CN113304054A

CN113304054A - Dental self-acid-etching adhesive with remineralization effect and preparation method thereof

Info

Publication number: CN113304054A
Application number: CN202110574170.0A
Authority: CN
Inventors: 周斌; 刘晓; 李相文
Original assignee: Shaanxi Hengyuan Biotechnology Co ltd
Current assignee: Shaanxi Hengyuan Biotechnology Co ltd
Priority date: 2021-05-25
Filing date: 2021-05-25
Publication date: 2021-08-27

Abstract

The invention provides a dental self-acid etching adhesive with remineralization effect and a preparation method thereof, and the dental self-acid etching adhesive comprises 8.0-10.5% of resin matrix, 5-7% of acid releasing agent, 0.7-1.2% of photoinitiator, 2.8-4.1% of remineralization component and the balance of auxiliary materials. Remineralization components are added into the self-acid-etching adhesive to be cooperated with the acid releasing agent, so that the remineralization of dentin is realized on the basis of reducing dentin sensitivity, the dentin exposure caused by excessive acid etching or mechanical damage in the use process of the self-acid-etching adhesive can be avoided, meanwhile, the remineralization of dentin can be continuously guided for a long time, and the long-term prevention of dentin hypersensitivity can be realized. The self-acid-etching adhesive does not contain fluoride, so that the product is safer, and on the other hand, the self-acid-etching adhesive is a single bottle of self-acid-etching adhesive, has good chemical stability and stronger bonding strength, and can achieve ideal effects when used together with dental materials such as pit and furrow sealants.

Description

Dental self-acid-etching adhesive with remineralization effect and preparation method thereof

Technical Field

The invention belongs to the field of tooth materials, and particularly relates to a dental self-acid-etching adhesive with a remineralization effect and a preparation method thereof.

Background

Current dental acid etching agents can be classified into full acid etching bonding systems and self acid etching bonding systems according to the treatment of the stain layer. The former uses 35% -38% phosphoric acid to remove the dirt layer completely, and the latter partly retains and modifies the dirt layer. The modified staining layer, the dentin demineralization layer and the adhesive form a mixed layer together, so that the purpose of adhesion is achieved. Since the total acid etching adhesive system is susceptible to postoperative sensitivity, it is gradually discarded by most people, and tends to use self-acid etching dentin adhesive. The self-acid etching adhesive is optimized through continuous development and is reduced from the traditional three-step bonding method to form the existing one-step self-acid etching adhesive.

The resin monomer in the self-acid etching adhesive is polymerized and then forms a mixed layer with the dentin collagen fiber net, meanwhile, the resin enters the dentin tubules, so that the dentin tubules are blocked, the influence of mechanical stimulation is weakened, meanwhile, the adhesive seals the dentin surface, the stimulation of drying on the dentin is reduced, and the sensitivity is greatly reduced. However, most of the current self-etching adhesives containing fluorine, such as CN101239024B, are fluorine-containing adhesives, and fluoride has strict control requirements in dental material application, mainly because long-term fluoride intake causes chronic systemic diseases, and especially for children, the fluoride intake is far from harming. And the current self-acid-etching adhesives may cause tooth hypersensitivity due to exposure of dentin caused by excessive acid etching or mechanical damage during use.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a dental self-acid-etching adhesive with a remineralization effect and a preparation method thereof, wherein the dental self-acid-etching adhesive does not contain fluorine, can effectively help remineralization of dentin, avoids tooth hypersensitivity caused by exposure of dentin due to excessive acid etching or mechanical damage in the use process of the self-acid-etching adhesive, can continuously guide remineralization of dentin for a long time, and can prevent the tooth hypersensitivity for a long time.

The invention is realized by the following technical scheme:

a dental self-acid etching adhesive with remineralization effect comprises 8.0-10.5% of resin matrix, 5-7% of acid releasing agent, 0.7-1.2% of photoinitiator, 2.8-4.1% of remineralization component and the balance of auxiliary materials.

Preferably, the resin matrix is one or a mixture of two or more of urethane dimethacrylate, bisphenol A glycerol dimethacrylate, bisphenol A glycidyl methacrylate, bisphenol A vinyl alcohol methyl diacrylate, 2-hydroxy-1, 3-propylene-2-acrylate and glycerol dimethacrylate.

