阅读说明：本技术 一种抗菌抗黏附耐酸防污疏水牙齿保护剂制备方法及应用 (Preparation method and application of antibacterial, anti-adhesion, acid-resistant, antifouling and hydrophobic tooth protective agent ) 是由 王小磊 廖岚 赵思语 许莹莹 杨学涛 朱嘉 于 2021-09-30 设计创作，主要内容包括：本发明公开了一种抗菌抗黏附耐酸防污疏水牙齿保护剂制备方法及应用,该牙齿保护剂包括：光响应抗菌剂、纳米粒子、疏水性改性剂、疏水胶黏剂、无水乙醇溶剂,利用疏水改性剂对纳米粒子疏水改性,并与光响应抗菌剂和疏水胶粘剂通过混合后得到可喷涂光响应抗菌抗黏附耐酸防污超疏水牙齿保护剂,该喷涂剂喷涂在牙齿上固化后形成保护膜具有光响应性、抗菌抗黏附性、耐酸防污性和超疏水性,能够有效防止食物残渣和细菌黏附在牙齿上,在500-750 nm的LED可见光光源激发下可以进一步提高抗菌性,及时杀灭侥幸黏附于牙齿的细菌,同时达到降解色素美白的效果。本发明方法对生产设备要求不高,生产工艺安全方便,使用简单,实用性强,可以大规模生产和普适于大众。(The invention discloses a preparation method and application of an antibacterial, anti-adhesion, acid-resistant, antifouling and hydrophobic tooth protective agent, wherein the tooth protective agent comprises the following components in parts by weight: the photoresponse antibacterial agent, the nano particles, the hydrophobic modifier, the hydrophobic adhesive and the absolute ethanol solvent are subjected to hydrophobic modification on the nano particles by utilizing the hydrophobic modifier, and are mixed with the photoresponse antibacterial agent and the hydrophobic adhesive to obtain the sprayable photoresponse antibacterial anti-adhesion acid-resistant anti-fouling super-hydrophobic tooth protective agent, the protective film formed after the spraying agent is sprayed on the teeth and cured has photoresponse, antibacterial anti-adhesion, acid-resistant anti-fouling property and super-hydrophobic property, food residues and bacteria can be effectively prevented from being adhered to the teeth, the antibacterial property can be further improved under the excitation of a 500-750nm LED visible light source, the bacteria which are haphazardly adhered to the teeth can be timely killed, and the effects of degrading pigments and whitening can be simultaneously achieved. The method has low requirement on production equipment, safe and convenient production process, simple use and strong practicability, and can be used for large-scale production and is generally suitable for the public.)

1. An antibacterial, anti-adhesion, acid-resistant, antifouling and hydrophobic tooth protective agent is characterized by comprising the following components in parts by weight:

0.5-2 parts of a photoresponsive antibacterial agent;

0.5-2 parts of nano particles;

0.1-1 part of a hydrophobic modifier;

50-150 parts of a hydrophobic adhesive;

100-200 parts of an absolute ethyl alcohol solvent.

2. The antibacterial, anti-adhesion, acid-resistant, stain-resistant and hydrophobic tooth protectant according to claim 1, wherein:

the photoresponse antibacterial agent is carbon-doped zinc oxide or carbon-doped titanium dioxide or a mixture of the carbon-doped zinc oxide and the carbon-doped titanium dioxide;

the nano particles are nano silicon dioxide or copper particles or a mixture of the nano silicon dioxide and the copper particles;

the hydrophobic modifier is one or more of heptadecafluorodecyltrimethoxysilane, octadecyl mercaptan or octadecyl trimethoxysilane;

the hydrophobic adhesive is polydimethylsiloxane oil or epoxy resin.

3. The antibacterial, anti-adhesion, acid-resistant, antifouling and hydrophobic tooth protectant according to claim 2, wherein the nanoparticles are a mixture of nano-silica or copper particles with different particle sizes.

4. A preparation method of an antibacterial, anti-adhesion, acid-resistant, antifouling and hydrophobic tooth protective agent is characterized by comprising the following steps:

step 1, adding the nano particles and a hydrophobic modifier into absolute ethyl alcohol according to a ratio for hydrophobic modification to obtain hydrophobic nano particles;

step 2, uniformly stirring the hydrophobic adhesive and the curing agent according to a ratio, adding the mixture into absolute ethyl alcohol containing a trace amount of hexane, and stirring and dispersing to obtain a mixed solution A;

and 3, adding the hydrophobic nano particles and the photoresponse antibacterial agent obtained in the step 1 into the mixed solution A obtained in the step 2 according to the proportion, and uniformly stirring to obtain the antibacterial anti-adhesion acid-resistant antifouling hydrophobic tooth protective agent.

