Resin-infiltrated ceramics and their preparation method

Abstract

The present invention relates to a resin-infiltrated ceramic and a method for preparing the same. The resin-infiltrated ceramic includes a ceramic body and a resin disposed inside and on the surface of the ceramic body. The ceramic body includes sodium aluminosilicate modified with polymethyl methacrylate. Raw materials for preparing the resin include an acrylate resin monomer and a cage silsesquioxane having a methacrylate ester functional group. The resin-infiltrated ceramic according to the present invention has excellent mechanical properties, fracture toughness, flexural strength, and hardness similar to those of human teeth, as well as low shrinkage. It is suitable for CAD / CAM cutting and can be used as a dental crown and bridge restorative material.

Description

[Technical Field]

[0001] The present invention relates to the field of resin-infiltrated ceramics technology, and in particular to resin-infiltrated ceramics and methods for preparing same.

[0002] Cross-reference to related applications This application claims priority based on a Chinese application bearing application number CN202211687527.7 and entitled "Resin-infiltrated ceramics and preparation method thereof" filed with the China Patent Office on December 27, 2022, the entire contents of which are incorporated herein by reference. [Background technology]

[0003] Resin-infiltrated ceramics involves infiltrating resin into a porous ceramic support to form a new type of composite transparent ceramic material with an interpenetrating network structure. This is a cutting-edge technology for crown and bridge restorations and material development using intraoral digital treatment.

[0004] Patent Document 1 discloses a resin-infiltrated ceramic composite material and its preparation method. This resin-infiltrated ceramic uses yttria-stabilized tetragonal zirconia as the porous ceramic body, a methacrylate resin as the mixed resin, and a benzoyl peroxide heat curing agent. Although the prepared resin-infiltrated ceramic has excellent mechanical properties, it is far removed from natural human teeth and lacks the potential for biomimetic properties, making it unsuitable for clinical use. For example, the prepared material has a much higher elastic modulus than human dentin. When used clinically by patients, this restorative material may wear and damage natural human teeth.

[0005] Patent Document 2 discloses a machinable resin-infiltrated glass-ceramic material for dental use and a method for preparing the same. This resin-infiltrated ceramic material uses a barium silylate glass-ceramic powder as the porous ceramic body and an acrylate resin monomer and benzoyl peroxide as the infiltrating resin. The prepared resin-infiltrated glass-ceramic material for dental restorations has mechanical properties similar to those of human teeth, but its elastic modulus is lower than that of natural teeth.

[0006] Patent Document 3 discloses a resin-infiltrated silicate composite and its preparation method. The resins used were the common bisphenol A glycerolate dimethacrylate and tetraethylene glycol dimethacrylate (CAS number: 109-17-1), and benzoyl peroxide was used as the curing agent. The resin was infiltrated into a porous ceramic block by vacuum capillary action and then cured to form a silicate / resin double network structure. This resin-infiltrated silicate composite had low flexural strength and hardness. In the prior art, there has been little research on resin-infiltrated ceramics. Most ceramic bodies are made of zirconia ceramics, alumina ceramics, or glass ceramics. Resin-infiltrated ceramics formed from porous ceramic skeletons prepared using these materials have significantly different mechanical properties compared to natural human teeth. This difference may cause wear on natural human teeth or adversely affect the transmission of occlusal stress between the restorative material and the natural tooth.

[0007] Therefore, the development of resin-infiltrated ceramic materials with elastic modulus close to that of human teeth is extremely important. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] CN106007802A [Patent Document 2] CN107903557A [Patent Document 3] CN108578250A Summary of the Invention

[0009] In view of the shortcomings of the prior art, the present invention aims to provide a resin-infiltrated ceramic and a method for preparing the same, which has excellent mechanical properties, fracture toughness, flexural strength, and hardness similar to those of human teeth, as well as low shrinkage, is suitable for CAD / CAM cutting, and can be used as a dental crown and bridge restorative material.

[0010] To achieve this goal, the present invention employs the following techniques. In a first aspect, the present invention provides a resin-infiltrated ceramic, the resin-infiltrated ceramic including a ceramic body and a resin provided inside and on a surface of the ceramic body. The ceramic body comprises sodium aluminosilicate modified with polymethylmethacrylate.

[0011] The raw materials for preparing the resin include an acrylic acid ester-based resin monomer and a cage-type silsesquioxane having a methacrylic acid ester as a functional group. In the present invention, polymethyl methacrylate-modified sodium aluminosilicate is used as the primary material of the ceramic body in combination with a resin system. In the resin system, the cage silsesquioxane having a methacrylic acid ester functional group is structurally similar to the acrylic acid ester-based resin, reducing the polymerization shrinkage of the resin-infiltrated ceramic while ensuring good compatibility and dispersibility of the infiltrated material with the acrylic resin. The polymethyl methacrylate-modified sodium aluminosilicate's good interfacial compatibility with the acrylic resin ensures good compatibility and dispersibility with the resin, thereby providing the resin-infiltrated ceramic with good fracture toughness, flexural strength, and hardness.

