CN104398390B - Silane coupling agent and its method are rinsed in dentine primary coat - Google Patents

Abstract

The present invention provides a kind of dentine primary coat and rinses silane coupling agent and its method, described dentine silane coupling agent is the situation that defect of teeth is repaired for the department of stomatology, pretreatment dentin surface is rinsed into the primary coat of dentine silane coupling agent, reapply Self-etching bond agent vertex-gluing graph body and dentine, department of stomatology primary coat rinses dentine silane coupling agent containing 60% 99.4% alcohol water blend, 0.5% 30% faintly acid function monomer and 0.1% 10% NMPIs.Make the slight demineralization of dentine containing weakly acidic 10 MDP；NMPI reduces the degraded of collagenous fibres；The method pretreatment dentine rinsed simultaneously with primary coat; the MDP Ca of generation are made more firmly to be engaged in hydroxyapatite; tooth adhesive strength can further be improved and persistence is bonded; the engagement of tooth and direct or indirect dummy is set more firmly, persistently, preferably to protect the health of tooth body residue tissue.

Description

Dentin primer-rinse primers and methods thereof

technical field

The present invention relates to the field of stomatology, in particular to a class of dentin primer-rinse primer (primer) and method (etch-&-rinse approach). It is used to directly or indirectly bond dental restorations such as organic polymer materials, ceramics, metals or other composite materials to defective teeth.

Background technique

With the continuous development of social economy and culture, people's aesthetic concept is also constantly improving, and countries all over the world are investing more and more in dental beauty and health. The most important content of dental cosmetic restoration is direct resin filling restoration and indirect resin bonding restoration, and these restoration methods all involve a core problem, that is, the bonding of dentin. In the past two decades, dentin adhesives and bonding technology have developed rapidly, and the bonding effect of dentin has been significantly improved. However, the bonding process is a complex physical and chemical process, which not only depends on the structure or state of the adhesive and the bonding interface, the surface treatment technology of the adhesive and the bonding surface, but also the particularity of the oral environment such as Temperature changes, high humidity, microorganisms, proteases, and occlusal stress, as well as degradation of exposed collagen in dentin and degradation of the adhesive itself, all severely affect dentin bond strength and durability.

Water is commonly used as a solvent for most dentin adhesives. In order for the dentin adhesive to have a better ability to wet and/or etch the dentin surface, the concentration of the hydrophilic ionic resin monomer is increased in the adhesive. Since the hydrophilic ionic resin monomer promotes the adsorption of moisture, the higher the concentration of the ionic resin monomer in the adhesive, the less volatile the moisture will be. Moisture retention not only increases the plasticization of the polymer, but also leads to a decrease in the mechanical properties of the polymer and a decrease in the strength of the resin-dentin bond. In addition, the hydrophilic dentin adhesive is also easily affected by the infiltration of water in the dentinal tubules, and the hydrophilic ionic resin monomer contains ester bonds, which are easy to hydrolyze.

Dentin consists of 50% inorganic matter, 30% collagen fibers, and 20% water by volume. The minerals of dentin can be divided into extrafibrillar minerals (separating the collagen fiber bundles) and intrafibrillar minerals (located in the interstices within the fibrils of the procollagen molecules). After demineralization of inorganic substances in dentin fibers, the gaps in collagen fiber microfilaments (microfibril) are about 1.26-1.33 nm, while the smallest functional monomer molecules in the adhesive such as HEMA are about 2.2 nm. Therefore, the three-dimensional structure of the functional monomer molecules in the binder prevents them from completely penetrating into the voids generated by demineralization in the fibers. These spaces are filled with water or proteolytic enzymes, so these collagen fibers are easily hydrolyzed. The biggest difficulty of dentin bonding technology is that the resin monomer cannot completely penetrate into the gaps in the collagen fibers caused by demineralization, resulting in the resin monomer being easily retained on the surface of the mixed layer. Such a dentin bonding interface is less stable and prone to premature fracture.

