Transparent fluorine protective agent as well as preparation method and application thereof

Abstract

The invention discloses a transparent fluorine protective agent as well as a preparation method and application thereof, and belongs to the technical field of oral protective materials. According to the invention, by controlling dissolution, the olafluorine can be fully dissolved in an organic system without precipitation or emulsification, so that the whole fluorine protective agent is in a clear and transparent state and has excellent appearance, and organic fluorine functional groups contained in the added olafluorine molecules can gradually release fluorine ions in an oral cavity environment to realize continuous contact with enamel, so that the oral cavity protective agent has a good oral cavity protection effect. And preferably, slash rosin resin is used as a film-forming substrate, so that moderate adhesiveness can be provided, a compact protective film can be formed on the surface of teeth, rapid loss of fluorine ions is prevented, and the system takes ethanol and propylene glycol as main solvents, and is safe, low in irritation, mild in smell and suitable for long-term use in the oral cavity; the fluorine protective agent system is simple in component, the fluorine protective agent can be stably and uniformly dispersed for a long time without an inorganic filler and an emulsifier, the preparation steps are simplified, and the cost is reduced.

Description

Technical Field

[0001] This invention relates to the field of oral protective materials technology, and more specifically, to a transparent fluoride protective agent, its preparation method, and its application. Background Technology

[0002] Fluoride protectant is a preventative material used to prevent tooth decay and strengthen tooth enamel. Its main functions are threefold: First, by releasing fluoride ions, it exchanges ions with hydroxyapatite on the enamel surface, promoting the deposition and remineralization of calcium and phosphorus in saliva in the enamel, early leukoplakia, or mildly demineralized areas, generating fluorapatite. This enhances the enamel's resistance to acid corrosion, re-hardens the affected area, and prevents further decay. Second, it inhibits the metabolic activity of cariogenic bacteria such as Streptococcus mutans, reducing acid production. Third, the use of fluoride protectant can also seal dentinal tubules, alleviating dentin hypersensitivity and providing protection against tooth sensitivity.

[0003] Currently, the fluoride protectants widely used in clinical practice mainly use inorganic fluorides (such as sodium fluoride and sodium monofluorophosphate) as the primary fluoride source. However, traditional inorganic fluorides have the following problems: First, inorganic fluorides have extremely low solubility in organic resin systems or systems containing organic solvents, easily precipitating out to form turbidity or sediment, making it difficult to obtain a transparent system, affecting appearance and film uniformity; second, when the system is opaque, the fluoride distribution is uneven, leading to unstable fluoride ion release rates and unsatisfactory anti-caries effects; third, to improve solubility, a large amount of aqueous phase or surfactant needs to be introduced, but this will reduce the storage stability of the fluoride protectant, damage the film-forming properties of the system, and even affect oral adaptability.

[0004] Therefore, how to achieve a fluorine protectant with high fluorine content, transparency and stability, uniform film formation and continuous release of fluoride ions in an organic system with rosin resin as the film-forming matrix is ​​a problem that urgently needs to be solved in this field. Summary of the Invention

[0005] In view of this, and in order to solve one of the above-mentioned technical problems, the present invention provides a transparent fluorinated protective agent, its preparation method and application, the specific technical solution of which is as follows: A transparent fluorinated protective agent comprising the following raw materials by weight percentage: 30%~50% resin, 16%~62% organic solvent, 7%~30% fluoride, 0.5%~2.0% fragrance, and 0.5%~2.0% sweetener.

[0006] Preferably, the fluoride is olarfluorine.

[0007] Preferably, the resin is rosin wetland resin.

[0008] Preferably, the organic solvent includes one or more of ethanol and propylene glycol.

[0009] Preferably, the sweetener includes at least one of xylitol, sucralose, and acesulfame potassium.

[0010] In addition, the present invention also provides a method for preparing a transparent fluorine protective agent, the preparation method comprising the following steps: (1) The organic solvent is divided into a first solvent and a second solvent. The resin, fragrance and the first solvent are mixed and stirred to dissolve, resulting in mixture A; (2) Mix the fluoride, sweetener, and second solvent, stir to dissolve, and obtain mixture B; (3) Mix the mixture A and the mixture B evenly to obtain a transparent fluorine protective agent.

