WO2023130629A1

WO2023130629A1 - Single-component visible-light-catalyzed teeth whitening gel having low hydrogen peroxide concentration, and preparation and use thereof

Info

Publication number: WO2023130629A1
Application number: PCT/CN2022/090439
Authority: WO
Inventors: 钱秋雨; 赵霞; 刘敏; 郭小平
Original assignee: 宁波楚月新材料科技有限公司; 中国科学院海洋研究所
Priority date: 2022-01-10
Filing date: 2022-04-29
Publication date: 2023-07-13
Also published as: CN114983849B; CN114983849A

Abstract

The invention relates to the technical field of teeth whitening, and relates to a single-component visible-light-catalyzed teeth whitening gel having a low hydrogen peroxide concentration, and a preparation and a use thereof. The teeth whitening gel is composed of copper and iron co-doped nano-titanium dioxide, a light stabilizer, a gelling agent, hydrogen peroxide, a desensitizing agent, a whitening filler, an auxiliary agent, and deionized water. The nano-titanium dioxide in the teeth whitening gel is prepared by a hydrothermal method, has visible light catalytic activity, and can synergistically catalyze the decomposition of the hydrogen peroxide. The mass concentration of the hydrogen peroxide in the whitening gel is lower than 3%, the room temperature storage time exceeds 12 months, and the whitening effect on teeth can provide remarkable whitening improvement after 10 uses.

Description

One-component low hydrogen peroxide concentration visible light catalyzed tooth whitening gel and its preparation and application

technical field

The invention belongs to the technical field of tooth whitening, and relates to a single-component low hydrogen peroxide concentration visible light catalyzed tooth whitening gel and its preparation and application.

Background technique

Nano-titanium dioxide is a new type of inorganic nano-material developed in the late 1980s. Its large specific surface area, strong ultraviolet absorption capacity, good thermal conductivity, high surface activity, and good dispersibility have attracted widespread attention. However, the large band gap of nano-titanium dioxide determines that it can only be excited by high-energy ultraviolet light and cannot be catalyzed by visible light, which limits the application of nano-titanium dioxide in the field of visible light catalysis tooth whitening gel. In tooth whitening gels, visible light catalyzed whitening gels are commonly used to achieve the whitening function of teeth, which limits the application of nano-titanium dioxide in whitening gels. The metal ion doping method refers to doping metal ions into the titanium dioxide lattice to form impurity energy levels and reduce the forbidden band width, thereby expanding the photoresponse range of titanium dioxide and realizing the effect of visible light catalysis. Whitening gel is a tooth whitening technology popular in Europe and America. Although the whitening gel technology is relatively mature, there are still some problems in the visible light irradiation tooth whitening gel products on the market. First of all, the concentration of hydrogen peroxide in the gel is relatively high. Generally, the concentration of hydrogen peroxide exceeds 5%, and some products even reach 10%. High-concentration hydrogen peroxide will have a better whitening effect, but at the same time damage the gums and oral cavity. Tooth pain is obvious after use; secondly, visible light whitening gel has a low utilization rate of hydrogen peroxide, visible light irradiation has limited catalytic oxidation performance of hydrogen peroxide, and whitening gel cannot achieve the effect of whitening teeth in a short period of time. At the same time, the storage stability of the existing whitening gel is not good, and the whitening gel will produce obvious thinning phenomenon during storage and transportation.

Therefore, how to develop a tooth whitening gel that can catalyze oxidation by mild light, such as visible light, and can synergistically decompose hydrogen peroxide to produce OH, and prolong the storage time of the whitening gel is to improve the safety of tooth whitening technology. Reliability is an urgent problem to be solved.

Contents of the invention

The main purpose of the present invention is to provide a single-component low hydrogen peroxide concentration visible light catalyzed tooth whitening gel and its preparation and application.

In order to achieve the above object, the technical solution adopted by the present invention is:

A single-component low hydrogen peroxide concentration visible light catalyzed tooth whitening gel, the tooth whitening gel comprises the following components in parts by weight: 10-15 parts of copper-iron co-doped nano-titanium dioxide, and 0.01-0.1 parts of light stabilizer , 2 to 3 parts of gelling agent, 3 to 9 parts of hydrogen peroxide with a mass fraction of 30%, 0.1 to 2 parts of desensitizing agent, 0.1 to 0.5 parts of auxiliary agent, 0.5 to 1.0 parts of whitening filler, 10 to 82 parts of deionized water share.