Preferably, the acidic releasing agent is one or a mixture of more than two of 2-acrylamide-2-methylpropanesulfonic acid, 2-methacryloyloxyethyl phosphorylcholine, methacrylic carboxylic acid, dimethylacrylic acid, methylene diphosphonic acid, 10- (2-methacryloyloxy) phosphoric acid monodecanyl ester, 4-methacryloyloxytrimellitic anhydride, biphenyl dimethylacrylic acid and methacrylic acid phosphate.

Preferably, the photoinitiator is one or a mixture of two or more of 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2 ' -methylenebis (4-tert-octyl-6-benzotriazole phenol), camphorquinone, N-dimethyl-p-toluidine, ethyl 4-dimethylaminobenzoate, ethyl 2,4, 6-trimethylbenzoylphenylphosphate, phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide and ethyl 4- (dimethylamino) benzoate.

Preferably, the remineralizing component is one or a mixture of more than two of casein phosphopeptide nano-composite, mesoporous silica, bioactive glass and dendrimer polyamidoamine.

Preferably, the auxiliary materials comprise one or more of reactive diluents, inorganic fillers, co-initiators, thickeners, solvents, stabilizers, polymerization inhibitors and colorants.

Further, the components and contents are shown in the following table:

further, the reactive diluent comprises one or more than two mixed components of 2-hydroxyethyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate and 2-hydroxyethyl methacrylate phosphate; the inorganic filler is one or more than two mixed components of gas-phase silicon dioxide, nano zirconia, alumina, strontium glass powder, barium glass powder and silanized silica.

Furthermore, the auxiliary initiator is one or two mixed components of N, N-dimethylamino ethyl methacrylate and p-dimethylamino isooctyl aminobenzoate.

The preparation method of the dental self-acid etching adhesive with the remineralization effect comprises the following steps:

(1) dissolving the resin matrix in the active diluent, heating, stirring and uniformly mixing;

(2) after the mixture in the step (1) is kept stand and cooled, adding a solvent, fully and uniformly stirring, adding the acidic release agent, the inorganic filler, the thickening agent, the remineralization component, the stabilizer and the coloring agent, and uniformly stirring;

(3) adding the photoinitiator, the initiator aid and the polymerization inhibitor into the mixture obtained in the step (2) in a dark box in a dark place or in a red light environment, and uniformly stirring;

(4) and (4) defoaming the mixture obtained in the step (3) to obtain the dental self-acid etching adhesive with the remineralization effect.

Compared with the prior art, the invention has the following beneficial technical effects:

the dental self-acid-etching adhesive product with the remineralization effect provided by the invention has the advantages that the remineralization component is added into the self-acid-etching adhesive, and the remineralization component and the acid releasing agent are in synergistic effect, so that the remineralization of dentin is realized on the basis of reducing dentin sensitivity, the tooth hypersensitivity caused by exposure of dentin due to excessive acid etching or mechanical damage in the using process of the self-acid-etching adhesive can be avoided, the remineralization of the dentin can be continuously guided for a long time, and the long-term prevention of the dentin hypersensitivity can be realized. The self-acid-etching adhesive does not contain fluoride, so that the product is safer, and on the other hand, the self-acid-etching adhesive is a single bottle of self-acid-etching adhesive, has good chemical stability and stronger bonding strength, and can achieve ideal effects when used together with dental materials such as pit and furrow sealants.

The preparation method of the dental self-etching adhesive product comprises the steps of fully dissolving and mixing the resin matrix and the active diluent, cooling to room temperature after complete mixing, and gradually adding the rest components into the mixture, so that the components of the mixture are uniformly dispersed, and the adverse effect of the preparation process on the components is reduced as much as possible. Thereby making the mechanical properties of the product more excellent.

Drawings

FIG. 1 is a graph comparing the remineralization effectiveness of examples 1-6;

figure 2 is a graph comparing the occlusion effect of dentinal tubules of examples 1-6.

Detailed Description

The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.

The dental self-acid-etching adhesive with the remineralization effect comprises a resin matrix, an active diluent, an acid releasing agent, an inorganic filler, a photoinitiator, an auxiliary initiator, a remineralization component, a thickening agent, a solvent, a stabilizer, a polymerization inhibitor and a coloring agent. Wherein the inorganic filler, the co-initiator and the colorant can be added as appropriate according to the specific conditions of the formulation.

Specifically, the composition ratios are shown in table 1.

TABLE 1 dental self-etching adhesive composition

The resin matrix comprises one or more than two of Urethane Dimethacrylate (UDMA), bisphenol A glycerol dimethacrylate (Bis-GMA), bisphenol A glycidyl methacrylate (Bis-AGM), bisphenol A vinyl alcohol methyl diacrylate (Bis-EMA), 2-acrylic acid-2-hydroxy-1, 3-propylene diester and glyceryl dimethacrylate.

