Indicator-containing pit and fissure sealant and methods of making and using the same

Abstract

The application provides a fissure sealant containing an indicator and a preparation method and application thereof, and belongs to the technical field of dental materials. The fissure sealant containing the indicator comprises the following raw materials in percentage by mass: 10-79% of an acrylate monomer; 0-1% of a photoinitiator; 0-0.6% of an indicator; 1-10% of titanium white; and 1-20% of a filler. The indicator is composed of a reaction indicator, an acid-base fluorescent indicator and an oxidation-reduction indicator. The fissure sealant cooperates with the three indicators to realize triple functions of fissure position calibration, damage indication and colony infection indication, ensures the effectiveness of protection of the fissure and monitoring of caries of children in the implementation of the fissure process, so as to realize the simultaneous identification of whether the fissure has a gap and leakage by naked eyes, accurate identification of the range of the fissure and accurate filling of the fissure, and direct judgment of the generation of colonies.

Description

Technical Field

[0001] This invention belongs to the field of dental materials technology, and in particular relates to a pit and fissure sealant containing an indicator, its preparation method, and its application. Background Technology

[0002] Pit and fissure sealants are primarily used to prevent tooth decay by sealing pits and fissures. Also known as pit and fissure sealants, they are a safe and painless method of protecting teeth from decay. The sealant is a protective plastic coating that can be applied to the occlusal surface of posterior teeth. It protects tooth enamel from bacterial and metabolic products, enhancing the teeth's resistance to caries, thus effectively preventing tooth decay.

[0003] Fissure sealants are suitable for sealing particularly deep fissures. The optimal time for fissure sealing is: 3-4 years old for primary molars, 6-7 years old for first permanent molars, and 11-13 years old for second permanent molars. The fissure sealing method is simple, involving cleaning the teeth, acid etching, rinsing and drying, applying the sealant, and allowing it to cure. This technique has been used internationally for over 50 years and is a painless and non-invasive method.

[0004] The principle behind fissure sealant for preventing pit and fissure caries is to fill the pits and fissures of teeth with a polymer material. On one hand, the sealant cuts off the nutrient source for bacteria, causing them to gradually die; on the other hand, it prevents caries-causing bacteria from entering. However, fissure sealants still carry a significant risk of falling off or breaking. Therefore, the sealing effect needs to be checked every 3-6 months. This check typically involves using a colony indicator and visual inspection to assess the sealant's effectiveness. However, currently used fissure sealants cannot be visually identified for leaks or gaps, and existing sealants cannot accurately identify the extent of the fissures and precisely fill them, nor can they directly identify bacterial colonies. Summary of the Invention

[0005] This invention provides a pit and fissure sealant containing an indicator, its preparation method, and its application. This pit and fissure sealant can not only visually identify whether there are gaps or leaks in the pits and fissures, but also accurately identify the extent of the pits and fissures and precisely fill them. It can also assist in judging the formation of bacterial colonies.

[0006] To achieve the above objectives, the present invention provides a pit and fissure sealant containing an indicator, comprising the following raw materials in the following mass percentages:

[0007] acrylate monomers 20-79%;

[0008] Photoinitiator 0.01-1%;

[0009] Indicator 0.01-0.6%;

[0010] Titanium dioxide 1-16%;

[0011] Filler content: 1-20%;

[0012] The indicator consists of a reaction indicator, an acid-base fluorescence indicator, and a redox indicator, each added at a rate of 0.01-0.2%, to enable accurate identification of the pit and fissure range and precise filling of the pits and fissures while visually identifying whether there are leaks or breaches, as well as to directly determine the formation of bacterial colonies.