The copper-iron co-doped nano-titanium dioxide is prepared by a hydrothermal method to obtain porous spherical copper-iron co-doped nano-titanium dioxide.

Further, specifically, butyl titanate is dissolved in butanol solution, which is recorded as solution A, and ferric nitrate and copper nitrate solutions are added to concentrated hydrochloric acid solution, which is recorded as solution B. Under low-speed stirring, solution B is added dropwise to In A, a mixed solution is formed, and the mixed solution is hydrothermally reacted in a reactor at 150-300°C for 8-12 hours, then centrifuged, washed with ethanol and deionized water in sequence, and calcined in a muffle furnace at 500-650°C After 3-4 hours, the copper-iron co-doped titanium dioxide nanopowder is obtained.

The copper-iron co-doped nano-titanium dioxide is that butyl titanate is dissolved in butanol solution, which is recorded as solution A, and ferric nitrate and copper nitrate solution are added into concentrated hydrochloric acid solution, which is recorded as solution B. Under low-speed stirring, the Solution B is added dropwise to A to form a mixed solution, and the mixed solution is hydrothermally reacted in a reactor at 150-300°C for 8-12 hours, then centrifuged, washed by centrifugation, and calcined in a muffle furnace at 500-650°C After 3-4 hours, the copper-iron co-doped titanium dioxide nanopowder is obtained.

The whitening filler is obtained by chemically grafting and modifying the surface of the filler material with an organic resin; wherein the filler material is one or more of nanometer zinc oxide, quartz powder and/or titanium dioxide.

The surface chemical grafting modification is to use an organic resin to carry out chemical grafting modification on the surface of the filler material in an organic solvent; wherein, the organic resin is one or more of epoxy resin, acrylic resin, polyester resin ; The organic solvent is one or more of xylene, n-butanol and ethyl acetate.

The mass ratio of the organic resin to the filler substance is 1:20-1:50.

The stabilizer is composed of an antioxidant and a light absorber at a mass ratio of 1:1 to 1:5, wherein the antioxidant is 2,6-tertiary butyl-4-methylphenol and/or bis( 3,5-tertiary butyl-4-hydroxyphenyl) sulfide, the light absorbing agent is dihydroartemisinin, erythromycin, kanamycin.

The gelling agent is carbomer and/or carboxymethyl cellulose; the desensitizing agent is calcium fluoride, sodium monofluorophosphate, strontium fluoride or strontium acetate; the auxiliary agent is disodium edetate, glycerin or polyethylene glycol.

A preparation method of single-component low hydrogen peroxide concentration visible light catalyzed tooth whitening gel:

1) Soak the gel in deionized water, add additives, and ultrasonically disperse to obtain mixture A;

2) Add a stabilizer to mixture A and stir evenly, then add copper-iron co-doped titanium dioxide, and stir evenly to obtain mixture B;

3) uniformly dispersing the filler material into an organic solvent, adding an organic resin to chemically graft and modify the filler material, centrifuging, and washing with deionized water to obtain the whitening filler C;

4) Mix the mixture B with the whitening filler C, then add hydrogen peroxide with a mass fraction of 30%, after mixing evenly, add a desensitizer and a stabilizer, and adjust the pH value with an alkaline solution to obtain mixture D, which is teeth whitening gel.

In step 1), the soaking time of the gel agent is 12 to 24 hours, and the soaking temperature is 5 to 35°C;

In step 2), the stirring time is 2 to 4 hours, and the rotating speed is 200 to 400r/min;

In step 3), the chemical graft modification time of the organic resin to the filler is 6 to 12 hours;

In step 4), the alkaline solution adjusts the pH value of the gel to a range of pH6.5-7.5.

The application of a single-component low hydrogen peroxide concentration visible light catalyzed tooth whitening gel, the application of the tooth whitening gel to tooth whitening under photocatalysis.

The wavelength of the visible light of the photocatalyst is 400-800 nm, and the irradiation time is 30-60 min.

The application process is to apply the tooth whitening gel on the teeth, and irradiate the visible light of the LED for a certain period of time to catalyze nano-titanium dioxide to generate oxidation electron holes, and hydrogen peroxide to generate strong oxidizing hydroxyl radicals (OH) and whitening fillers. , the three work together to complete the tooth whitening effect.