The active diluent comprises one or more than two mixed components of 2-hydroxyethyl methacrylate (HEMA), Ethylene Glycol Dimethacrylate (EGDMA), triethylene glycol dimethacrylate (TEGDMA) and 2-hydroxyethyl methacrylate phosphate.

The acidic releasing agent is one or more than two mixed components of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), 2-Methacryloyloxyethyl Phosphorylcholine (MPC), methacrylic acid, dimethyl acrylic acid, methylene diphosphonic acid, 10- (2-methacryloyloxy) phosphoric acid monodecanyl ester, 4-methacryloyloxy trimellitic anhydride (4-META), biphenyl dimethyl acrylic acid (BPDM) and methacrylic acid phosphate.

The inorganic filler comprises one or more than two mixed components of fumed silica, nano zirconia, alumina, strontium glass powder, barium glass powder and silanized silica.

The photoinitiator comprises one or more than two mixed components of 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2 ' -methylenebis (4-tert-octyl-6-benzotriazole phenol), camphorquinone, N-dimethyl-p-toluidine, ethyl 4-dimethylaminobenzoate (EDAB), ethyl 2,4, 6-trimethylbenzoylphenylphosphate (TPO-L), phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (XBPO) and ethyl 4- (dimethylamino) benzoate (EDMAB).

The coinitiator is one or two of N, N-dimethylamino ethyl methacrylate (DMAEMA) and p-dimethylamino isooctyl benzoate (ODAB).

The remineralization component comprises one or more than two of casein phosphopeptide nano-composite (CPP-ACP), mesoporous silicon dioxide, bioactive glass and dendrimer Polyamidoamine (PAMAM).

The thickener comprises one or more than two of high molecular polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, polyethylene glycol, sodium benzene sulfinate, polyvinyl butyral, xanthan gum and carrageenan.

The solvent comprises one or more of purified water, acetone, tert-butanol, n-butanol, ethanol, isopropanol, dimethyl sulfoxide, dimethylformamide and ethyl acetate.

The stabilizer comprises one or two mixed components of p-hydroxyanisole (MEHQ) and 2, 6-di-tert-butyl-4-methylphenol (BHT).

The polymerization inhibitor comprises one or two of 2, 5-di-tert-butylhydroquinone (DBHQ) and 3, 5-di-tert-butylcatechol (DTBC).

The colorant comprises one or more than two of titanium dioxide, allura red, erythrosine, amaranth, carmine, azofuchsin, brilliant blue, indigo blue, lemon yellow and sunset yellow.

The average particle diameter of the inorganic filler component is shown in table 2 below.

TABLE 2 average particle diameter of inorganic filler component

In the remineralization component, the average particle size of a casein phosphopeptide nano composite (CPP-ACP) is 0.010-0.5 mu m, the average particle size of mesoporous silica is 0.2-0.5 mu m, the average particle size of bioactive glass is 0.1-5 mu m, and dendrimer Polyamidoamine (PAMAM) is a 0-5 generation polymer material comprising hydroxyl, carboxyl and amino terminals.

(2) after the mixture is kept stand and cooled, firstly adding a solvent into the mixture, and after the mixture is fully stirred uniformly, adding the acidic releasing agent, the inorganic filler, the thickening agent, the remineralization component, the stabilizer and the coloring agent into the mixture, and fully stirring to uniformly disperse the solid powder;

(3) adding the photoinitiator, the initiator aid and the polymerization inhibitor into the mixture in a dark box in a dark place or in a red light environment, and uniformly stirring;

(4) and defoaming and filling the prepared mixture to obtain the dental self-acid-etching adhesive with the remineralization effect.

In the step (1), the stirring and mixing conditions are as follows: the temperature is 30-80 ℃, the stirring speed is 500-1500rpm, and the stirring time is 0.5-2 h.

In the step (2), the stirring and mixing conditions are as follows: standing the mixture and cooling to room temperature, initially stirring at 1500-1500 rpm, and increasing the rotation speed to 1000-3000rpm after the solid powder in the components is completely wetted, wherein the stirring time is 0.5-2 h.

In the step (3), the stirring and mixing conditions are as follows: the stirring speed is 1000-3000rpm, and the stirring time is 0.5-2 h.

In the step (3), the wavelength range of the red light is 600-700 nm.

The mixture stirring device used in the preparation method is a planetary stirring device.