The acid etching-rinsing or self-etching adhesive systems used in stomatology for dental defect bonding will cause the release of calcium ions in the dentin, thereby activating the matrix metalloproteinases (MMPs) in the dentin. ), MMPs are a group of zinc/calcium-dependent proteases that can degrade the extracellular matrix under neutral conditions ^[4] , thereby causing the degradation of collagen fibers in the adhesive mixed layer and affecting the durability of dentin adhesion ^{[ 5]} .

In our previous research, we also found that phosphate, the main component of self-etching adhesives, can form soluble calcium salts and insoluble calcium salts with hydroxyapatite or enamel, the main component of teeth ^[6] , but these Soluble calcium salts will reduce the bonding strength of enamel ^[7] .

1. Bertassoni LE, Stankoska K, Swain MV. Insights into the structure and composition of the peritubular dentin organic matrix and the laminalimitans [J]. Micron, 2012, 43: 229-236.

2. Liu Y, Tjäderhane L , Breschi L, Mazzoni A, Li N, Mao J, PashleyDH, Tay FR.. Limitations in bonding to dentin and experimental strategies to prevent bond degradation[J]. J Dent Res 2011, 90: 953- 968.

3.Brackett MG, Li N, Brackett, WW, Sword, RJ, Qi YP, Niu LN, PucciCR,Dib A,Pashley DH, Tay FR.. The critical barrier to progress in dentinebonding with the etch-and-rinse technique[ J]. J Dent 2011, 39: 238-248.

4. Pashley DH, Tay FR, Yiu C, et al. Collagen degradation by host-derived enzymes during aging. J Dent Res, 2004, 83:216-222

5. Martin-De Las Heras S, Valenzuela A, Overall CM. The matrixmetalloproteinase gelatinase A in human dentine. Arch Oral Biol, 2000, 45:757-765.

6. Fu B*, Sun X, Qian W, Shen Y, Chen R, Hannig M. Evidence of Chemical bonding to hydroxyapatite by phosphoric acid esters. Biomaterials, 2005, 26:5104-5110.

7. Zhang ZL, Zhang L, Liang B, Tang T, Fu B *, Hannig M. The Contribution of chemical bonding to the short- and long-term enamel bondstrengths. Dental Materials 2013, 29:e103-e112.

Contents of the invention

The problem to be solved by the present invention is to provide a dentin primer-rinsing primer and its method, which can effectively prolong the durability of dentin bonding, thereby improving the service life of remaining tooth tissue and its restorations, and protecting patients Oral dental health.

The present invention is used for the scheme that solves the problem as follows:

A dentin primer-rinsing primer comprises, by mass percentage: 60%-99.4% alcohol aqueous solution, 0.5%-30% weakly acidic functional monomer and 0.1%-10% matrix metalloproteinase inhibitor.

The weight ratio of alcohol to water in the alcohol aqueous solution is 1:1.

The weakly acidic functional monomer is 10-methacryloyloxydecyl phosphate, which can slightly demineralize the superficial layer of the dentin without demineralization within and between the collagen fiber filaments.

The matrix metalloproteinase inhibitor is one of benzalkonium chloride, polyvinyl phosphate, proanthocyanidins, glutaraldehyde or chlorhexidine.

The primer method of the dentin primer is as follows: the dentin primer pretreats the dentin surface for 15-60s, then rinses with water vapor for 30s, and blows dry with an air gun, and then bonds the dentin. Removal of soluble phosphate-hydroxyapatite complexes to enhance the bond strength of dentin.

10-methacryloyloxydecyl phosphate (10-MDP) is a kind of phosphoric acid ester with excellent performance, and the incompatibility calcium salt (MDP-Ca) formed by the reaction with hydroxyapatite (HAp) forms a "nanolayer ” structure, which is strongly adsorbed on the surface of HAp, which can enhance the adhesive performance. The removal of soluble phosphate-hydroxyapatite complexes by rinsing can significantly enhance the bonding strength of dentin, that is, priming-rinsing or etching-rinsing followed by priming-rinsing can be used as a new type of Dental bonding methods.