5. The method for preparing the antibacterial, anti-adhesion, acid-resistant and antifouling hydrophobic tooth protecting agent according to claim 4, wherein the order of adding the nanoparticles and the hydrophobic modifier into the absolute ethyl alcohol in the step 1 is as follows: firstly, adding the nanoparticles into absolute ethyl alcohol, then adding a hydrophobic modifier, and filtering and drying after modification to obtain the hydrophobic nanoparticles.

6. The method as claimed in claim 4, wherein the excitation light source of the photoresponsive antibacterial agent is LED visible light with a wavelength of 500-750 nm.

7. The application of the antibacterial, anti-adhesion, acid-resistant, antifouling and hydrophobic tooth protective agent is characterized in that the tooth protective agent is contained in a spray bottle to be used as a spray, and when the tooth protective agent is used, the spray bottle is sprayed on the surface of teeth to form a protective film, so that the aims of antibiosis, anti-adhesion, acid resistance, antifouling and hydrophobicity are fulfilled.

Technical Field

The invention relates to the technical field of preparation processes of super-hydrophobic coatings, in particular to a preparation method and application of an antibacterial, anti-adhesion, acid-resistant and antifouling hydrophobic tooth protective agent.

Background

With the continuous development and progress of society, the living standard is continuously improved, the tooth health problem is concerned by more and more people, people no longer just find dentists for toothache and simply brush teeth, and people gradually change the concept from treating tooth diseases to regular tooth care. Most tooth care modes are to remove residual food residues on teeth in time, avoid halitosis, prevent teeth from yellowing and blackening, and prevent caries, gingivitis, periodontitis and the like caused by bacteria growing and producing acid on the surfaces of the teeth.

At present, people mainly clean and care the teeth daily through a toothbrush, dental floss, mouthwash and the like, but improper use of oral cleaning tools such as the toothbrush and the dental floss actually performs subtraction on the teeth, so that the cleaning effect cannot be achieved, and irreversible tooth damage is caused. Meanwhile, as the pace of life is faster and faster, people have difficulty in brushing teeth in time after eating every time and performing daily cleaning and nursing by using dental floss and mouthwash, so that food remained on teeth becomes a hotbed for nourishing bacteria, the bacteria multiply in large quantity and generate metabolites, and oral diseases such as caries, gingivitis, periodontitis and the like are caused.

In order to solve the problems, the invention designs a super-hydrophobic tooth protective agent capable of spraying photoresponse, anti-adhesion, acid resistance and stain resistance, the protective agent can be solidified into a film after being sprayed on teeth, has photoresponse, anti-bacterial, anti-adhesion, acid resistance and super-hydrophobic characteristics, realizes the 'addition' protection of the teeth, effectively prevents food residues and bacteria from being adhered to the teeth, can further improve the antibacterial property under the excitation of 500-750nm wavelength LED visible light, can kill bacteria which are adhered to the teeth in time, and has the effects of degrading pigments and whitening under the irradiation of 500-750nm wavelength LED visible light.

Disclosure of Invention

Technical problem to be solved

The invention aims to solve the problems and provides a preparation method and application of an antibacterial, anti-adhesion, acid-resistant, antifouling and hydrophobic tooth protective agent, so as to solve the problems that teeth are damaged by improper tooth care and food residues and bacteria adhered to the teeth cannot be effectively removed in time in fast-paced life, so that caries and gum diseases are caused to high degree.

Disclosure of the invention

In order to solve the technical problems, the invention provides an antibacterial, anti-adhesion, acid-resistant, antifouling and hydrophobic tooth protective agent, which comprises the following components in parts by weight:

0.5-2 parts of a photoresponsive antibacterial agent;

0.5-2 parts of nano particles;

0.1-1 part of a hydrophobic modifier;

50-150 parts of a hydrophobic adhesive;

100-200 parts of an absolute ethyl alcohol solvent.

The photoresponse antibacterial agent is carbon-doped zinc oxide or carbon-doped titanium dioxide or a mixture of the carbon-doped zinc oxide and the carbon-doped titanium dioxide;

the nano particles are a mixture of nano silicon dioxide and copper particles;

the hydrophobic modifier is one or more of heptadecafluorodecyltrimethoxysilane, octadecyl mercaptan or octadecyl trimethoxysilane;

the hydrophobic adhesive is polydimethylsiloxane oil or epoxy resin.

Preferably, the nanoparticles are a mixture of nano-silica or copper particles having different particle sizes in order to provide better wear resistance after curing the tooth protective film.

The invention also provides a preparation method of the antibacterial, anti-adhesion, acid-resistant, antifouling and hydrophobic tooth protective agent, which comprises the following steps:

step 1, adding the nano particles and a hydrophobic modifier into absolute ethyl alcohol according to a ratio for hydrophobic modification to obtain hydrophobic nano particles;

step 2, uniformly stirring the hydrophobic adhesive and the curing agent according to a ratio, adding the mixture into absolute ethyl alcohol containing a trace amount of hexane, and stirring and dispersing to obtain a mixed solution A;

and 3, adding the hydrophobic nano particles and the photoresponse antibacterial agent obtained in the step 1 into the mixed solution A obtained in the step 2 according to the proportion, and uniformly stirring to obtain the antibacterial anti-adhesion acid-resistant antifouling hydrophobic tooth protective agent.

Preferably, the order of adding the nanoparticles and the hydrophobic modifier into the absolute ethyl alcohol in the step 1 is as follows: firstly, adding the nanoparticles into absolute ethyl alcohol, then adding a hydrophobic modifier, and filtering and drying after modification to obtain the hydrophobic nanoparticles.

Preferably, the photoresponsive antibacterial agent can generate active oxygen under the irradiation of LED visible light with the wavelength of 500-750nm, kill bacteria which are lucky and adhered to the surfaces of the teeth and degrade pigments deposited on the surfaces of the teeth.

The embodiment of the invention also provides application of the antibacterial, anti-adhesion, acid-resistant, antifouling and hydrophobic tooth protective agent, wherein the tooth protective agent is contained in the spray bottle to be used as a spray, and is sprayed to the surface of teeth to form a protective film when in use, so that the aims of antibiosis, anti-adhesion, acid resistance, antifouling and hydrophobicity are fulfilled.

(III) advantageous effects

1. The photoresponse antibacterial agent can sterilize as required under the irradiation of the LED visible light without stimulating oral tissues;

2. the super-hydrophobicity effectively prevents food residues and bacteria from adhering and the pigmentation of teeth and reduces oral diseases such as decayed teeth, gum diseases and the like by a physical mode, and the occurrence of drug-resistant bacteria is avoided;

3. the proportion of the hydrophobic nano silicon dioxide with different particle sizes and the curing agent is regulated and controlled, so that the tooth protective film has better wear resistance after being cured;

4. simple process, good biological safety, simple operation method and obvious protection effect.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 is an electron microscope comparison of a tooth covered with a tooth protecting agent (left) and a normal tooth (right) according to an embodiment of the present invention;

FIG. 2 is a schematic representation of contact and roll angles of a tooth surface covered with a tooth protectant in accordance with an embodiment of the invention;

FIG. 3 is a graph showing the abrasion resistance and acid erosion resistance of a tooth-protecting agent coated on a tooth according to an embodiment of the present invention;

FIG. 4 is a comparison graph of antibacterial property of a tooth covered with a tooth protecting agent in an embodiment of the present invention after being irradiated by an LED visible light source with a wavelength of 500nm for a period of time;

FIG. 5 is a graph showing the protection of teeth against acid erosion in mice according to an embodiment of the present invention;

FIG. 6 is a graph showing the results of HE staining of relevant tissues of a mouse in an example of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Approximating language, as used herein in the following examples, may be applied to identify quantitative representations that could permissibly vary in number without resulting in a change in the basic function. Thus, a value modified by a language such as "about", "left or right" is not to be limited to the precise value itself, and in some embodiments "about" means that the value to which the modification is allowed varies within plus or minus ten percent (10%).

Example 1

The invention relates to an antibacterial, anti-adhesion, acid-resistant, antifouling and hydrophobic tooth protective agent, which comprises the following components in parts by weight:

0.5-2 parts of a photoresponsive antibacterial agent;

0.5-2 parts of nano particles;

0.1-1 part of a hydrophobic modifier;

50-150 parts of a hydrophobic adhesive;

100-200 parts of an absolute ethyl alcohol solvent.

Specifically, the photoresponse antibacterial agent is carbon-doped zinc oxide or carbon-doped titanium dioxide or a mixture of the carbon-doped zinc oxide and the carbon-doped titanium dioxide;

specifically, the nano particles are nano silicon dioxide or copper particles or a mixture of the nano silicon dioxide and the copper particles;

specifically, the hydrophobic modifier is one or more of heptadecafluorodecyltrimethoxysilane, octadecyl mercaptan or octadecyl trimethoxysilane;

specifically, the hydrophobic adhesive is polydimethylsiloxane oil or epoxy resin.

Specifically, the nano particles are a mixture of nano silicon dioxide or copper particles with different particle sizes.

Example 2

The invention relates to a preparation method of an antibacterial, anti-adhesion, acid-resistant, antifouling and hydrophobic tooth protective agent, which comprises the following steps:

step 1, adding the nano particles and a hydrophobic modifier into absolute ethyl alcohol according to a ratio for hydrophobic modification to obtain hydrophobic nano particles;

step 2, uniformly stirring the hydrophobic adhesive and the curing agent according to a ratio, adding the mixture into absolute ethyl alcohol containing a trace amount of hexane, and stirring and dispersing to obtain a mixed solution A;

and 3, adding the hydrophobic nano particles and the photoresponse antibacterial agent obtained in the step 1 into the mixed solution A obtained in the step 2 according to the proportion, and uniformly stirring to obtain the antibacterial anti-adhesion acid-resistant antifouling hydrophobic tooth protective agent.

Specifically, the excitation light source of the light response antibacterial agent is LED visible light with the wavelength of 500-750 nm.

Example 3

A preparation method of an antibacterial, anti-adhesion, acid-resistant, antifouling and hydrophobic tooth protective agent comprises the following steps:

step 1, adding about 2 parts by mass of nano silicon dioxide into an absolute ethyl alcohol solution, adding 1 part by mass of heptadecafluorodecyltrimethoxysilane for hydrophobic modification, filtering, drying and storing after the modification is finished;

step 2, taking about 1 part by mass of polydimethylsiloxane and 0.1 part by mass of curing agent, fully mixing, adding into 10 parts by mass of absolute ethyl alcohol containing trace hexane, and uniformly mixing;

and 3, adding the hydrophobic nano silicon dioxide prepared in the step 1 and 0.02 part by mass of doped zinc oxide into the mixed solution prepared in the step 2, and uniformly mixing to obtain the antibacterial anti-adhesion acid-resistant anti-fouling hydrophobic tooth protective agent.

Filling the antibacterial, anti-adhesion, acid-resistant, antifouling and hydrophobic tooth protective agent prepared according to the steps into a spray bottle, spraying the spray bottle on incisors of mice to form a tooth protective film, corroding the teeth of the mice protected by the protective film and without the protective film through acid, feeding the mice with bacteria-containing food for a period of time, observing the surface condition of the teeth, and simultaneously filling the tooth protective agent into the stomach of the mice in a stomach filling mode to observe the tissue reaction change of the mice; the results are shown in FIGS. 1 to 6.

As shown in fig. 1, which is an electron microscope comparison image of a tooth (left) covered with a tooth protectant and a common tooth (right), it can be seen that the tooth covered with the tooth protectant has a micro-nano rough structure on the surface, which is beneficial to realizing super-hydrophobicity, and the surface is cleaner and has no damage compared with the tooth without membrane protection, which indicates that the protective film can effectively resist the adhesion of various substances including bacteria, and can well protect the tooth;

as shown in fig. 2, which is a schematic view showing contact angles and rolling angles of the surfaces of teeth covered with the tooth protecting agent, it can be seen that the contact angles and rolling angles of water drops on the surfaces of the teeth covered with the tooth protecting agent are small, indicating that the teeth have super-hydrophobicity after the tooth protecting agent prepared by the present invention is used, and can effectively prevent adhesion of food residue and bacteria, pigmentation of teeth, and reduce occurrence of oral diseases such as dental caries and gum disease;

as shown in fig. 3, which is a graph illustrating the wear resistance and acid corrosion resistance of the tooth protective agent after covering the teeth, it can be seen that the film has better wear resistance and good acid corrosion resistance through the strategy of mixing and doping nanoparticles with different particle sizes, which indicates that the tooth protective agent prepared by the present invention can adapt to the complex environment of the oral cavity after being sprayed on the teeth to form the protective film;

as shown in fig. 4, which is a schematic diagram of the antibacterial property cultivation result of the tooth covered with the tooth protection film after being irradiated by the LED visible light source with wavelength of 500-750nm for a period of time, it can be seen from the diagram that the number of bacteria of the tooth covered with the tooth protective agent after being irradiated by the LED visible light source with wavelength of 500-750nm is obviously less than that of the tooth group without protection, which indicates that the tooth protective agent prepared by the invention can be sterilized under the irradiation of the LED visible light, and the sterilization mode adopting the light source irradiation can not stimulate the oral tissue;

fig. 5 is a comparison graph of the anti-acid corrosion protection of the teeth of the mouse, wherein the left side is the teeth without the tooth protective film, and the right side is the teeth without the tooth protective film.

FIG. 6 is a schematic diagram of HE staining results of relevant tissues of a mouse, and it can be seen from the diagram that HE staining of tissues such as heart, liver, spleen, lung and kidney of the mouse perfused with the tooth protective agent is not greatly different from HE staining of tissues such as heart, liver, spleen, lung and kidney of the mouse perfused with pure water, and obvious extravasated blood degeneration, inflammatory cells and the like are not found, so that the tooth protective agent prepared by the invention is high in biological safety and can be used as an oral health product.

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.