Compared with the prior art, the technical progress achieved by the present invention lies in:

The teeth whitening gel of the present invention, its active ingredient copper-iron co-doped titanium dioxide has visible light excitation activity, forms strong oxidizing electron holes under visible light irradiation, and can also synergistically catalyze and decompose hydrogen peroxide to produce OH, electron holes Caves and OH can quickly oxidize the pigment and dirt on the tooth surface, and improve the whitening effect of the whitening gel on the teeth;

The teeth whitening gel of the present invention is added with organic resin chemical media modified whitening fillers, and the whitening fillers can enhance the tooth whitening effect of the gel without reducing the storage stability of the whitening gel.

The teeth whitening gel of the present invention is a single-component gel, the concentration of hydrogen peroxide is less than 3%, the harm to the gums is small, safe and efficient, easy to operate, and suitable for industrial production.

Description of drawings

Fig. 1 is an ultraviolet diffuse reflectance spectrum diagram of the copper-iron co-doped titanium dioxide nanopowder prepared in Example 1 provided by the embodiment of the present invention.

Fig. 2 is the XRD spectrum of the copper-iron co-doped titanium dioxide nanopowder prepared in Example 1 provided by the examples of the present invention.

Fig. 3 is a scanning electron micrograph of the copper-iron co-doped titanium dioxide nanopowder prepared in Example 2 provided by the embodiment of the present invention, the left picture is magnified 1000 times, and the right picture is magnified 3000 times.

Fig. 4 is a scanning electron micrograph of coated nano-zinc oxide prepared in Example 1 provided by the embodiment of the present invention, the left picture is magnified 2000 times, and the right picture is magnified 3000 times.

Detailed ways

The present invention will be described in further detail below through specific embodiments, and it should be understood that the described embodiments are only used to explain the present invention, and do not limit the present invention.

The nano-titanium dioxide in the tooth whitening gel of the present invention is prepared by a hydrothermal method to obtain a porous spherical shape, which has visible light catalytic activity and can synergistically catalyze and decompose hydrogen peroxide. The mass concentration of hydrogen peroxide in the whitening gel is less than 3%, the storage time at room temperature exceeds 12 months, and the whitening effect on teeth can be significantly improved after being used 10 times.

Embodiment 1 A kind of visible light tooth whitening gel, preparation method and application

1) Preparation of copper-iron co-doped titanium dioxide and coated whitening filler

Dissolve 15mL of butyl titanate in 50mL of n-butanol solution, and record it as solution A, add 3mL of 0.5M iron nitrate and 0.3mL 0.1M copper nitrate solution into 10mL of concentrated hydrochloric acid solution, and record it as solution B. Under magnetic stirring, solution B was slowly added dropwise to solution A to form a mixed solution, and the mixed solution was hydrothermally reacted in a closed reactor at 200°C for 10 hours, centrifuged to remove the supernatant, and then washed with ethanol and deionized water successively. After washing 5 times, calcining in a muffle furnace at 630°C for 4 hours, the copper-iron co-doped titanium dioxide nanopowder was obtained (see Figure 1).

Figure 1 is the ultraviolet diffuse reflectance spectrum of copper-iron co-doped titanium dioxide nanopowders. The ultraviolet diffuse reflectance spectrum shows that copper-iron co-doped titanium dioxide has better visible light catalytic performance. Fig. 2 is the XRD spectrum of the prepared copper-iron co-doped titanium dioxide nanopowder, the surface of the XRD spectrum copper and iron elements have been doped into the titanium dioxide crystal structure.

Disperse 0.8Kg nano-zinc oxide into 200mL xylene solution at high speed, add 40g thermoplastic acrylic resin (Japanese DIC56-1155), stir magnetically at 500r/mim for 2h, centrifugally disperse, and after drying, ultrasonically wash 5 times with 500mL deionized water, that is The chemically grafted modified zinc oxide filler was obtained, and the scanning electron micrograph of the chemically grafted modified nano zinc oxide is shown in FIG. 4 .

It can be seen from Figure 4 that the thermoplastic acrylic resin is evenly grafted on the surface of zinc oxide, and the acrylic resin can slow down the catalytic decomposition of zinc oxide to hydrogen peroxide during storage.

