ethylhexyl) sulfosuccinate, uniformly mixing, and then adding a reducing agent and alkali into the alcoholic solution to form a suspension, wherein the suspension is used as the reaction solution.

4. The heterostructure bacteriostatic agent of claim 3, wherein: at least one of the water-soluble zinc salt and the water-soluble copper salt is a citrate salt.

5. The bacteriostatic agent according to claim 3, wherein: the reducing agent is sodium borohydride.

6. The heterostructure bacteriostatic of claim 1, wherein the polysiloxane microspheres are prepared by the following method:

to contain said Cu₂Solution of O-AO heterostructure: silane monomer in a weight ratio of 2-3: 1-2, and Cu₂Mixing the solution of the O-AO heterostructure with the silane monomer, and standing until a white precipitate is obtained, wherein the white precipitate is the polysiloxane microspheres; the silane monomer is selected from silane monomers containing methoxyl or ethoxyl.

7. The heterostructure bacteriostatic agent of claim 1, wherein: the raw materials also comprise a silane coupling agent, and the silane coupling agent comprises the following components in percentage by mass: the ratio of the polysiloxane microspheres is 0.5-3: 10.

8. The heterostructure bacteriostatic agent of claim 1, wherein: the raw materials further comprise 1-5% of metal ions according to mass percentage, and the metal particles comprise at least one of silver ions and copper ions.

9. The heterostructure bacteriostatic agent of claim 1, wherein: the raw material also comprises 1-10% of hydroxyapatite by mass percentage.

10. The heterostructure bacteriostatic agent of claim 9, wherein: the hydroxyapatite is modified by sodium citrate.

Technical Field

The invention belongs to the technical field of antibiosis, and particularly relates to a heterostructure bacteriostatic agent.

Background

A technique for converting light energy into chemical energy by photocatalytic degradation, in which a photocatalyst absorbs electromagnetic radiation of a specific wavelength and is excited to generate electrons (e)^－) And a cavity (h)⁺) The interaction of electrons and holes with the medium such as air or water produces OH and O with strong oxidizing property^2－And the like contains oxygen active groups, and the oxygen active groups and organic matters and various bacteria in the air are subjected to degradation reaction, so that the functions of purifying the air, resisting bacteria, preventing mildew, preventing fouling, deodorizing and the like are achieved.

Cu₂O has a band gap width of 2.0-2.2 eV and can be excited by light having a wavelength of 400-760 nm to excite Cu₂The O is applied to photocatalytic degradation, the utilization rate of visible light in the photocatalytic degradation process can be improved, the theoretical value of the photoelectric conversion rate is higher, and based on the fact that the Cu is used as the theoretical value₂O is taken as a very potential photocatalytic semiconductor and is highly valued in the field of environmental governance. However, Cu₂O has low efficiency of separating photogenerated electrons and holes, which is not good for Cu₂The photocatalytic activity of O forms a significant limitation. On the other hand, Cu₂O is hardly soluble in water and is easily oxidized in humid air to convert it into Cu²⁺This is also not advantageous for Cu₂The application of O in aqueous fog.

Disclosure of Invention

The invention aims to provide a heterostructure bacteriostatic agent, which is used for applying Cu2O to an aqueous bacteriostatic agent with high bacteriostatic activity.

According to one aspect of the invention, a heterostructure bacteriostatic agent is provided, which comprises the following raw materials in percentage by mass: 10-30% of polysiloxane microspheres and 30-80% of aqueous solvent, wherein the polysiloxane microspheres comprise Cu₂O-AO heterostructure and polysiloxane shell, Cu₂The O-AO heterostructure is encapsulated in a polysiloxane shell in Cu₂In the O-AO heterostructure, AO represents an n-type semiconductor having a band gap width of not less than 3 eV. The present invention utilizes n-type semiconductor with wide band gap and Cu with narrow band gap₂O forms a p-n junction heterostructure: relative to Cu₂For an O narrow band gap semiconductor, the heterostructure formed by the O narrow band gap semiconductor can inhibit the recombination of photo-generated electron-hole pairs through a built-in electric field, so that the service life of a photo-generated carrier is prolonged, and the photocatalytic activity of a semiconductor photocatalyst is improved; compared with wide band gap semiconductors represented by AO, the band gap width can be reduced, and the effective excitation wavelength range of the semiconductor photocatalyst can be widened. In another aspect, the invention is achieved by coating Cu-containing materials with a silicone shell₂Hetero-structure of O, avoiding Cu₂The exposure of O to the moisture in the solvent and the air effectively delays the Cu₂And O is oxidized, so that the service life of the bacteriostatic agent is prolonged. On the other hand, the water-insoluble Cu can be avoided by wrapping with a polysiloxane shell₂The agglomeration and sedimentation of O improve the uniformity and storage stability of the bacteriostatic agent, and the transparent polysiloxane shell does not influence Cu₂Absorption of excitation light by O-AO heterostructure, enabled Cu₂The O-AO heterostructure exerts its photocatalytic effect normally and continuously under a relatively stable environment. Based on the above reasons, the bacteriostatic agent with an inhibiting structure provided by the invention can effectively inhibit and kill various harmful bacteria under the excitation of visible light.