From the perspective of inhibiting the activity of matrix metalloproteinases, use broad-spectrum collagenase inhibitors such as chlorhexidine, benzalkonium chloride, etc., or graft quaternary ammonium salt groups on monomers, thereby inhibiting the organization of MMPs and cysteine. Protease activity; use collagen fiber crosslinking agents such as glutaraldehyde, anthocyanin, etc., to resist the degradation of collagen by MMPs and cysteine cathepsins; thereby reducing the degradation of collagen fibers, while using polyvinyl phosphate (PVPA) , not only MMPs, but also remineralization of collagen fibers after demineralization, enhancing the stability of the mixed layer, thereby prolonging the durability of dentin bonding.

The beneficial effects of the present invention are that the weakly acidic primer-rinsing dentin primer removes the soluble phosphate-hydroxyapatite complex by washing, and this method can significantly enhance the bonding strength of the dentin; and It can slightly demineralize the surface layer of dentin, the collagen fibers (collagen fibers) are not completely exposed, and hydroxyapatite remains outside the collagen fibers, while intra- and inter-fibrillar collagen ) without demineralization. In this way, the resin monomer does not need to penetrate into the collagen fiber filaments, thereby solving the problem that the resin monomer cannot penetrate into the mixed layer; inhibits the activity of MMPs, reduces the degradation of collagen fibers; and has the mineralization potential of dentin collagen fibers.

Description of drawings

Fig. 1 is the SEM observation figure of control group;

Fig. 2 is the SEM observation figure of embodiment one;

Fig. 3 is the SEM observation figure of embodiment two;

Fig. 4 is the SEM observation picture of embodiment four.

detailed description

A dentin primer-rinsing primer comprises, by mass percentage: 60%-99.4% alcohol aqueous solution, 0.5%-30% weakly acidic functional monomer and 0.1%-10% matrix metalloproteinase inhibitor.

The weight ratio of alcohol to water in the alcohol aqueous solution is 1:1.

The weakly acidic functional monomer is 10-methacryloyloxydecyl phosphate, which can slightly demineralize the superficial layer of the dentin without demineralization within and between the collagen fiber filaments.

The matrix metalloproteinase inhibitor is one of benzalkonium chloride, polyvinyl phosphate, proanthocyanidins, glutaraldehyde or chlorhexidine.

The primer method of the dentin primer is as follows: the dentin primer pretreats the dentin surface for 15-60s, then rinses with water vapor for 30s, and blows dry with an air gun, and then bonds the dentin. Removal of soluble phosphate-hydroxyapatite complexes to enhance the bond strength of dentin.

Primer is used for pretreatment of dentin prior to dentin bonding treatment. Prepare different dentin primers with alcohol aqueous solution (1:1w/w), in which the concentration of 10-MDP is 0.5%-30%wt, the concentration of BAC is 0.5-2%wt, and the concentration of PVPA is 500-3000μg/ml. Alcohol solutions with different concentrations and different pretreatment times of dentin composed of MDP and MMPs inhibitors, such as MDP-BAC alcohol solution, MDP-PVPA alcohol solution, MDP-proanthocyanidin alcohol solution, and different experimental groups. Spread on the surface of the dentin, pretreat the dentin for 15-60 s, rinse with water vapor for 30 s, and blow dry with an air gun. Dentin bonding is then performed.