[0011] Preferably, the first solvent includes ethanol.

[0012] Preferably, the second solvent includes one or both of ethanol and propylene glycol.

[0013] In addition, the present invention also provides an application of a transparent fluoride protective agent, wherein the transparent fluoride protective agent is used as a dental caries prevention material to strengthen tooth enamel.

[0014] Compared with the prior art, the present invention has the following beneficial effects: 1. By controlling the dissolution, this invention allows olaflu to fully dissolve in organic systems without precipitation or emulsification, resulting in a clear and transparent fluoride protectant with an excellent appearance. The transparent fluoride protectant is more aesthetically pleasing, and when applied thinly to the tooth surface, it can directly reflect the tooth's natural color, thus offering better applicability.

[0015] 2. The organic fluoride functional groups contained in the olafol molecule of the present invention can gradually release fluoride ions in the oral environment, achieving continuous contact with tooth enamel, thereby improving the durability of caries prevention.

[0016] 3. The resin used in this invention is wet rosin resin, which serves as a film-forming matrix, providing both moderate adhesion and the ability to form a dense protective film on the tooth surface to prevent rapid loss of fluoride ions.

[0017] 4. The system of the present invention uses ethanol and propylene glycol as the main solvents, which is safe, low in irritation, and has a mild odor, making it suitable for long-term oral use.

[0018] 5. The fluorinated protective agent system of the present invention has a simple composition and can achieve long-term stability and uniform dispersion of the fluorinated protective agent without the need for inorganic fillers and emulsifiers, which simplifies the preparation steps and reduces costs. Attached Figure Description

[0019] The invention will be further understood from the following description taken in conjunction with the accompanying drawings. The components in the drawings are not necessarily drawn to scale, but rather the emphasis is on illustrating the principles of the embodiments. In different views, the same reference numerals designate corresponding parts.

[0020] Figure 1 This is a schematic diagram of the appearance of the fluorine protective agent prepared in Example 1 of the present invention; Figure 2 This is a schematic diagram of the appearance of the fluorinated protective agent prepared in Example 2 of the present invention; Figure 3 This is a schematic diagram of the appearance of the fluorinated protective agent prepared in Example 3 of the present invention; Figure 4 This is a schematic diagram of the appearance of the fluorinated protective agent prepared in Comparative Example 1; Figure 5 This is a schematic diagram of the appearance of the fluorine protective agent prepared in Comparative Example 2; Figure 6 This is a schematic diagram of fluoride ion release from the fluorine protective agents prepared in Examples 1-3; Figure 7 This is a schematic diagram showing the peeling of the coating formed by the fluorine protective agent prepared in Example 1 at different time points; Figure 8 This is a schematic diagram showing the peeling of the coating formed by the fluorine protective agent prepared in Example 2 at different time points; Figure 9 This is a schematic diagram showing the peeling of the coating formed by the fluorine protective agent prepared in Example 3 at different time points. Detailed Implementation

[0021] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to its embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the scope of protection of the invention.

[0022] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0023] A transparent fluorinated protective agent according to an embodiment of the present invention comprises the following raw materials in weight percentage: 30%~50% resin, 16%~62% organic solvent, 7%~30% fluoride, 0.5%~2.0% fragrance, and 0.5%~2.0% sweetener.

[0024] In this invention, the fluorine protective agent uses resin as a matrix and is combined with an organic solvent. By optimizing the component ratio, the fluorine protective agent can achieve a stable fluoride ion release, which can continuously and stably release fluoride ions for 24 hours. The high fluoride ion release within 24 hours results in a coating with strong adhesion that is not easily detached.

[0025] The fluorine protectant formulation described in this invention features a reasonable ratio of resin, organic solvent, and fluoride, which allows for better release of fluoride ions while maintaining the transparency and stability of the fluorine protectant, enabling long-term preservation.

[0026] In one embodiment, the amount of resin added is preferably 33.1% by weight.

[0027] In one embodiment, the amount of resin added is preferably 41.1% by weight.

[0028] In one embodiment, the amount of resin added is preferably 49.1% by weight.