[0012] In the present invention, the acrylic acid ester-based resin monomer used to prepare the resin is not particularly limited, and may be any monomer that meets actual needs. In the present invention, the acrylic acid ester-based monomer may be a monofunctional (meth)acrylic acid ester or a polyfunctional (meth)acrylic acid ester. Exemplary acrylic acid ester-based monomers include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, paracumylphenoxyethylene glycol methacrylate (CMP-1E), 2-(2-biphenyloxy)ethyl methacrylate, bisphenol A dimethacrylate, bis-GMA (an adduct of methacrylic acid and bisphenol A diglycidyl ether), UDMA (an adduct of 2-hydroxyethyl methacrylate and 2,2,4-trimethylhexamethylene-1,6-diisopropyl acrylate), and the like. anthracene adduct), diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, glycerol dimethacrylate, glycerol trimethacrylate, 1,4-butanediol dimethacrylate, 1,10-decanediol dimethacrylate (D3MA), bis(methylacryloyloxymethyl)tricyclo-[5.2.1.02,6]decane (DCP), polyethylene glycol dimethacrylate or polypropylene glycol dimethacrylate, polyethylene glycol 200 dimethacrylate, polyethylene glycol 400 dimethacrylate, 1,12-dodecanediol dimethacrylate, or mixtures thereof.

[0013] Preferably, the mass percentage of the ceramic body is 70% to 80%, for example, 72%, 74%, 76%, or 78%, with the total mass of the resin-infiltrated ceramic being 100%.

[0014] Preferably, the mass percentage of the resin is 20% to 30%, for example, 22%, 24%, 26%, or 28%, with the total mass of the resin-impregnated ceramic being 100%.

[0015] Preferably, the porosity of the ceramic body is 10% to 55%, for example, 20%, 30%, 40%, or 50%.

[0016] Preferably, the raw materials for preparing the ceramic body include sodium aluminosilicate, a solvent, a silane coupling agent, a methyl methacrylate monomer, and an initiator.

[0017] Preferably, the average particle size of the sodium aluminosilicate is 0.4 to 3.2 μm, for example, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, or 3 μm.

[0018] Preferably, the solvent comprises absolute ethanol.

[0019] Preferably, the initiator comprises azobisisobutyronitrile.

[0020] Preferably, the raw materials for preparing the ceramic body contain the following components in mass percentages, with the total mass of the raw materials for preparing the ceramic body being 100%.

[0021] Sodium aluminosilicate: 20% to 40%. Solvent: 30%~60%. Silane coupling agent: 10% to 25%. Methyl methacrylate monomer: 15% to 25%. Initiator: 0.02%~0.1%. In the present invention, the mass percentage of the sodium aluminosilicate is 20% to 40%, for example, 25%, 30%, or 35%.

[0022] In the present invention, the mass percentage of the solvent is preferably 30% to 60%, for example, 35%, 40%, 45%, 50%, or 55%. In the present invention, the mass percentage of the silane coupling agent is preferably 10% to 25%, for example, 12%, 14%, 16%, 18%, 20%, 22%, or 24%. In the present invention, the mass percentage of the methyl methacrylate monomer is preferably 15% to 25%, for example, 16%, 18%, 20%, 22%, or 24%.

[0023] In the present invention, the mass percentage of the initiator is preferably 0.02% to 0.1%, for example, 0.04%, 0.06%, or 0.08%. Preferably, the formula of the cage silsesquioxane having a methacrylic acid ester as a functional group is (RSiO 3 / 2 )n.

[0024] The n is 6, 8, 10, 12, or 14, and at least one of R is selected from the functional group methacrylate ester. POSS is a type of organic-inorganic hybrid monomer with an average particle size of about 1.5 nm and a molecular formula of (RSiO 3 / 2 )n, where n is usually 6, 8, or 10. POSS exhibits properties intermediate between silicon dioxide (SiO2) and silicone resin (R2SiO)n, and has an inorganic framework of nanostructured SiO2 polyhedrons at its center, with organic functional groups at each vertex. The organic functional groups of functionalized cage-type silsesquioxanes are highly reactive and exhibit good compatibility and chemical bonding with various polymers, allowing the formation of nanoscale inorganic-organic hybrid composite materials.

[0025] Preferably, the structural formula of the cage silsesquioxane having a methacrylic acid ester as a functional group (POSS-MA) is as shown in Formula I. [ka] R is independently selected from hydrogen, a methacrylate functional group, and other unsaturated bond-containing functional groups, and is more preferably a methacrylate functional group.

[0026] In this invention, we use a POSS derivative, i.e., polyhedral oligomeric silsesquioxane-methacrylate ester (POSS-MA), in which eight R groups are methacrylate functional groups. When POSS-MA is combined with an acrylic resin, the two exhibit excellent compatibility and can undergo simultaneous curing reactions. When added to dental resin materials, its inorganic support structure maintains its spatial structure during polymerization, effectively reducing the volumetric shrinkage of the material. This effectively prevents interfacial cracking between the resin and ceramic framework after immersion curing due to volumetric shrinkage during polymerization, thereby imparting excellent mechanical properties to the resin-infiltrated ceramic material.

[0027] All acrylate group-containing POSS according to the present invention are available synthetically or commercially. Preferably, the resin preparation ingredients further comprise a thermal initiator. Preferably, the thermal initiator comprises one or a combination of at least two of dicumyl peroxide, t-butyl peroxide, and benzoyl peroxide; exemplary, but non-limiting, combinations include a combination of dicumyl peroxide and t-butyl peroxide, a combination of t-butyl peroxide and benzoyl peroxide, and a combination of dicumyl peroxide, t-butyl peroxide, and benzoyl peroxide.

[0028] Preferably, the t-butyl peroxide comprises t-butyl peracetate and / or t-butyl peroxybenzoate.

[0029] Preferably, the raw materials for preparing the resin contain the following components in mass percentages, with the total mass of the raw materials for preparing the resin being 100%: Acrylate ester resin monomer: 70% to 95%. Cage-type silsesquioxane having methacrylate ester as a functional group: 0.003% to 18%. Thermal initiator: 0.35%~2%.

[0030] In the present invention, the mass percentage of the acrylic acid ester resin monomer is preferably 70% to 95%, for example, 75%, 80%, or 85%.

[0031] In the present invention, the mass percentage of the cage silsesquioxane having a methacrylic acid ester as a functional group is preferably 0.003% to 18%, for example, 0.5%, 1%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, or 18%.

[0032] In the present invention, the mass percentage of the thermal initiator is preferably 0.35% to 2%, for example, 0.5%, 1%, or 1.5%. In a second aspect, the present invention provides a method for preparing the resin-infiltrated ceramic according to the first aspect, the method including the step of infiltrating a ceramic body with a resin to obtain the resin-infiltrated ceramic.

[0033] Preferably, the preparation method comprises the following steps: Step (1): An acrylic acid ester-based resin monomer, a thermal initiator, and a cage silsesquioxane having a methacrylic acid ester as a functional group are mixed and reacted to obtain the resin. Sodium aluminosilicate, a solvent, a silane coupling agent, a methyl methacrylate monomer, and an initiator are mixed and polymerized in situ, and then pressed to obtain the ceramic body. Step (2): The ceramic body is immersed in a resin, and the resin is allowed to infiltrate and harden to obtain the resin-infiltrated ceramic.

[0034] Preferably, in step (1), said in-situ polymerization comprises the steps of: Step (a): Sodium aluminosilicate, a solvent, a silane coupling agent, and a methyl methacrylate monomer are mixed and dispersed, reacted by heating, and then post-treated. Step (b): The raw material obtained from the post-treatment in step (a), methyl methacrylate monomer, and an initiator are mixed and reacted to complete in-situ polymerization.

[0035] In this study, we selected low-cost sodium aluminosilicate as the porous ceramic support for resin-infiltrated ceramics. The primary objective was to obtain a PMMA-coated sodium aluminosilicate nanocomposite as the ceramic framework material for resin-infiltrated ceramics by grafting polymethyl methacrylate (PMMA) onto the surface of sodium aluminosilicate via in situ polymerization, thereby modifying the interface. On the one hand, this improves the dispersibility of sodium aluminosilicate in resin-infiltrated ceramics, facilitating the formation of interconnected pores in the interpenetrating network. On the other hand, it improves the interfacial compatibility between sodium aluminosilicate and acrylic resin. Because sodium aluminosilicate and PMMA are bonded by stable chemical bonds, with PMMA molecular chains essentially "attached" to the sodium aluminosilicate nanoparticles, there is no distinction between the inorganic and organic phases. The resin-infiltrated ceramics prepared in this way have significantly improved mechanical functions, making it possible to provide resin-infiltrated ceramic materials with excellent mechanical properties (fracture toughness, flexural strength, and hardness similar to those of human teeth) and low shrinkage. These materials are suitable for CAD / CAM cutting and can be used as dental crown and bridge restorative materials.

[0036] Preferably, in step (a), the mixing and dispersing method includes stirring and ultrasonic waves. Preferably, the temperature of the heating reaction is 70 to 90°C, for example, 75°C, 80°C, or 85°C.

[0037] Preferably, the time for the heating reaction is 1 to 5 hours, for example, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, or 4.5 hours.

[0038] Preferably, the post-treatment includes washing and drying. Preferably, in step (b), the mixing comprises first mixing the raw material obtained in the post-treatment of step (a) with methyl methacrylate monomer, and then mixing with an initiator.

[0039] Preferably, the reaction includes a first reaction, a second reaction, and a third reaction. Preferably, the first reaction is carried out at a temperature of 70 to 80°C (for example, 72°C, 74°C, 76°C, or 78°C) and is continued until the reaction system becomes viscous.

[0040] Preferably, the time for the first reaction is 3 to 5 hours, for example, 3.5 hours, 4.5 hours, or 5 hours. Preferably, the temperature of the second reaction is 40 to 60°C, for example, 45°C, 50°C, or 55°C. Preferably, the time for the second reaction is 10 to 30 hours, for example, 15 hours, 20 hours, or 25 hours.

[0041] Preferably, the temperature of the third reaction is 90 to 110°C, for example, 95°C, 100°C, or 105°C. Preferably, the time for the third reaction is 1 to 5 hours, for example, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, or 4.5 hours.

[0042] Preferably, the pressure of the press is 1 to 10 MPa, for example, 2 MPa, 4 MPa, 6 MPa, or 8 MPa. Preferably, the pressing time is 1 to 5 minutes, for example, 2 minutes, 3 minutes, or 4 minutes.

[0043] Preferably, in step (2), the infiltration is carried out under vacuum. Preferably, the permeation time is 3 to 4 hours, for example 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours. Preferably, the curing temperature is 120 to 160°C, for example 130°C, 140°C, or 150°C.

[0044] Preferably, the curing pressure is 200 to 300 MPa, for example, 220 MPa, 240 MPa, 260 MPa, or 280 MPa. Preferably, the curing time is 60 to 90 minutes, for example, 65 minutes, 70 minutes, 75 minutes, 80 minutes, or 85 minutes.