Preferably, AO is TiO₂Or ZnO. TiO 2₂ZnO and ZnO both belong to semiconductor materials with wide forbidden band widths, the forbidden band widths of the ZnO and the ZnO are about 3.2eV, and TiO with wide forbidden band is adopted₂Or ZnO and Cu₂The heterostructure formed by O has good photocatalytic activity.

Preferably, AO is ZnO, Cu₂O-AO heterostructure of Cu₂An O-ZnO heterostructure. ZnO is a semiconductor metal oxide with excellent properties, and TiO₂In comparison, ZnO has higher light absorption efficiency and thus can exhibit higher photocatalytic activity and antibacterial property, and, in addition, ZnO is produced at a cost higher than TiO₂Lower, and has wider popularization and application prospect.

Preferably, Cu₂The O-ZnO heterostructure is prepared by a hydrothermal method, and the hydrothermal reaction condition is that the O-ZnO heterostructure reacts at 70-100 ℃ for 2.5 e4 h; the reaction solution for hydrothermal reaction was prepared as follows: s1, according to Zn²⁺:Cu²⁺Weighing water-soluble zinc salt and water-soluble copper salt according to the molar ratio of 2: 0.3-0.6, and mixing the water-soluble zinc salt and the water-soluble copper salt with water to form an aqueous solution; s2, dropwise adding the water solution prepared in the step S1 into an alcoholic solution of sodium bis- (2-ethylhexyl) sulfosuccinate, uniformly mixing, and then adding a reducing agent and alkali into the alcoholic solution until a suspension is formed, wherein the suspension is used as a reaction solution. The method has simple operation and mild reaction, and the prepared Cu₂The O-ZnO heterostructure has smaller grain diameter and larger specific surface area, thereby providing more active reaction sites for photocatalytic reaction.

Preferably, at least one of the water soluble zinc salt and the water soluble copper salt is a citrate salt. Method for preparing Cu by using citrate as zinc source or copper source₂Hydrothermal reaction of O-ZnO heterostructure, wherein citrate in reactant is converted into carbon quantum dot in hydrothermal reaction process, and the carbon quantum dot is doped with Cu₂In the product of the O-ZnO heterostructure, the recombination of photogenerated electron-hole pairs can be further inhibited, and the Cu content is improved₂Photocatalytic activity of O-ZnO heterostructures.

Preferably, the reducing agent is sodium borohydride. The sodium borohydride has good reducibility and can reduce copper salt participating in hydrothermal reaction into Cu₂O, and after the hydrothermal reaction, the boron element derived from sodium borohydride is doped with Cu₂In the product of the O-ZnO heterostructure, the recombination of photogenerated electron-hole pairs can be further inhibited, and the Cu content is improved₂Photocatalytic activity of O-ZnO heterostructures.

Preferably, the polysiloxane microspheres are prepared as follows: by containing Cu₂Solution of O-AO heterostructure: the silane monomer is 2-3: 1-2 by weight, and Cu is contained₂Mixing the solution of the O-AO heterostructure with a silane monomer, and standing until a white precipitate is obtained, wherein the white precipitate is polysiloxane microspheres; the silane monomer is selected from silane monomers containing methoxyl or ethoxyl. The polysiloxane microspheres prepared by the method are microspherical.