[0029] In one embodiment, the amount of organic solvent added is preferably 40 wt% by mass percentage.

[0030] In one embodiment, the amount of organic solvent added is preferably 48 wt% by mass percentage.

[0031] In one embodiment, the amount of organic solvent added is preferably 56 wt% by mass percentage.

[0032] In one embodiment, the amount of fluoride added is preferably 7.9% by mass percentage.

[0033] In one embodiment, the amount of organic solvent added is preferably 29.7% by mass percentage.

[0034] In one embodiment, the amount of flavoring added is preferably 1.0 wt% by weight.

[0035] In one embodiment, the amount of flavoring added is preferably 1.5 wt% by weight.

[0036] In one embodiment, the amount of sweetener added is preferably 1.0 wt% by weight.

[0037] In one embodiment, the amount of sweetener added is preferably 1.5 wt% by weight.

[0038] In one embodiment, the fluoride is oraflu.

[0039] In one embodiment, the resin is rosin wetland resin.

[0040] In one embodiment, the organic solvent includes one or more of ethanol and propylene glycol.

[0041] In one embodiment, the organic solvent is preferably a mixture of ethanol and propylene glycol.

[0042] In one embodiment, the mass ratio of ethanol to propylene glycol is preferably (24~40):16.

[0043] In one embodiment, the sweetener includes at least one of xylitol, sucralose, and acesulfame potassium.

[0044] In addition, the present invention also provides a method for preparing a transparent fluorine protective agent, the preparation method comprising the following steps: (1) The organic solvent is divided into a first solvent and a second solvent. The resin, fragrance and the first solvent are mixed and stirred to dissolve, resulting in mixture A; (2) Mix the fluoride, sweetener, and second solvent, stir to dissolve, and obtain mixture B; (3) Mix the mixture A and the mixture B evenly to obtain a transparent fluorine protective agent.

[0045] In one embodiment, the first solvent includes ethanol, one or both of ethanol.

[0046] In one embodiment, the second solvent includes one or both of ethanol and propylene glycol.

[0047] In one embodiment, the first solvent and the second solvent are preferably a mixture of ethanol and propylene glycol, and the mass ratio of ethanol to propylene glycol is preferably (24~40):16.

[0048] In one embodiment, in step (1), the amount of the first solvent added accounts for 1 / 2 of the total volume of organic solvent.

[0049] In one embodiment, in step (1), the stirring and dissolving process is as follows: magnetic stirring is used, and the temperature is heated to 45°C to 60°C at a speed of 50r / min to 100r / min, and the stirring process is carried out for 20min to 30min.

[0050] In one embodiment, in step (2), the amount of the second solvent added accounts for 1 / 2 of the total volume of organic solvent.

[0051] In one embodiment, in step (2), the stirring and dissolving is performed by using magnetic stirring at a speed of 50 r / min to 100 r / min at room temperature for 10 min to 20 min.

[0052] In addition, the present invention also provides an application of a transparent fluoride protective agent, wherein the transparent fluoride protective agent is used as a dental caries prevention material to strengthen tooth enamel.

[0053] The embodiments of the present invention will be described in detail below with reference to specific examples. The rosin resin was purchased from Guangdong Kemao Forestry Chemical Group Co., Ltd.; and the olaflurium was purchased from Suzhou Laihui Biotechnology Co., Ltd.

[0054] The difference between Examples 1 and 3 lies in the different component ratios of the transparent fluorine protective agent, as shown in Table 1. Examples 1-3 describe a method for preparing a transparent fluorinated protective agent, comprising the following steps: (1) The organic solvent is divided into a first solvent and a second solvent. The resin, fragrance and the first solvent are mixed and stirred at 50 r / min and 45°C for 20 min to obtain mixture A. (2) Mix the fluoride, sweetener and second solvent, and stir at 50 r / min at room temperature for 10 min to dissolve them, to obtain mixture B; (3) Mix the mixture A and the mixture B evenly to obtain a transparent fluorine protective agent.

[0055] Comparative Examples 1-2: Compared with Example 3, Comparative Examples 1 and 2 differ in the composition ratio of the fluorinated protective agent, as shown in Table 1. The preparation process is the same as that of Example 3.

