Water-based glass ionomer cement and obtained dental restoration material

Abstract

The invention provides water-based glass ionomer cement and an obtained dental restoration material, and belongs to the technical field of dental materials. The water-based glass ionomer cement consists of powder and liquid, the powder at least consists of 80-99% of fluorine-containing aluminosilicate glass powder in percentage by mass; the liquid agent is at least composed of 20%-60% of water, 20%-60% of polyolefin acid, 0.01%-20% of a polymerizable monomer containing a phosphoric acid group and 0.01%-20% of a polymerizable monomer containing a carboxylic acid group. According to the water-based glass ionomer cement product, the mechanical property and the bonding property of the product are effectively improved, and the bonding requirements of various dental materials such as enamel, dentin, metal, silicate-based ceramics and zirconia ceramics can be met at the same time; the problem that a traditional glass ionomer cement product is low in bonding strength to a zirconium oxide material is effectively solved, clinical selection of dentists can be facilitated, the medical burden of patients is expected to be reduced, and popularization of dental ceramic repair is further promoted.

Description

Technical Field

[0001] The invention belongs to the technical field of dental materials, and in particular relates to a water-based glass ionomer cement and a tooth restoration material obtained therefrom. Background Art

[0002] In recent years, all-ceramic dental restoration materials have gained popularity due to their aesthetics and good biocompatibility, and their application in oral restoration has gradually increased. Zirconia is the most commonly used dental restoration material, with excellent aesthetic properties, outstanding mechanical properties and biosafety, and has gradually become the first choice of dental restoration physicians.

[0003] However, the long-term bonding of zirconia dentures still faces certain challenges. This is because the chemical properties of zirconia are relatively stable and it does not contain a silicon glass phase. It is difficult to improve the bonding strength between it and the resin cement material through traditional acid etching and silanization treatments, which makes the restoration easy to fall off and cause the restoration to fail.

[0004] Currently, the commonly used zirconia bonding systems mainly include two categories: resin adhesives and glass ionomer adhesives. Studies have shown that from the perspective of compression bonding strength and tensile bonding strength after the adhesive is bonded to the tooth surface, the performance of resin adhesives is far superior to that of glass ionomer adhesives, so resin adhesives have a dominant position in the bonding of all-ceramic restorations. However, resin adhesives have a certain degree of polymerization shrinkage during the curing process, which can easily lead to marginal microleakage, which may then cause adverse events such as secondary caries; moreover, the price of resin adhesive materials is relatively high, resulting in higher treatment costs for patients.

[0005] Glass ionomer adhesives, such as glass ionomer cement (GIC), are cements solidified by the reaction of aluminosilicate glass powder and an aqueous solution of olefinic acid, or by the reaction of aluminosilicate glass powder / polyacid powder and water or an aqueous solution of tartaric acid. They can be used for filling, bonding, lining and pit and fissure sealing. They are one of the most important restorative materials in current oral clinics, and are also the most ideal restorative material for non-traumatic filling and restorative treatment of caries.

[0006] Although traditional glass ionomer cement is low in cost, the curing reaction of glass ionomer is relatively complex. In essence, it is an acid-base reaction between polyacid and glass powder. In addition, traditional glass ionomer cement mainly achieves mechanical retention of zirconia restorations through the design of zirconia restoration retention type, and the retention force is weak. It is also difficult to improve the bonding strength between zirconium oxide and glass ionomer cement through traditional acid etching and silanization treatment. In addition, glass ionomer cement materials that are in a moist oral environment for a long time have a certain solubility, which may eventually cause the zirconia restoration to fall off. Summary of the invention

[0007] The present invention provides a water-based glass ionomer cement and the obtained tooth restoration material. The water-based glass ionomer cement product effectively improves the mechanical properties and bonding properties of the product, can simultaneously meet the bonding requirements of various dental materials such as enamel, dentin, metal, silicate-based ceramics and zirconia ceramics, and effectively solves the problem of low bonding strength of traditional glass ionomer cement products to zirconia materials.

[0008] In order to achieve the above-mentioned purpose, the present invention provides a water-based glass ionomer cement, which is composed of a powder and a liquid. In terms of mass percentage, the powder is composed of at least 80%-99% of fluorine-containing aluminosilicate glass powder; the liquid is composed of at least 20%-60% of water, 20%-60% of polyolefin acid, 0.01%-20% of a polymerizable monomer containing a phosphoric acid group and 0.01%-20% of a polymerizable monomer containing a carboxylic acid group; the mass ratio of the powder to the liquid is (1.5-3.0):1.

[0009] Preferably, the fluorine-containing aluminosilicate glass powder comprises, by mass percentage, 20-40% Al2O3, 20-60% SiO2, 10-40% MO, 1-5% ZnO, 0-10% P2O5, and 1-20% F, wherein MO is a mixture of one or both of SrO and CaO, and the molar ratio of SiO2 to Al2O3 is (0.5-3): 1. It is understood that the fluorine-containing aluminosilicate glass powder can be commercially available fluorine-containing aluminosilicate glass powder, such as Reactive Dental Glass of Schott.

[0010] Preferably, the powder further comprises, by mass percentage, at least one of 0.1%-10% polyolefin acid and 0.01%-5% chemical initiator.

[0011] Preferably, the polyolefin acid is selected from at least one of polyacrylic acid, a binary copolymer of acrylic acid and maleic acid, a binary copolymer of acrylic acid and itaconic acid, and a terpolymer of acrylic acid, maleic acid and itaconic acid, and the weight average molecular weight of the polyolefin acid is in the range of 10000-300000;

[0012] The chemical initiator is selected from at least one of peroxide initiators and azo initiators to promote the polymerization of polymerizable monomers. It is understood that the peroxide initiator is selected from at least one of benzoyl peroxide, lauroyl peroxide, tert-butyl perbenzoate, potassium persulfate, sodium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, ammonium peroxydisulfate, sodium peroxydiphosphate, potassium peroxydiphosphate, ammonium peroxydiphosphate, and p-chlorobenzoyl peroxide; the azo initiator is selected from at least one of azobisisobutyronitrile and azobisisoheptonitrile. It is understood that the addition of the chemical initiator can promote the polymerization between polymerizable monomers containing phosphoric acid groups, polymerizable monomers containing carboxylic acid groups, water-soluble multifunctional (meth) acrylic polymerizable monomers and polyolefin acids, and improve the mechanical properties of the system after curing.

[0013] Preferably, the preparation method of water-based glass ionomer cement powder is as follows:

[0014] Surface treatment of glass powder: dilute the original slurry of glass powder with water, wherein the volume ratio of the original slurry to water is (5-10):1, then add acid to the diluted original slurry, wherein the volume of the acid accounts for 1-20% of the volume of the diluted original slurry, stir at room temperature for 1-2 hours, wet screen, precipitate and filter to remove the suspended liquid to obtain powder; the acid can be any one of acetic acid, oxalic acid, hydrochloric acid, phosphoric acid or nitric acid, and the concentration of the acid solution is 0.5-3%;

[0015] Drying: vacuum drying the above powder at 70-120℃ for 12-24h;

[0016] Grinding: Put the powder obtained after the drying process into a fast grinder and grind it at a speed of 300-600r / min for 5-30min;

[0017] Screening: Screening the powder obtained in the grinding process with a 300-500 mesh sieve to obtain fluorine-containing aluminosilicate glass powder;

[0018] Mixing: Weigh fluorine-containing aluminosilicate glass powder, polyolefin acid powder and chemical initiator in a certain proportion, use a conical mixer, mix at a speed of 10 to 100 r / min for 30 to 120 minutes, and obtain a powder of water-based glass ionomer cement.

[0019] It is understandable that glass ionomer cement powder can also be prepared according to the method disclosed in CN114129455B.

[0020] Preferably, the powder has a particle size of less than 40 μm, a d50 of 1 to 8 μm, and a d90 of 10 to 30 μm.

[0021] Preferably, the polymerizable monomer containing a phosphoric acid group is selected from at least one of 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP), methacrylate phosphate (MHP), 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate (PM2), 2-methacryloyloxyethyl phosphorylcholine (PM1520) and alkyl acrylate phosphate (PM1570);

[0022] The polymerizable monomer containing a carboxylic acid group is selected from at least one of 4-methacryloyloxyethyl trimellitic acid (4-MET), 4-acryloyloxyethyl trimellitic acid (4-AET), 4-methacryloyloxyethyl trimellitic anhydride (4-META), methacryloyloxyethyl maleate (MOEM), methacryloyloxyethyl succinate (MOES) and 2-methacryloyloxyethyl phthalate (PAMA).

[0023] It can be understood that the addition of polymerizable monomers containing phosphoric acid groups can chemically bond with zirconia dental ceramic restorations, thereby improving the bonding performance between the system and zirconia dental ceramics; the addition of polymerizable monomers containing carboxylic acid groups can chemically bond with metal or dental ceramic restorations, thereby improving the bonding performance between the system and dental restorations.

[0024] Preferably, the liquid further comprises, by mass percentage, at least one of 5%-20% volatile organic solvent, 0.01%-20% water-soluble multifunctional (meth) acrylic polymerizable monomer, 0.1%-5% dentin collagen crosslinker, 0.1%-5% collagen hydrolase inhibitor and 0.01-5% surfactant.

[0025] Preferably, the water-soluble multifunctional (meth) acrylic polymerizable monomer is selected from at least one of hydroxyethyl methacrylate and polyethylene glycol methacrylate. It is understood that the addition of the water-soluble multifunctional (meth) acrylic polymerizable monomer can improve the stability of the polymerizable monomer containing phosphoric acid group and the polymerizable monomer containing carboxylic acid group in the liquid.

[0026] Preferably, the collagenase inhibitor is selected from at least one of chlorhexidine acetate, chlorhexidine hydrochloride, chlorhexidine gluconate, benzalkonium chloride and polyhexamethylene biguanide. It is understandable that the addition of the collagenase inhibitor can delay the degradation of collagen fibers in the teeth, improve the stability of the mixed layer, thereby improving the surface state of the dentin and enhancing the bonding performance of the system to the teeth.

[0027] Preferably, the dentin collagen crosslinking agent is selected from at least one of glutaraldehyde, acrolein, genipin and tannic acid. It is understood that the addition of the dentin collagen crosslinking agent can improve the biomechanical properties of dentin collagen and its resistance to proteolytic enzyme hydrolysis, and improve the bonding performance of the system to teeth.

[0028] Preferably, the volatile organic solvent is selected from at least one of methanol, ethanol, ethylene glycol, acetone, dimethyl sulfoxide, tetrahydrofuran, ethylene glycol methyl ether, and ethylene glycol ethyl ether. It is understood that the addition of the volatile organic solvent can further improve the stability of the polymerizable monomer containing phosphoric acid groups and the polymerizable monomer containing carboxylic acid groups in the liquid.

[0029] Preferably, the surfactant is selected from at least one of sorbitan monopalmitate, polysorbate and polyethylene glycol.

[0030] Preferably, the liquid is prepared by the following method:

[0031] Add polyolefin acid into water, stir at a speed of 100-500r / min for 0.5-2h, and let stand for 5-12h;

[0032] Add a polymerizable monomer containing a phosphoric acid group, a polymerizable monomer containing a carboxylic acid group, and a water-soluble multifunctional (meth) acrylic acid polymerizable monomer to a volatile organic solvent in sequence, stir at a speed of 100-500 r / min for 0.5-2 h, and stand for 5-12 h;

[0033] The above polymerizable monomer organic solution is added into the polyolefin acid aqueous solution, stirred at a speed of 100-500 r / min for 0.5-2 h, and allowed to stand for 5-12 h to obtain a water-based glass ionomer cement solution.

[0034] Preferably, the water-based glass ionomer cement provided by the present invention can be used in combination with fluorescent agents, indicators, pH regulators, polymerization inhibitors, promoters, viscosity regulators, wetting agents, tackifiers, colorants, stabilizers and diluents, etc., under the premise of being able to exert its intended use and effect, according to actual product needs. It is understandable that the various ingredients used in combination can be within the conventional range recognized by those skilled in the art.

[0035] The present invention also provides a tooth restoration material, which is prepared by bonding any one of enamel, dentin, dental zirconia ceramics, dental lithium disilicate glass ceramics, and dental cobalt-chromium alloy parts using the water-based glass ionomer cement described in any of the above technical solutions.

[0036] Compared with the prior art, the advantages and positive effects of the present invention are:

[0037] 1. The water-based glass ionomer cement provided by the present invention improves the formula of powder and liquid, effectively improves the mechanical properties and bonding properties of the product, can simultaneously meet the bonding needs of various dental materials such as enamel, dentin, metal, silicate-based ceramics and zirconia ceramics, and can facilitate clinical selection by dentists, which is expected to reduce the medical burden of patients and further promote the promotion of dental ceramic restorations. DETAILED DESCRIPTION

[0038] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0039] The invention provides a water-based glass ionomer cement, which consists of a powder and a liquid. In terms of mass percentage, the powder consists of at least 80%-99% of fluorine-containing aluminosilicate glass powder; the liquid consists of at least 20%-60% of water, 20%-60% of polyolefin acid, 0.01%-20% of a polymerizable monomer containing a phosphoric acid group and 0.01%-20% of a polymerizable monomer containing a carboxylic acid group.

[0040] In one embodiment, the powder is composed of 80%-99% fluorine-containing aluminosilicate glass powder and at least one of 0.1%-10% polyolefin acid and 0.01%-5% chemical initiator.

[0041] In one embodiment, the powder is composed of 80%-99% fluorine-containing aluminosilicate glass powder, 0.1%-10% polyolefin acid and 0.01%-5% chemical initiator.

[0042] In the above embodiment, the polyolefin acid is selected from at least one of polyacrylic acid, a binary copolymer of acrylic acid and maleic acid, a binary copolymer of acrylic acid and itaconic acid, and a ternary copolymer of acrylic acid, maleic acid and itaconic acid, and the weight average molecular weight of the polyolefin acid is in the range of 10,000-300,000.

[0043] In the above embodiment, the chemical initiator is selected from at least one of a peroxide initiator and an azo initiator to promote the polymerization of the polymerizable monomer. It is understood that the peroxide initiator is selected from at least one of benzoyl peroxide, lauroyl peroxide, tert-butyl perbenzoate, potassium persulfate, sodium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, ammonium peroxydisulfate, sodium peroxydiphosphate, potassium peroxydiphosphate, ammonium peroxydiphosphate, and p-chlorobenzoyl peroxide; the azo initiator is selected from at least one of azobisisobutyronitrile and azobisisoheptylonitrile.

[0044] In one embodiment, the liquid agent is composed of at least 20%-60% water, 20%-60% polyolefin acid, 0.01%-20% polymerizable monomer containing phosphoric acid group, 0.01%-20% polymerizable monomer containing carboxylic acid group and 5%-20% volatile organic solvent, 0.01%-20% water-soluble multifunctional (meth) acrylic polymerizable monomer, 0.1%-5% dentin collagen crosslinker, 0.1%-5% collagen hydrolase inhibitor and 0.01-5% surfactant.

[0045] In one embodiment, the liquid agent is composed of 20%-60% water, 20%-60% polyolefin acid, 0.01%-20% polymerizable monomer containing phosphoric acid group, 0.01%-20% polymerizable monomer containing carboxylic acid group, 5%-20% volatile organic solvent, 0.01%-20% water-soluble multifunctional (meth) acrylic polymerizable monomer, 0.1%-5% dentin collagen crosslinking agent, 0.1%-5% collagen hydrolase inhibitor and 0.01-5% surfactant.

[0046] In the above embodiment, the polymerizable monomer containing a phosphoric acid group is selected from at least one of 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP), methacrylate phosphate (MHP), 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate (PM2), 2-methacryloyloxyethyl phosphorylcholine (PM1520) and alkyl acrylate phosphate (PM1570).

[0047] In the above embodiment, the polymerizable monomer containing a carboxylic acid group is selected from at least one of 4-methacryloyloxyethyl trimellitic acid (4-MET), 4-acryloyloxyethyl trimellitic acid (4-AET), 4-methacryloyloxyethyl trimellitic anhydride (4-META), methacryloyloxyethyl maleate (MOEM), methacryloyloxyethyl succinate (MOES) and 2-methacryloyloxyethyl phthalate (PAMA).

[0048] In the above embodiment, the water-soluble multifunctional (meth) acrylic polymerizable monomer is selected from at least one of hydroxyethyl methacrylate and polyethylene glycol methacrylate. It is understandable that the addition of the water-soluble multifunctional (meth) acrylic polymerizable monomer can improve the stability of the polymerizable monomer containing a phosphoric acid group and the polymerizable monomer containing a carboxylic acid group in the liquid.

[0049] In the above embodiment, the collagenase inhibitor is selected from at least one of chlorhexidine acetate, chlorhexidine hydrochloride, chlorhexidine gluconate, benzalkonium chloride and polyhexamethylene biguanide. It is understandable that the addition of the collagenase inhibitor can delay the degradation of collagen fibers in the teeth, improve the stability of the mixed layer, thereby improving the surface state of the dentin and enhancing the bonding performance of the system to the teeth.

[0050] In the above embodiment, the dentin collagen crosslinking agent is selected from at least one of glutaraldehyde, acrolein, genipin and tannic acid. It is understandable that the addition of the dentin collagen crosslinking agent can improve the biomechanical properties of dentin collagen and its resistance to proteolytic enzyme hydrolysis, and improve the bonding performance of the system to teeth.

[0051] In the above embodiment, the volatile organic solvent is selected from at least one of methanol, ethanol, ethylene glycol, acetone, dimethyl sulfoxide, tetrahydrofuran, ethylene glycol methyl ether, and ethylene glycol ethyl ether. It is understood that the addition of the volatile organic solvent can further improve the stability of the polymerizable monomer containing phosphoric acid groups and the polymerizable monomer containing carboxylic acid groups in the liquid.

[0052] In the above embodiment, the surfactant is selected from at least one of sorbitan monopalmitate, polysorbate, and polyethylene glycol.

[0053] The scheme of the present application will be further described below in conjunction with Examples 1-6 and Comparative Examples 1-4. These Examples and Comparative Examples are exemplary embodiments and are not intended to limit the scope of the present application. The specific schemes of Examples 1-6 and Comparative Examples 1-3 are shown in Table 1.

[0054]

[0055]

[0056]

[0057] Performance Testing

[0058] The performance tests of the water-based glass ionomer cements of Examples 1-6 and Comparative Examples 1-4 are as follows.

[0059] Net curing time

[0060] The determination of net curing time is carried out in accordance with "YY 0271.1-2016 Dental Water-based Cement Part 1: Powder / Liquid Acid-Base Cement", and the specific method is as follows:

[0061] First, the powder and liquid of the water-based glass ionomer cement of the present invention are blended at a powder-liquid mass ratio of 1.8:1, and then left to stand for 20 seconds until the organic solvent evaporates, thereby obtaining a cement paste.

[0062] Place a metal mold heated to 23℃±2℃ on aluminum foil, fill the metal mold with the test cement paste, and scrape its surface flat.

[0063] 60 seconds after the mixing is completed, the assembly consisting of the metal mold, aluminum foil and cement sample is placed on the metal retaining block and placed together in a storage box. In addition, it is also necessary to ensure that the metal mold, aluminum foil and metal retaining block are fully fitted.

[0064] 90 seconds after the mixing is completed, carefully move the hardness tester vertically downward to the surface of the cement and leave it there for 5 seconds. Subsequently, a trial test is conducted to determine the approximate curing time of the tested cement, and the indentation test is repeated within 30 seconds until a magnifying glass with a magnification of 2 times is used to check that the indenter needle cannot carve a complete indentation ring on the cement surface. If necessary, the indenter can be cleaned during the indentation test. However, the indentation test must be repeated within the 10-second time limit and from 30 seconds before the approximate curing time.

[0065] Finally, the time required from the end of self-adjustment until the indenter could not carve a complete indentation ring on the cement surface was recorded as the curing time of the test sample. The results are shown in Table 2.

[0066] Compressive strength

[0067] The compressive strength is determined in accordance with "YY 0271.1-2016 Dental Water-Based Cement Part 1: Powder / Liquid Acid-Base Cement", and the specific method is as follows:

[0068] First, at room temperature of 23°C±2°C, the powder and liquid of the water-based glass ionomer cement of the present invention are blended in a powder-liquid mass ratio of 1.8:1, and then allowed to stand for 20 seconds to obtain a cement paste after the organic solvent evaporates; within 60 seconds, the test cement paste is filled into a split mold with a height of 6.0 mm±0.1 mm and an inner diameter of 4.0 mm±0.1 mm.

[0069] In order to make the cement mixture in the split mold compact without gaps and avoid the adverse effects of air bubbles, the most suitable part of the mixture should be injected into the split mold. At the same time, use a suitable tool to press it hard to one side until the split mold is filled with excess mixture. Then, place the filled split mold on the metal base plate and continue to press.

[0070] Then, scrape off the mixture on the edge of the split mold, cover it with a metal plate and squeeze it, and then clamp the split mold and the metal plate together with a clamp. 120 seconds after the cement mixture is prepared, put the entire assembly into a constant temperature box.

[0071] 60 minutes after the cement mixture is mixed, remove the metal plate from the split mold and grind the end face of the test sample flat so that the end face plane is perpendicular to its long axis. When grinding, 400# wet silicon carbide sandpaper is generally used, but the end plane of the test sample should not be ground too rough in any case.

[0072] When it is smooth and no air bubbles or burrs are found by visual inspection, the split mold is immediately opened, the test specimens are taken out, and any defective test specimens are discarded.

[0073] The specimen thus prepared should be immediately immersed in deionized or distilled water at a temperature of 37°C ± 1°C for a period of 23h ± 0.5h.

[0074] 24 hours after the cement mixture was prepared, each smooth end surface of the test sample was clamped between the pressure plates of the mechanical properties testing machine, and pressure was applied along the long axis of the test sample. Then, the reading of the mechanical properties testing machine when the test sample broke was recorded, which was the compressive strength of the sample. The results are shown in Table 2.

[0075] Table 2 Performance and compressive strength of glass ionomer cement after curing of the present invention

[0076]

[0077]

[0078] Compared with the samples of Examples 1-6 and Comparative Examples 1-4, in Comparative Example 1, no polymerizable monomer containing a phosphate group and no polymerizable monomer containing a carboxylic acid group were added, and the strength of Comparative Example 1 was 158 MPa, which was much lower than that of the examples; in Comparative Example 2, no polymerizable monomer containing a phosphate group was added, and the compressive strength of Comparative Example 2 was 201 MPa, which was lower than that of the examples, but higher than that of Comparative Example 1; in Comparative Example 3, no polymerizable monomer containing a carboxylic acid group was added, and the compressive strength of Comparative Example 3 was 218 MPa, which was similar to that of Comparative Example 2; in Comparative Example 4, no collagen hydrolase inhibitor and dentin collagen cross-linking agent were added, and the compressive strength was 241 MPa, which was relatively lower than that of the examples; the above test results confirm the purpose of the present invention.

[0079] Bond strength test

[0080] 10 standard specimens of enamel, dentin, dental zirconium oxide ceramics, dental lithium disilicate glass ceramics, and dental cobalt-chromium alloy with a diameter of 16 mm and a thickness of 4 mm were prepared respectively. Each specimen was polished on one side with 200 mesh, 400 mesh, and 600 mesh water-abrasive paper in turn to form a standard bonding surface. The water-based glass ionomer cement of the present invention was blended at a powder-liquid ratio of 1.8:1, and applied to the surface of the specimen after standing for 20 seconds. The shear bonding strength of the specimen was measured according to the standard of "YY / T0518-2009 Polymer-based Adhesives for Dental Restorations", and the data were statistically analyzed using SPSS software. At the same time, a comparative example was added: Fuji GC I type glass ionomer cement was used, and the mixing method of the powder and the liquid was carried out according to the instructions. The test results of the shear bonding strength are shown in Table 3.

[0081] Table 3 Shear bonding properties between water-based glass ionomer cement of the present invention and various materials

[0082]

[0083]

[0084] Compared with the samples of Examples 1-6 and Comparative Examples 1-4, no polymerizable monomer containing a phosphate group or a polymerizable monomer containing a carboxylic acid group was added in Comparative Example 1, so the bonding strength of Comparative Example 1 to enamel, dentin, dental zirconia ceramics, dental lithium disilicate glass ceramics, and dental cobalt-chromium alloy standard specimens was much lower than that of the examples; however, collagen hydrolase inhibitor and dentin collagen crosslinking agent were added to Comparative Example 1, and the bonding strength between the Comparative Example 1 and enamel and dentin was higher than that of the commercially available glass ionomer cement products (GC Fuji I); in Comparative Example 2, no polymerizable monomer containing a phosphate group was added, so the bonding strength of Comparative Example 2 to zirconium oxide and lithium disilicate glass ceramics was lower than that of the embodiment; in Comparative Example 3, no polymerizable monomer containing a carboxylic acid group was added, so the bonding strength to enamel, dentin, dental zirconium oxide ceramics, dental lithium disilicate glass ceramics, and dental cobalt-chromium alloy was lower than that of the embodiment; in Comparative Example 4, no collagen hydrolase inhibitor and dentin collagen cross-linking agent were added, and the bonding strength between the comparative example and dentin was lower than that of the embodiment; the above test results confirm the purpose of the present invention.

Claims

1. A water-based glass ionomer cement, characterized in that: It consists of a powder and a liquid; in terms of mass percentage, the powder is composed of at least 80%-99% of fluorine-containing aluminosilicate glass powder; the liquid is composed of at least 20%-60% of water, 20%-60% of polyolefin acid, 0.01%-20% of a polymerizable monomer containing a phosphoric acid group and 0.01%-20% of a polymerizable monomer containing a carboxylic acid group; the mass ratio of the powder to the liquid is (1.5-3.0):

1.

2. The water-based glass ionomer cement according to claim 1, characterized in that: In terms of mass percentage, the fluorine-containing aluminosilicate glass powder includes 20-40% Al2O3, 20-60% SiO2, 10-40% MO, 1-5% ZnO, 0-10% P2O5, and 1-20% F, wherein MO is a mixture of one or two of SrO and CaO, and the molar ratio of SiO2 to Al2O3 is (0.5-3):

1.