Preferably, the raw materials further comprise a silane coupling agent, and the mass ratio of the silane coupling agent: the ratio of the polysiloxane microspheres is 0.5-3: 10. The silane coupling agent in the formula is matched with the polysiloxane shell of the polysiloxane microspheres, so that the polysiloxane microspheres can be uniformly dispersed in the aqueous solvent, and the bacteriostatic agent provided by the invention has good uniformity and storage stability.

Preferably, the raw materials further comprise 1-5% of metal ions by mass percentage, and the metal particles comprise at least one of silver ions and copper ions. The copper ions and the silver ions are doped, so that the sterilization effect of the photocatalyst composition is effectively improved. The silver ion can strongly attract the sulfhydryl (-SH) on the protease in the bacterial body, and can be quickly combined with the sulfhydryl (-SH) on the protease, so that the protease can lose activity, and the bacteria can be killed, after the bacteria are killed by the silver ion, the silver ion can be dissociated from the bacterial corpse, and can be contacted with other bacterial colonies, and the above-mentioned processes can be repeatedly carried out, so that the photocatalyst composition can have durable bactericidal activity. The direct interaction between the copper ions and the bacterial outer membrane leads the bacterial outer membrane to be broken, and then the copper ions act on broken holes on the bacterial outer membrane, thus leading the cells to lose necessary nutrient substances and water and finally to shrink; because the main protection (outer membrane) of the cell is broken, the copper ion current can enter the cell without obstruction, and the excessive copper ion destroys some important processes in the cell and obstructs cell metabolism (such as biochemical reaction necessary for life), thereby achieving the effect of sterilization.

Preferably, the raw material further comprises 1-10% of hydroxyapatite by mass percentage. The hydroxyl groups in the hydroxyapatite can interact with formaldehyde, so that the bactericide can generate obvious degradation effect on the formaldehyde, and on the other hand, the hydroxyl groups in the hydroxyapatite can form hydrogen bonds with the aqueous solvent and are uniformly dispersed in the aqueous solvent.

Preferably, the hydroxyapatite is subjected to a sodium citrate modification treatment. The sodium citrate modified hydroxyapatite can show excellent catalytic activity on formaldehyde catalytic oxidation.

Detailed description of the preferred embodiments

In order to make the technical solutions of the present invention better understood by those skilled in the art, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.

The following materials used in the following examples are all commercially available products:

copper citrate (CAS number: 10402-15-0), zinc citrate dihydrate (CAS number: 5990-32-9), sodium borohydride (CAS number: 16940-66-2), sodium hydroxide (CAS number: 1310-73-2), copper acetate (CAS number: 142-71-2), zinc acetate (CAS number: 557-34-6), tetrabutyl titanate (CAS number: 5593-70-4), hydroxyapatite (CAS number: 1306-06-5), (3-mercaptopropyl) trimethoxysilane (CAS number: 4420-74-0), copper nitrate trihydrate (CAS number: 10031-43-3), silver nitrate (CAS number: 7761-88-8)

Example 1

1.Cu₂Preparation of O-ZnO heterostructure

A reaction solution for hydrothermal reaction was prepared by the following steps:

s1, adding 0.0072g of copper citrate and 0.0610g of zinc citrate (molar ratio, Cu) into 80mL of deionized water²⁺:Zn²⁺2:10), ultrasonically dispersing until the metal salt is completely dissolved to form a metal salt aqueous solution;

s2, dissolving 0.1335g of sodium bis- (2-ethylhexyl) sulfosuccinate in 10mL of n-butanol to form an AOT solution, dropwise adding the metal salt aqueous solution prepared in the step S1 into the AOT solution, and fully stirring for 1 hour;

s3, adding 0.015g of sodium borohydride into the mixed solution prepared in the S2, then dropwise adding 2mL of 1M sodium hydroxide aqueous solution into the mixed solution, and stirring for 2 hours to obtain a suspension.

Transferring the suspension prepared according to the steps into a 100mL polytetrafluoroethylene reaction kettle, and reacting for 2 hours at 90 ℃ to obtain the Cu-containing material₂Mixed liquid of O-ZnO heterostructure.

2. Preparation of polysiloxane microspheres

2g of the above-mentioned material is taken out and subjected to hydrothermal reaction to obtain the product containing Cu₂Adding mixed solution of O-ZnO heterostructureAdding the mixture into 40mL of aqueous solution containing 1.2g of urea propyl triethoxysilane, magnetically stirring for 30 minutes, standing for 4 hours, and performing suction filtration, washing and drying on the generated white precipitate to obtain the polysiloxane microspheres, wherein the polysiloxane microspheres have polysiloxane shells and Cu₂The O-ZnO heterostructure is encapsulated in a polysiloxane shell.