[0056] Table 1: Ingredient Ratio

[0057] Comparative Example 3: The difference between Comparative Example 3 and Example 3 is that sodium fluoride was used instead of olaflurium in Comparative Example 3, and the organic solvent was replaced with a single n-hexane. Otherwise, they were the same as in Example 3.

[0058] Comparative Example 4: The difference between Comparative Example 4 and Example 3 is that Comparative Example 4 uses frankincense resin instead of wetland rosin resin, while the rest is the same as Example 3.

[0059] I. The transparency and stability of the fluorinated protective agent samples obtained in Examples 1-3 and Comparative Examples 1-4 were tested. The test results are shown in Table 1 below.

[0060] The transparency test method was as follows: The fluorine protective agent samples obtained in Examples 1-3 and Comparative Examples 1-4 were left to stand at room temperature for at least 24 hours to eliminate bubble interference; then, they were added to a quartz cuvette with a light intensity of 1 cm, avoiding the formation of bubbles; using an empty quartz cuvette as a blank, baseline correction was performed on the UV spectrophotometer; the transmission spectrum of the fluorine protective agent samples was scanned in the wavelength range of 400–800 nm, and the transmittance T at 600 nm was recorded. 600 When T 600 When T ≥ 90%, the transparent fluorinated protective agent is determined to be a transparent or highly transparent system; preferably, when T 600 When the transparency is ≥95%, it is judged as a highly transparent system. 600 At 90-95%, it is considered a relatively transparent system; when T... 600 At 80-90%, it is determined to be a slightly turbid system. 600 When the concentration is less than 80%, it is considered a significantly turbid system, and there are particulate or colloidal structures present.

[0061] The stability test method is as follows: The fluorinated protective agent samples obtained in Examples 1-3 and Comparative Examples 1-4 were dispensed into sealed brown glass bottles and stored at (25±2)℃ under light-protected conditions; samples were taken at 0 days and 90 days of storage, and the T values ​​at each time point were tested according to the transparency test method described above. 600 And compare them, if T 600 If the change does not exceed 5% of the initial value, the fluorinated preservative is considered to have good room temperature storage stability.

[0062] Table 2: Results of Transparency and Stability Tests

[0063] As can be seen from the data analysis in Table 2, the present invention, through optimization of the components and component ratios, can obtain a fluorinated protective agent with better transparency and higher stability, and thus better application performance.

[0064] In addition, combined Figures 1-5Further analysis reveals the following figures: Figure 1 is a schematic diagram of the appearance of the fluoride protective agent prepared in Example 1 of the present invention; Figure 2 is a schematic diagram of the appearance of the fluoride protective agent prepared in Example 2 of the present invention; Figure 3 is a schematic diagram of the appearance of the fluoride protective agent prepared in Example 3 of the present invention; Figure 4 is a schematic diagram of the appearance of the fluoride protective agent prepared in Comparative Example 1; and Figure 5 is a schematic diagram of the appearance of the fluoride protective agent prepared in Comparative Example 2. It can be seen that the fluoride protective agents prepared in Examples 1-3 of the present invention are clear, transparent, and uniform in appearance. The fluoride protective agents in Comparative Examples 1-2 are pale yellow emulsions, uniformly dispersed, but their appearance is significantly inferior to that of Examples 1-3. This indicates that the content of the organic solvent ethanol needs to be greater than that of propylene glycol to achieve a transparent appearance. Ethanol, acting as a co-solvent, improves the overall solubility and uniformity of the fluoride protective agent system, ensuring the transparency and absence of turbidity. A transparent fluoride protective agent applied thinly to the tooth surface can more directly reflect the color of the tooth itself, offering advantages in both aesthetics and practicality.

[0065] 2. Further performance tests were conducted on the transparent fluorine protective agents obtained in Examples 1-3, including the determination of fluoride ion release and adhesion.

