Silanization modified zirconium oxide powder, cleaning agent and preparation method of silanization modified zirconium oxide powder

Abstract

The invention provides silanization modified zirconium oxide powder, a cleaning agent and a preparation method of the silanization modified zirconium oxide powder, surface grafting groups of the silanization modified zirconium oxide powder comprise amino groups and epoxy groups, and the cleaning agent is alkaline and contains the silanization modified zirconium oxide powder. A large number of amino groups and epoxy groups are grafted on the surface of the silanization modified zirconium oxide powder, the amino groups can generate charge adsorption with salivary protein in an alkaline environment so as to weaken the binding force between a protein film and a dental restoration, and the epoxy groups are activated in the alkaline environment so as to open a ring and generate hydroxyl groups, so that the silanization modified zirconium oxide powder can be used for preparing the dental restoration. According to the invention, silanized zirconium oxide is added into a dental restoration, so that a Zr-O-P bond between a protein membrane and the restoration made of the zirconium oxide material is broken, the affinity of Zr < 4 + > in the silanized zirconium oxide to a phosphate group in saliva is higher than that of the restoration made of the zirconium oxide material, and finally, the cleaning agent can effectively clean saliva and blood remaining on the dental restoration.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of dental cleaning agent materials, in particular to a silanized modified zirconia powder, a cleaning agent and a preparation method thereof. BACKGROUND

[0002] In order to clean the surface of the dental restoration after try-in, restore its shear bond strength, the commonly used methods include sandblasting, using solvents to remove saliva and blood contamination on the inner surface of the restoration. Sandblasting is the most effective method to remove the contamination on the surface of the restoration, and air sandblasting can remove the contaminants on the surface of the restoration by mechanical impact, expose the fresh bonding surface, so that the resin adhesive and the restoration material form a chemical and durable bonding effect. For example, compared with the non-contamination group, sandblasting can increase the shear bond strength of the contaminated zirconia restoration. However, there is still controversy about re-sandblasting, and sandblasting has an adverse effect on the phase transition of zirconia, which may weaken the mechanical strength of zirconia. In addition, the complex geometry of the inner surface of the clinical restoration is not as flat as used in experiments, and it is difficult to remove contaminants by sandblasting. Common solvents include phosphoric acid, ethanol and cleaning agent Ivoclean, but the cleaning effect is not satisfactory. Although phosphoric acid can effectively remove carbon-based contaminants in saliva and blood contamination, the shear bond strength is improved, but the shear bond strength does not return to the level of non-contact contamination, because the zirconia surface will have phosphorus residues after phosphoric acid treatment, and the residual phosphoric acid group will chemically combine with the hydroxyl group on the surface of zirconia, thereby occupying the binding site of the phosphoric acid monomer and zirconia in the bonding system, resulting in a decrease in the shear bond strength of the zirconia restoration. Therefore, it is not recommended to use phosphoric acid as a cleaning method to remove saliva contamination. Ethanol treatment of saliva and blood contamination will cause the denaturation and fixation of protein residues therein, making it difficult to remove, and thus cannot effectively remove organic contaminants such as saliva, thereby resulting in a decrease in the shear bond strength of the zirconia restoration. Therefore, it is not recommended to use ethanol as a cleaning method to remove saliva and blood contamination.

[0003] Therefore, how to solve the problem of the decrease in the shear bond strength of the dental restoration when the dental restoration is contaminated by saliva and blood after try-in and then bonded with the tooth in the subsequent process is urgently needed to be researched. SUMMARY

[0004] The purpose of the present application is to provide a silanized modified zirconia powder, a cleaning agent and a preparation method thereof, so as to solve the problem of the decrease in the shear bond strength of the dental restoration when the dental restoration is contaminated by saliva and blood after try-in and then bonded with the tooth in the subsequent process.

[0005] To achieve the above purpose, the present application provides the following technical solutions:

[0006] A silanized modified zirconia powder, wherein the surface grafted groups of the silanized modified zirconia powder include amino and epoxy groups.

[0007] To achieve the above objectives, the present invention also provides the following technical solution:

[0008] A method for preparing the above-mentioned silanized zirconium oxide, the method comprising the following steps:

[0009] S1, providing zirconia powder and adding water to form a slurry, or providing a slurry containing zirconia powder;

[0010] S2, mix the slurry from step S1 with the stabilizer;

[0011] S3, Adjust the pH value of the material obtained in step S2;

[0012] S4. The material obtained in step S3 is mixed with an amino-containing silane coupling agent and an epoxy-containing silane coupling agent, and reacted to obtain a slurry containing the silanized modified zirconium oxide powder.

[0013] To achieve the above objectives, the present invention also provides the following technical solution:

[0014] A cleaning agent for dental restorations, the cleaning agent comprising:

[0015] Such as the silanized modified zirconia powder described above, or the silanized modified zirconia powder obtained by the above method;

[0016] water;

[0017] The cleaning agent has a pH value greater than 13.

[0018] To achieve the above objectives, the present invention also provides the following technical solution:

[0019] A method for preparing the above-mentioned cleaning agent, the method comprising the following steps:

[0020] S1, providing zirconia powder and adding water to form a slurry, or providing a slurry containing zirconia powder;

[0021] S2, mix the slurry containing zirconium oxide powder from step S1 with a stabilizer;

[0022] S3, Adjust the pH value of the material obtained in step S2;

[0023] S4, the material obtained in step S3 is mixed with an amino-containing silane coupling agent and an epoxy-containing silane coupling agent, and reacted to obtain a slurry containing silanized modified zirconium oxide powder.

[0024] S5, mix the slurry obtained in step S4 with water to obtain the cleaning agent.

[0025] Other applicable areas will become apparent from the description provided in this disclosure.

[0026] The descriptions and specific examples in the invention summary are intended to be illustrative only and are not intended to limit the scope of this disclosure.

[0027] Compared with the prior art, the technical solution provided by the present invention has the following beneficial effects:

[0028] 1. This invention provides a silanized modified zirconia powder, a cleaning agent, and a method for preparing the same. The surface grafted groups of the silanized modified zirconia powder include amino and epoxy groups, and the cleaning agent is alkaline and contains the aforementioned silanized modified zirconia powder.

[0029] 2. The silanized modified zirconia powder provided by this invention has a large number of amino and epoxy groups grafted onto its surface. In an alkaline environment, the amino groups can undergo charge adsorption with salivary proteins, thereby weakening the binding force between the protein membrane and the dental restoration. Meanwhile, the epoxy groups are activated in an alkaline environment, opening the ring and generating hydroxyl groups, thus breaking the Zr-OP bond between the protein membrane and the zirconia restoration. Furthermore, the Zr in the silanized modified zirconia powder... 4+ The dental restoration has a stronger affinity for the phosphate groups in saliva than that made of zirconium oxide, which ultimately allows the cleaning agent to effectively remove saliva and blood residue from the dental restoration.

[0030] 3. The cleaning agent provided by this invention can effectively clean the saliva and blood remaining on the dental restoration after trial fitting, thereby ensuring that a high shear bond strength can be obtained when the dental restoration is subsequently bonded to the tooth. Attached Figure Description

[0031] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those skilled in the art, other solutions can be obtained based on these drawings without creative effort.

[0032] Figure 1 A flowchart illustrating a method for preparing silanized zirconium oxide according to some embodiments of the present invention;

[0033] Figure 2 This is a flowchart illustrating a method for preparing a cleaning agent according to some embodiments of the present invention. Detailed Implementation

[0034] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. It should be understood that the specific embodiments described herein are only for illustration and explanation of the present invention and are not intended to limit the present invention.

[0035] Any specific numerical values ​​disclosed herein (including the endpoints of numerical ranges) are not limited to their exact values, but should be understood to also include values ​​close to the exact value, such as all possible values ​​within ±5% of the exact value. Furthermore, with respect to the disclosed numerical ranges, one or more new numerical ranges can be obtained by arbitrarily combining the endpoint values ​​of the range, the endpoint values ​​with specific point values ​​within the range, and the specific point values ​​themselves; these new numerical ranges should also be considered as specifically disclosed herein.

[0036] The terminology used in this disclosure is for the purpose of describing particular exemplary embodiments only and is not intended to be limiting. Unless the context clearly indicates otherwise, the singular forms “a,” “an,” and “the” as used in this disclosure are intended to include the plural forms as well. The terms “comprising,” “including,” “containing,” and “having” are inclusive and thus describe the presence of said features, elements, compositions, steps, integers, operations, and / or components, but do not exclude the presence or inclusion of one or more other features, integers, steps, operations, elements, components, and / or sets thereof. Although the open-ended term “comprising” should be understood as a non-limiting term used to describe and claim the various embodiments described in this disclosure, in some aspects it may instead be understood as a more restrictive and limiting term, such as “consisting of” or “substantially consisting of.” Thus, for any given embodiment describing a composition, material, component, element, feature, integer, operation, and / or process step, this disclosure also particularly includes embodiments consisting of or substantially consisting of such compositions, materials, components, elements, features, integers, operations, and / or process steps. In the case of “consisting of…”, the alternative embodiments exclude any additional compositions, materials, components, elements, features, integers, operations and / or process steps. In the case of “essentially composed of…”, any additional compositions, materials, components, elements, features, integers, operations and / or process steps that substantially affect the essential and novel characteristics are excluded from such embodiments. However, any compositions, materials, components, elements, features, integers, operations and / or process steps that do not substantially affect the essential and novel characteristics may be included in the embodiments.

[0037] Any method steps, processes, and operations described in this disclosure should not be construed as necessarily requiring them to be performed in a particular order as discussed or shown, unless explicitly specified. It should also be understood that additional or alternative steps may be used unless otherwise stated.

[0038] In this application, except where expressly stated, any matters or issues not mentioned are directly applicable to those known in the art without any modification. Furthermore, any implementation described in this disclosure may be freely combined with one or more other implementations described in this disclosure, and the resulting technical solutions or concepts shall be considered part of the original disclosure or original record of this application, and should not be regarded as new content not disclosed or anticipated in this disclosure, unless those skilled in the art consider the combination to be clearly unreasonable.

[0039] Unless otherwise stated, the terms used herein have the same meaning as commonly understood by those skilled in the art, and if a term is defined herein and its definition differs from the common understanding in the art, the definition herein shall prevail.

[0040] Unless otherwise stated, when % is mentioned in this document, it refers to wt%.

[0041] First aspect

[0042] This invention provides a silanized modified zirconia powder, wherein the surface-grafted groups of the silanized modified zirconia powder include amino and epoxy groups. It is worth noting that the amino groups grafted onto the surface of the silanized modified zirconia powder can undergo charge adsorption with salivary proteins in an alkaline environment, thereby weakening the binding force between the protein membrane and the dental restoration. Meanwhile, the epoxy groups are activated in an alkaline environment, opening the ring and generating hydroxyl groups, thus breaking the Zr-OP bond between the protein membrane and the zirconia restoration. Furthermore, the Zr in the silanized zirconia... 4+ The dental restoration has a stronger affinity for the phosphate groups in saliva than that made of zirconium oxide, which ultimately allows the cleaning agent to effectively remove saliva and blood residue from the dental restoration.

[0043] In some embodiments of the present invention, the content of the amino group is 0.001 to 0.6 wt% of the mass of the zirconia powder. Within this content range, the positively charged amino groups can attract the negatively charged salivary proteins in an alkaline environment, thereby allowing the silanized zirconia to adsorb the salivary proteins. This weakens the electrostatic bonding between the protein film and the dental restoration, making the salivary proteins easily rinsed away, thus achieving cleaning of the dental restoration after trial fitting. Exemplarily, the content of the amino group can be any one of 0.003 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.3 wt%, or 0.5 wt%, or a range consisting of any two of these values, or any value within that range.

[0044] In some embodiments of the present invention, the content of the epoxy groups is 0.001 to 1 wt% of the mass of the zirconia powder. Epoxy groups within this content range can be activated under alkaline conditions, then undergo ring-opening to generate hydroxyl groups, thereby disrupting the Zr-OP bonds formed between the protein film in saliva and the zirconia dental restoration. This weakens the adsorption between the salivary protein film and the dental restoration, allowing the salivary proteins to be easily rinsed away, thus achieving cleaning of the dental restoration after trial fitting. For example, the content of the epoxy groups can be any one of 0.003 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.5 wt%, or 0.7 wt%, or a range consisting of any two of these values, or any value within that range.

[0045] In some embodiments of the present invention, the grafting rate of the silanized modified zirconia powder is 0.1–8 wt%. It is worth noting that in the specification of the present invention, the grafting rate of the silanized modified zirconia powder is quantified as a percentage or mass fraction of the mass of the grafted groups relative to the total mass of the silanized modified zirconia powder. It is understood that the grafting rate of the silanized modified zirconia powder can be measured by methods such as the calcination loss-on-weight method. That is, the mass of the silanized modified zirconia powder before calcination is subtracted from the mass of the calcined silanized modified zirconia powder after calcination; the larger the difference, the larger the mass of the silanized layer, i.e., the larger the grafting rate. Alternatively, the difference between the mass of the silanized modified zirconia powder before calcination and the mass of the calcined silanized modified zirconia powder after calcination can be divided by the mass of the silanized modified zirconia powder before calcination, and then multiplied by 100%; the larger the percentage value obtained, the larger the mass of the silanized layer, i.e., the larger the grafting rate.

[0046] In some embodiments of the present invention, the particle size D50 of the silanized modified zirconia powder is 1–10 μm, and the D90 is 10–50 μm. Exemplarily, D50 can be any one of 3 μm, 5 μm, or 8 μm, or a range consisting of any two values, or any value within that range; D90 can be any one of 20 μm, 30 μm, or 40 μm, or a range consisting of any two values, or any value within that range.

[0047] In some embodiments of the present invention, the particle size D50 of the zirconia powder is 0.1 to 20 μm. Exemplarily, D50 can be any one of 0.5 μm, 1 μm, 5 μm, 8 μm, 10 μm, 13 μm, 15 μm, or 18 μm, or a range consisting of any two of these values, or any value within that range.

[0048] In some embodiments of the present invention, the particle size D90 of the zirconia powder is 5 to 50 μm. Exemplarily, D90 can be any one of 7 μm, 10 μm, 20 μm, 30 μm, 40 μm, 45 μm, 47 μm, or 49 μm, or a range consisting of any two of these values, or any value within that range.

[0049] In some embodiments of the present invention, the particle size D100 of the zirconia powder is less than 100 μm. Exemplarily, D100 can be any one of 0.5 μm, 1 μm, 5 μm, 10 μm, 20 μm, 30 μm, 60 μm, or 70 μm, or a range of any two of these values, or any value within that range.

[0050] In some embodiments of the present invention, the initial particle size of the silanized modified zirconia powder is <100 nm, for example, any one or any two values ​​from 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, or 100 nm, or any value within that range, preferably 10 nm to 80 nm. It should be noted that the initial particle size, also known as the primary particle size, refers to the particle size of the primary particles forming the zirconia powder.

[0051] In some embodiments of the present invention, the amino group is attached to the zirconia powder via a silicon atom. The linking group between the amino group and the silicon atom may include an alkylene group, an ether group, or an amino group; the silicon atom may be attached to the zirconia surface via oxygen.

[0052] In some embodiments of the present invention, the epoxy group is attached to the zirconium oxide powder via a silicon atom. The linking group between the epoxy group and the silicon atom may include an alkylene group or an ether group; the silicon atom may be attached to the zirconium oxide surface via oxygen.

[0053] In some embodiments of the present invention, the silanized modified zirconia powder is used for dental cleaning, preferably for cleaning dental restorations. It is worth noting that the silanized modified zirconia powder provided by the present invention has a large number of amino and epoxy groups grafted onto its surface. The amino groups, in an alkaline environment, can undergo charge adsorption with salivary proteins, thereby weakening the binding force between the protein membrane and the dental restoration. The epoxy groups, in an alkaline environment, are activated, opening the ring and generating hydroxyl groups, thereby breaking the Zr-OP bond between the protein membrane and the zirconia restoration. Furthermore, the Zr in the silanized zirconia... 4+ The dental restoration has a stronger affinity for the phosphate groups in saliva than that made of zirconium oxide, which ultimately allows the cleaning agent to effectively remove saliva and blood residue from the dental restoration.

[0054] In some embodiments of the present invention, the silanized modified zirconium oxide powder described above is placed in an alkaline environment to clean dental restorations.

[0055] In some embodiments of the present invention, the silanized modified zirconia powder is used to clean dental restorations made of zirconia material; specifically, it can be used to clean saliva and blood adhering to the dental restorations after trial fitting.

[0056] Second aspect

[0057] See Figure 1 The present invention provides a method for preparing the above-mentioned silanized modified zirconia powder, the method comprising the following steps: S1, providing zirconia powder and adding water to form a slurry, or providing a slurry containing zirconia powder; S2, mixing the slurry of step S1 with a stabilizer; S3, adjusting the pH value of the material obtained in step S2; S4, mixing the material obtained in step S3 with an amino-containing silane coupling agent and an epoxy-containing silane coupling agent, reacting to obtain the silanized modified zirconia powder.

[0058] In some embodiments of the present invention, in step S1, the mass ratio of zirconium oxide powder to water in the slurry is 1:(1-5). Exemplary ratios may be 1:2, 1:3, or 1:4.

[0059] In some embodiments of the present invention, the particle size of the zirconium oxide powder provided in step S1 is <100nm, for example, any one or any two values ​​of 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm or 100nm, or any value within that range, preferably 10nm to 80nm. It should be noted that the present invention uses zirconia powder with an original particle size of less than 100 nm to prepare the above-mentioned silanized surface-modified zirconia powder. During the preparation process, the above-mentioned nano-sized zirconia powder will agglomerate, and many nano-sized zirconia agglomerates will agglomerate to form larger micron-sized zirconia powder, or zirconia agglomerates. In some embodiments, the D50 of these micron-sized zirconia powder agglomerates is 0.1-20 μm, the D90 is 5-50 μm, and the D100 is less than 100 μm. Of course, in other embodiments, the particle size of the above-mentioned micron-sized agglomerates can also only meet one of the parameter ranges of D50, D90, and D100, depending on the required design requirements.

[0060] In some embodiments of the present invention, in step S2, the amount of stabilizer added is 0.1 to 5 wt% of the zirconium oxide powder. For example, the amount of stabilizer added can be any one of 0.5 wt%, 1 wt%, 2 wt%, or 3.5 wt%, or a range consisting of any two of these values, or any value within that range.

[0061] In some embodiments of the present invention, in step S2, the stabilizer is at least one of polydiallyl dimethyl ammonium chloride and propylene glycol block polyether.

[0062] In some embodiments of the present invention, in step S2, the mixture is stirred at 500-1000 rpm for 30-60 minutes at 40-50°C.

[0063] In some embodiments of the present invention, in step S3, the pH value of the material is adjusted to be greater than 13.

[0064] In some embodiments of the present invention, in step S3, a strong alkali is added at a stirring speed of at least 1200 rpm to adjust the pH value.

[0065] In some embodiments of the present invention, in step S3, the strong alkali is at least one of sodium hydroxide and potassium hydroxide.

[0066] In some embodiments of the present invention, in step S3, the amount of strong alkali added is 0.5 to 10 wt% of the material obtained in step S2. For example, the amount of strong alkali added can be any one of 0.8 wt%, 1 wt%, 2 wt%, 4 wt%, 6 wt%, 8 wt%, or 10 wt%, or a range of any two of these values, or any value within that range.

[0067] In some embodiments of the present invention, in step S4, the amino-containing silane coupling agent is at least one of N-aminoethyl-γ-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane.

[0068] In some embodiments of the present invention, in step S4, the silane coupling agent containing an epoxy group is at least one of γ-glycidoxypropyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0069] In some embodiments of the present invention, in step S4, the silane coupling agent is a mixture of N-aminoethyl-γ-aminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane in a mass ratio of (1-3):1.

[0070] In some embodiments of the present invention, in step S4, the mass ratio of γ-glycidyl etheroxypropyltrimethoxysilane to zirconium oxide powder is (1-10):100. Exemplarily, this mass ratio can be any one of 2:100, 5:100, or 8:100, or a range of any two of these values, or any value within that range.

[0071] In some embodiments of the present invention, in step S4, the reaction time is 60 to 120 minutes, the reaction temperature is 60 to 95°C, and the stirring speed during the reaction is at least 1200 rpm.

[0072] In some embodiments of the present invention, step S4.5 is further included between step S4 and step S5: drying the slurry containing the silanized modified zirconium oxide powder to obtain dry powder of silanized modified zirconium oxide powder, the drying temperature being 50-150°C and the drying time being 1-20 hours; correspondingly, step S5 is: mixing the dry powder of silanized modified zirconium oxide obtained in step S4.5 with water to obtain the cleaning agent, wherein the mass ratio of the dry powder of silanized modified zirconium oxide to water is 1:(1-10); exemplaryly, this mass ratio can be any one of 1:3, 1:5 or 1:8.

[0073] Third aspect

[0074] This invention provides a cleaning agent for dental restorations, comprising: the aforementioned silanized modified zirconia powder, or the silanized modified zirconia powder obtained by the aforementioned method; water; wherein the pH value of the cleaning agent is greater than 13. It is worth noting that the silanized modified zirconia powder provided by this invention has a large number of amino and epoxy groups grafted onto its surface. In an alkaline environment, the amino groups can undergo charge adsorption with salivary proteins, thereby weakening the binding force between the protein membrane and the dental restoration. The epoxy groups are activated in an alkaline environment, opening the ring and generating hydroxyl groups, thereby breaking the Zr-OP bond between the protein membrane and the zirconia restoration. Furthermore, the Zr in the silanized modified zirconia powder... 4+ The dental restoration has a stronger affinity for the phosphate groups in saliva than that made of zirconium oxide, which ultimately allows the cleaning agent to effectively remove saliva and blood residue from the dental restoration.

[0075] For example, the pH value of the cleaning agent can be 13.5, 14, 14.5, or 15. The alkaline substances in the cleaning agent can denature salivary proteins, making the protein molecules loose and easier to detach from the surface of the zirconia dental restoration under the action of rinsing force.

[0076] In some embodiments of the present invention, the cleaning agent further includes a colorant. It is worth noting that the colorant contained in the cleaning agent is a metal oxide colorant, which can be an indicator cleaning agent for restorations, ensuring no residue remains after cleaning.

[0077] In some embodiments of the present invention, the colorant is at least one of iron oxide and cerium oxide.

[0078] In some embodiments of the present invention, the cleaning agent further includes a wetting agent. It is worth noting that the cleaning agent provided by the present invention, compared with some existing cleaning agents, not only uses the aforementioned silanized modified zirconia powder, but also further adds a wetting agent; in other words, some existing cleaning agents do not contain a wetting agent. The cleaning agent provided by the present invention, composed of surface-modified zirconia powder, a wetting agent, and water, has the following advantages compared to existing cleaning agents that do not contain a wetting agent: the wetting agent can reduce the surface tension of the cleaning agent, allowing it to spread rapidly on the surface of the dental restoration and penetrate into the micropores of the protein membrane, thereby accelerating the penetration of the cleaning agent at the interface between contaminants and zirconia, and preventing the re-adhesion of protein fragments, making them easier to remove, thus improving the cleaning effect of the cleaning agent.

[0079] In some embodiments of the present invention, the wetting agent is at least one of a nonionic wetting agent, a fluorocarbon wetting agent, and a silicone-based wetting agent. It is understood that the wetting agent can improve the penetration efficiency of the restoration cleaning agent, accelerate the penetration of the cleaning agent at the interface between the contaminant and zirconium oxide, and enhance the cleaning effect of the cleaning agent.

[0080] In some embodiments of the present invention, the nonionic wetting agent is at least one of polyethylene glycol octylphenyl ether, polyoxyethylene-polyoxypropylene block copolymer, polysorbate 80, and polyethylene glycol.

[0081] It is worth noting that polyethylene glycol octylphenyl ether is also known as Triton X-100, polyoxyethylene-polyoxypropylene block copolymer is also known as Pluronic F-127, polysorbate 80 is also known as Tween 80, and polyethylene glycol is also known as PEG600.

[0082] In some embodiments of the present invention, the fluorocarbon wetting agent is a fluoroalkyl polyoxyethylene ether.

[0083] It is worth noting that fluoroalkyl polyoxyethylene ether is also known as ZonylFS-300.

[0084] In some embodiments of the present invention, the silicon-based wetting agent is a trisiloxaneoxyoxygenate.

[0085] It is worth noting that trisiloxaneoxyides are also known as SilwetL-77.

[0086] It should be noted that wetting agents can improve the penetration efficiency of cleaning agents in restorations and accelerate the penetration of cleaning agents at the interface between contaminants and zirconium oxide. The mechanism of action is as follows: reducing the surface tension of the liquid, allowing the cleaning agent to spread rapidly and penetrate into the micropores of the protein membrane; and inhibiting secondary adsorption at the interface to prevent the re-attachment of detached protein fragments.

[0087] In some embodiments of the present invention, the content of the silanized modified zirconium oxide powder is 10 to 30 wt% of the total mass of the cleaning agent. For example, it can be any one of 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, or any range of any two of the above values, or any value within that range.

[0088] In some embodiments of the present invention, the content of the wetting agent is 0.01 to 6 wt% of the total mass of the cleaning agent; for example, it can be any one of 0.05 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt%, or a range of any two of the values ​​and any one of the values ​​within that range.

[0089] In some embodiments of the present invention, the content of the colorant is 1 to 15 wt% of the total mass of the cleaning agent; for example, it can be any one of 1.5 wt%, 3 wt%, 5 wt%, 8 wt%, 10 wt%, or 12.5 wt%, or a range of any two of the values, or any value within that range.

[0090] In some embodiments of the present invention, the cleaning agent may contain additives conventional in the art, including but not limited to preservatives, bactericides, antistatic agents, fluorescent whitening agents, viscosity modifiers, etc.

[0091] In some embodiments of the present invention, the cleaning agent may contain a significant amount of water.

[0092] The cleaning agent provided by this invention can effectively clean saliva and blood residue on dental restorations after trial fitting, thereby ensuring high shear bond strength when the dental restoration is subsequently bonded to the tooth.

[0093] Fourth aspect

[0094] See Figure 2 The present invention provides a method for preparing the above-mentioned cleaning agent, the method comprising the following steps: S1, providing zirconia powder and adding water to form a slurry, or providing a slurry containing zirconia powder; S2, mixing the slurry containing zirconia powder from step S1 with a stabilizer; S3, adjusting the pH value of the material obtained in step S2; S4, mixing the material obtained in step S3 with an amino-containing silane coupling agent and an epoxy-containing silane coupling agent, reacting to obtain a slurry containing silanized modified zirconia powder; S5, mixing the slurry obtained in step S4 with water to obtain the cleaning agent.

[0095] In some embodiments of the present invention, in step S1, the mass ratio of zirconium oxide powder to water in the slurry is 1:(1-5). Exemplarily, it can be any one of 1:2, 1:3, or 1:4, or a range of any two values, or any value within that range.

[0096] In some embodiments of the present invention, in step S1, the particle size of the provided zirconium oxide powder is <100nm, for example, any one or any two values ​​of 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm or 100nm, or any value within that range, preferably 10nm to 80nm. It should be noted that the present invention uses zirconia powder with an original particle size of less than 100 nm to prepare the above-mentioned silanized surface-modified zirconia powder. During the preparation process, the above-mentioned nano-sized zirconia powder will agglomerate, and many nano-sized zirconia agglomerates will agglomerate to form larger micron-sized zirconia powder, or zirconia agglomerates. In some embodiments, the D50 of these micron-sized zirconia powder agglomerates is 0.1-20 μm, the D90 is 5-50 μm, and the D100 is less than 100 μm. Of course, in other embodiments, the particle size of the above-mentioned micron-sized agglomerates can also only meet one of the parameter ranges of D50, D90, and D100, depending on the required design requirements.

[0097] In some embodiments of the present invention, in step S2, the amount of stabilizer added is 0.1 to 5 wt% of the zirconium oxide powder. For example, the amount of stabilizer added can be any one of 1 wt%, 3 wt%, or 4 wt%, or a range consisting of any two of these values, or any value within that range.

[0098] In some embodiments of the present invention, the stabilizer is at least one of polydiallyldimethylammonium chloride and propylene glycol block polyether.

[0099] It is worth noting that polydiallyl dimethyl ammonium chloride is also known as PDDA, and propylene glycol block polyether is also known as L64.

[0100] In some embodiments of the present invention, the mixture is stirred at 500-1000 rpm for 30-60 minutes at 40-50°C.

[0101] In some embodiments of the present invention, in step S3, the pH value of the material is adjusted to be greater than 13. For example, the pH value of the material can be any one of 13.5, 14, 14.5, 15, 15.5, 16, or a range of any two values ​​and any value within that range.

[0102] In some embodiments of the present invention, a strong alkali is added at a stirring speed of at least 1200 rpm to adjust the pH value.

[0103] In some embodiments of the present invention, the strong alkali is at least one of sodium hydroxide and potassium hydroxide.

[0104] In some embodiments of the present invention, the amount of the strong alkali added is 0.5 to 10 wt% of the material obtained in step S2.

[0105] In some embodiments of the present invention, the amino-containing silane coupling agent is at least one selected from N-aminoethyl-γ-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane.

[0106] In some embodiments of the present invention, the silane coupling agent containing an epoxy group is at least one of γ-glycidoxypropyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0107] In some embodiments of the present invention, the silane coupling agent is a mixture of N-aminoethyl-γ-aminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane in a mass ratio of (1-3):1.

[0108] In some embodiments of the present invention, the mass ratio of the γ-glycidyl etheroxypropyltrimethoxysilane to the zirconium oxide powder is (1-10):100.

[0109] In some embodiments of the present invention, the reaction duration is 60 to 120 minutes, the reaction temperature is 60 to 95°C, and the stirring speed during the reaction is at least 1200 rpm.

[0110] In some embodiments of the present invention, in step S5, the material obtained in step S4 is mixed with a wetting agent, water and a colorant to obtain the cleaning agent.

[0111] In some embodiments of the present invention, in step S5, the material obtained in step S4 is mixed with a wetting agent and water to obtain the cleaning agent. The wetting agent can reduce the surface tension of the cleaning agent, allowing it to spread rapidly on the surface of the dental restoration and penetrate into the micropores of the protein membrane, thereby accelerating the penetration of the cleaning agent at the interface between contaminants and zirconium oxide and preventing the re-adhesion of protein fragments, making them easier to remove, and thus improving the cleaning effect of the cleaning agent.

[0112] In some embodiments of the present invention, the colorant is at least one of iron oxide and cerium oxide.

[0113] In some embodiments of the present invention, the content of the wetting agent is 0.01 to 6 wt% of the total mass of the cleaning agent.

[0114] In some embodiments of the present invention, the content of the colorant is 1 to 15 wt% of the total mass of the cleaning agent.

[0115] In some embodiments of the present invention, the content of the silanized modified zirconium oxide powder is 10 to 30 wt% of the total mass of the cleaning agent. For example, it can be any one of 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, or any range of any two of the above values, or any value within that range.

[0116] In some embodiments of the present invention, the cleaning agent may contain a significant amount of water. It should be noted that the water content is, for example, the sum of the water added in steps S1 and S5.

[0117] In some embodiments of the present invention, in step S5, the mass ratio of the obtained slurry to water is (1-15):1.

[0118] In some embodiments of the present invention, step S4 further includes: drying the slurry containing the silanized modified zirconium oxide powder to obtain dry powder of silanized modified zirconium oxide powder, the drying temperature being 50-150°C and the drying time being 1-20 hours; and in step S5, mixing the dry powder of silanized modified zirconium oxide powder with water to obtain the cleaning agent, wherein the mass ratio of the dry powder of silanized modified zirconium oxide powder to water is 1:(1-10). It is worth noting that in these embodiments, the dry powder of silanized modified zirconium oxide powder is first obtained by drying in step S4, and then water is added to the dry powder of silanized modified zirconium oxide powder in step S5 to obtain the above-mentioned cleaning agent. Furthermore, similar to some of the above embodiments, any one or both of the above-mentioned wetting agent and coloring agent can be added to the cleaning agent.

[0119] Example 1

[0120] Weigh 10g of zirconia nanoparticles with a particle size of 50nm, dilute with 50g of water to obtain a slurry; then add 0.4g of stabilizer polydiallyldimethylammonium chloride (PDDA) to the diluted slurry, and stir at 800rpm for 40min at 45℃; then add 2g of KOH at a stirring speed of 1500rpm and continue stirring for 40min.

[0121] 0.4 g of N-aminoethyl-γ-aminopropyltrimethoxysilane (aminosilane KH-792) and 0.2 g of γ-glycidyl etheroxypropyltrimethoxysilane (epoxysilane KH-560) were added sequentially. The reaction time was 60 min, the system temperature was 80 °C, and the stirring speed was 1500 rpm.

[0122] To the silanized zirconia slurry, 6g Triton X-100 as a wetting agent, 1g iron oxide as a colorant, 3g KOH and 27g water were added sequentially. The mixture was stirred at 800 rpm for 45 minutes to obtain a cleaning agent.

[0123] The silane grafting rate of the silanized modified zirconia powder obtained in this embodiment is 4.3%.

[0124] Example 2

[0125] Weigh 10g of zirconia nanoparticles with a particle size of 60nm, dilute with 50g of water to obtain a slurry; then add 0.5g of propylene glycol block polyether (L64) stabilizer to the diluted slurry, and stir at 700rpm for 50min at 50℃; then add 1g of NaOH at a stirring speed of 1400rpm and continue stirring for 40min.

[0126] 0.4 g of N-aminoethyl-γ-aminopropyltrimethoxysilane (aminosilane KH-792) and 0.2 g of γ-glycidyl etheroxypropyltrimethoxysilane (epoxysilane KH-560) were added sequentially. The reaction time was 60 min, the system temperature was 80 °C, and the stirring speed was 1500 rpm.

[0127] To the silanized zirconium oxide slurry, 3g Pluronic F-127 and 3g PEG600 were added sequentially as wetting agents, 2g iron oxide and 6g cerium oxide as colorants, 1g NaOH and 22.9g water were added, and the mixture was stirred at 800 rpm for 50 minutes to obtain a cleaning agent.

[0128] The silane grafting rate of the silanized modified zirconia powder obtained in this embodiment is 4.2%.

[0129] Example 3

[0130] Weigh 20g of zirconia nanoparticles with a particle size of 60nm, dilute with 50g of water to obtain a slurry; then add 1g of stabilizer polydiallyldimethylammonium chloride (PDDA) to the diluted slurry and stir at 40℃ for 60min (1000rpm); then add 2g of NaOH at a stirring speed of 1500rpm and continue stirring for 40min.

[0131] 0.4 g of N-aminoethyl-γ-aminopropyltrimethoxysilane (aminosilane KH-792) and 0.2 g of γ-glycidyl etheroxypropyltrimethoxysilane (epoxysilane KH-560) were added sequentially. The reaction time was 60 min, the system temperature was 80 °C, and the stirring speed was 1500 rpm.

[0132] To the silanized zirconia slurry, 2g Pluronic F-127 and 1g ZonylFS-300 were added sequentially as wetting agents, 1g iron oxide as a colorant, 1g NaOH and 12.4g water, and the mixture was stirred at 1000rpm for 50min to obtain a cleaning agent.

[0133] The silane grafting rate of the silanized modified zirconia powder obtained in this embodiment is 4.2%.

[0134] Example 4

[0135] Weigh 15g of zirconia nanoparticles with a particle size of 30nm, dilute with 50g of water to obtain a slurry; then add 0.6g of propylene glycol block polyether (L64) stabilizer to the diluted slurry, and stir at 900rpm for 50min at 50℃; then add 2g of NaOH at a stirring speed of 1500rpm and continue stirring for 40min.

[0136] 0.4 g of N-aminoethyl-γ-aminopropyltrimethoxysilane (aminosilane KH-792) and 0.2 g of γ-glycidyl etheroxypropyltrimethoxysilane (epoxysilane KH-560) were added sequentially. The reaction time was 60 min, the system temperature was 80 °C, and the stirring speed was 1500 rpm.

[0137] To the silanized zirconium oxide slurry, 1g Pluronic F-127 and 3g Silwet L-77 were added sequentially as wetting agents, 8g iron oxide as a colorant, 2g NaOH and 17.8g water, and the mixture was stirred at 1000rpm for 50min to obtain a cleaning agent.

[0138] The silane grafting rate of the silanized modified zirconia powder obtained in this embodiment is 4.2%.

[0139] Example 5

[0140] Weigh 18g of zirconia nanoparticles with a particle size of 50nm, dilute with 50g of water to obtain a slurry; then add 0.5g of stabilizer propylene glycol block polyether (L64) to the diluted slurry, and stir at 800rpm for 40min at 45℃; then add 2g of KOH at a stirring speed of 1500rpm and continue stirring for 40min.

[0141] 0.4 g of N-aminoethyl-γ-aminopropyltrimethoxysilane (aminosilane KH-792) and 0.2 g of γ-glycidyl etheroxypropyltrimethoxysilane (epoxysilane KH-560) were added sequentially. The reaction time was 60 min, the system temperature was 80 °C, and the stirring speed was 1500 rpm.

[0142] To the silanized zirconium oxide slurry, 0.5g Triton X-100, 0.5g PEG600, 0.5g ZonylFS-300 and 0.5g Silwet L-77 were added sequentially as wetting agents, 1g iron oxide and 6g cerium oxide were added as colorants, 2g KOH and 17.9g water were added, and the mixture was stirred at 800 rpm for 45 minutes to obtain a cleaning agent.

[0143] The silane grafting rate of the silanized modified zirconia powder obtained in this embodiment is 4.3%.

[0144] Example 6

[0145] Weigh 30g of zirconia nanoparticles with a particle size of 40nm, dilute with 40g of water to obtain a slurry; then add 0.5g of stabilizer polydiallyldimethylammonium chloride (PDDA) to the diluted slurry, and stir at 800rpm for 40min at 45℃; then, add 0.4g of KOH at a stirring speed of 1500rpm and continue stirring for 40min.

[0146] 0.4 g of N-aminoethyl-γ-aminopropyltrimethoxysilane (aminosilane KH-792) and 0.2 g of γ-glycidyl etheroxypropyltrimethoxysilane (epoxysilane KH-560) were added sequentially. The reaction time was 60 min, the system temperature was 80 °C, and the stirring speed was 1500 rpm.

[0147] To the silanized zirconia slurry, 1g Triton X-100, 1g Pluronic F-127 and 2g PEG600 were added sequentially as wetting agents, 1g iron oxide as a colorant, 0.1g NaOH and 8.4g water, and the mixture was stirred at 1000rpm for 50min to obtain a cleaning agent.

[0148] The silane grafting rate of the silanized modified zirconia powder obtained in this example is 4.4%.

[0149] Example 7

[0150] Weigh 15g of zirconia nanoparticles with a particle size of 30nm, dilute with 50g of water to obtain a slurry; then add 0.6g of propylene glycol block polyether (L64) stabilizer to the diluted slurry, and stir at 900rpm for 50min at 50℃; then add 2g of NaOH at a stirring speed of 1500rpm and continue stirring for 40min.

[0151] To a zirconia slurry, 1g Pluronic F-127 and 3g Silwet L-77 were added sequentially as wetting agents, 8g iron oxide as a colorant, 2g NaOH and 18.4g water, and the mixture was stirred at 1000 rpm for 50 minutes to obtain a cleaning agent.

[0152] Example 8

[0153] Weigh 10g of zirconia nanoparticles with a particle size of 50nm, dilute with 50g of water to obtain a slurry; then add 0.4g of stabilizer polydiallyldimethylammonium chloride (PDDA) to the diluted slurry, and stir at 800rpm for 40min at 45℃; then add 2g of KOH at a stirring speed of 1500rpm and continue stirring for 40min.

[0154] 0.4 g of N-aminoethyl-γ-aminopropyltrimethoxysilane (aminosilane KH-792) and 0.2 g of γ-glycidyl etheroxypropyltrimethoxysilane (epoxysilane KH-560) were added sequentially. The reaction time was 60 min, the system temperature was 80 °C, and the stirring speed was 1500 rpm.

[0155] The slurry containing silanized modified zirconia powder obtained in the above steps was dried at a drying temperature of 100℃ and a drying time of 12h to obtain silanized modified zirconia powder in dry powder state.

[0156] 11g of silanized modified zirconium oxide powder in dry state was mixed with 6g Triton X-100 as a wetting agent, 1g iron oxide as a colorant, 5g KOH and 77g water, and stirred at 800rpm for 45min to obtain a cleaning agent.

[0157] The silane grafting rate of the silanized modified zirconia powder obtained in this embodiment is 4.2%.

[0158] Comparative Example 1

[0159] Weigh 15g of zirconia nanoparticles with a particle size of 30nm, dilute with 50g of water to obtain a slurry; then add 0.6g of propylene glycol block polyether (L64) stabilizer to the diluted slurry, and stir at 900rpm for 50min at 50℃; then add 2g of NaOH at a stirring speed of 1500rpm and continue stirring for 40min.

[0160] 0.4 g of N-aminoethyl-γ-aminopropyltrimethoxysilane (aminosilane KH-792) and 0.2 g of γ-glycidyl etheroxypropyltrimethoxysilane (epoxysilane KH-560) were added sequentially. The reaction time was 60 min, the system temperature was 80 °C, and the stirring speed was 1500 rpm.

[0161] Add 8g of iron oxide as a colorant, 2g of NaOH and 21.8g of water to the zirconia slurry in sequence, stir at 1000rpm for 50min to obtain the cleaning agent.

[0162] The silane grafting rate of the silanized modified zirconia powder obtained in this embodiment is 4.2%.

[0163] Comparative Example 2

[0164] Weigh 15g of zirconia nanoparticles with a particle size of 30nm, dilute with 50g of water to obtain a slurry; then add 0.6g of propylene glycol block polyether (L64) stabilizer to the diluted slurry, and stir at 900rpm for 50min at 50℃; then add 2g of NaOH at a stirring speed of 1500rpm and continue stirring for 40min.

[0165] Add 8g of iron oxide as a colorant, 2g of NaOH and 22.4g of water to the zirconia slurry in sequence, stir at 1000rpm for 50min to obtain the cleaning agent.

[0166] Comparative Example 3

[0167] Weigh 15g of zirconia nanoparticles with a particle size of 30nm, dilute with 50g of water to obtain a slurry; then add 0.6g of propylene glycol block polyether (L64) stabilizer to the diluted slurry, and stir at 900rpm for 50min at 50℃; then add 2g of NaOH at a stirring speed of 1500rpm and continue stirring for 40min.

[0168] Add 0.6g of N-aminoethyl-γ-aminopropyltrimethoxysilane (aminosilane KH-792), react for 60 min, maintain the system temperature at 80℃, and stir at 1500 rpm.

[0169] Add 1g Pluronic F-127, 3g Silwet L-77, 8g iron oxide colorant, 2g NaOH and 17.8g water to the silanized zirconium oxide slurry in sequence, stir at 1000rpm for 50min to obtain the cleaning agent.

[0170] The silane grafting rate of the silanized modified zirconia powder obtained in this example was 4.1%.

[0171] Comparative Example 4

[0172] Weigh 15g of zirconia nanoparticles with a particle size of 30nm, dilute with 50g of water to obtain a slurry; then add 0.6g of stabilizer propylene glycol block polyether (L64) to the diluted slurry and stir at 900rpm for 50min at 50℃.

[0173] Add 0.6g of γ-glycidyl etheroxypropyltrimethoxysilane (epoxysilane KH-560), react for 60min, maintain the system temperature at 80℃, and stir at 1500rpm.

[0174] Add 1g Pluronic F-127, 3g Silwet L-77, 8g iron oxide colorant, 2g NaOH and 17.8g water to the silanized zirconium oxide slurry in sequence, stir at 1000rpm for 50min to obtain the cleaning agent.

[0175] The silane grafting rate of the silanized modified zirconia powder obtained in this example was 4.1%.

[0176] Test case

[0177] The silanized zirconium oxide and cleaning agents obtained in the above embodiments and comparative examples were tested using the following test methods:

[0178] 1. Zirconia surface grafting rate test

[0179] The grafting rate of silanized zirconia surface was determined using the calcination loss-of-gravity method. Zirconia samples obtained from the above examples and comparative examples after silanization modification were dried. 50g of silanized zirconia powder was ultrasonically cleaned three times with ethanol (10 minutes each time, 10kHz), and then centrifuged and dried. Calcination was performed in a muffle furnace, with the temperature increased to 800℃ at a rate of 20℃ / min and held for 2 hours. After cooling, the sample was weighed and its mass recorded as m. The grafting rate η of silanized zirconia surface was calculated using the following formula: η=(50-m) / 50×100%.

[0180] 2. pH value test

[0181] Instruments: pH meter, analytical balance.

[0182] Test method: Accurately weigh 0.5g of sample into a 100ml beaker, dilute with water to 100 times, insert a pH meter, and read the pH value of the sample after the reading stabilizes.

[0183] Table 1. pH values ​​of the cleaning agents obtained from each example and comparative example.

[0184] Serial number pH value Example 1 14.16 Example 2 13.98 Example 3 14.13 Example 4 14.28 Example 5 14.23 Example 6 13.15 Example 7 14.27 Example 8 14.06 Comparative Example 1 14.21 Comparative Example 2 14.24 Comparative Example 3 14.27 Comparative Example 4 14.26 Ivoclean 13.01

[0185] 3. Pollution Cleaning Ability Test - Shear Bond Strength Comparison

[0186] 3.1 Fabrication of Zirconia Tooth Cups

[0187] Standard dental zirconia ceramic specimens with a diameter of 16 mm and a thickness of 4 mm were prepared as dental restorations made of the aforementioned zirconia material. They were divided into 35 groups of 10 specimens each. Each specimen was polished on one side with 200-grit, 400-grit, and 600-grit wet sandpaper to form a standard bonding surface.

[0188] 3.2 Contaminated Zirconia Surface

[0189] In Examples 1, 2, 3, 4, 7, 8 and Comparative Examples 1, 3, 4, a sterile medical cotton swab was used to collect saliva in the oral cavity, ensuring the swab was completely soaked with saliva. The saliva-soaked cotton swab was then applied to the zirconia bonding surface of the zirconia tooth cup for 30 seconds, ensuring the saliva completely covered the zirconia surface. After standing for 30 seconds, the swab was rinsed with running water. In Examples 5, 6 and Comparative Example 2, a sterile medical cotton swab was used to collect fresh sheep blood, ensuring the swab was completely soaked with blood. The blood-soaked cotton swab was then applied to the zirconia bonding surface of the zirconia tooth cup for 30 seconds, ensuring the blood completely covered the zirconia bonding surface. After standing for 30 seconds, the swab was rinsed with running water.

[0190] 3.3 Cleaning of Zirconia Surface

[0191] Apply the restoration cleaner evenly to the bonding surface of the zirconia restoration using a brush; leave the cleaner on for 30 seconds to clean, then rinse thoroughly with water and air dry with oil-free air; Ivoclean restoration cleaner from Ivocar is used as a comparison.

[0192] 3.4 Shear bond strength test

[0193] The shear bond strength of the specimens was determined according to the standard YY / T0518-2009 Polymer-based Adhesives for Dental Prosthetics, and the data were statistically analyzed using SPSS software. 3M's RelyX Ultimate resin cement was used as the bonding cement, and Bisco's Z-PrimePlus pretreatment agent was used as the bonding surface treatment agent. Shear bond strength tests were conducted on the specimens from Example 4 and the Ivoclean saliva cleaning group after storage at 60°C for 7 days. The test results of the shear bond strength are shown in Table 2.

[0194] Table 2 Comparison of shear bond strength of zirconia dental restorations before and after cleaning with the cleaning agents obtained in each embodiment and comparative example.

[0195]

[0196]

[0197] According to Table 3, comparing the samples of Examples 4 and 7 with those of Comparative Examples 1 and 2, the shear bond strength of Example 4 after cleaning the zirconia surface contaminated with saliva was 18.56 MPa, recovering to 99.52% of the original strength. Comparative Example 1 did not use a wetting agent, so its shear bond strength after cleaning the zirconia surface contaminated with saliva was 16.57 MPa, recovering to 89.91% of the original strength. Example 7 did not use modified zirconia powder but contained a wetting agent, so its shear bond strength after cleaning the zirconia surface contaminated with saliva was 15.98 MPa, recovering to 90.95% of the original strength. Comparative Example 2 did not use modified zirconia powder or a wetting agent, so its shear bond strength after cleaning the zirconia surface contaminated with saliva was 14.62 MPa, recovering to 78.22% of the original strength. After Ivoclean cleaned the zirconia surface contaminated with saliva, the shear bond strength was 16.38 MPa, recovering to 87.50% of the original strength, similar to Example 7. After Example 5 cleaned the zirconia surface contaminated with blood, the shear bond strength was 16.95 MPa, recovering to 99.53% of the original strength. After Ivoclean cleaned the zirconia surface contaminated with blood, the shear bond strength was 15.52 MPa, recovering to 82.91% of the original strength. The saliva-cleaned groups of Example 4 and Ivoclean were stored at 60°C for 7 days, and an aging shear bond strength test was conducted. The results showed that after Example 4 cleaned the zirconia surface contaminated with saliva, the shear bond strength was 18.07 MPa, maintaining 96.89% of the original shear bond strength. After Ivoclean cleaned the zirconia surface contaminated with saliva, the shear bond strength was 13.48 MPa, a significant decrease compared to 16.38 MPa before aging. The above test results confirm the purpose of this invention.

[0198] Furthermore, as can be seen from Examples 1, 3, and 4 in Table 3, the synergistic application of amino-containing silane coupling agents and epoxy-containing silane coupling agents to modify the surface of zirconia can significantly enhance the performance of silanized zirconia, thereby making the cleaning effect of the cleaning agent more outstanding, and thus further improving the shear bond strength between the cleaned restoration and the tooth.

[0199] As can be seen from Table 3, by comparing the cleaning effects of Examples 4, 5, and 7 with Comparative Examples 1 and 2 and the commercially available Ivoclean cleaner on saliva and blood, the experimental data comparison shows that after adding modified zirconia powder and wetting agent, the repair cleaner of the present invention can solve the problem that existing repair cleaners are unable to completely remove protein biofilm residues, which leads to a decrease in repair durability and shear bond strength, and at the same time meet the need to clean saliva and blood contamination.

[0200] Table 3 shows that in Example 8, the slurry containing silanized modified zirconia powder was first converted into dry powder silanized modified zirconia powder by drying. Then, water was added to the dry powder silanized modified zirconia powder to obtain the above-mentioned cleaning agent. Similarly, the restoration can obtain a sufficiently high shear bond strength after being contaminated by saliva through cleaning.

[0201] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims. Furthermore, specific examples have been used in the specification to illustrate the principles and implementation methods of the present invention. The above description of the embodiments is only for the purpose of helping to understand the method and core ideas of the present invention, and the content of this specification should not be construed as a limitation of the present invention.

Claims

1. A silanized modified zirconium oxide powder, characterized in that, The surface grafted groups of the silanized modified zirconia powder include amino and epoxy groups.

2. The zirconium oxide powder according to claim 1, characterized in that, The content of the amino group is 0.001 to 0.6 wt% of the mass of the zirconia powder, and / or the content of the epoxy group is 0.001 to 1 wt% of the mass of the zirconia powder.

3. The zirconium oxide powder according to claim 1, characterized in that, The grafting rate of the zirconia powder is 0.1–8 wt%.

4. The zirconium oxide powder according to claim 1, characterized in that, It has at least one of the following characteristics: The particle size D50 of the zirconium oxide powder is 0.1–20 μm; The particle size D90 of the zirconium oxide powder is 5-50 μm; The particle size D100 of the zirconia powder is less than 100 μm.

5. The zirconium oxide powder according to claim 1, characterized in that, The initial particle size of the zirconium oxide powder is <100 nm.

6. The zirconium oxide powder according to claim 1, characterized in that, The amino group is attached to the zirconia powder via a silicon atom, and / or the epoxy group is attached to the zirconia powder via a silicon atom.

7. A method for preparing silanized modified zirconium oxide powder as described in any one of claims 1 to 6, characterized in that, The method includes the following steps: S1, providing zirconia powder and adding water to form a slurry, or providing a slurry containing zirconia powder; S2, mix the slurry from step S1 with the stabilizer; S3, Adjust the pH value of the material obtained in step S2; S4. The material obtained in step S3 is mixed with an amino-containing silane coupling agent and an epoxy-containing silane coupling agent, and reacted to obtain a slurry containing the silanized modified zirconium oxide powder.

8. The method according to claim 7, characterized in that, In step S1, the mass ratio of zirconium oxide powder to water in the slurry is 1:(1-5); And / or, in step S1, the particle size of the provided zirconium oxide powder is <100 nm.

9. The method according to claim 7, characterized in that, In step S2, at least one feature is present: The amount of stabilizer added is 0.1 to 5 wt% of the zirconium oxide powder; The stabilizer is at least one of polydiallyldimethylammonium chloride and propylene glycol block polyether; Stir at 500-1000 rpm for 30-60 minutes at 40-50°C.

10. The method according to claim 7, characterized in that, In step S3, at least one feature is present: Adjust the pH value of the material to be greater than 13; A strong alkali is added at a stirring speed of at least 1200 rpm to adjust the pH value. Preferably, the strong alkali is at least one of sodium hydroxide and potassium hydroxide. Preferably, the amount of the strong alkali added is 0.5 to 10 wt% of the material obtained in step S2.

11. The method according to claim 7, characterized in that, In step S4, at least one of the following features is present: The amino-containing silane coupling agent is at least one of N-aminoethyl-γ-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane; The silane coupling agent containing an epoxy group is at least one of γ-glycidoxypropyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; Preferably, the silane coupling agent is a mixture of N-aminoethyl-γ-aminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane in a mass ratio of (1-3):1; Preferably, the mass ratio of the γ-glycidyl etheroxypropyltrimethoxysilane to the zirconium oxide powder is (1-10):100; The reaction duration is 60–120 min, the reaction temperature is 60–95 °C, and the stirring speed during the reaction is at least 1200 rpm.

12. The method according to any one of claims 7 to 11, characterized in that, Step S4 further includes: drying the slurry containing the silanized modified zirconium oxide powder to obtain dry powder state of silanized modified zirconium oxide powder, the drying temperature is 50-150℃, and the drying time is 1-20h.

13. A cleaning agent for dental restorations, characterized in that, The cleaning agent includes: The silanized modified zirconia powder according to any one of claims 1 to 6, or the silanized modified zirconia powder obtained by the method according to any one of claims 7 to 12; water; The cleaning agent has a pH value greater than 13.

14. The cleaning agent according to claim 13, characterized in that, The cleaning agent also includes a colorant; Preferably, the colorant is at least one of iron oxide and cerium oxide.

15. The cleaning agent according to claim 13 or 14, characterized in that, It has at least one of the following characteristics: The cleaning agent also includes a wetting agent; Preferably, the wetting agent is at least one of nonionic wetting agents, fluorocarbon wetting agents, and silicone-based wetting agents; More preferably, the nonionic wetting agent is at least one of polyethylene glycol octylphenyl ether, polyoxyethylene-polyoxypropylene block copolymer, polysorbate 80, and polyethylene glycol; More preferably, the fluorocarbon wetting agent is a fluoroalkyl polyoxyethylene ether; More preferably, the silicon-based wetting agent is a trisiloxane alkoxylate; The content of the silanized modified zirconium oxide powder is 10-30 wt% of the total mass of the cleaning agent; The content of the wetting agent is 0.01 to 6 wt% of the total mass of the cleaning agent; The colorant content is 1 to 15 wt% of the total mass of the cleaning agent.

16. A method for preparing a cleaning agent as described in any one of claims 13 to 15, characterized in that, The method includes the following steps: S1, providing zirconia powder and adding water to form a slurry, or providing a slurry containing zirconia powder; S2, mix the slurry containing zirconium oxide powder from step S1 with a stabilizer; S3, Adjust the pH value of the material obtained in step S2; S4, the material obtained in step S3 is mixed with an amino-containing silane coupling agent and an epoxy-containing silane coupling agent, and reacted to obtain a slurry containing silanized modified zirconium oxide powder. S5, mix the slurry obtained in step S4 with water to obtain the cleaning agent.

17. The method according to claim 16, characterized in that, In step S1, the mass ratio of zirconium oxide powder to water in the slurry is 1:(1-5); And / or, in step S1, the particle size of the provided zirconium oxide powder is <100 nm.

18. The method according to claim 16, characterized in that, In step S2, at least one feature is present: The amount of stabilizer added is 0.1 to 5 wt% of the zirconium oxide powder; The stabilizer is at least one of polydiallyldimethylammonium chloride and propylene glycol block polyether; Stir at 500-1000 rpm for 30-60 minutes at 40-50°C.

19. The method according to claim 16, characterized in that, In step S3, at least one feature is present: Adjust the pH value of the material to be greater than 13; A strong alkali is added at a stirring speed of at least 1200 rpm to adjust the pH value. Preferably, the strong alkali is at least one of sodium hydroxide and potassium hydroxide. Preferably, the amount of the strong alkali added is 0.5 to 10 wt% of the material obtained in step S2.

20. The method according to claim 16, characterized in that, In step S4, at least one of the following features is present: The amino-containing silane coupling agent is at least one of N-aminoethyl-γ-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane; The silane coupling agent containing an epoxy group is at least one of γ-glycidoxypropyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; Preferably, the silane coupling agent is a mixture of N-aminoethyl-γ-aminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane in a mass ratio of (1-3):1; Preferably, the mass ratio of the γ-glycidyl etheroxypropyltrimethoxysilane to the zirconium oxide powder is (1-10):100; The reaction duration is 60–120 min, the reaction temperature is 60–95 °C, and the stirring speed during the reaction is at least 1200 rpm.

21. The method according to claim 16, characterized in that, In step S5, the material obtained in step S4 is mixed with a wetting agent and water to obtain the cleaning agent. Preferably, in step S5, the material obtained in step S4 is mixed with a wetting agent, water and a colorant to obtain the cleaning agent, wherein the colorant is preferably at least one of iron oxide and cerium oxide.

22. The method according to claim 21, characterized in that, It has at least one of the following characteristics: The content of the wetting agent is 0.01 to 6 wt% of the total mass of the cleaning agent; The colorant content is 1 to 15 wt% of the total mass of the cleaning agent.

23. The method according to claim 16, characterized in that, In step S5, the mass ratio of the obtained slurry to water is (1-15):

1.

24. The method according to any one of claims 16 to 22, characterized in that, The step between step S4 and step S5 includes step S4.5: drying the slurry containing the silanized modified zirconium oxide powder to obtain silanized modified zirconium oxide powder in dry powder state, with a drying temperature of 50-150℃ and a drying time of 1-20h. Accordingly, step S5 is: mixing the silanized modified zirconium oxide powder in dry powder state obtained in step S4.5 with water to obtain the cleaning agent, wherein the mass ratio of the silanized modified zirconium oxide powder in dry powder state to water is 1:(1~10).

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