Example 2

1.Cu₂Preparation of O-ZnO heterostructure

Copper acetate was used in place of copper citrate used in example 1, and zinc acetate was used in place of zinc citrate used in example 1, as a solvent for preparing Cu₂As a raw material of O-ZnO heterostructure, in this example, the amount of charged copper acetate was 0.0036g and the amount of charged zinc acetate was 0.0183g (molar ratio, Cu)²⁺:Zn²⁺2: 10). Other materials and operation steps are consistent in example 1, and are not described herein. After the hydrothermal reaction is finished, Cu is prepared₂Mixed liquid of O-ZnO heterostructure.

2. Preparation of polysiloxane microspheres

Cu obtained after completion of the hydrothermal reaction in this example₂The mixed solution of the O-ZnO heterostructure is used as a raw material, other raw materials and operation steps are uniform, and the embodiment 1 keeps the same, and the details are not repeated. The polysiloxane microspheres thus obtained have a polysiloxane shell, Cu₂The O-ZnO heterostructure is encapsulated in a polysiloxane shell.

Example 3

1.Cu₂O-TiO₂Preparation of heterostructures

Copper acetate was used in place of copper citrate used in example 1, and tetrabutyl titanate was used in place of zinc citrate used in example 1, as a material for preparing Cu₂O-TiO₂In this example, the amount of the raw material for the heterostructure was 0.0036g in terms of copper acetate and 0.0340g in terms of tetrabutyl titanate (molar ratio, Cu)²⁺:Ti⁴⁺2: 10). Other materials and operation steps are consistent in example 1, and are not described herein. After the hydrothermal reaction is finished, Cu is prepared₂O-TiO₂HeterostructureThe mixed solution of (1).

2. Preparation of polysiloxane microspheres

Cu obtained after completion of the hydrothermal reaction in this example₂O-TiO₂The mixed liquid of the heterostructure is used as a raw material, other raw materials and operation steps are uniform, and the embodiment 1 keeps consistency, and the details are not repeated. The polysiloxane microspheres thus obtained have a polysiloxane shell, Cu₂O-TiO₂The heterostructure is encased in a silicone casing.

Example 4

1.Cu₂Preparation of O-ZnO heterostructure

Ascorbic acid was used as a reducing agent in the hydrothermal reaction instead of sodium borohydride used in example 1, and the amount of ascorbic acid charged in this example was 0.0705 g. Other materials and operation steps are consistent in example 1, and are not described herein. After the hydrothermal reaction is finished, Cu is prepared₂Mixed liquid of O-ZnO heterostructure.

2. Preparation of polysiloxane microspheres

Cu obtained after completion of the hydrothermal reaction in this example₂The mixed solution of the O-ZnO heterostructure is used as a raw material, other raw materials and operation steps are uniform, and the embodiment 1 keeps the same, and the details are not repeated. The polysiloxane microspheres thus obtained have a polysiloxane shell, Cu₂The O-ZnO heterostructure is encapsulated in a polysiloxane shell.

Example 5

1.Cu₂Preparation of O

Only copper citrate is used as a metal salt in a reaction liquid for preparing a hydrothermal reaction, other raw materials and operation steps are uniform, and the details are not repeated herein, and example 1 is consistent. After the hydrothermal reaction is finished, Cu is prepared₂And (3) a mixed solution of O.

2. Preparation of polysiloxane microspheres

Cu obtained after completion of the hydrothermal reaction in this example₂The mixture of O is used as the raw material, and other raw materials and operation steps are kept consistent in example 1, which is not described herein again. The thus obtained siliconeThe alkane microspheres have a polysiloxane shell, Cu₂The O heterostructure is encased in a polysiloxane shell.

Example 6

Preparation of ZnO

Only copper citrate is used as a metal salt in a reaction liquid for preparing a hydrothermal reaction, other raw materials and operation steps are uniform, and the details are not repeated herein, and example 1 is consistent. And preparing a mixed solution containing ZnO after the hydrothermal reaction is finished.

2. Preparation of polysiloxane microspheres

The mixed solution of ZnO obtained after the completion of the hydrothermal reaction in this example is used as a raw material, and other raw materials and operation steps are uniform and consistent in example 1, which is not described herein again. The polysiloxane microspheres obtained by the method have a polysiloxane shell, and the ZnO heterostructure is wrapped in the polysiloxane shell.

Example 7

1.Cu₂Preparation of O-ZnO heterostructure

The amounts of copper citrate and zinc citrate charged in the reaction solution for preparing the hydrothermal reaction were adjusted to 0.0048g and 0.0610g (molar ratio, Cu) in the present example²⁺:Zn²⁺1.5: 10). Other materials and operation steps are consistent in example 1, and are not described herein. After the hydrothermal reaction is finished, Cu is prepared₂Mixed liquid of O-ZnO heterostructure.

2. Preparation of polysiloxane microspheres

Cu obtained after completion of the hydrothermal reaction in this example₂The mixed solution of the O-ZnO heterostructure is used as a raw material, other raw materials and operation steps are uniform, and the embodiment 1 keeps the same, and the details are not repeated. The polysiloxane microspheres thus obtained have a polysiloxane shell, Cu₂The O-ZnO heterostructure is encapsulated in a polysiloxane shell.

Example 8

1.Cu₂Preparation of O-ZnO heterostructure

Adjusting copper citrate and citric acid in reaction solution for preparing hydrothermal reactionThe amount of zinc charged in this example was 0.0096g for copper citrate and 0.0610g for zinc citrate (molar ratio, Cu)²⁺:Zn²⁺3: 10). Other materials and operation steps are consistent in example 1, and are not described herein. After the hydrothermal reaction is finished, Cu is prepared₂Mixed liquid of O-ZnO heterostructure.

2. Preparation of polysiloxane microspheres

Cu obtained after completion of the hydrothermal reaction in this example₂The mixed solution of the O-ZnO heterostructure is used as a raw material, other raw materials and operation steps are uniform, and the embodiment 1 keeps the same, and the details are not repeated. The polysiloxane microspheres thus obtained have a polysiloxane shell, Cu₂The O-ZnO heterostructure is encapsulated in a polysiloxane shell.

Test example 1

1. Formulated ginseng test bacteriostat

The test bacteriostat of the test example was prepared by using the polysiloxane microspheres prepared in examples 1-8 according to the formulation shown in table 1, and the water-soluble acrylic resin was used as the film-forming resin in the formulation in the test example.

TABLE 1 reference composition of bacteriostatic agent components

Raw materials	Polysiloxane microspheres	Film-forming resin	Anhydrous ethanol	Deionized water
					Mass percent (%)	30	5	32.5	32.5

After the materials are prepared, the reference bacteriostat is prepared according to the following steps:

s1, mixing deionized water and absolute ethyl alcohol, and uniformly stirring to prepare an aqueous solvent;

s2, adding film-forming resin into the aqueous solvent, and homogenizing and stirring for 60 minutes in vacuum;

and S3, adding the polysiloxane microspheres into the slurry prepared in the step S2, and homogenizing and stirring for 60 minutes in vacuum to prepare the test-reference bacteriostatic agent.

2. Test of antibacterial Property

Visible light irradiation group: the test bacteriostat of the test example is tested for bactericidal rate by referring to GBT 30706-. Escherichia coli, Staphylococcus aureus, Penicillium, Trichophyton rubrum were used as test bacteria.

Ultraviolet light illumination group: referring to the GBT 30706-. Escherichia coli, Staphylococcus aureus, Penicillium, Trichophyton rubrum were used as test bacteria.

3. Test results

Under the condition of ultraviolet light illumination, except the test bacteriostat corresponding to the embodiment 5, the rest of test bacteriostats can reach the bacteriostasis rate of more than 95 percent, and on one hand, the bacteriostats contain ZnO or TiO₂The bacteriostat has excellent response activity under the excitation of ultraviolet light, on the other hand, the ultraviolet light also has certain bactericidal effect, and under the same excitation condition, the bacteriostat of the reference bacteriostat corresponding to the embodiment 5 has lower bacteriostasis rate, which just explains that Cu₂The antibacterial ability of O itself is not high, although the O can be effectively excited, the effective bactericidal factor generated after the O is excitedNot much. Under the condition that visible light is used as an excitation light source: the corresponding bacteriostatic rate of the embodiment 1 is highest; comparison of examples 1, 2 and 3 for the production of Cu₂The type of metal salt and the type of reducing agent of the O-ZnO heterostructure can also influence the bacteriostatic ability of the bacteriostatic agent, and the metal salt containing citrate and the sodium borohydride serving as the reducing agent are beneficial to improving the bacteriostatic rate of the bacteriostatic agent; by comparing examples 1, 5 and 6, ZnO or Cu alone was used under visible light excitation₂O is used as a photocatalyst in the bacteriostatic agent, has relatively low bacteriostatic rate and is used for Cu₂O is not high in bacteriostatic ability even if it can be effectively excited because of easy recombination of photogenerated electrons and holes, whereas ZnO has excellent photocatalytic potential because of its large band gap width, but it cannot be effectively excited under irradiation of visible light.