[0066] The fluoride ion release test method is as follows: Accurately weigh 0.200 grams of fluoride protectant (based on the dosage guidelines for deciduous dentition), and apply it to a dry glass slide using a brush; then, with the fluoride protectant-coated slide facing upwards, add 100 ml of deionized water; set the shaker temperature to 37℃ and the rotation speed to 200 rpm, simulate oral cavity abrasion in vitro, and measure the free fluoride ion release at 2 hours, 4 hours, 12 hours, and 24 hours to evaluate the sustained-release capacity of free fluoride. Three parallel samples are used for each group.

[0067] The adhesion strength test method is as follows: accurately weigh 0.200 g of fluoride protectant (according to the dosage guide for fluoride protectant (varnish) in deciduous dentition) and apply it to a dry glass slide with a brush; then, with the glass slide coated with fluoride protectant facing upwards, add 100 ml of deionized water; set the shaker temperature to 37℃ and the rotation speed to 200 rpm, simulate intraoral abrasion in vitro, and observe the shedding situation after 12 hours and 24 hours, with three parallel samples for each group.

[0068] Results analysis: such as Figure 6As shown in Figure 6, the fluoride ion release of the transparent fluoride protectant prepared in Example 1 of the present invention is as follows: The fluoride ions of the fluoride protectant of the present invention are gradually released over 24 hours, eventually reaching a release rate of over 80%. Furthermore, the fluoride ion release of the fluoride protectants prepared in Examples 1-3 increases with the decrease of wetland rosin resin content, proving that the addition of wetland rosin resin within a suitable range can enhance the fluoride ion release capacity of the fluoride protectant.

[0069] Figure 7 is a schematic diagram showing the peeling of the coating formed by the fluorine protective agent prepared in Example 1 at different time points; wherein, Figure 7 Figure a shows the shedding situation after 12 hours. Figure 7 Figure b in Figure 8 shows the peeling situation after 24 hours. Figure 8 is a schematic diagram showing the peeling situation of the coating formed by the fluorine protective agent prepared in Example 2 at different time points; among them, Figure c in Figure 8 shows the peeling situation after 12 hours. Figure 8 Figure d in Figure 9 shows the peeling situation after 24 hours. Figure 9 is a schematic diagram showing the peeling situation of the coating formed by the fluorine protective agent prepared in Example 3 at different time points; among them, Figure e in Figure 9 shows the peeling situation after 12 hours. Figure 9 Figure f shows the detachment situation over 24 hours; from Figures 7-9 It can be clearly seen that the transparent fluorinated protective agent coatings prepared in Examples 1-3 of the present invention have basically no peeling, proving that the addition of wetland resin gives the fluorinated protective agent effective adhesion.

[0070] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0071] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A transparent fluorine protective agent, characterized in that, The transparent fluorinated protective agent comprises the following raw materials in weight percentages: 30%~50% resin, 16%~62% organic solvent, 7%~30% fluoride, 0.5%~2.0% fragrance, and 0.5%~2.0% sweetener.

2. The transparent fluorine protective agent according to claim 1, characterized in that, The fluoride is olaraflu.

3. The transparent fluorine protective agent according to claim 1, characterized in that, The resin is rosin wetland resin.

4. The fluorine protective agent according to claim 1, characterized in that, The organic solvent includes one or both of ethanol and propylene glycol.

5. The fluorine protective agent according to any one of claims 1, characterized in that, The sweetener includes at least one of xylitol, sucralose, and acesulfame potassium.

6. A method for preparing a transparent fluorinated protective agent, characterized in that, The preparation method includes the following steps: (1) The organic solvent is divided into a first solvent and a second solvent. The resin, fragrance and the first solvent are mixed and stirred to dissolve, resulting in mixture A; (2) Mix the fluoride, sweetener, and second solvent, stir to dissolve, and obtain mixture B; (3) Mix the mixture A and the mixture B evenly to obtain a transparent fluorine protective agent.

7. The preparation method according to claim 6, characterized in that, The first solvent includes ethanol, or one or two of ethanol.

8. The preparation method according to claim 6, characterized in that, The second solvent includes one or both of ethanol and propylene glycol.

9. The application of a transparent fluorine protective agent, characterized in that, The application is the transparent fluoride protective agent as described in any one of claims 1 to 5, which is suitable as a dental caries prevention material to strengthen tooth enamel.

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