The preparation method of the dental self-etching adhesive product comprises the steps of fully dissolving and mixing the resin matrix and the active diluent in a temperature control and specific stirring mode, cooling to room temperature after complete mixing, and gradually adding the rest components into the mixture, so that the components of the mixture are uniformly dispersed, and the adverse effect of the preparation process on the components is reduced as much as possible. Thereby making the mechanical properties of the product more excellent.

Example 1

This example provides a dental self-etching adhesive with remineralization effect, whose components and contents are shown in table 3 below, and a method for preparing the same.

Table 3 composition and content of self-etching adhesive in example 1

The formulation of example 1 is as follows:

(1) the weight of each component was weighed according to the above table according to the formulation amount. Dissolving the weighed resin matrix in an active diluent, heating to 60 ℃, stirring at 800rpm for 30min, and uniformly mixing;

(2) after the mixture is kept stand and cooled, the weighed solvent is added into the mixture, and then the mixture is stirred at 800rpm for 30min and is uniformly mixed. Adding the weighed acid releasing agent, inorganic filler, thickening agent, remineralization component, stabilizing agent and coloring agent into the mixture, starting stirring, starting the initial stirring at the rotation speed of 800rpm, stirring for 10min, increasing the rotation speed to 1200rpm after the solid powder is completely wetted, and stirring for 1h until the solid powder is fully stirred to be uniformly dispersed;

(3) adding weighed photoinitiator, initiator aid and polymerization inhibitor into the mixture in a dark box in a dark place or in a red light environment, and stirring for 30min at the stirring speed of 1200 rpm;

Example 2

This example provides a dental self-etching adhesive with remineralization effect, whose components and contents are shown in table 4 below, and a method for preparing the same.

Table 4 example 2 composition and content of self-etching adhesive

The formulation of example 2 is as follows:

Example 3

This example provides a dental self-etching adhesive with remineralization effect, whose components and contents are shown in table 5 below, and a method for preparing the same.

Table 5 example 3 composition and amount of self-etching adhesive

The formulation of example 3 is as follows:

(2) after the mixture is kept stand and cooled, the weighed solvent is added into the mixture, and then the mixture is stirred at 800rpm for 30min and is uniformly mixed. Adding the weighed acidic releasing agent, inorganic filler, thickening agent, remineralization component and stabilizing agent into the mixture, starting stirring, starting the initial stirring at the rotation speed of 800rpm, stirring for 10min, increasing the rotation speed to 1200rpm after the solid powder is completely wetted, and stirring for 1h until the solid powder is fully stirred to be uniformly dispersed;

(3) adding the weighed photoinitiator and polymerization inhibitor into the mixture in a dark box in a dark place or in a red light environment, stirring at the rotating speed of 1200rpm, and stirring for 30 min;

Example 4

This example provides a dental self-etching adhesive with remineralization effect, whose components and contents are shown in table 6 below, and a method for preparing the same.

Table 6 example 4 composition and amount of self-etching adhesive

The formulation of example 4 is as follows:

Example 5

This example provides a dental self-etching adhesive with remineralization effect, whose components and contents are shown in table 7 below, and a method for preparing the same.

TABLE 7 example 5 composition and amount of self-etching adhesive

The formulation of example 5 is as follows:

Example 6

This example provides a dental self-etching adhesive with remineralization effect, whose components and contents are shown in table 8 below, and a method for preparing the same.

TABLE 8 example 6 composition and amount of self-etching adhesive

The formulation of example 6 is as follows:

FIG. 1 is a graph comparing the remineralization effectiveness of examples 1-6. Fig. 1 shows the remineralization effect of examples 1-6 of the present invention at 3d, 7d, 14d and 21d, respectively, and it can be seen that the mineralization effect of examples 1-6 is more significant over time, and a large amount of mineralized matter is deposited on the dentin surface. From the results of experiment 21d, it can be seen that the remineralization effect was very significant in examples 2, 3,5 and 6, and the mineralized material began to deposit inside the dentinal tubules.

Figure 2 is a graph comparing the occlusion effect of dentinal tubules of examples 1-6. Fig. 2 shows the plugging effect of the examples 1-6 of the present invention on dentinal tubules, and it can be seen from the figures that the examples 1-6 can achieve effective dentin plugging. According to the detection results, the plugging rates of the examples 1 to 6 on the dentinal tubules reach 96.42%, 97.24%, 96.22%, 97.18% and 95.86% respectively. The mean value of the plugging rate reaches more than 96 percent, which shows that the examples 1 to 6 can realize the effective plugging of the dentin tubules.

