Dental acid-resistant glass powder as well as preparation method and application thereof

Abstract

The invention discloses dental acid-resistant glass powder, which belongs to the technical field of dental materials and comprises the following raw materials: 40 to 65 weight percent of silicon dioxide, 20 to 40 weight percent of barium carbonate, 2 to 13 weight percent of boric oxide, 6 to 15 weight percent of aluminum oxide, 0 to 4 weight percent of magnesium oxide, 0 to 2 weight percent of zinc oxide and 1 to 5 weight percent of sodium oxide. The invention further discloses a preparation method of the dental acid-resistant glass powder. The preparation method comprises the steps of raw material mixing, melting, ball milling, acid etching treatment, silanization treatment and drying. The dental acid-resistant glass powder disclosed by the invention has the characteristics of good compatibility with resin, high hardness, good transparency, good X-ray resistance and good acid resistance, and is particularly suitable for being used as a filler in acidic dental materials such as a dental self-acid etching adhesive, a dental self-adhesive resin cement, a dual-curing resin cement and the like; and long-term coexistence with an acidic monomer of a dental material can be realized.

Description

Technical Field

[0001] The invention belongs to the technical field of dental materials, and in particular relates to an acid-resistant glass powder for dentistry and a preparation method and application thereof. Background Art

[0002] Dental resin materials are generally composed of resin matrix, fillers, curing aids, etc. The fillers are generally required to have good bonding with the resin and have good transparency, X-ray radiopacity and good reinforcement properties.

[0003] Glass powder is widely used as a filler in dental materials because of its advantages of high hardness, good transparency, diverse morphology, good reinforcement, and controllable particle size. It is often used as a filler in dental products such as dental composite resins, dental adhesives, and resin cements to enhance the mechanical properties of the materials and give the materials X-ray radiopacity, making it easier to detect the repair effect of the materials with an X-ray machine after oral restoration.

[0004] At present, more and more resin materials use adhesive monomers to enhance the hydrophilicity of the product and the adhesion to teeth, such as phosphate esters and anhydride materials, which generally have a certain acidity; the addition of adhesive monomers has put forward new requirements for glass powder fillers, because general glass powder is ordinary silicate glass with a certain alkalinity. When it coexists with acidic monomers for a long time (for example, commercial products require a shelf life of at least 18 months), acid-base neutralization will occur, affecting the stability of the product.

[0005] Although other types of fillers such as silica and alumina do not have the acid resistance problem, they do not have radiopacity and cannot meet the requirements of X-ray radiopacity of the product. In addition, if radiopacity materials such as barium carbonate and barium sulfate are directly used as fillers, although the radiopacity requirements are met, because barium carbonate and barium sulfate cannot be modified with silane coupling agents on the surface like glass powder, silica, alumina and other fillers, they are not tightly combined with the resin material after addition, which affects the final strength of the product and is not suitable as a filler for dental resin materials.

[0006] Therefore, it is necessary to consider improving the acid resistance of glass powder. Acid-resistant glass powder is already available in the prior art. For example, patent CN104944788 A discloses a glass powder for all-ceramic dental porcelain and its preparation method, which claims that it has good acid resistance, but the application scenario of its glass powder for all-ceramic dental porcelain is to resist the short-term weak acid environment in the oral cavity. In addition, patent CN 105731812 A discloses a lead-free low softening point acid-resistant glass powder for chip component slurry and its preparation method, which introduces that its glass powder has acid resistance, but the application scenario is to prevent it from producing adverse reactions when it comes into contact with the electroplating solution for a short time.

[0007] However, the glass powder used in dental resin materials needs to coexist with the acidic monomer for a long time for at least 18 months. Therefore, the acid-resistant glass powder in the prior art is not suitable as a filler for dental resin materials. In dental resin materials, glass powder needs to consider more about not having adverse effects on the acidic monomer and the entire material for a long time, thereby affecting product performance. For example, if glass powder is added to dental self-adhesive resin cement products and partially neutralized with the acidic monomer, the acidity of the self-adhesive resin cement product will be reduced, and the self-etching performance will be reduced when used by dentists, which will reduce the overall bonding strength and affect tooth restoration. In addition, compatibility with the resin and X-ray radiopacity need to be considered. Summary of the invention

[0008] In view of one or more of the above defects or improvement needs in the prior art, the present invention provides an acid-resistant glass powder for dentistry and a preparation method thereof, which can coexist with the acid monomer of dental materials for a long time.