TABLE 2 statistics of bacteriostatic rate

Example 9

1. Preparation of modified hydroxyapatite

(1) Hexadecyl trimethyl ammonium bromide modified apatite

Adding 0.01 weight part of surfactant cetyl trimethyl ammonium bromide into 1 weight part of apatite, and performing ultrasonic treatment for 10min to obtain cetyl trimethyl ammonium bromide modified apatite.

(2) Sodium dodecyl sulfate-modified apatite

And adding 0.01 part by weight of sodium dodecyl sulfate serving as a surfactant into 5 parts by weight of apatite, and performing ultrasonic treatment for 10min to obtain the sodium dodecyl sulfate modified apatite.

(3) Sodium citrate modified apatite

And adding 0.01 part by weight of surfactant sodium citrate into 10 parts by weight of apatite, and performing ultrasonic treatment for 10min to obtain sodium citrate modified apatite.

2. Preparing ginseng test antibacterial film agent

The modified hydroxyapatite obtained in the example and the Cu-containing hydroxyapatite obtained in example 1 were used in the test groups₂The test bacteriostat of the test example is prepared by preparing polysiloxane microspheres with O-ZnO heterostructure according to the formula in the table 3, and the corresponding relation between the serial number of each test group and the corresponding modified hydroxyapatite is as follows: test group a, hexadecyltrimethylammonium bromide modified apatite; run group B, sodium dodecyl sulfate modified apatite; run C, sodium citrate modified apatite. In this example, a water-soluble acrylic resin was used as the film-forming resin in the formulation.

TABLE 3 reference bacteriostatic component compositions

After the materials are prepared, the reference bacteriostat is prepared according to the following steps:

s1, mixing deionized water and absolute ethyl alcohol, and uniformly stirring to prepare an aqueous solvent;

s2, adding film-forming resin into the aqueous solvent, and homogenizing and stirring for 60 minutes in vacuum;

s3, adding polysiloxane microspheres into the slurry prepared in the S2, and carrying out vacuum homogenization and stirring for 60 minutes;

and S4, adding the modified hydroxyapatite into the slurry prepared in the step S3, and homogenizing and stirring for 60 minutes in vacuum to prepare the test bacteriostatic agent.

This example also provided control group a and control group B. And replacing the modified hydroxyapatite in the table 3 with the commercially available hydroxyapatite in the control group A to prepare the reference bacteriostatic agent, and replacing the modified hydroxyapatite related in the step with the commercially available hydroxyapatite according to the step of preparing the reference bacteriostatic agent in the test group to prepare the reference bacteriostatic agent in the control group A. Deleting the modified hydroxyapatite in the formula shown in the table 3 to serve as the formula of the control group B for preparing the reference bacteriostatic agent, referring to the step of preparing the reference bacteriostatic agent by the test group, deleting the operation steps related to the modified hydroxyapatite in the steps, and preparing the reference bacteriostatic agent of the control group B.

Test example 2

In this test example, the antibacterial performance test was carried out using the test bacteriostatic agents prepared in control group A, control group B, test group A, test group B and test group C of example 9. In the test example, the test bacteriostat of the test example is subjected to bactericidal rate test by referring to GBT 30706-.

Table 4 shows the statistics of the test results of the antibacterial performance tests of each of the tested bacteriostatic agents. The introduction of hydroxyapatite or modified hydroxyapatite is beneficial to improving the bacteriostasis rate of the bacteriostat by taking the control group B as a reference. In example 9, the hydroxyapatite is modified by cetyl trimethyl ammonium bromide or sodium dodecyl sulfate, and the bacteriostatic effect of the hydroxyapatite is not significantly improved, however, the bacteriostatic effect of the hydroxyapatite can be significantly improved by modifying the hydroxyapatite by sodium citrate, and the bacteriostatic rate of the corresponding bacteriostatic agent is higher.