[0045] In a preferred embodiment, the preparation method comprises the following steps: Step (1): An acrylic acid ester-based resin monomer, a thermal initiator, and a cage silsesquioxane having a methacrylic acid ester as a functional group are mixed and reacted to obtain the resin. Sodium aluminosilicate, a solvent, a silane coupling agent, and methyl methacrylate monomer are mixed and dispersed under stirring and ultrasonic waves, and then reacted at 70 to 90°C for 1 to 5 hours, washed, and dried. The resulting raw material is then mixed with methyl methacrylate monomer and an initiator in that order, and reacted at 70 to 80°C until the reaction system becomes viscous. Then, the reaction is continued at 40 to 60°C for 10 to 30 hours, and finally, the reaction is continued at 90 to 110°C for 1 to 5 hours to obtain a ceramic body raw material. The ceramic body raw material is immersed in the dispersion liquid and pressed under a pressure of 1 to 10 MPa for 1 to 5 minutes to obtain the ceramic body. Step (2): The ceramic body is immersed in resin, and the resin is allowed to infiltrate under vacuum for 3 to 4 hours, and then cured for 60 to 90 minutes under conditions of a temperature of 120 to 160°C and a pressure of 200 to 300 MPa to obtain the resin-infiltrated ceramic. Compared with the prior art, the present invention has the following beneficial effects: (1) The resin-infiltrated ceramics of the present invention have excellent mechanical properties, fracture toughness, bending strength, and hardness similar to those of human teeth, as well as low shrinkage characteristics, making them suitable for CAD / CAM cutting and applicable as dental crown and bridge restorative materials. (2) The resin-infiltrated ceramic according to the present invention has an elastic modulus of 20.5±1.4 to 24.2±1.4 GPa, a flexural strength of 211.8±5.4 to 291.8±8.1 MPa, a Vickers hardness of 2.2±0.2 to 3.3±0.2 GPa, and a shrinkage rate of 1.87% or less. DETAILED DESCRIPTION OF THE INVENTION

[0046] The technology of the present invention will be further described below through specific embodiments. The following examples are only for those skilled in the art to understand the present invention, and are not intended to specifically limit the present invention.

[0047] Example 1 This embodiment provides a resin-infiltrated ceramic, which includes a ceramic body and a resin provided inside and on the surface of the ceramic body. The ceramic body comprises sodium aluminosilicate modified with polymethylmethacrylate. The raw materials for preparing the resin include an acrylic acid ester-based resin monomer and a cage-type silsesquioxane having a methacrylic acid ester as a functional group.

[0048] In this example, the structural formula of the cage-type silsesquioxane having a methacrylic acid ester as a functional group (POSS-MA) is shown in Formula I. [ka] Each R is a methacrylic acid ester functional group, specifically a methacryloyloxypropyl group, and has the following structural formula: [ka]

[0049] The resin-infiltrated ceramics can be obtained by the following preparation method, which includes the following steps: Step (1) Preparation of resin 0.5% benzoyl peroxide and 5% POSS-MA were added to triethylene glycol dimethacrylate (TEGDMA) and stirred at room temperature at 150 rpm for 1 hour. Then, bisphenol A glycidyl methacrylate (Bis-GMA, CAS number: 1565-94-2) was weighed out in a 5:5 ratio and added to the reaction system. The mixture was stirred for 2 hours until thoroughly mixed uniformly, and then set aside. Step (2) Preparation of sodium aluminosilicate ceramic powder 1000 mL of absolute ethanol, 30 g of KH-570, and 30 g of sodium aluminosilicate powder were added to a 3000 mL three-neck flask, ultrasonically dispersed with stirring in an ultrasonic cleaner for 15 minutes, and then refluxed in an 80°C water bath for 3 hours. After the reaction was completed, the mixture was centrifuged, and the precipitate was washed three times each with absolute ethanol and distilled water, dried in a vacuum, and finally finely ground in a mortar to obtain modified sodium aluminosilicate. 300 mL of MMA was added to a 3000 mL three-neck flask, followed by 600 g of modified sodium aluminosilicate. After 30 minutes of ultrasonic vibration dispersion, AIBN was added and prepolymerization was carried out in a 75°C water bath with stirring. After 3 hours of reaction, the reaction mixture began to thicken. It was then quickly poured into a 50 mL test tube and polymerization continued in a 50°C water bath for another 20 hours. Finally, the temperature was raised to 100°C and reaction continued for another 3 hours. After cooling and demolding, the resulting sodium aluminosilicate ceramic powder, polymethylmethacrylate-modified sodium aluminosilicate, was obtained. Step (3) Preparation of ceramic body 100 g of the prepared sodium aluminosilicate ceramic powder was weighed out and uniformly impregnated with 20 mL of a 3% aqueous solution of polyvinyl alcohol. The powder was then dried in an oven at 80°C, transferred to a steel mold, and pressed at 5 MPa for 3 minutes to form a ceramic body with a porosity of 25%. Step (4) Preparation of resin-infiltrated ceramics The ceramic body prepared by the above steps was completely immersed in the resin system, and the whole was placed in a vacuum device to a vacuum degree of -0.1 MPa. The body was kept immersed in the vacuum state for 3 hours until the body was completely immersed in the resin system. The sodium aluminosilicate ceramic body completely immersed in the resin was placed in a hot isostatic press and cured at 130°C and 300 MPa for 60 minutes under high temperature and pressure to obtain a translucent sodium aluminosilicate resin-infiltrated ceramic block, which was the resin-infiltrated ceramic.

[0050] Example 2 This embodiment provides a resin-infiltrated ceramic, which includes a ceramic body and a resin provided inside and on the surface of the ceramic body. The ceramic body comprises sodium aluminosilicate modified with polymethylmethacrylate. The raw materials for preparing the resin include an acrylic acid ester-based resin monomer and a cage-type silsesquioxane having a methacrylic acid ester as a functional group.

[0051] The preparation method of this example is the same as that of Example 1, except for the preparation of sodium aluminosilicate ceramic powder in step (2). Step (2) of this example is specifically as follows:

[0052] 1000 mL of absolute ethanol, 30 g of KH-570, and 30 g of sodium aluminosilicate powder were added to a 3000 mL three-neck flask, ultrasonically dispersed with stirring in an ultrasonic cleaner for 15 minutes, and then refluxed in an 80°C water bath for 3 hours. After the reaction was completed, the mixture was centrifuged, and the precipitate was washed three times each with absolute ethanol and distilled water, dried in a vacuum, and finally finely ground in a mortar to obtain modified sodium aluminosilicate.

[0053] 300 mL of MMA was added to a 3000 mL three-neck flask, followed by 300 g of modified sodium aluminosilicate. After ultrasonic vibration dispersion for 30 minutes, AIBN was added and prepolymerization was carried out in a 75°C water bath with stirring. When the reaction mixture began to thicken, it was quickly poured into a 50 mL test tube and polymerization continued in a 50°C water bath for another 20 hours. Finally, the temperature was raised to 100°C and the reaction continued for 3 hours. After cooling and demolding, the resulting sodium aluminosilicate ceramic powder, polymethylmethacrylate-modified sodium aluminosilicate, was obtained.

[0054] Example 3 This embodiment provides a resin-infiltrated ceramic, which includes a ceramic body and a resin provided inside and on the surface of the ceramic body. The ceramic body comprises sodium aluminosilicate modified with polymethylmethacrylate.

[0055] The raw materials for preparing the resin include an acrylic acid ester-based resin monomer and a cage-type silsesquioxane having a methacrylic acid ester as a functional group. The preparation method of this example is the same as that of Example 1, except for the preparation of sodium aluminosilicate ceramic powder in step (2). Step (2) of this example is specifically as follows:

[0056] 1000 mL of absolute ethanol, 30 g of KH-570, and 30 g of sodium aluminosilicate powder were added to a 3000 mL three-neck flask, ultrasonically dispersed with stirring in an ultrasonic cleaner for 15 minutes, and then refluxed in an 80°C water bath for 3 hours. After the reaction was completed, the mixture was centrifuged, and the precipitate was washed three times each with absolute ethanol and distilled water, dried in vacuum, and finally finely ground in a mortar.

[0057] 300 mL of MMA was added to a 3000 mL three-neck flask, followed by 100 g of modified sodium aluminosilicate. After 30 minutes of ultrasonic vibration dispersion, AIBN was added and prepolymerization was carried out in a 75°C water bath with stirring. When the reaction mixture began to thicken, it was quickly poured into a 50 mL test tube and polymerization continued in a 50°C water bath for another 20 hours. Finally, the temperature was raised to 100°C and the reaction continued for 3 hours. After cooling and demolding, the resulting sodium aluminosilicate ceramic powder, polymethylmethacrylate-modified sodium aluminosilicate, was obtained.

[0058] Example 4 This embodiment provides a resin-infiltrated ceramic, which includes a ceramic body and a resin provided inside and on the surface of the ceramic body. The ceramic body comprises sodium aluminosilicate modified with polymethylmethacrylate. The raw materials for preparing the resin include an acrylic acid ester-based resin monomer and a cage-type silsesquioxane having a methacrylic acid ester as a functional group. In this example, the cage silsesquioxane having a methacrylic acid ester as the functional group is the same as that in Example 1.

[0059] The resin-infiltrated ceramics can be obtained by the following preparation method, which includes the following steps: Step (1) Preparation of resin 1.5% benzoyl peroxide and 12% POSS-MA are added to triethylene glycol dimethacrylate (TEGDMA) and stirred at room temperature at 150 rpm for 1 hour. UDMA (an addition product of 2-hydroxyethyl methacrylate and 2,2,4-trimethylhexamethylene-1,6-diisocyanate) is then weighed out in a ratio of 3:7 and added to the reaction system. The mixture is stirred for 2 hours until it is thoroughly mixed uniformly, and then set aside. Step (2) Preparation of sodium aluminosilicate ceramic powder 1000 mL of absolute ethanol, 30 g of KH-570, and 120 g of sodium aluminosilicate powder were added to a 3000 mL three-neck flask, ultrasonically dispersed with stirring in an ultrasonic cleaner for 20 minutes, and then refluxed in an 80°C water bath for 3 hours. After the reaction was completed, the mixture was centrifuged, and the precipitate was washed three times each with absolute ethanol and distilled water, dried in vacuum, and finally finely ground in a mortar to obtain modified sodium aluminosilicate. A 3000 mL three-neck flask was charged with 400 mL of MMA and 80 g of modified sodium aluminosilicate. After 30 minutes of ultrasonic vibration dispersion, AIBN was added and prepolymerization was carried out in a 72°C water bath with stirring. After 5 hours of reaction, the reaction mixture began to thicken. The mixture was quickly poured into a 1000 mL beaker and polymerization continued in a 60°C water bath for another 15 hours. Finally, the temperature was raised to 105°C and reaction continued for 4 hours. After cooling and demolding, the resulting sodium aluminosilicate ceramic powder, polymethylmethacrylate-modified sodium aluminosilicate, was obtained. Step (3) Preparation of ceramic body 100 g of the prepared sodium aluminosilicate ceramic powder was weighed out and uniformly impregnated with 20 mL of a 3% aqueous solution of polyvinyl alcohol. The powder was then dried in an oven at 80°C, transferred to a steel mold, and pressed at 6 MPa for 2 minutes to form a ceramic body with a porosity of 22%. Step (4) Preparation of resin-infiltrated ceramics The ceramic body prepared by the above steps was completely immersed in the resin system, and the whole was placed in a vacuum device to a vacuum degree of -0.1 MPa. The body was kept immersed in the vacuum state for 3.5 hours until the body was completely immersed in the resin system. The sodium aluminosilicate ceramic body completely immersed in the resin was placed in a hot isostatic press and cured at 140°C and 250 MPa for 70 minutes under high temperature and pressure to obtain a translucent sodium aluminosilicate resin-infiltrated ceramic block, which was the resin-infiltrated ceramic.

[0060] Example 5 This embodiment provides a resin-infiltrated ceramic, which includes a ceramic body and a resin provided inside and on the surface of the ceramic body. The ceramic body comprises sodium aluminosilicate modified with polymethylmethacrylate. The raw materials for preparing the resin include an acrylic acid ester-based resin monomer and a cage-type silsesquioxane having a methacrylic acid ester as a functional group. In this example, the cage silsesquioxane having a methacrylic acid ester as the functional group is the same as that in Example 1.

[0061] The resin-infiltrated ceramics can be obtained by the following preparation method, which includes the following steps: Step (1) Preparation of resin 1.5% benzoyl peroxide and 8% POSS-MA were added to 1,10-decanediol dimethacrylate and stirred at room temperature at 150 rpm for 1 hour. Then, bisphenol A glycidyl methacrylate (Bis-GMA) was weighed out in a ratio of 4:6 and added to the reaction system. The mixture was stirred for 2 hours until thoroughly mixed and uniform, and then set aside. Step (2) Preparation of sodium aluminosilicate ceramic powder 1000 mL of absolute ethanol, 30 g of KH-570, and 120 g of sodium aluminosilicate powder were added to a 3000 mL three-neck flask, ultrasonically dispersed with stirring in an ultrasonic cleaner for 20 minutes, and then refluxed in an 80°C water bath for 3 hours. After the reaction was completed, the mixture was centrifuged, and the precipitate was washed three times each with absolute ethanol and distilled water, dried in vacuum, and finally finely ground in a mortar to obtain modified sodium aluminosilicate. A 3000 mL three-neck flask was charged with 400 mL of MMA and 80 g of modified sodium aluminosilicate. After 30 minutes of ultrasonic vibration dispersion, AIBN was added and prepolymerization was carried out in a 78°C water bath with stirring. After 3.5 hours of reaction, the reaction mixture began to thicken. The mixture was quickly poured into a 1000 mL beaker and polymerization continued in a 60°C water bath for another 15 hours. Finally, the temperature was raised to 110°C and the mixture was reacted for 3 hours. After cooling and demolding, the resulting sodium aluminosilicate ceramic powder, polymethylmethacrylate-modified sodium aluminosilicate, was obtained. Step (3) Preparation of ceramic body 100 g of the prepared sodium aluminosilicate ceramic powder was weighed out and uniformly impregnated with 25 mL of a 3% aqueous solution of polyvinyl alcohol. The powder was then dried in an oven at 80°C, transferred to a steel mold, and pressed under a pressure of 6 MPa for 2 minutes to form a ceramic body with a porosity of 28%. Step (4) Preparation of resin-infiltrated ceramics The ceramic body prepared by the above steps was completely immersed in the resin system, and the whole was placed in a vacuum device to a vacuum degree of -0.1 MPa. The body was kept immersed in the vacuum state for 4 hours until the body was completely immersed in the resin system. The sodium aluminosilicate ceramic body completely immersed in the resin was placed in a hot isostatic press and cured at 140°C and 220 MPa for 90 minutes under high temperature and pressure to obtain a translucent sodium aluminosilicate resin-infiltrated ceramic block, which was the resin-infiltrated ceramic.

[0062] Example 6 In this example, R in the cage silsesquioxane having a methacrylic acid ester as the functional group is a vinyl group, and the rest is the same as in Example 1.

[0063] Comparative Example 1 In this comparative example, the ceramic body is unmodified sodium aluminosilicate, that is, the preparation does not include step (2), and sodium aluminosilicate is used in step (3), and the rest is the same as in Example 1.

[0064] Comparative Example 2 In this comparative example, the raw materials for preparing the resin were the same as those in Example 1, except that a cage silsesquioxane without a methacrylic acid ester was used instead of a cage silsesquioxane with a methacrylic acid ester as a functional group. The structural formula is as follows, where R is a vinyl group. [ka]

[0065] Comparative Example 3 In this comparative example, the raw material for preparing the resin was the same as in Example 1, except that a cage silsesquioxane without a methacrylic acid ester was used instead of a cage silsesquioxane having a methacrylic acid ester as a functional group. The structural formula is as follows, where R is a formyl group. [ka]

[0066] Comparative Example 4 In this comparative example, the sodium aluminosilicate was replaced with the same mass of zirconia, and the other conditions were the same as in Example 1.

[0067] Functional testing The following tests were carried out using the resin-infiltrated ceramics according to Examples 1 to 6 and Comparative Examples 1 to 4 and blank human teeth. (1) Elastic modulus and flexural strength: The resin-infiltrated ceramics were cut into test pieces measuring 1.2 mm x 4.0 mm x 18 mm, and the surfaces were wet-polished with 2000-mesh emery paper. Using a tensile testing device, a three-point bending test was carried out under conditions of a support interval of 12 mm and a crosshead speed of 1.0 mm / min, and the elastic modulus and flexural strength were evaluated as the average value of 10 samples. (2) Vickers hardness: The test surface of the resin-impregnated ceramic was wet-polished with 2000-mesh emery paper to make the sample surface smooth. The test was carried out using a Vickers hardness tester, with the test force value set to "2," and measurements were taken at three points on the resin-impregnated ceramic to calculate the average value. (3) Shrinkage: The shrinkage of resin-infiltrated ceramics is expressed as the volumetric shrinkage rate. That is, the volumetric shrinkage rate is calculated by measuring the density of the same resin-infiltrated ceramic block before and after hardening. Total volume shrinkage rate = (specimen density after curing - specimen density before curing) / specimen density after curing × 100%

[0068] The test results are summarized in Table 1. [Table 1]

[0069] As can be seen from an analysis of the data in Table 1, the resin-infiltrated ceramic according to the present invention has an elastic modulus of 20.5±1.4 to 24.2±1.4 GPa, a flexural strength of 211.8±5.4 to 291.8±8.1 MPa, a Vickers hardness of 2.2±0.2 to 3.3±0.2 GPa, and a shrinkage rate of 1.87% or less. The resin-infiltrated ceramic according to the present invention has excellent mechanical properties, fracture toughness, flexural strength, and hardness similar to those of human teeth, as well as low shrinkage, making it suitable for CAD / CAM cutting and applicable as a dental crown and bridge restorative material.

[0070] As can be seen from an analysis of Comparative Examples 1 to 4 and Example 1, the functions of Comparative Examples 1 to 4 are inferior to that of Example 1, thus proving that the resin-impregnated ceramics according to the present invention have superior functions.

[0071] As can be seen from the analysis of Example 6 and Example 1, the functionality of Example 6 is inferior to that of Example 1. Therefore, it is preferable that all R groups in the cage silsesquioxane having a methacrylate ester as the functional group are methacrylate ester functional groups, which has been proven to contribute to improving the functionality of resin-infiltrated ceramics.

[0072] Although the detailed method of the present invention has been described through the above examples, the present invention is not limited to the above detailed method, i.e., the present invention is not implemented depending on the above detailed method. Those skilled in the art should understand that any improvement of the present invention, equivalent substitution of each raw material in the product of the present invention, addition of auxiliary ingredients, selection of specific methods, etc., are all within the protection scope and disclosed scope of the present invention.

Claims

1. a ceramic body and a resin provided inside and on a surface of the ceramic body, the ceramic body comprises sodium aluminosilicate modified with polymethylmethacrylate; The raw materials for preparing the resin include an acrylic ester resin monomer and a cage-type silsesquioxane having a methacrylic ester as a functional group. Resin-infiltrated ceramics characterized by:

2. The total mass of the resin-infiltrated ceramic is 100%, and the mass percentage of the ceramic body is 70% to 80%; The total mass of the resin-impregnated ceramic is 100%, and the mass percentage of the resin is 20% to 30%.

2. The resin-impregnated ceramic according to claim 1.

3. The porosity of the ceramic body is 10% to 55%.

3. The resin-impregnated ceramic according to claim 1 or 2.

4. The raw materials for preparing the ceramic body include sodium aluminosilicate, a solvent, a silane coupling agent, a methyl methacrylate monomer, and an initiator; The total mass of the raw materials for preparing the ceramic body is 100%, and the raw materials for preparing the ceramic body are Sodium aluminosilicate: 20% to 40% Solvent: 30% to 60% Silane coupling agent: 10% to 25% Methyl methacrylate monomer: 15% to 25%; Initiator: 0.02% to 0.1% 4. The resin-impregnated ceramic according to claim 1.

5. The sodium aluminosilicate has an average particle size of 0.4 to 3.2 μm, the solvent comprises absolute ethanol; The initiator comprises azobisisobutyronitrile 5. The resin-impregnated ceramic according to claim 4.

6. The chemical formula of a cage-type silsesquioxane having a methacrylate ester as a functional group is (RSiO ３／２ ) n, The n is 6, 8, 10, 12, or 14, and at least one of the n Rs is selected from functional methacrylic acid esters; The resin preparation raw materials further include a thermal initiator; The thermal initiator includes one or a combination of at least two of dicumyl peroxide, t-butyl peroxide, and benzoyl peroxide; The t-butyl peroxide includes t-butyl peracetate and / or t-butyl peroxybenzoate.

4. The resin-impregnated ceramic according to claim 1.

7. The structural formula of the cage-type silsesquioxane having a methacrylic acid ester as a functional group is as shown in Formula I, 【Chemistry 1】 R is independently selected from hydrogen, a methacrylate functional group, and other unsaturated bond-containing functional groups.

7. The resin-impregnated ceramic according to claim 6.

8. The total mass of the raw materials for preparing the resin is 100%, and the raw materials for preparing the resin are expressed as mass percentages as follows: Acrylic acid ester resin monomer: 70% to 95% Cage-type silsesquioxane having a methacrylic acid ester as a functional group: 0.003% to 18%; Thermal initiator: 0.35% to 2% 7. The resin-impregnated ceramic according to claim 6.

9. The acrylic acid ester-based resin monomer includes a monofunctional (meth)acrylic acid ester or a polyfunctional (meth)acrylic acid ester.

9. The resin-impregnated ceramic according to claim 1, 7 or 8.

10. The acrylic acid ester resin monomers include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, paracumylphenoxyethylene glycol methacrylate, 2-(2-biphenyloxy)ethyl methacrylate, bisphenol A dimethacrylate, an adduct of methacrylic acid and bisphenol A diglycidyl ether, an adduct of 2-hydroxyethyl methacrylate and 2,2,4-trimethylhexamethylene-1,6-diisocyanate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and the like. methacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, glycerol dimethacrylate, glycerol trimethacrylate, 1,4-butanediol dimethacrylate, 1,10-decanediol dimethacrylate, bis(methylacryloyloxymethyl)tricyclo-[5.2.1.02,6]decane, polyethylene glycol dimethacrylate or polypropylene glycol dimethacrylate, polyethylene glycol 200 dimethacrylate, polyethylene glycol 400 dimethacrylate, 1,12-dodecanediol dimethacrylate, or a mixture thereof.

10. The resin-impregnated ceramic according to claim 9.

11. A method for preparing the resin-infiltrated ceramic according to any one of claims 1 to 10, comprising: and a step of infiltrating the resin into the ceramic body to obtain the resin-infiltrated ceramic.

11. A method for preparing resin-infiltrated ceramics according to any one of claims 1 to 10.

12. a step (1) of mixing and reacting an acrylic ester-based resin monomer, a thermal initiator, and a cage-type silsesquioxane having a methacrylic ester functional group to obtain the resin, and then mixing sodium aluminosilicate, a solvent, a silane coupling agent, a methyl methacrylate monomer, and an initiator to polymerize in situ, and pressing the mixture to obtain the ceramic body; and (2) a step of immersing the ceramic body in a resin, allowing the resin to penetrate and harden, thereby obtaining the resin-infiltrated ceramic.

12. The method of claim 11 .

13. In step (1), the in situ polymerization comprises: Step (a) of mixing and dispersing sodium aluminosilicate, a solvent, a silane coupling agent, and a methyl methacrylate monomer, reacting them by heating, and then performing post-treatment; and step (b) mixing and reacting the raw material obtained from the post-treatment of step (a) with methyl methacrylate monomer and an initiator to complete the in-situ polymerization.

12. The method of claim 11 .

14. In step (a), the mixing and dispersing method includes stirring and ultrasonic waves; The temperature of the heating reaction is 70 to 90°C, The heating reaction time is 1 to 5 hours, The post-treatment includes washing and drying.

14. The method of claim 13.

15. In step (b), the mixing step includes first mixing the raw material obtained by the post-treatment in step (a) with methyl methacrylate monomer, and then mixing with an initiator.

14. The method of claim 13.

16. In step (b), the reaction includes a first reaction, a second reaction, and a third reaction; The first reaction is carried out at a temperature of 70 to 80°C and continued until the reaction system becomes viscous. The first reaction time is 3 to 5 hours, The temperature of the second reaction is 40 to 60°C, The time for the second reaction is 10 to 30 hours, The temperature of the third reaction is 90 to 110°C, The third reaction time is 1 to 5 hours.

14. The method of claim 13.

17. The pressure of the press is 1 to 10 MPa, The pressing time is 1 to 5 minutes.

13. The method of claim 12.

18. In step (2), the infiltration is carried out under vacuum; The duration of the penetration is 3 to 4 hours, The curing temperature is 120 to 160°C, The pressure of the curing is 200 to 300 MPa, The curing time is 60 to 90 minutes.

13. The method of claim 12.

19. a step (1) of mixing and reacting an acrylic acid ester-based resin monomer, a thermal initiator, and a cage-type silsesquioxane having a methacrylic acid ester as a functional group to obtain the resin; mixing and dispersing sodium aluminosilicate, a solvent, a silane coupling agent, and a methyl methacrylate monomer under stirring and ultrasonic waves; reacting at 70 to 90°C for 1 to 5 hours; washing and drying; mixing the obtained raw material with the methyl methacrylate monomer and the initiator in order; reacting at 70 to 80°C until the reaction system becomes viscous; subsequently reacting at 40 to 60°C for 10 to 30 hours; and finally reacting at 90 to 110°C for 1 to 5 hours to obtain a ceramic body raw material; immersing the ceramic body raw material in the dispersion and pressing under a pressure of 1 to 10 MPa for 1 to 5 minutes to obtain the ceramic body; and (2) a step of immersing the ceramic body in a resin, infiltrating the resin under vacuum for 3 to 4 hours, and then curing the resin for 60 to 90 minutes under conditions of a temperature of 120 to 160°C and a pressure of 200 to 300 MPa to obtain the resin-infiltrated ceramic.

19. A method according to any one of claims 11 to 18.

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