[0009] According to one aspect of the present invention, there is provided a dental acid-resistant glass powder, the raw materials of which include

[0010] 40-65wt% silicon dioxide, 20-40wt% barium carbonate, 2-13wt% boron oxide, 6-15wt% aluminum oxide, 0-4wt% magnesium oxide, 0-2wt% zinc oxide, and 1-5wt% sodium oxide.

[0011] As a further improvement of the present invention, the average particle size of each raw material of the dental acid-resistant glass powder is 0.5 to 50 μm.

[0012] According to a second aspect of the present invention, a method for preparing an acid-resistant glass powder for dental use is provided, which is used to prepare the acid-resistant glass powder for dental use, comprising the following steps:

[0013] (1) Mixing: weighing the raw materials according to the weight percentage and mixing them uniformly;

[0014] (2) Melting: Melting the mixed raw materials and cooling them to room temperature to obtain a transparent glass block;

[0015] (3) ball milling: ball milling the transparent glass block to a desired particle size to obtain glass powder;

[0016] (4) Acid etching: The obtained glass powder is subjected to acid etching treatment with a boric acid solution, and after washing and drying, the acid-etched glass powder is obtained;

[0017] (5) Silanization treatment: The acid-etched glass powder is silanized using a silane coupling agent, and then washed, dried, and sieved to obtain the acid-resistant dental glass powder.

[0018] As a further improvement of the present invention, in step (2), the melting temperature is 1400-1800° C., and the melting time is 4-12 hours.

[0019] As a further improvement of the present invention, in step (3), the particle size of the glass powder is 0.5 to 15 μm.

[0020] As a further improvement of the present invention, in step (4), the acid etching treatment specifically includes the following steps: adding the glass powder obtained in step (3) to a boric acid solution with a mass concentration of 5% to 10%, and the mass ratio of the glass powder to the boric acid solution is 1:1 to 1:2; heating to 70 to 90°C, maintaining for 2 to 6 hours, centrifuging and washing, and drying to obtain the acid-etched glass powder.

[0021] As a further improvement of the present invention, in step (5), the silane coupling agent includes one or more of KH570, KH550, KH792, and A151.

[0022] As a further improvement of the present invention, in step (5), the silanization treatment specifically comprises the following steps:

[0023] Add the silane coupling agent to a 50% mass concentration ethanol aqueous solution, adjust the solution pH to 2-3, and heat to 60-80°C for pre-hydrolysis;

[0024] Add acid-etched glass powder, heat to 70-90°C, react for 4 hours, centrifuge and wash, dry and sieve to obtain acid-resistant glass powder;

[0025] The mass of the silane coupling agent is 2-15% of the mass of the glass powder; the mass of the ethanol aqueous solution is 1-2 times of the mass of the glass powder.

[0026] According to a third aspect of the present invention, there is provided a use of dental acid-resistant glass powder as a filler in an acidic dental material, the dental acid-resistant glass powder being used or the dental acid-resistant glass powder being obtained by the preparation method.

[0027] In general, the above technical solution conceived by the present invention has the following beneficial effects compared with the prior art:

[0028] The acid-resistant glass powder for dentistry of the present invention improves the existing glass formula, increases the content of acid-resistant materials such as silicon dioxide, magnesium oxide, zinc oxide, reduces the alkaline raw materials such as sodium oxide and potassium oxide in the material, and adds boron oxide to facilitate the firing of the vitreous body and suppress the overflow of alkali metal ions. When preparing the acid-resistant glass powder for dentistry, the surface activity of the glass is further reduced by acid etching, which is conducive to the long-term coexistence of the glass powder and the acidic monomer, and the compatibility of the glass powder and the resin matrix can be further improved by silanization. The prepared glass powder has the characteristics of good compatibility with resin, high hardness, good transparency, X-ray resistance, and good acid resistance, and is suitable for materials such as dental resins, dental adhesives, and resin cements as fillers, and is particularly suitable for dental self-etching adhesives, dental self-adhesive resin cements, dual-curing resin cements and other acidic dental materials as fillers, and can coexist with the acidic monomers of dental materials for a long time. DETAILED DESCRIPTION

[0029] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0030] The invention provides an acid-resistant glass powder for dentistry. The raw materials of the glass powder include 40-65wt% of silicon dioxide, 20-40wt% of barium carbonate, 2-13wt% of boron oxide, 6-15wt% of aluminum oxide, 0-4wt% of magnesium oxide, 0-2wt% of zinc oxide and 1-5wt% of sodium oxide.

[0031] More preferably, the raw materials of the dental acid-resistant glass powder include 45-65wt% silicon dioxide, 20-35wt% barium carbonate, 5-13wt% boron oxide, 8-15wt% aluminum oxide, 0-2wt% magnesium oxide, 0-1wt% zinc oxide, and 1-2wt% sodium oxide.

[0032] In the glass powder raw material of the embodiment of the present invention, the content of silicon dioxide is at least 40%, preferably at least 50%. The content of silicon dioxide has a beneficial effect on the required property of acid resistance.

[0033] In the glass powder raw material of the embodiment of the present invention, the content of aluminum oxide is 6-15%, and aluminum oxide forms aluminum silicate together with silicon dioxide, and its solubility product constant is much lower than the solubility product constant of calcium silicate in general glass, which can form a more stable basic glass structure.

[0034] In the glass powder raw material of the embodiment of the present invention, the content of barium carbonate is 20-40%, which can give the prepared glass powder X-ray opacity.

[0035] Furthermore, in order to facilitate the molding of glass and improve acid resistance, the glass powder raw material of the embodiment of the present invention contains 2-13% boron oxide, preferably 5-13%, and more preferably 5-8%; boron oxide is an acidic oxide, which can bond with the sodium ions in sodium oxide to form glassy borates and metaborates. Thereby, the sodium ions are more firmly present in the glass structure, improving the acid resistance of the glass. However, the boron oxide content should not be too high, as too high a content will affect the hydrolysis stability of the glass.

[0036] In addition, compared with the traditional silicate glass of sodium calcium silicate, sodium aluminum silicate and sodium borosilicate, only a small amount of sodium is added to the glass of the present invention, because sodium silicate is a strong base weak acid salt, which is not conducive to the stability of glass under acidic conditions. In addition, 0-2% magnesium oxide and 0-1% zinc oxide are added to the raw materials of the embodiment of the present invention, and a small amount of Mg and Zn can also improve the acid resistance of the product.

[0037] The present invention also provides a method for preparing an acid-resistant glass powder for dental use, comprising the following steps:

[0038] (1) Mixing: Weigh the above raw materials according to their weight percentage and mix them evenly;

[0039] (2) Melting: Melting the mixed raw materials and cooling them to room temperature to obtain a transparent glass block;

[0040] (3) Ball milling: ball milling the transparent glass block to the desired particle size to obtain glass powder;

[0041] (4) Acid etching: The obtained glass powder is subjected to acid etching treatment with a boric acid solution, and after washing and drying, the acid-etched glass powder is obtained;

[0042] (5) Silanization treatment: The acid-etched glass powder is silanized (hydrophobicized) using a silane coupling agent, washed, dried, and sieved to obtain an acid-resistant glass powder for dental use.

[0043] The glass powder of the embodiment of the present invention is subjected to an acid etching treatment with a boric acid solution. Boric acid is a weak acid that can react with alkali metals on the surface of the glass to further reduce the surface activity of the glass, thereby facilitating the long-term coexistence of the glass powder and the acidic monomer. In addition, the acid etching treatment can also increase the roughness of the surface of the glass powder and improve its compatibility and adhesion with the resin matrix.

[0044] The glass powder of the embodiment of the present invention is subjected to silanization treatment, and a coupling agent is used to form chemical bonds on the surface of the acid-etched glass powder, which can further improve the compatibility of the glass powder with the resin matrix.

[0045] Preferably, in step (2), the melting temperature is 1400-1800° C., and the melting time is 4-12 hours.

[0046] Preferably, in step (3), the particle size of the glass powder is 0.5 to 15 μm.

[0047] Preferably, in step (4), the acid etching treatment specifically comprises the following steps: adding the glass powder obtained in step (3) to a boric acid solution with a mass concentration of 5% to 10%, wherein the mass ratio of the glass powder to the boric acid solution is 1:1 to 1:2; heating to 70 to 90° C., maintaining for 2 to 6 hours, centrifuging and washing, and drying to obtain the acid-etched glass powder.

[0048] Preferably, in step (5), the silane coupling agent includes one or more of KH570, KH550, KH792, and A151. The silanization treatment specifically includes the following steps:

[0049] Add the silane coupling agent to a 50% mass concentration ethanol aqueous solution, adjust the solution pH to 2-3, and heat to 60-80°C for pre-hydrolysis;

[0050] Adding acid-etched glass powder, heating to 70-90°C, reacting for 4 hours, centrifuging and washing, drying and sieving to obtain acid-resistant glass powder; drying and sieving to obtain dental acid-resistant glass powder;

[0051] The silane coupling agent is 2-15% of the mass of the glass powder; and the mass of the ethanol aqueous solution is 1-2 times of the mass of the glass powder.

[0052] In a specific embodiment of the present invention, the method for preparing the above-mentioned acid-resistant glass powder for dental use comprises the following steps:

[0053] (1) Mixing: weigh the raw materials according to the weight percentage and mix them evenly in a mixer;

[0054] (2) Melting: Pour the mixed raw materials into a corundum crucible and melt them in a high-temperature resistance furnace at a melting temperature of 1400 to 1800°C for 4 to 12 hours. Then, cool them naturally to room temperature in the resistance furnace to obtain a transparent glass block.

[0055] (3) Ball milling: taking out the cooled transparent glass block and ball milling it to a particle size of 0.5 to 15 μm to obtain glass powder;

[0056] (4) Acid etching treatment: adding the obtained glass powder to a boric acid solution having a mass concentration of 5% to 10%, wherein the mass ratio of the glass powder to the boric acid solution is 1:1 to 1:2; heating to 70 to 90° C., maintaining for 2 to 6 hours, centrifuging and washing, and drying to obtain the acid-etched glass powder;

[0057] (5) Silanization treatment: add a silane coupling agent to a 50% mass concentration of ethanol aqueous solution, adjust the solution pH to 2-3, and heat to 60°C-80°C for pre-hydrolysis; add the acid-etched glass powder, heat to 70-90°C, react for 4 hours, centrifuge and wash, dry and sieve to obtain acid-resistant glass powder; dry and sieve to obtain dental acid-resistant glass powder; the silane coupling agent is 2-15% of the mass of the glass powder; the mass of the ethanol aqueous solution is 1-2 times the mass of the glass powder, that is, the ratio of the mass of the ethanol aqueous solution to the mass of the glass powder is 1:1-2:1.

[0058] The following are specific embodiments:

[0059] Unless otherwise specified, all the following components are in mass percentages, the water used is deionized water, and the test environment conditions are 23±2°C and 50±5% relative humidity.

[0060] Example 1

[0061] In this embodiment, the raw materials of the dental acid-resistant glass powder include:

[0062] 50% silicon dioxide, 30% barium carbonate, 8% boron oxide, 8.2% aluminum oxide, 2% magnesium oxide, 0.3% zinc oxide, 1.5% sodium oxide.

[0063] The preparation method of the dental acid-resistant glass powder in this embodiment is:

[0064] (1) Mixing: Mix the raw materials according to the weight percentage in a V-type mixer for 10 minutes to make the raw materials uniform;

[0065] (2) Melting: Pour the mixed materials into a corundum crucible and melt them in a high-temperature resistance furnace at a melting temperature of 1550°C for 4 hours. Then, cool them naturally to room temperature in the resistance furnace. After cooling, the sample is a transparent glass block.

[0066] (3) Ball milling: Take out the cooled transparent glass block and ball mill it into glass powder with a particle size of 5 μm;

[0067] (4) Acid etching treatment: The obtained glass powder is added to a boric acid solution with a mass concentration of 8%, and the mass ratio of the glass powder to the boric acid solution is 1:1; the glass powder is heated to 75° C., maintained for 4 hours, and then centrifuged and washed, and then dried to obtain the acid-etched glass powder.

[0068] (5) Silanization treatment: add silane coupling agent KH570 to 50% mass concentration of ethanol aqueous solution, adjust the solution pH to 2, and heat to 70°C for pre-hydrolysis; add acid-etched glass powder, heat to 80°C, react for 4 hours, centrifuge and wash, dry and sieve to obtain acid-resistant glass powder; the mass of silane coupling agent is 10% of the mass of glass powder; the mass ratio of ethanol aqueous solution to glass powder is 1:1.

[0069] Example 2

[0070] In this embodiment, the raw materials of the dental acid-resistant glass powder include: 45wt% silicon dioxide, 30% barium carbonate, 8.8% boron oxide, 13% aluminum oxide, 0.2% magnesium oxide, 1% zinc oxide, and 2% sodium oxide.

[0071] The preparation method of the dental acid-resistant glass powder in this embodiment is:

[0072] (1) Mixing: Mix the raw materials according to the weight percentage in a V-type mixer for 10 minutes to make the raw materials uniform;

[0073] (2) Melting: Pour the mixed materials into a corundum crucible and melt them in a high-temperature resistance furnace at a melting temperature of 1650°C for 4 hours. Then, cool them naturally to room temperature in the resistance furnace. After cooling, the sample is a transparent glass block.

[0074] (3) Ball milling: Take out the cooled transparent glass block and ball mill it into glass powder with a particle size of 10 μm;

[0075] (4) Acid etching treatment: The obtained glass powder is added to a 5% mass concentration boric acid solution, and the mass ratio of the glass powder to the boric acid solution is 1:2; the glass powder is heated to 70° C., maintained for 6 hours, and then centrifuged and washed, and then dried to obtain the acid-etched glass powder.

[0076] (5) Silanization treatment: Add silane coupling agent KH570 to ethanol aqueous solution, adjust the solution pH to 2, and heat to 80°C for pre-hydrolysis; add acid-etched glass powder, heat to 70°C, react for 4 hours, centrifuge and wash, dry and sieve to obtain acid-resistant glass powder; the mass of silane coupling agent is 8% of the mass of glass powder; the mass ratio of ethanol aqueous solution to glass powder is 2:1.

[0077] Example 3

[0078] In this embodiment, the raw materials of the dental acid-resistant glass powder include: 46wt% silicon dioxide, 35% barium carbonate, 6.5% boron oxide, 10% aluminum oxide, 0.2% magnesium oxide, 0.3% zinc oxide, and 2% sodium oxide.

[0079] The preparation method of the dental acid-resistant glass powder in this embodiment is:

[0080] (1) Mixing: Mix the raw materials according to the weight percentage in a V-type mixer for 10 minutes to make the raw materials uniform;

[0081] (2) Melting: Pour the mixed materials into a corundum crucible and melt them in a high-temperature resistance furnace at a melting temperature of 1600°C for 4 hours. Then, cool them naturally to room temperature in the resistance furnace. After cooling, the sample is a transparent glass block.

[0082] (3) Ball milling: Take out the cooled transparent glass block and ball mill it into glass powder with a particle size of 15 μm;

[0083] (4) Acid etching treatment: The obtained glass powder is added to a 10% mass concentration boric acid solution, and the mass ratio of the glass powder to the boric acid solution is 1:1; the glass powder is heated to 80° C., maintained for 3 hours, and then centrifuged and washed, and then dried to obtain the acid-etched glass powder.

[0084] (5) Silanization treatment: Add silane coupling agent KH570 to ethanol aqueous solution, adjust the solution pH to 3, and heat to 60°C for pre-hydrolysis; add acid-etched glass powder, heat to 90°C, react for 4 hours, centrifuge and wash, dry and sieve to obtain acid-resistant glass powder; the mass of silane coupling agent is 6% of the mass of glass powder; the mass ratio of ethanol aqueous solution to glass powder is 1:1.

[0085] Comparative Example 1

[0086] In this comparative example, the raw materials of the glass powder include: 35wt% silicon dioxide, 14% barium carbonate, 15% boron oxide, 25% aluminum oxide, 1% zinc oxide, and 10% sodium oxide.

[0087] The preparation method of the glass powder in this comparative example is:

[0088] (1) Mixing: Mix the raw materials according to the weight percentage in a V-type mixer for 10 minutes to make the raw materials uniform;

[0089] (2) Melting: Pour the mixed materials into a corundum crucible and melt them in a high-temperature resistance furnace at a melting temperature of 1550°C for 4 hours. Then, cool them naturally to room temperature in the resistance furnace. After cooling, the sample is a transparent glass block.

[0090] (3) Ball milling: Take out the cooled transparent glass block and ball mill it into glass powder with a particle size of 5 μm;

[0091] (4) Acid etching treatment: The obtained glass powder is added to a boric acid solution with a mass concentration of 8%, and the mass ratio of the glass powder to the boric acid solution is 1:1; the glass powder is heated to 75° C., maintained for 4 hours, and then centrifuged and washed, and then dried to obtain the acid-etched glass powder.

[0092] (5) Silanization treatment: add silane coupling agent KH570 to 50% mass concentration of ethanol aqueous solution, adjust the solution pH to 2, and heat to 70°C for pre-hydrolysis; add acid-etched glass powder, heat to 80°C, react for 4 hours, centrifuge and wash, dry and sieve to obtain acid-resistant glass powder; the mass of silane coupling agent is 10% of the mass of glass powder; the mass ratio of ethanol aqueous solution to glass powder is 1:1.

[0093] Comparative Example 2

[0094] In this comparative example, the raw materials of the glass powder include:

[0095] 50% silicon dioxide, 30% barium carbonate, 8% boron oxide, 8.2% aluminum oxide, 2% magnesium oxide, 0.3% zinc oxide, 1.5% sodium oxide.

[0096] (1) Mixing: Mix the raw materials according to the weight percentage in a V-type mixer for 10 minutes to make the raw materials uniform;

[0097] (2) Melting: Pour the mixed materials into a corundum crucible and melt them in a high-temperature resistance furnace at a melting temperature of 1550°C for 4 hours. Then, cool them naturally to room temperature in the resistance furnace. After cooling, the sample is a transparent glass block.

[0098] (3) Ball milling: Take out the cooled transparent glass block and ball mill it into glass powder with a particle size of 5 μm;

[0099] (4) Silanization treatment: adding silane coupling agent KH570 to 50% mass concentration of ethanol aqueous solution, adjusting the solution pH to 2, heating to 70°C for pre-hydrolysis; adding the glass powder in step (3), heating to 80°C, reacting for 4 hours, centrifuging and washing, drying and sieving to obtain acid-resistant glass powder; the mass of the silane coupling agent is 10% of the mass of the glass powder; the mass ratio of the ethanol aqueous solution to the mass of the glass powder is 1:1.

[0100] The products prepared in each embodiment and comparative example were tested for X-ray radioactivity, particle size D50, hydrophobicity and acid resistance. The testing method is:

[0101] (1) X-ray opacity: The prepared glass powder was pressed into a sheet with a thickness of 1±0.1 mm using a tablet press at 5 MPa for 60 seconds. The sheet was tested using the X-ray opacity test method in the appendix of "YY 0127.2-2016 Dental Water-Based Cement Part 2: Resin-Modified Cement". If the thickness of the equivalent aluminum plate tested was ≥1 mm, the material was X-ray opaque.

[0102] (2) Particle size D50: The particle size of glass powder is measured using a laser particle size analyzer.

[0103] (3) Hydrophobicity: Take a 10mL test tube and place it vertically. Add 7mL of deionized water. Weigh 0.10g of glass powder sample, accurate to 0.1mg. Spread it evenly on the liquid surface and shake it slightly (the powder should not aggregate). Add anhydrous ethanol dropwise on the sample powder until the sample is completely immersed in the deionized water. Record the mass of anhydrous ethanol used. If the amount of anhydrous ethanol is ≥0.07g, it means that the material is hydrophobic.

[0104] (4) Acid resistance: Accurately weigh 10g of dried glass powder, record the mass as a0, add it into a conical flask containing 100ml of 0.1mol / l hydrochloric acid solution: anhydrous ethanol = 8:2, soak it in a 37℃ water bath for 6h, then centrifuge and dry it, record the mass of the sample after the test as a1, and calculate the acid resistance = a1 / a0*100%. The results are shown in Table 1 below.

[0105] Table 1 Performance test results of the products of the embodiments and comparative examples

[0106]

[0107] It can be seen that the glass powders prepared in Examples 1 to 3 are all X-ray-blocking and hydrophobic, and their acid resistance is greater than 99.5%. Comparative Example 1 has low barium carbonate content, and according to the standard test method, it does not have X-ray blocking properties. At the same time, other components are not within the scope specified in this application, and the acid resistance is poor. There is a higher risk of long-term coexistence with acidic resin materials. Comparative Example 2 has X-ray blocking and hydrophobic properties, but because it is not acid-etched, its acid resistance is worse than that of the sample that has been acid-etched.

[0108] Furthermore, the glass powder prepared in Example 1 and the glass powder prepared in Comparative Examples 1 and 2 were added to dental self-adhesive resin cement products to obtain Products 1 to 3 (the formulas are shown in Tables 2 to 4 below, respectively).