TABLE 4 statistics of bacteriostatic rate

Example 10

This example sets up 3 treatment groups separately to prepare three different bacteriostatic agents.

Treatment I:

(1) cu preparation as provided in example 1₂Method for preparing Cu by O-ZnO heterostructure₂An O-ZnO heterostructure, directly collecting Cu contained in the reaction kettle after the hydrothermal reaction is finished₂Mixed liquid of O-ZnO heterostructure.

(2) Using the above-mentioned Cu-containing₂The mixed solution of O-ZnO heterostructure was used to prepare polysiloxane microspheres according to the method provided in example 1 for preparing polysiloxane microspheres.

(3) Formulated bacteriostatic agent

The sodium citrate-modified apatite prepared in example 9 was prepared according to the formulation shown in Table 5. And preparing the bacteriostatic agent according to the following steps:

s1, mixing deionized water and absolute ethyl alcohol, and uniformly stirring to prepare an aqueous solvent;

s2, adding water-soluble acrylic resin into the water-based solvent, and carrying out vacuum homogenization and stirring for 60 minutes;

s3, adding polysiloxane microspheres into the slurry prepared in the S2, and carrying out vacuum homogenization and stirring for 60 minutes;

and S4, adding the sodium citrate modified hydroxyapatite into the slurry prepared in the step S3, and homogenizing and stirring for 60 minutes in vacuum to prepare the bacteriostatic agent I.

TABLE 5 bacteriostatic formulations for treatment I

And (4) treatment II:

(1) cu preparation as provided in example 1₂Method for preparing Cu by O-ZnO heterostructure₂An O-ZnO heterostructure, directly collecting Cu contained in the reaction kettle after the hydrothermal reaction is finished₂Mixed liquid of O-ZnO heterostructure.

(2) Using the above-mentioned Cu-containing₂The mixed solution of O-ZnO heterostructure was used to prepare polysiloxane microspheres according to the method provided in example 1 for preparing polysiloxane microspheres.

(3) Formulated bacteriostatic agent

The sodium citrate modified apatite prepared in example 9 was prepared according to the formula shown in Table 6, in which (3-mercaptopropyl) trimethoxysilane was used as the silane coupling agent in Table 6, silver nitrate in the formula was used to provide silver ions in an amount of 2% by mass of the formula, and copper nitrate in the formula was used to provide copper ions in an amount of 1% by mass of the formula. The bacteriostatic agent is prepared according to the following steps:

s1, mixing and stirring deionized water and polysiloxane microspheres for 30 minutes;

s2, adding absolute ethyl alcohol into the slurry prepared in the S1, and mixing and stirring for 30 minutes;

s3, adding silver nitrate and copper nitrate into the slurry prepared in the S2, and carrying out vacuum homogenizing and stirring for 30 minutes;

s4, adding water-soluble acrylic resin into the slurry prepared in the step S3, and carrying out vacuum homogenizing and stirring for 30 minutes;

s5, adding a silane coupling agent into the slurry prepared in the step S4, and carrying out vacuum homogenizing and stirring for 60 minutes;

s6, adding the sodium citrate modified hydroxyapatite of each test group into the slurry prepared in the S5, and homogenizing and stirring for 60 minutes in vacuum to prepare the bacteriostatic agent II.

TABLE 6 bacteriostatic formulations for treatment II

Treatment III:

(1) cu preparation as provided in example 1₂Method for preparing Cu by O-ZnO heterostructure₂An O-ZnO heterostructure, directly collecting Cu contained in the reaction kettle after the hydrothermal reaction is finished₂Mixed liquid of O-ZnO heterostructure.