2) Tooth whitening gel and preparation method thereof

(1) Add 1.5kg of carbomer and 0.8kg of carboxymethyl cellulose to 80.3kg of deionized water, soak and swell completely, add 0.3kg of glycerin and 0.1kg of disodium edetate, stir and mix well, Obtain mixture A1;

(2) Under the condition of maintaining stirring, add 12 kg of copper-iron co-doped titanium dioxide nano-powder and 0.8 kg of coated nano-zinc oxide prepared above to mixture A1, stir and mix to obtain mixture B1;

(3) 3.5kg30% hydrogen peroxide was added to mixture B1, followed by 0.12kg sodium monofluorophosphate, 0.05kg bis(3,5-tertiary butyl-4-hydroxyphenyl)sulfide and 0.03kg erythromycin , after stirring at room temperature for 4 hours, add 0.5 kg of potassium hydroxide to detect the pH value, adjust the pH value to 7.0, and completely thicken the thickener to obtain the mixture C1, which is the tooth whitening gel;

Fill the tooth whitening gel into the PVC tube, pack, DEK commercially available visible light tooth whitening gel.

The obtained visible light tooth whitening gel is suitable for visible light tooth whitening.

Apply the above to obtain visible light teeth whitening gel:

100 subjects were selected and randomly divided into two groups, one group was smeared with the tooth whitening gel prepared in Example 1 during the test, and the other group was smeared with the commercially available visible light tooth whitening gel during the test;

a1) Apply the tooth whitening gel prepared in Example 1 on the teeth of 50 subjects respectively, with a thickness of 0.5mm, and irradiate with LED visible light at a wavelength of 460nm for 30min, and use it once a day for ten consecutive days to complete Teeth whitening. Compared with untreated teeth, all achieved significant whitening effect, and all showed no discomfort symptoms.

a2) Take the traditional visible light tooth whitening gel (purchased from Novashine Company), and apply it on the teeth of another 50 subjects respectively, with a thickness of 0.5mm, and irradiate with LED visible light with a wavelength of 460nm for 30min, and use it once a day for ten consecutive days. Day, teeth whitening is done. Compared with no treatment, 42 people produced a significant whitening effect, and 8 people showed no teeth whitening effect. Two of them had symptoms of teeth bleeding and pain, and two had symptoms of vertigo and dazzle.

Example 2 Tooth whitening gel, preparation method and application are basically the same as Example 1, the only difference is that the calcination temperature of nano-titanium dioxide powder is 500 ° C, the application process of Example 2 is the same as Example 1, the difference is only trial The results are different, see Table 1 for details. The scanning electron microscope photos of the prepared copper-iron co-doped titanium dioxide are shown in Figure 3. Its morphology is porous and spherical, which can significantly improve its catalytic performance under visible light.

Example 3 Tooth whitening gel, preparation method and application are basically the same as in Example 1, the only difference is that during the preparation process of the whitening gel, the resin used for the chemically grafted modified whitening filler zinc oxide is a high molecular weight epoxy resin, The application process of embodiment 3 is the same as that of embodiment 1, the only difference is the difference in trial results, see Table 1 for details.

Comparative Examples 1-3 Teeth Whitening Gel, Preparation Method and Application

Comparative Examples 1-2 are respectively a visible light tooth whitening gel, its preparation method and its application. Their steps are basically the same as those of Example 1, the only difference being the difference in the preparation process parameters of the whitening gel. Comparative Example 1 does not add Copper-iron co-doped titanium dioxide nanopowder, comparative example 2 does not add light stabilizer, the whitening filler of comparative example 3 does not carry out the zinc oxide of chemical graft modification treatment, their application process is the same as that of embodiment 1, the difference The difference is only in the whitening effect of the trial and the concentration of hydrogen peroxide during storage, see Table 1 for details:

The evaluation of the above-mentioned remarkable teeth whitening effect is based on the tooth whiteness color chart. The tooth whiteness color chart divides teeth into 12 levels, of which level 1 is the whitest and level 12 is the yellowest. The subjects took pictures to record the whiteness of the teeth before applying the whitening gel, and took pictures of the whiteness of the teeth after using the whitening gel 10 times. If the whiteness of the teeth increased by 5 levels or more before and after use, it was recorded as the subject's significant teeth whitening Effect.

It should be noted that the above-mentioned embodiments only illustrate the technical conception and characteristics of the present invention, and its purpose is to allow those familiar with this technology to understand the content of the present invention and implement it accordingly. Any skilled person familiar with this profession may use the above-mentioned technology The content is changed or modified as an equivalent embodiment as a revelation, but any simple modification, equivalent change and modification made to the above embodiments without departing from the technical essence of the claims of the present invention still belong to the rights of the present invention Scope of protection claimed.

