CN117017790A - Pit and groove sealing agent containing indicator, and preparation method and application thereof - Google Patents

Abstract

The invention provides a pit and fissure sealant containing an indicator and its preparation method and application, which belongs to the technical field of dental materials. The indicator-containing pit and fissure sealant of the present invention includes the following mass percentage of raw materials: acrylate monomer 10-79%; photoinitiator 0-1%; indicator 0-0.6%; titanium dioxide 1-10%; Filling 1-20%; wherein, the indicator consists of a reaction indicator, an acid-base fluorescent indicator and a redox indicator. This pit and fissure sealant cooperates with three indicators to achieve the triple functions of pit and fissure position calibration, damage indication and bacterial colony infection indication, ensuring the effectiveness of pit and fissure protection and caries monitoring in children during the implementation of pit and fissures, so as to achieve the goal of using While visually identifying whether there are holes and leaks in pits and fissures, it can also accurately identify the range of pits and fissures, accurately fill pits and fissures, and directly determine the generation of bacterial colonies.

Description

Pit and fissure sealant containing indicator and preparation method and application thereof

Technical field

The invention belongs to the technical field of dental materials, and in particular relates to a pit and fissure sealant containing an indicator and its preparation method and application.

Background technique

Pit and fissure sealants are mainly used to seal pits and fissures to prevent dental caries. Pit and fissure sealant, also known as pit and fissure sealant, is a safe and painless method of protecting teeth from tooth decay. Sealants are protective plastic coatings that are applied to the biting surfaces of your back teeth. It is an effective anti-caries method that protects tooth enamel from being eroded by bacteria and metabolites, and enhances the ability of teeth to resist caries.

Pit and fissure sealants are suitable for sealing pits and fissures with particularly deep pits and fissures. The best time for pit and fissure sealing is: 3-4 years old for deciduous molars, 6-7 years old for first permanent molars, and 11-13 years old for second permanent molars. The method of pit and fissure sealing is very simple. It can be completed by cleaning the teeth, etching, rinsing and drying, applying sealant and curing. This technology has been used internationally for more than 50 years and is a painless and non-invasive method.

The principle of pit and fissure sealing to prevent pit and fissure caries is to use polymer materials to fill the pits and fissures of teeth. On the one hand, after pit and fissure sealing, the nutritional source of bacteria is cut off, and the bacteria gradually die; on the other hand, the cariogenic bacteria can no longer be isolated from the outside. Enter. However, the pit and fissure sealant still has a high risk of falling off and breaking, so the sealing effect of the pit and fissure sealant needs to be checked every 3 to 6 months. The inspection usually involves judging the pit and fissure sealing effect through bacterial colony indicators and visual observation. However, currently commonly used pit and fissure sealants cannot visually identify whether they have holes or leaks, and existing pit and fissure sealants cannot accurately identify the range of pits and fissures and directly and accurately fill pits and fissures, as well as directly identify bacterial colonies.

Contents of the invention

The invention provides a pit and fissure sealant containing an indicator and its preparation method and application. The pit and fissure sealant can not only identify with the naked eye whether there are holes and leaks in pits and fissures, but also accurately distinguish the range of pits and fissures. It can accurately fill pits and fissures, and can also help determine the occurrence of bacterial colonies.

In order to achieve the above object, the present invention provides a pit and fissure sealant containing an indicator, including the following mass percentage of raw materials:

Acrylate monomer 20-79%;

Photoinitiator 0.01-1%;

Indicator 0.01-0.6%;

Titanium dioxide 1-16%;

Filling 1-20%;

Wherein, the indicator is composed of a reaction indicator, an acid-base fluorescent indicator and a redox indicator, and the addition amount of each is 0.01-0.2%, so as to identify whether there are loopholes and leaks in pits and fissures with the naked eye. , accurately distinguish the range of pits and fissures, accurately fill pits and fissures, and directly determine the generation of bacterial colonies.