(2) Formulated bacteriostatic agent

Directly using the above-mentioned Cu-containing₂The O-ZnO heterostructure mixture and the sodium citrate-modified apatite prepared in example 9 were prepared according to the formulation shown in Table 7, in which (3-mercaptopropyl) trimethoxysilane was used as the materialAlkane as the silane coupling agent in table 7, silver nitrate in the formulation was used to provide silver ions at 2% by mass of the formulation, and copper nitrate in the formulation was used to provide copper ions at 1% by mass of the formulation; the formula contains Cu by conversion₂The dosage of the mixed liquid of the O-ZnO heterostructure and the Cu-containing bacteriostatic agent prepared in the treatment I and the treatment II₂The usage amount of the mixed liquid of the O-ZnO heterostructure is the same. The bacteriostatic agent is prepared according to the following steps:

s1, deionized water and Cu-containing solution₂Mixing and stirring the mixed solution of the O-ZnO heterostructure for 30 minutes;

s2, adding absolute ethyl alcohol into the slurry prepared in the S1, and mixing and stirring for 30 minutes;

s3, adding silver nitrate and copper nitrate into the slurry prepared in the S2, and carrying out vacuum homogenizing and stirring for 30 minutes;

s4, adding water-soluble acrylic resin into the slurry prepared in the step S3, and carrying out vacuum homogenizing and stirring for 30 minutes;

s5, adding a silane coupling agent into the slurry prepared in the step S4, and carrying out vacuum homogenizing and stirring for 60 minutes;

s6, adding the sodium citrate modified hydroxyapatite of each test group into the slurry prepared in the S5, and homogenizing and stirring for 60 minutes in vacuum to prepare the bacteriostatic agent III.

TABLE 7 bacteriostatic formulations for treatment II

Test example 3

In this example, the performance of bacteriostatic agent I, bacteriostatic agent II and bacteriostatic agent III prepared in example 10 was tested.

(1) Performance test of purifying organic pollutants:

sample group: respectively adding bacteriostatic agent I, bacteriostatic agent II and bacteriostatic agent III at 1m³0.2 in the metal caseAnd (3) spraying on the paint plates with the size of m multiplied by 0.2m, wherein 1 circulating fan is arranged in the metal box, the spraying amount of each paint plate is 5mL, formaldehyde solution is respectively injected into the paint plates to ensure that the concentration of formaldehyde in the metal box is 3mg/mL, and the initial concentration of formaldehyde in the metal box is recorded.

Blank group: a paint plate of 0.2m multiplied by 0.2m is placed in a metal box, formaldehyde solution is injected into the metal box to ensure that the concentration of formaldehyde in the metal box is 3mg/mL, and the initial concentration of formaldehyde in the metal box is recorded.

The illumination condition is as follows: and a visible light irradiation group for carrying out solar light irradiation, and recording the concentration of formaldehyde in each metal box respectively after 2 hours of irradiation.

The formaldehyde was replaced with hydrogen sulfide, dimethylamine, dimethyl sulfide and the same procedure was repeated.

Calculating the degradation rate of organic pollutants such as formaldehyde and the like: the removal rate of the pollutants is (pollutant concentration value of blank control group-pollutant concentration value of sample group) ÷ pollutant concentration value of blank control group multiplied by 100%.

(2) The test bacteriostat of the test example is tested for bactericidal rate by referring to GBT 30706-.

(3) And (3) physical property testing: and (3) spraying the bacteriostatic agent I, the bacteriostatic agent II and the bacteriostatic agent III on a paint board, and then testing the physical property of the paint board according to GB/T9286-88 for testing the adhesive force of the photocatalyst composite material.

(4) Test results

The performance tests of the 3 reference bacteriostats of this test example are shown in tables 8 and 9. The introduction of copper ions and silver ions is beneficial to improving the bacteriostatic effect of the bacteriostatic agent, so that the bacteriostatic agent I shows excellent organic pollutant degradation performance and bacteriostatic performance. In addition, by comparing bacteriostat I and bacteriostat III, bacteriostat III is significantly bluish in color due to the Cu content thereof₂Conversion of O to Cu²⁺So that the degradation effect of the organic pollutants of the bacteriostatic agent III is obviously reduced, and the bacteriostatic effect is also reduced to a certain extent (but because of Cu²⁺Also has certain bacteriostatic ability, so the decline range of the bacteriostatic rate is smaller than the decline range of the degradation rate of the organic pollutants). On the other hand, in the presence ofCompared with the antibacterial agent (bacteriostatic agent III) without polysiloxane microspheres, the introduction of the silane coupling agent can effectively improve the uniformity and the film-forming property of the antibacterial agent.

TABLE 8 testing of photocatalytic Properties of bacteriostats

Table 9 results of coating film physical property test.

Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the true spirit and scope of the present invention.