Claims

A single-component low hydrogen peroxide concentration visible light catalyzed tooth whitening gel, characterized in that: the tooth whitening gel includes the following components in parts by weight: 10-15 parts of copper-iron co-doped nano-titanium dioxide, light stabilizer 0.01 to 0.1 parts, 2 to 3 parts of gelling agent, 3 to 9 parts of hydrogen peroxide with a mass fraction of 30%, 0.1 to 2 parts of desensitizing agent, 0.1 to 0.5 parts of auxiliary agent, 0.5 to 1.0 parts of whitening filler, deionized 10-82 parts of water.
The single-component low hydrogen peroxide concentration visible light catalyzed tooth whitening gel according to claim 1 is characterized in that: the copper-iron co-doped nano-titanium dioxide is prepared by hydrothermal method to obtain porous spherical copper-iron co-doped nano-titanium dioxide. Titanium dioxide.
The single-component low hydrogen peroxide concentration visible light catalyzed tooth whitening gel according to claim 2 is characterized in that: the copper-iron co-doped nano-titanium dioxide is butyl titanate dissolved in butanol solution, which is recorded as solution A. Add ferric nitrate and copper nitrate solution into concentrated hydrochloric acid solution and record it as solution B. Add solution B dropwise to A under low-speed stirring to form a mixed solution. Put the mixed solution in a reaction kettle at 150-300°C Hydrothermal reaction for 8-12 hours, then centrifugal separation, after centrifugal washing, calcining in a muffle furnace at 500-650°C for 3-4 hours to obtain copper-iron co-doped titanium dioxide nanopowder.
The single-component low hydrogen peroxide concentration visible light catalyzed tooth whitening gel according to claim 1 is characterized in that: the whitening filler is obtained by carrying out surface chemical grafting modification of the filler material through an organic resin; wherein the filler material It is one or more of nano zinc oxide, quartz powder and/or titanium dioxide.
The single-component low hydrogen peroxide concentration visible light catalyzed tooth whitening gel according to claim 4 is characterized in that: the surface chemical grafting modification is to use organic resin to chemically graft the surface of the filler material in an organic solvent branch modification; wherein, the organic resin is one or more of epoxy resin, acrylic resin, and polyester resin; the organic solvent is one or more of xylene, n-butanol, and ethyl acetate.
The single-component low hydrogen peroxide concentration visible light catalyzed tooth whitening gel according to claim 4, characterized in that the mass ratio of the organic resin to the filler material is 1:20-1:50.
The single-component low hydrogen peroxide concentration visible light catalyzed tooth whitening gel according to claim 1, characterized in that: the stabilizer is composed of an antioxidant and a light absorber in a mass ratio of 1:1 to 1:5 , wherein the antioxidant is 2,6-tertiary butyl-4-methylphenol and/or bis(3,5-tertiary butyl-4-hydroxyphenyl) sulfide, and the light absorber is dihydrogen Artemisinin, erythromycin, kanamycin.
The single-component low hydrogen peroxide concentration visible light catalyzed tooth whitening gel according to claim 1 is characterized in that: the gelling agent is carbomer and/or carboxymethylcellulose; the desensitizing agent is fluorinated Calcium, sodium monofluorophosphate, strontium fluoride or strontium acetate; additives are disodium edetate, glycerin or polyethylene glycol.
A preparation method of the single-component low hydrogen peroxide concentration visible light catalyzed tooth whitening gel according to claim 1, characterized in that:

1) Soak the gel in deionized water, add additives, and ultrasonically disperse to obtain mixture A;

2) Add a stabilizer to mixture A and stir evenly, then add copper-iron co-doped titanium dioxide, and stir evenly to obtain mixture B;

3) uniformly dispersing the filler material into an organic solvent, adding an organic resin to chemically graft and modify the filler material, centrifuging, and washing with deionized water to obtain the whitening filler C;

4) Mix the mixture B with the whitening filler C, then add hydrogen peroxide with a mass fraction of 30%, after mixing evenly, add a desensitizer and a stabilizer, and adjust the pH value with an alkaline solution to obtain mixture D, which is teeth whitening gel.
An application of the single-component low hydrogen peroxide concentration visible light catalyzed tooth whitening gel according to claim 1, characterized in that: the application of the tooth whitening gel to tooth whitening under photocatalysis.