3. The water-based glass ionomer cement according to claim 1 or 2, characterized in that: The powder further comprises, by mass percentage, at least one of 0.1% to 10% of polyolefin acid and 0.01% to 5% of a chemical initiator.

4. The water-based glass ionomer cement according to claim 1 or 3, characterized in that: The polyolefin acid is at least one selected from polyacrylic acid, a binary copolymer of acrylic acid and maleic acid, a binary copolymer of acrylic acid and itaconic acid, and a terpolymer of acrylic acid, maleic acid and itaconic acid, and the weight average molecular weight of the polyolefin acid is in the range of 10,000-300,000; The chemical initiator is selected from at least one of a peroxide initiator and an azo initiator to promote the polymerization of the polymerizable monomer.

5. The water-based glass ionomer cement according to any one of claims 1 to 4, characterized in that: The particle size of the powder is less than 40 μm, d50 is 1 to 8 μm, and d90 is 10 to 30 μm.

6. The water-based glass ionomer cement according to claim 1, characterized in that: The polymerizable monomer containing a phosphoric acid group is selected from at least one of 10-methacryloyloxydecyl dihydrogen phosphate, methacrylic acid phosphate, 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate, 2-methacryloyloxyethyl phosphorylcholine and alkyl acrylate phosphate; The carboxylic acid group-containing polymerizable monomer is at least one selected from 4-methacryloyloxyethyl trimellitic acid, 4-acryloyloxyethyl trimellitic acid, 4-methacryloyloxyethyl trimellitic anhydride, methacryloyloxyethyl maleic acid monoester, methacryloyloxyethyl succinic acid monoester and 2-methacryloyloxyethyl phthalate.

7. The water-based glass ionomer cement according to claim 6, characterized in that: By mass percentage, the liquid also includes at least one of 5%-20% volatile organic solvent, 0.01%-20% water-soluble multifunctional (meth) acrylic polymerizable monomer, 0.1%-5% dentin collagen crosslinker, 0.1%-5% collagen hydrolase inhibitor and 0.01-5% surfactant.

8. The water-based glass ionomer cement according to claim 7, characterized in that: The water-soluble multifunctional (meth) acrylic polymerizable monomer is at least one selected from hydroxyethyl methacrylate and polyethylene glycol methacrylate; The collagenase inhibitor is selected from at least one of chlorhexidine acetate, chlorhexidine hydrochloride, chlorhexidine gluconate, benzalkonium chloride and polyhexamethylene biguanide; The dentin collagen cross-linking agent is at least one selected from glutaraldehyde, acrolein, genipin and tannic acid; The surfactant is selected from at least one of sorbitan monopalmitate, polysorbate, and polyethylene glycol; The volatile organic solvent is selected from at least one of methanol, ethanol, ethylene glycol, acetone, dimethyl sulfoxide, tetrahydrofuran, ethylene glycol methyl ether and ethylene glycol ethyl ether.

9. The water-based glass ionomer cement according to any one of claims 1, 6 to 8, characterized in that: The liquid is prepared by the following method: Add polyolefin acid into water, stir at a speed of 100-500r / min for 0.5-2h, and let stand for 5-12h; Add a polymerizable monomer containing a phosphoric acid group, a polymerizable monomer containing a carboxylic acid group, and a water-soluble multifunctional (meth) acrylic acid polymerizable monomer to a volatile organic solvent in sequence, stir at a speed of 100-500 r / min for 0.5-2 h, and stand for 5-12 h; The above polymerizable monomer organic solution is added into the polyolefin acid aqueous solution, stirred at a speed of 100-500 r / min for 0.5-2 h, and allowed to stand for 5-12 h to obtain a water-based glass ionomer cement solution.

10. A tooth restoration material, characterized in that: The material is prepared by bonding with the water-based glass ionomer cement described in any one of claims 1 to 9 selected from any one of enamel, dentin, dental zirconia ceramics, dental lithium disilicate glass ceramics, and dental cobalt-chromium alloy parts.

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