[0013] Preferably, the acrylate monomer is selected from at least one of bisphenol A glycerol dimethacrylate (BisGMA), triethylene glycol dimethacrylate (TEGDMA), methacrylate (MMA), hydroxyethyl methacrylate (HEMA), urethane dimethacrylate (UDMA), ethoxylated bisphenol A glycerol dimethacrylate (BisEMA), polyethylene glycol acrylate (PEGDMA), 6-ethoxylated bisphenol A glycerol dimethacrylate (BisEMA6), and ethylene glycol dimethacrylate (EGDMA).

[0014] Preferably, the acrylate monomer is selected from at least one of bisphenol A glycerol dimethacrylate, urethane dimethacrylate, triethylene glycol dimethacrylate, 6-ethoxylated bisphenol A glycerol dimethacrylate, and hydroxyethyl methacrylate.

[0015] Preferably, the photoinitiator is selected from camphorquinone, TPO, and at least one of benzoin and its derivatives, benzoyl groups, alkyl phenyl ketones, acyl phosphorus oxides, benzophenones, thioxanthones, and cationic photoinitiators; preferably, the photoinitiator is camphorquinone.

[0016] Preferably, the benzoin and its derivatives are selected from at least one of benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin butyl ether; the benzoin derivatives are selected from at least one of diphenyl ethyl ketone and α,α-dimethoxy-α-phenyl acetophenone; the alkyl acetone derivatives are selected from at least one of α,α-diethoxyacetophenone, α-hydroxyalkyl acetone, and α-aminealkyl acetone; the acylphosphine oxide is selected from at least one of aromatic acylphosphine oxide and bisbenzoylphenylphosphine oxide; the benzophenone derivatives are selected from at least one of benzophenone, 2,4-dihydroxybenzophenone, and michalcone; the thioxanthone derivatives are selected from at least one of thiopropoxythioxanthone and isopropylthioxanthone; and the cationic photoinitiator is selected from at least one of diarylioiodonium salt, triarylioiodonium salt, alkyliodonium salt, and cumeneferrocene hexafluorophosphate.

[0017] Preferably, the photoinitiator further includes an auxiliary photoinitiator selected from ethyl 4-dimethylaminobenzoate (EDMAB) and diphenyliodonium hexafluorophosphate (DPIHP).

[0018] Preferably, the reaction indicator is selected from at least one of resazurin, Bengal tiger red, methylene blue, β-carotene, dibromofluorescein, and diosgenin Y, and the addition amount is 0.01-0.2%, preferably 0.01-0.05%; preferably, the reaction indicator is resazurin and Bengal tiger red;

[0019] The acid-base fluorescent indicator is selected from at least one of salicylic acid, 2-naphthylamine, 1-naphthylamine, quinine, 2-hydroxy-3-naphthoic acid, quinoline, 2-naphthol, and coumarin, and the addition amount is 0.01-0.2%, preferably 0.01-0.05%; preferably, the acid-base fluorescent indicator is salicylic acid and 2-naphthylamine;

[0020] The redox indicator is selected from at least one of fluorescein, dichlorofluorescein, eosin, bromophenol blue, bromocresol green, xylenol orange, rhodamine 6G, fuchsin, Congo red, alizarin red S, methyl red, diphenylamine, o-dimethoxybenzidine, and acid rose red, and the addition amount is 0.01-0.2%, preferably 0.01-0.05%; preferably, the redox indicator is selected from at least one of dichlorofluorescein, eosin, and bromophenol blue.

[0021] Preferably, the titanium dioxide is at least one of rutile titanium dioxide, anatase titanium dioxide, and silica powder.

[0022] Preferably, the filler is selected from at least one of silica powder, including quartz powder, silica powder, and fumed silica, glass powder including quartz barium glass powder, and ytterbium fluoride powder, with a particle size of 0.1-2 μm and a surface treated with silanization.

[0023] The present invention also provides a method for preparing a pit and fissure sealant containing an indicator according to any of the above technical solutions, comprising the following steps:

[0024] Acrylic ester monomers, photoinitiators, indicators, titanium dioxide, and fillers are mixed to obtain a pit and fissure sealant.

[0025] The present invention also provides the application of the pit and fissure sealant according to any of the above technical solutions in pit and fissure sealing.

[0026] The present invention also provides a dental composite material comprising the fissure sealant according to any of the above-described technical solutions.

[0027] Compared with the prior art, the advantages and positive effects of the present invention are as follows:

[0028] This invention provides a fissure sealant that, in conjunction with three indicators, achieves a triple effect of fissure location marking, damage indication, and colony infection indication. This ensures the effectiveness of fissure protection and caries monitoring for children during fissure treatment. The principle is as follows: the three indicators work together through color changes. The reaction indicator primarily provides electron acceptors to monitor the reaction process; the acid-base fluorescence indicator marks microorganisms and their excrement, especially anaerobic organisms; and the redox indicator monitors aerobic processes during the reaction and marks oxygen-involved metabolic processes. The optimized composition of the three indicators ensures specific indication effects during curing, damage, and colony infection. This allows for accurate identification and precise filling of fissures while visually recognizing leaks and gaps, and directly determining colony formation. Detailed Implementation

[0029] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0030] Example 1

[0031] Weigh out the corresponding masses of acrylate monomers (Bis-GMA, UDMA, TEGDMA, Bis-EMA6), photoinitiators (TPO, DPIHP), reaction indicators (rezazulen), acid-base fluorescence indicators (2-naphthylamine), redox indicators (dichlorofluorescein), titanium dioxide (rutile, anatase, silica powder), and fillers (silica) from Table 1, mix them evenly, and obtain the pit and fissure sealant.

[0032] Example 2

[0033] Weigh out the corresponding masses of acrylate monomers (Bis-GMA, UDMA, TEGDMA, Bis-EMA6), photoinitiators (camphorquinone, DPIHP), reaction indicators (rezazulen, Bengal tiger red), acid-base fluorescence indicators (salicylic acid), redox indicators (eosin), titanium dioxide (rutile, anatase), and fillers (silica, barium glass powder) from Table 1, mix them evenly, and obtain the pit and fissure sealant.

[0034] Example 3

[0035] Weigh out the corresponding masses of acrylate monomers (Bis-GMA, UDMA, TEGDMA, Bis-EMA6, HEMA), photoinitiators (TPO, DPIHP), reaction indicators (azuranium, Bengal red), acid-base fluorescence indicators (salicylic acid), redox indicators (dichlorofluorescein), titanium dioxide (rutile, anatase), and fillers (silica, barium glass powder) from Table 1, mix them evenly, and obtain the pit and fissure sealant.

[0036] Example 4

[0037] Weigh out the corresponding masses of acrylate monomers (Bis-GMA, UDMA, TEGDMA, Bis-EMA6, HEMA), photoinitiators (camphorquinone, DPIHP), reaction indicators (rezazulen), acid-base fluorescence indicators (2-naphthylamine), redox indicators (eosin), titanium dioxide (anatase, silica powder), and fillers (silica), mix them evenly, and obtain the pit and fissure sealant.

[0038] Comparative Example 1

[0039] Weigh out the corresponding masses of acrylate monomers (Bis-GMA, UDMA, TEGDMA, Bis-EMA6), photoinitiator (camphorquinone), reaction indicator (resazurite), redox indicator (dichlorofluorescein), titanium dioxide (rutile type, silica powder), and filler (silica) from Table 1, mix them evenly, and obtain the pit and fissure sealant.

[0040] Comparative Example 2

[0041] Weigh out the corresponding masses of acrylate monomers (Bis-GMA, UDMA, TEGDMA, Bis-EMA6), photoinitiators (camphorquinone, DBMAB), reaction indicators (rezazulen, Bengal red), acid-base fluorescence indicators (salicylic acid), titanium dioxide (anatase), and fillers (silica) from Table 1, mix them evenly, and obtain the pit and fissure sealant.

[0042] Comparative Example 3

[0043] Weigh out the corresponding masses of acrylate monomers (Bis-GMA, UDMA, TEGDMA, Bis-EMA6), photoinitiators (camphorquinone, DBMAB), acid-base fluorescence indicators (salicylic acid), redox indicators (dichlorofluorescein), titanium dioxide (rutile, anatase, silica powder), and fillers (silica) from Table 1, mix them evenly, and obtain the pit and fissure sealant.

[0044] Table 1. Group distribution ratios for each embodiment

[0045]

[0046] Performance testing

[0047] 1. Color changes of fissure sealant before and after curing

[0048] A colorimeter was used to test the color of the fissure sealant before and after curing to determine the location of the fissure filling.

[0049] The color of the fissure sealant before application is measured using a colorimeter based on the L*a*b* color system. For example, L1, a1, and b1 can be used to mark the color of the fissure sealant before curing; L2, a2, and b2 can be used to mark the color of the fissure sealant after curing.

[0050] Based on the various chromaticities mentioned above, the formula can be used. Calculate the color difference ΔE* (maximum value ≥ 2 and ≤ 15), where ΔE* is the color difference before and after curing; ΔL* is the difference of L* value before and after curing; Δa* is the difference of a* value before and after curing; and Δb* is the difference of b* value before and after curing.

[0051] Table 2 Color changes of fissure sealant before and after curing

[0052]

[0053] As shown in Table 2, after curing with light, the color of the fissure sealant changed from red to milky white, and the red coefficient (a) value decreased significantly. Furthermore, the gloss level decreased, and the color change was obvious, indicating a clear monitoring of the curing process. Comparative Example 2 had a higher content of reaction indicator, and its color change (red coefficient a and yellow coefficient b) was slightly more pronounced than the other examples. However, due to the lack of synergistic effect, the overall color change was not significant compared to the examples.

[0054] 2. Color changes before and after damage to the fissure sealant

[0055] A colorimeter was used to test the cured pit and fissure sealant. The color of the sealant before and after damage was compared to determine the extent of damage. The damaged sealant was then soaked in saliva to test the color change.

[0056] The color of the fissure sealant before application is based on the L*a*b* color system and measured using a colorimeter. L3, a3, and b3 can be used to mark the color of the fissure sealant before it is damaged; L4, a4, and b4 can be used to mark the color of the fissure sealant after it is damaged.

[0057] Based on the various chromaticities mentioned above, the formula can be used. Calculate the difference in chroma ΔE*, where ΔE* is the difference in chroma before and after the damage; ΔL* is the difference in L* value before and after the damage; Δa* is the difference in a* value before and after the damage; and Δb* is the difference in b* value before and after the damage.

[0058] Table 3 Color changes after damage to the fissure sealant.

[0059]

[0060] As shown in Table 3, after damage, the color of the deeper layers of the fissure sealant changed from milky white to yellow. The red coefficient (a) and yellow coefficient (b) values ​​increased significantly, and the gloss decreased, indicating a clear color change. The damage was clearly visible. The deeper the damage, the deeper and more pronounced the color change. The color change process requires the synergistic action of reaction indicators and acid / base and fluorescent indicators; if any one of these indicators is missing, the color change effect will be less noticeable.

[0061] 3. Color changes before and after the adhesion of the pit and fissure sealant colonies

[0062] The indication effect of dental caries colonies on pit and fissure sealant was tested by visual inspection. Colony culture was performed on the cured pit and fissure sealant. Culture medium was applied to the surface of the pit and fissure sealant, and the colonies were incubated on the culture medium at 37°C for 7 days to determine the situation after the colonies adhered to the pits and fissures. The color change of the pit and fissure sealant after colony adhesion was tested.

[0063] Table 4 Color changes of different bacterial colonies in the fissure sealant.

[0064]

[0065]

[0066] In summary, the fissure sealant provided by this invention can monitor the curing reaction and damage process with color, and can more significantly display the degree of reaction and damage. It can also indicate bacterial invasion to a certain extent, ensuring the effectiveness of fissure protection and caries monitoring during fissure treatment in children. Due to the inclusion of a small amount of fluorescent reaction indicator, some bacterial communities could be identified in the comparative example, but the range was small. In the example with sufficient amounts of all three indicators, all bacteria showed identification indication function mainly because, in addition to fluorescent labeling, the labeling ability of antibacterial communities was enhanced with the cooperation of acid-base indicators.

Claims

1. A pit and fissure sealant containing an indicator, characterized in that, The raw materials include the following percentages by weight: The composition includes: 20-79% acrylate monomer; 0.01-1% photoinitiator; 0.01-0.6% indicator; 1-16% titanium dioxide; and 1-20% filler. The indicator comprises a reaction indicator, an acid-base fluorescence indicator, and a redox indicator, each added at a rate of 0.01-0.2%. The reaction indicator is selected from at least one of resazurite and Bengal tiger red. The acid-base fluorescence indicator is selected from at least one of salicylic acid and 2-naphthylamine. The redox indicator is selected from at least one of dichlorofluorescein and eosin. The acrylate monomer is selected from at least one of bisphenol A glycerol dimethacrylate, diethylene glycol dimethacrylate, methacrylate, hydroxyethyl methacrylate, urethane dimethacrylate, ethoxylated bisphenol A glycerol dimethacrylate, polyethylene glycol acrylate, 6-ethoxylated bisphenol A glycerol dimethacrylate, and ethylene glycol dimethacrylate. The photoinitiator is selected from camphorquinone, TPO, and at least one of benzoin and its derivatives, benzoyl groups, alkyl phenyl ketones, benzophenones, thioxanthones, and cationic photoinitiators.

2. The fissure sealant according to claim 1, characterized in that, The acrylate monomer is selected from at least one of bisphenol A glycerol dimethacrylate, urethane dimethacrylate, triethylene glycol dimethacrylate, 6-ethoxylated bisphenol A glycerol dimethacrylate, and hydroxyethyl methacrylate.

3. The fissure sealant according to claim 1, characterized in that, The photoinitiator is camphorquinone.

4. The fissure sealant according to claim 1, characterized in that, The benzoin and its derivatives are selected from at least one of benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin butyl ether; benzoin derivatives are selected from at least one of diphenyl ethyl ketone and α,α-dimethoxy-α-phenyl acetophenone; alkyl acetones are selected from at least one of α,α-diethoxyacetophenone, α-hydroxyalkyl acetone, and α-aminealkyl acetone; benzophenones are selected from at least one of benzophenone, 2,4-dihydroxybenzophenone, and michalcone; thioxanthones are selected from at least one of thiopropoxythioxanthone and isopropylthioxanthone; and cationic photoinitiators are selected from at least one of diarylioiodonium salt, triarylioiodonium salt, alkyliodonium salt, and cumeneferrocene hexafluorophosphate.

5. The fissure sealant according to claim 1, characterized in that, The titanium dioxide is at least one of rutile titanium dioxide, anatase titanium dioxide, and silica powder.

6. The fissure sealant according to claim 1, characterized in that, The filler is selected from at least one of silica powder, including quartz powder, silica powder, and fumed silica, glass powder including quartz barium glass powder, and ytterbium fluoride powder, with a particle size of 0.1-2 μm and a surface treated with silanization.

7. A method for preparing a pit and fissure sealant containing an indicator according to any one of claims 1-6, characterized in that, Includes the following steps: Acrylic ester monomers, photoinitiators, indicators, titanium dioxide, and fillers are mixed to obtain a pit and fissure sealant.

8. The application of the fissure sealant according to any one of claims 1-6 in fissure sealing.

9. A dental composite material, characterized in that, The dental composite material includes the pit and fissure sealant according to any one of claims 1-6.

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