[0109] Table 2 Formulation of Product 1

[0110]

[0111]

[0112] Table 3 Formulation of Product 2

[0113]

[0114] Table 4 Formulation of Product 3

[0115]

[0116] The bonding strength between tooth enamel and composite resin of products 1 to 3 was tested with reference to the standard "YY 0519-2022 Bonding Test of Dentistry and Tooth Structure". Products 1 to 3 were prepared according to the formulas in Tables 2 to 4 above, and their appearance was observed and their bonding strength was tested when newly prepared and after 18 months of storage. The results are shown in Table 5 below:

[0117] Table 5 Performance test results of products 1 to 3

[0118]

[0119] The results show that products 1 to 3 have good performance before storage. After 18 months of storage, products 2 and 3 become darker in color and have slight color inhomogeneity, and the bonding strength is significantly reduced, indicating that the glass powder prepared in Comparative Examples 1 and 2 reacts with the acidic monomer (methacrylic acid phosphate) during long-term coexistence, causing the appearance of products 2 and 3 to change, and the bonding strength to decrease. However, product 1 has no significant color change after 18 months of storage, and still has a high bonding strength, indicating that the glass powder of Example 1 of the present invention has a long-term acid resistance effect.

[0120] It will be easily understood by those skilled in the art that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A dental acid-resistant glass powder, characterized in that: Its raw materials include: 40-65wt% silicon dioxide, 20-40wt% barium carbonate, 2-13wt% boron oxide, 6-15wt% aluminum oxide, 0-4wt% magnesium oxide, 0-2wt% zinc oxide, and 1-5wt% sodium oxide.

2. The acid-resistant glass powder for dentistry according to claim 1, characterized in that: The average particle size of each raw material of the dental acid-resistant glass powder is 0.5 to 50 μm.

3. A method for preparing an acid-resistant glass powder for dental use, for preparing the acid-resistant glass powder for dental use according to claim 1 or 2, characterized in that: The steps include: (1) Mixing: weighing the raw materials according to the weight percentage and mixing them uniformly; (2) Melting: Melting the mixed raw materials and cooling them to room temperature to obtain a transparent glass block; (3) ball milling: ball milling the transparent glass block to a desired particle size to obtain glass powder; (4) Acid etching: The obtained glass powder is subjected to acid etching treatment with a boric acid solution, and after washing and drying, the acid-etched glass powder is obtained; (5) Silanization treatment: The acid-etched glass powder is silanized using a silane coupling agent, and then washed, dried, and sieved to obtain the acid-resistant dental glass powder.

4. The method for preparing the acid-resistant glass powder for dental use according to claim 3, characterized in that: In step (2), the melting temperature is 1400-1800° C., and the melting time is 4-12 hours.

5. The method for preparing the acid-resistant glass powder for dental use according to claim 3, characterized in that: In step (3), the particle size of the glass powder is 0.5 to 15 μm.

6. The method for preparing the acid-resistant glass powder for dental use according to claim 3, characterized in that: In step (4), the acid etching treatment specifically comprises the following steps: adding the glass powder obtained in step (3) into a boric acid solution with a mass concentration of 5% to 10%, wherein the mass ratio of the glass powder to the boric acid solution is 1:1 to 1:2; The mixture is heated to 70-90° C., maintained for 2-6 hours, centrifuged and cleaned, and dried to obtain acid-etched glass powder.

7. The method for preparing the acid-resistant glass powder for dental use according to claim 3, characterized in that: In step (5), the silane coupling agent includes one or more of KH570, KH550, KH792, and A151.

8. The method for preparing the acid-resistant glass powder for dental use according to claim 3 or 7, characterized in that: In step (5), the silanization treatment specifically comprises the following steps: Add the silane coupling agent to a 50% mass concentration ethanol aqueous solution, adjust the solution pH to 2-3, and heat to 60-80°C for pre-hydrolysis; Add acid-etched glass powder, heat to 70-90°C, react for 4 hours, centrifuge and wash, dry and sieve to obtain acid-resistant glass powder; The mass of the silane coupling agent is 2-15% of the mass of the glass powder; the mass of the ethanol aqueous solution is 1-2 times of the mass of the glass powder.

9. Use of dental acid-resistant glass powder as filler in acidic dental materials, the dental acid-resistant glass powder according to claim 1 or 2 being used or the dental acid-resistant glass powder being obtained by the preparation method according to any one of claims 3 to 8.

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