Embodiment one

Alcohol 47.5%

Water 47.5%

10-MDP 5%

Embodiment two

Alcohol 47%

water 47%

10-MDP 5%wt

BAC 1%wt

Embodiment three

Alcohol 47.5%

Water 47.5%

10-MDP 5%wt

PVPA 1000μg/ml

Effect observation

Micro-tensile strength test (μTBS): before the experiment, the human third molars without cracks, defects, and caries were placed in a water bath at 37°C for 24 hours, and the length of the teeth perpendicular to the crown was cut with a low-speed microtome under running water. 1/3 of the crown was incised to expose 1/3 of the dentin in the crown, polished with 320#SiC on a polishing instrument for 30 s, rinsed with distilled water for 30 s, and set aside. Control group: self-etching adhesive Clearfil S3 Bond was applied to the dentin surface for 20 seconds, blown for more than 5 seconds, light-cured for 10 seconds, and filled with composite resin layer by layer, each layer thickness was 1 mm, a total of 4 layers, each time Light curing 20s. Primer group: apply different dentin primers on the dentin surface, let it stand for 30 s, rinse with water vapor for 30 s, blow dry with an air gun, and then apply the corresponding self-etching adhesive ClearfilS3 Bond to the dentin according to the instructions. 20s for the essential surface, strong blowing for more than 5s, light curing for 10s, and layered filling with composite resin, each layer thickness is about 1mm, a total of 4 layers, each light curing for 20s. Under running water, cut the sample into dentin resin strips of about 1*1*8mm perpendicular to the bonding surface with a slow cutting instrument. Then micro-tensile experiments were carried out using a micro-tensile tester with a tensile speed of 1 mm/min. Use a vernier caliper to measure the length and width of the cross-section of the dentin resin strip, and calculate the bonding surface area. Microtensile strength (μTBS ) was calculated in MPa (Fig. 1). The remaining resin dentin strips were stored in tap water at 37°C, the tap water was replaced once a week, and the micro-tensile strength test was carried out after 6 months.

Table 1

By the values in Table 1, it is found that the micro-tensile strength of Examples one to three after 6 months has no significant change compared with the immediate 24-hour micro-tensile strength value, and the control group without using dentin primer, after 6 months After one month, the micro-tensile strength value decreased significantly. It can be seen that the bonding durability of Examples 1-3 is good, and the 24-hour micro-tensile strength of Examples 1-3 after using the primer agent is improved immediately.

Scanning Electron Microscope Observation of Resin Dentin Mixed Layer

The isolated teeth were treated the same as above. After the control group and the primer group were cut into resin-dentin strips, they were treated in 0.1mol/l hydrochloric acid solution for 2 seconds, rinsed for 30 seconds, fixed with glutaraldehyde, dehydrated in alcohol series, and dried at the critical point. After spraying platinum, the resin-dentin interface was observed by SEM. The other part of the resin-dentin strips was stored for 6 months as above and then observed by SEM.

From Figure 1-Figure 4, it can be seen that the dentin mixed layer in the 24h group is complete and the joint is tight. After 6 months in the control group, there are obvious cracks in the resin-dentin interface observed by SEM, while the resin-dentin interface in Examples 1-3 is continuous It is complete, no obvious cracks are seen, and it has good bonding durability compared with the control group.

Claims (4)

1. a dentin primer-rinsing primer, characterized in that, by mass percent by 60%-99.4% alcoholic water solution, 0.5%-30% weakly acidic functional monomer and 0.1%-10% matrix It is composed of metalloproteinase inhibitors; the weakly acidic functional monomer is 10-methacryloyloxydecyl phosphate, which can slightly demineralize the surface layer of dentin, but not demineralize within and between collagen fiber filaments. 2. dentin primer according to claim 1-rinsing primer, is characterized in that, the weight ratio of alcohol and water in the described alcohol aqueous solution is 1:1. 3. dentin primer-flushing primer according to claim 1, is characterized in that, described matrix metalloproteinase inhibitor is benzalkonium chloride, polyvinyl phosphate, proanthocyanidins, glutaraldehyde or chlorhexidine One of. 4. a non-treatment purpose primer method of dentin primer-rinsing primer as claimed in claim 1, is characterized in that: described dentin primer-rinsing primer pretreatment dentin surface 15- 60s, then rinsed with water vapor for 30s, and dried with an air gun to remove the soluble phosphate-hydroxyapatite complex through rinsing to enhance the bonding strength of dentin.