Preferably, the acrylate monomer is selected from the group consisting of bisphenol A glycerol bismethacrylate (BisGMA), triethylene glycol dimethacrylate (TEGDMA), methacrylate (MMA), methyl Hydroxyethyl acrylate (HEMA), urethane dimethacrylate (UDMA), ethoxylated bisphenol A glycerol bismethacrylate (BisEMA), polyethylene glycol acrylate (PEGDMA), 6ethoxy At least one of bisphenol A glycerol bismethacrylate (BisEMA6) and ethylene glycol dimethacrylate (EGDMA).

Preferably, the acrylate monomer is selected from the group consisting of bisphenol A glycerol bismethacrylate, urethane dimethacrylate, triethylene glycol dimethacrylate, and 6-ethoxylated bisphenol A At least one of glycerol bismethacrylate and hydroxyethyl methacrylate.

Preferably, the photoinitiator is selected from camphorquinone, TPO, and benzoin and its derivatives, benzils, alkylphenones, acylphosphorus oxides, benzophenones, and thiaxanthenes At least one photoinitiator of ketones and cationic photoinitiators; preferably, the photoinitiator is camphorquinone.

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; benzoyl is selected from diphenyl ethyl ketone, α , at least one of α-dimethoxy-α-phenylacetophenone; the alkylphenones are selected from α,α-diethoxyacetophenone, α-hydroxyalkylphenone, α- At least one of the amine alkyl benzophenones; the acyl phosphorus oxide is selected from at least one of the aroyl phosphine oxide and bisbenzoylphenyl phosphine oxide; the benzophenones are selected from the group consisting of benzophenone, 2 , at least one of 4-dihydroxybenzophenone and Michler's ketone; thioxanthone is selected from at least one of thioxanthone and isopropyl thioxanthone; cationic The photoinitiator is selected from at least one of diaryliodonium salts, triaryliodonium salts, alkyl iodonium salts, and cumene ferrocene hexafluorophosphoric acid.

Preferably, the photoinitiator also includes an auxiliary photoinitiator selected from the group consisting of ethyl 4-dimethylaminobenzoate (EDMAB) and diphenyliodonium hexafluorophosphate (DPIHP).

Preferably, the reaction indicator is selected from at least one of resazurin, Bengal tiger red, methylene blue, β-carotene, dibromofluorescein, and potato dye 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;

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. species, 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;

The redox indicator is selected from fluorescent yellow, dichlorofluorescent yellow, eosin, bromophenol blue, bromocresol green, xylenol orange, rhodamine 6G, magenta, Congo red, alizarin red S, methyl At least one of red, diphenylamine, o-dimethoxybenzidine and acidic rose bengal, the addition amount is 0.01-0.2%, preferably 0.01-0.05%; preferably, the redox indicator is selected from dichlorofluorescence At least one of yellow, eosin, and bromophenol blue.

Preferably, the titanium dioxide is at least one of rutile titanium dioxide, anatase titanium dioxide, and silica micropowder.

Preferably, the filler is selected from the group consisting of silica powder including at least one of quartz powder, silica powder, and white carbon black, glass powder including quartz barium glass powder, and ytterbium fluoride powder. At least one type has a particle size of 0.1-2um and a silanized surface. A particle size of 0.1-2um and a silanized surface.

The present invention also provides a method for preparing the indicator-containing pit and fissure sealant according to any of the above technical solutions, including the following steps:

Mix acrylate monomer, photoinitiator, indicator, titanium dioxide and filler to obtain a pit and fissure sealant.

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

The present invention also provides a dental composite material, which includes the pit and fissure sealant according to any one of the above technical solutions.

Compared with the existing technology, the advantages and positive effects of the present invention are:

The pit and fissure sealant provided by the present invention cooperates with three indicators to achieve the triple functions of pit and fissure position calibration, damage indication and bacterial colony infection indication, ensuring the effectiveness of pit and fissure protection and caries monitoring in children during the process of pit and fissure implementation. The principle is that three kinds of indicators change colors collaboratively. The reaction indicator mainly provides electron acceptors to monitor the reaction process. The acid-base fluorescent indicator calibrates microorganisms and microbial excreta, especially the calibration of anaerobic organisms. The redox indicator The agent monitors the process involving oxygen during the reaction and calibrates the metabolic process involving oxygen. Combining the optimized composition of the three indicators can ensure that it has a specific indicating effect during the curing, damage and colony infection process, thus enabling the naked eye to identify whether there are holes and leaks in the pits and fissures, and at the same time accurately distinguish the pits and fissures. The range of grooves can be accurately filled in, and the formation of bacterial colonies can be directly determined.

Detailed ways

The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only some of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.

Example 1

Weigh the corresponding masses of acrylate monomers (Bis-GMA, UDMA, TEGDMA, Bis-EMA6), photoinitiators (TPO, DPIHP), reaction indicators (resazurin), and acid-base fluorescent indicators ( 2-Naphthylamine), redox indicator (dichlorofluorescein yellow), titanium dioxide (rutile type, anatase type, silica powder) and filler (white carbon black), mix evenly to obtain a pit and fissure sealant.

Example 2

Weigh the corresponding masses of acrylate monomers (Bis-GMA, UDMA, TEGDMA, Bis-EMA6), photoinitiators (camphorquinone, DPIHP), reaction indicators (resazurin, Bengal tiger red), and acids in Table 1. Alkali fluorescent indicator (salicylic acid), redox indicator (eosin), titanium dioxide (rutile type, anatase type) and filler (silica black, barium glass powder), mix evenly to obtain a pit and fissure sealant .

Example 3

Weigh the corresponding masses of acrylate monomers (Bis-GMA, UDMA, TEGDMA, Bis-EMA6, HEMA), photoinitiators (TPO, DPIHP), reaction indicators (resazurin, Bengal tiger red), Acid-base fluorescent indicator (salicylic acid), redox indicator (dichlorofluorescein yellow), titanium dioxide (rutile type, anatase type) and filler (silica black, barium glass powder), mix evenly to obtain a nest Groove sealants.

Example 4

Weigh the corresponding masses of acrylate monomers (Bis-GMA, UDMA, TEGDMA, Bis-EMA6, HEMA), photoinitiators (camphorquinone, DPIHP), reaction indicators (resazurin), and acid-base fluorescence in Table 1 Mix the indicator (2-naphthylamine), redox indicator (eosin), titanium dioxide (anatase type, silica powder) and filler (white carbon black) evenly to obtain a pit and fissure sealant.

Comparative example 1

Weigh the corresponding masses of acrylate monomers (Bis-GMA, UDMA, TEGDMA, Bis-EMA6), photoinitiator (camphorquinone), reaction indicator (resazurin), and redox indicator (dichloride) in Table 1. Fluorescent yellow), titanium dioxide (rutile type, silica powder) and filler (white carbon black), mix evenly to obtain a pit and fissure sealant.

Comparative example 2

Weigh the corresponding masses of acrylate monomers (Bis-GMA, UDMA, TEGDMA, Bis-EMA6), photoinitiators (camphorquinone, DBMAB), reaction indicators (resazurin, Bengal tiger red), and acids in Table 1. Alkali fluorescent indicator (salicylic acid), titanium dioxide (anatase type) and filler (white carbon black) are mixed evenly to obtain a pit and fissure sealant.

Comparative example 3

Weigh the corresponding masses of acrylate monomers (Bis-GMA, UDMA, TEGDMA, Bis-EMA6), photoinitiators (camphorquinone, DBMAB), acid-base fluorescent indicators (salicylic acid), and redox indicators in Table 1. Agent (dichlorofluorescein yellow), titanium dioxide (rutile type, anatase type, silica powder) and filler (white carbon black), mix evenly to obtain a pit and fissure sealant.

Table 1 Component proportions of each embodiment

Performance Testing

1. Color change of pit and fissure sealant before and after curing

Use a colorimeter to test the pit and fissure sealant before and after curing to compare the color of the pit and fissure sealant to determine the location of the pit and fissure filling.

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

According to the above various chromaticities, the formula can be used Calculate the difference in color ΔE* (maximum value ≥ 2 and ≤ 15), where ΔE* is the difference in chromaticity before and after curing; ΔL* is the difference in L* values before and after curing; Δa* is a* before and after curing The difference in values; Δb* is the difference in b* values before and after curing.

Table 2 Color changes of pit and fissure sealants before and after curing

Combining the data in Table 2, it can be seen that after being illuminated by the curing light, the color of the pit and fissure sealant changed from the original red to milky white, and the red coefficient (a) value dropped significantly. In addition, the brightness dropped, the color changed significantly, and the curing process monitoring was more obvious. . In Comparative Example 2, the content of the reaction indicator is higher, and its discoloration (red coefficient a and yellow coefficient b) is slightly more obvious than that of the other pairs. However, due to the lack of synergy, the overall discoloration is not obvious compared with the examples.

2. Color changes of pit and fissure sealant before and after damage

Use a colorimeter to test the cured pit and fissure sealant. Compare the color of the pit and fissure sealant before and after damage to determine the condition of pit and fissure damage. Soak the damaged pit and fissure sealant in saliva to test the pit and fissure sealant after damage. Color change of the agent.

The chromaticity before pit and fissure sealant is applied is based on the L*a*b* color system and is measured using a colorimeter. L3, a3, and b3 can be used to mark the chromaticity before pit and fissure sealant is damaged; L4, a4, and b4 Can be used to mark the color of damaged pit and fissure sealants;

According to the above various chromaticities, the formula can be used Calculate the difference in color ΔE*, where ΔE* is the difference in chromaticity before and after damage; ΔL* is the difference in L* value before and after damage; Δa* is the difference in a* value before and after damage; Δb* is the difference in L* value before and after damage The difference in b* values.

Table 3 Color changes after pit and fissure sealants are damaged

It can be seen from the data in Table 3 that after damage occurs, the color of the deep layer of the pit and fissure sealant changes, from the original milky white to yellow, and the red coefficient (a) and yellow coefficient (b) values increase significantly. In addition, the brightness decreases, and the color The changes are obvious. The damage situation is displayed more clearly. The deeper the damage, the deeper the color change and the more obvious the color change. The color-changing process requires the synergistic effect of reaction indicators, acid-base and fluorescent indicators. If any indicator is missing, the color-changing effect will not be obvious.

3. Color changes before and after the attachment of pit and fissure sealant colonies

Use the naked eye to test the indicator effect of the caries colony appearance of the pit and fissure sealant, conduct colony culture on the cured pit and fissure sealant, apply the culture medium on the surface of the pit and fissure sealant, and culture the colonies on the culture medium at 37°C After 7 days, determine the situation after the bacterial colonies attach to the pits and fissures, and test the color change of the pit and fissure sealant after the bacterial colonies attach.

Table 4 Color changes of different colonies of pit and fissure sealants

In summary, it can be seen from the above analysis that the pit and fissure sealant provided by the present invention can perform color monitoring of the curing reaction and the damage process, and can more significantly display the degree of reaction and damage, and can indicate bacterial invasion to a certain extent, ensuring that children The effectiveness of pit and fissure protection and caries monitoring during the implementation of pits and fissures. Due to the inclusion of a small amount of fluorescent reaction indicator, some bacterial groups can be identified in the comparative example but within a smaller range. In the embodiment in which sufficient three indicators are added, all bacteria have the identification and indication function mainly because in addition to fluorescent markers, the anti-bacteria labeling ability will be improved with the cooperation of acid-base indicators.

Claims (10)

1. The pit and groove sealing agent containing the indicator is characterized by comprising the following raw materials in percentage by mass:

20-79% of acrylate monomer;

0.01-1% of photoinitiator;

0.01-0.6% of indicator;

1-16% of titanium dioxide;

1-20% of filler;

wherein the indicator consists of a reaction indicator, an acid-base fluorescence indicator and a redox indicator, and the respective addition amount of the indicator is 0.01-0.2%.

2. The pit and fissure blocking agent according to claim 1, wherein the acrylate monomer is selected from at least one of bisphenol a glycerol dimethacrylate, triethylene glycol dimethacrylate, hydroxyethyl methacrylate, urethane dimethacrylate, ethoxylated bisphenol a glycerol dimethacrylate, polyethylene glycol acrylate, 6 ethoxylated bisphenol a glycerol dimethacrylate, ethylene glycol dimethacrylate;

preferably, the acrylate monomer is at least one selected from bisphenol a glycerol dimethacrylate, urethane dimethacrylate, triethylene glycol dimethacrylate, 6 ethoxylated bisphenol a glycerol dimethacrylate and hydroxyethyl methacrylate.

3. The pit and fissure blocking agent according to claim 1, wherein the photoinitiator is selected from camphorquinone, TPO, and at least one of photoinitiators selected from benzoin and derivatives, benzils, alkyl phenones, acyl phosphorus oxides, benzophenones, thioxanthones, and cationic photoinitiators; preferably, the photoinitiator is camphorquinone.

4. A pit and groove sealer according to claim 3 wherein the benzoin and derivative is selected from at least one of benzoin, benzoin dimethyl ether, benzoin diethyl ether, benzoin isopropyl ether, benzoin butyl ether; the benzil is selected from at least one of diphenylethanone and alpha, alpha-dimethoxy-alpha-phenylacetophenone; the alkyl benzene ketone is at least one selected from alpha, alpha-diethoxyacetophenone, alpha-hydroxyalkyl benzene ketone and alpha-amine alkyl benzene ketone; the acyl phosphorus oxide is selected from at least one of aroyl phosphine oxide and dibenzoyl phenyl phosphine oxide; the diphenyl ketone is selected from at least one of diphenyl ketone, 2, 4-dihydroxydiphenyl ketone and Mi ketone; the thioxanthone is at least one selected from thiopropoxy thioxanthone and isopropyl thioxanthone; the cationic photoinitiator is at least one selected from diaryl iodonium salt, triaryliodonium salt, alkyl iodonium salt and isopropylbenzene ferrocene hexafluorophosphoric acid.

5. The pit and groove sealer according to claim 1, wherein the reaction indicator is at least one selected from the group consisting of resazurin, mandshurica red, methylene blue, beta-carotene, dibromofluorescein, and potato red Y, and is added in an amount of 0-0.2%; preferably, the reaction indicator is resazurin and mangash;

the acid-base fluorescence indicator is at least one selected from salicylic acid, 2-naphthylamine, 1-naphthylamine, quinine, 2-hydroxy-3-naphthoic acid, quinoline, 2-naphthol and coumarin, and the addition amount is 0-0.2%; preferably, the acid-base fluorescence indicator is salicylic acid and 2-naphthylamine;

the redox indicator is at least one of fluorescein, dichloro fluorescein, eosin, bromophenol blue, bromocresol green, xylenol orange, rhodamine 6G, fuchsin, congo red, alizarin red S, methyl red, diphenylamine, o-dimethoxy benzidine and acid rose bengal, and the addition amount is 0-0.2%; preferably, the redox indicator is selected from at least one of dichlorofluorescein, eosin, bromophenol blue.

6. The pit and fissure sealer according to claim 1, wherein the titanium white is at least one of rutile titanium white, anatase titanium white, and fine silica powder.

7. The pit and groove sealer according to claim 1, wherein the filler is at least one selected from silica powder including at least one of quartz powder, silica powder, white carbon black, glass powder including Dan Yingbei glass powder, and ytterbium fluoride powder, and has a particle size of 0.1 to 2 μm and a silanized surface.

8. A method of preparing an indicator-containing pit and fissure sealant according to any one of claims 1 to 7, comprising the steps of:

and mixing the acrylate monomer, the photoinitiator, the indicator, the titanium pigment and the filler to obtain the pit and groove sealing agent.

9. Use of a pit and groove blocking agent according to any one of claims 1-7 for pit and groove blocking.

10. A dental composite material, characterized in that it comprises a pit and fissure sealer according to any one of claims 1-7.