The results obtained by conducting the high temperature (40 ℃ C.) acceleration test for examples 1 to 6 are shown in Table 9.

Table 9 examples 1-6 accelerated test results for self-etching adhesives

The result shows that the dental self-acid-etching adhesive with the remineralization effect has good product stability, and all the performances of the product are qualified in the high-temperature acceleration experiment, thereby meeting the expected shelf life.

The results of the long-term stability tests conducted on examples 1 to 6 are shown in Table 10.

TABLE 10 long term stability test results for self-acid-etching adhesives of examples 1-6

The result shows that the dental self-acid-etching adhesive with the remineralization effect has good product stability, and all the performances of the product are qualified in detection in a long-term acceleration experiment and meet the expected shelf life.

The performance of the examples is compared with the performance of the similar products sold in the market, and the shear bonding strength and the tensile bonding strength of the examples 1 to 6 and the similar products sold in the market are respectively detected and compared according to the detection methods and the performance requirements of YY/T0518-. The results are shown in Table 11.

TABLE 11 EXAMPLES 1-6 evaluation of the Performance of the self-etching adhesives and commercial products

According to the experimental results, comprehensively, compared with the commercial products, the dental self-acid etching adhesive product with the remineralization effect has greatly optimized and improved shear bonding strength and tensile bonding strength.

The above-mentioned embodiments are merely preferred embodiments of the present invention, and are not intended to be specific protection schemes. It should be noted that several optimizations and modifications made without departing from the principles of the present invention are also considered within the scope of the present invention by those skilled in the art.

Claims

1. A dental self-acid etching adhesive with remineralization effect is characterized by comprising 8.0-10.5% of resin matrix, 5-7% of acid release agent, 0.7-1.2% of photoinitiator, 2.8-4.1% of remineralization component and the balance of auxiliary materials.

2. The dental self-etching adhesive with remineralizing effect according to claim 1, wherein the resin matrix is one or a mixture of two or more of urethane dimethacrylate, bisphenol-A glycerol dimethacrylate, bisphenol-A glycidyl methacrylate, bisphenol-A vinyl alcohol methyl diacrylate, 2-propenoic acid-2-hydroxy-1, 3-propane diester and glyceryl dimethacrylate.

3. The dental self-etching adhesive with remineralization effect as claimed in claim 1, wherein the acid releasing agent is one or more of 2-acrylamido-2-methylpropanesulfonic acid, 2-methacryloyloxyethyl phosphorylcholine, methacrylic carboxylic acid, dimethylacrylic acid, methylenediphosphonic acid, 10- (2-methacryloyloxy) monodecanyl phosphate, 4-methacryloyloxytrimellitic anhydride, biphenyldimethylacrylic acid, and methacrylic acid phosphate.

4. The dental self-etching adhesive having a remineralizing effect according to claim 1, wherein the photoinitiator is one or a mixture of two or more of 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2 ' -methylenebis (4-tert-octyl-6-benzotriazolylphenol), camphorquinone, N-dimethyl-p-toluidine, ethyl 4-dimethylaminobenzoate, ethyl 2,4, 6-trimethylbenzoylphenylphosphate, phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, and ethyl 4- (dimethylamino) benzoate.

5. The dental self-etching adhesive with remineralization effect as claimed in claim 1, wherein the remineralization component is one or more of casein phosphopeptide nanocomposite, mesoporous silica, bioactive glass and dendrimer polyamidoamine.

6. The dental self-etching adhesive with remineralization effect as claimed in claim 1, wherein the auxiliary materials include one or more of reactive diluents, inorganic fillers, co-initiators, thickeners, solvents, stabilizers, polymerization inhibitors and coloring agents.

7. The dental self-etching adhesive with remineralization effect of claim 6, wherein the components and contents thereof are as shown in the following table:

8. the dental self-etching adhesive with remineralization effect as claimed in claim 6, wherein the reactive diluent comprises one or more of 2-hydroxyethyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate and 2-hydroxyethyl methacrylate phosphate; the inorganic filler is one or more than two mixed components of gas-phase silicon dioxide, nano zirconia, alumina, strontium glass powder, barium glass powder and silanized silica.

9. The dental self-etching adhesive with remineralizing effect according to claim 6, wherein the co-initiator is one or two of N, N-dimethylamino ethyl methacrylate and iso-octyl p-dimethylaminobenzoate.

10. A method for preparing a dental self-etching adhesive having a remineralizing effect according to any one of claims 6 to 9, comprising the steps of: