Antibacterial composition for dental material, and method for preparing dental material by using same

Abstract

The present invention relates to a composition for a dental material, comprising acrylate copolymer particles, an acrylate-based monomer and a cross-linking agent, and, more specifically, to a composition for a dental material, comprising: a first composition comprising acrylate copolymer particles in which methyl methacrylate, ethyl methacrylate and 2-hexylethyl methacrylate are copolymerized; and a second composition comprising an acrylate-based monomer and a cross-linking agent. The composition for a dental material, according to the present invention, has excellent flexural strength, and has excellent antibacterial properties against bacteria generated in the oral cavity, and thus can be widely used as a material for dentures and the like. In addition, solid acrylate copolymer particles and a liquid composition in the composition for a dental material, according to the present invention, do not change in appearance and physical properties even during long-term storage, and thus present invention is more advantageous for commercialization due to long-term storage of materials.

Description

Antimicrobial composition for dental materials and method for manufacturing dental materials using the same

[0001] The present invention relates to a composition for dental materials comprising acrylate copolymer particles, an acrylate-based monomer, and a crosslinking agent, and more specifically, to a composition for dental materials comprising a first composition comprising acrylate copolymer particles copolymerized with methyl methacrylate, ethyl methacrylate, and 2-hexylethyl methacrylate, and a second composition comprising an acrylate-based monomer and a crosslinking agent.

[0002] This application claims priority based on Korean Patent Application No. 10-2024-0130717 filed on September 26, 2024, and all contents described in the specification of said application are incorporated into this application.

[0003] The dental biomaterials market and the dental 3D printing market are showing remarkable growth due to the improvement in living standards and increased life expectancy.

[0004] Conventional denture base resins (dentures) and crown resins (artificial teeth) are used by mixing acrylic polymer materials such as polymethyl methacrylate and polyethyl acrylate, monomers such as methyl methacrylate, ethacrylate and butyl acrylate, and crosslinking agents, catalysts, initiators, etc.

[0005] However, since the physical properties of dental medical device products made by mixing polymer materials and monomers are generally low, there is a need to improve their physical properties.

[0006] Among dental materials, prior art regarding impact modifiers mainly used in dentures includes the acrylic impact modifier disclosed in Korean Patent Registration No. 10-2168346 and the methacrylate resin impact modifier with excellent impact strength and optical properties disclosed in Korean Patent Registration No. 10-1497756; however, since the resin compositions formed by mixing polymer materials and monomers in the above prior art have low physical properties, there is a need to improve the physical properties.

[0007] In addition, inorganic materials such as silver particles are used as antimicrobial agents to prevent infection or colonization of biomedical devices by pathogenic microorganisms in dental materials, but they are problematic in terms of biocompatibility, such as causing severe deformation of cells.

[0008] Therefore, for dental applications, there is a need for highly stable materials that hinder the proliferation of oral bacteria and fungi and do not release substances that cause adverse effects on the human body, such as allergies and endocrine disruption.

[0009] [Prior Art Literature]

[0010] [Patent Literature]

[0011] Korean Registered Patent No. 10-2168346

[0012] Korean Registered Patent No. 10-1497756

[0013]

[0014] Accordingly, the inventors of the present invention completed the present invention by making research efforts to develop a dental material with excellent physical properties and antibacterial properties, and by discovering that a dental material obtained by mixing acrylate copolymer particles copolymerized with a specific monomer with a liquid composition containing an acrylate monomer and a crosslinking agent exhibits excellent flexural strength, antibacterial properties, and storage stability.

[0015] Accordingly, the present invention aims to provide a composition for dental materials with excellent physical properties and antibacterial properties, comprising acrylate copolymer particles, an acrylate-based monomer, and a crosslinking agent.

[0016] The present invention comprises a first composition comprising acrylate copolymer particles copolymerized with methyl methacrylate, ethyl methacrylate, and 2-hexylethyl methacrylate; and

[0017] A composition for dental materials is provided, comprising a second composition including an acrylate-based monomer and a crosslinking agent.

[0018] The above acrylate-based monomer may be one or more compounds selected from methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, hydroxyethyl methacrylate, acrylic acid, and methacrylic acid.

[0019] The above crosslinking agent may be one or more compounds selected from ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol dimethacrylate, dipropylene glycol diacrylate, and dipropylene glycol dimethacrylate.

[0020] The above acrylate copolymer particles may be copolymerized with 1 to 50 parts by weight of ethyl methacrylate and 0.1 to 10 parts by weight of 2-hexylethyl methacrylate per 100 parts by weight of methyl methacrylate.

[0021] The above acrylate copolymer particles may be copolymerized by further including 0.1 to 10 parts by weight of methoxymethyl methacrylate, methoxymethyl acrylate, or a mixture thereof with respect to 100 parts by weight of methyl methacrylate.

[0022] The first composition above may further include one or more inorganic materials selected from Ag, Zn, and Ga.

[0023] The above acrylate copolymer particles may have a weight-average molecular weight in the range of 100,000 to 1,000,000.

[0024] The above acrylate copolymer particles can have an average particle size of 10 to 200 μm.

[0025] The first composition and the second composition may be mixed in a weight ratio of 1:0.5 to 2.

[0026] In addition, the present invention,

[0027] A step of mixing methyl methacrylate, ethyl methacrylate, 2-hexylethyl methacrylate, and a polymerization initiator, and proceeding with a polymerization reaction to produce acrylate copolymer particles;

[0028] A step of preparing a liquid composition comprising an acrylate-based monomer and a crosslinking agent; and

[0029] A method for manufacturing a dental material is provided, comprising the step of mixing the above-mentioned acrylate copolymer particles with the above-mentioned liquid composition and polymerizing them.

[0030] At this time, after mixing the acrylate copolymer particles with the liquid composition, polymerization can be carried out at 50 to 100°C.

[0031]

[0032] The dental material composition according to the present invention has excellent flexural strength and excellent antibacterial properties against bacteria occurring in the oral cavity, so it can be widely used as a material for dentures, etc.

[0033] In addition, the solid acrylate copolymer particles and the liquid composition in the dental material composition according to the present invention do not undergo changes in appearance or physical properties even during long-term storage, making it more advantageous for commercialization due to the long-term storage of the material.

[0034]

[0035] The present invention will be described in detail below. Prior to this, terms and words used in this specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a meaning and concept consistent with the technical spirit of the present invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention. Accordingly, the configurations described in the embodiments described in this specification are merely one preferred embodiment of the present invention and do not represent all of the technical spirit of the present invention; therefore, it should be understood that various equivalents and modifications capable of replacing them may exist at the time of filing this application.

[0036] The dental material composition of the present invention is,

[0037] A first composition comprising acrylate copolymer particles copolymerized with methyl methacrylate, ethyl methacrylate, and 2-hexylethyl methacrylate; and

[0038] It includes a second composition comprising an acrylate-based monomer and a crosslinking agent.

[0039] The acrylate copolymer particles in the first composition may be copolymerized with 1 to 50 parts by weight of ethyl methacrylate and 0.1 to 10 parts by weight of 2-hexylethyl methacrylate per 100 parts by weight of methyl methacrylate, preferably with 5 to 40 parts by weight of ethyl methacrylate and 1 to 8 parts by weight of 2-hexylethyl methacrylate per 100 parts by weight of methyl methacrylate, and more preferably with 10 to 30 parts by weight of ethyl methacrylate and 2 to 5 parts by weight of 2-hexylethyl methacrylate per 100 parts by weight of methyl methacrylate.

[0040] The above acrylate copolymer particles may be copolymerized with 0.1 to 10 parts by weight of methoxymethyl methacrylate, methoxymethyl acrylate, or a mixture thereof added to 100 parts by weight of methyl methacrylate, and preferably may be copolymerized with 1 to 5 parts by weight of methoxymethyl methacrylate, methoxymethyl acrylate, or a mixture thereof added.

[0041] The above acrylate copolymer particles may have a weight-average molecular weight in the range of 100,000 to 1,000,000, and preferably 300,000 or more.

[0042] In addition, the acrylate copolymer particles may have an average particle size of 10 to 200 μm, and preferably 50 μm or more.

[0043] The first composition may further include one or more inorganic materials selected from Ag, Zn, and Ga, and said inorganic materials may be included within the acrylate copolymer particles. The inorganic materials may be included in an amount of 0.1 to 10 parts by weight, and preferably 1 to 5 parts by weight, per 100 parts by weight of methyl methacrylate.

[0044] The second composition above exists in a liquid form containing an acrylate monomer and a crosslinking agent.

[0045] The above acrylate-based monomer may be one or more compounds selected from methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, hydroxyethyl methacrylate, acrylic acid, and methacrylic acid, and preferably may be one or more compounds selected from methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate.

[0046] The crosslinking agent may be one or more compounds selected from ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol dimethacrylate, dipropylene glycol diacrylate, and dipropylene glycol dimethacrylate, and preferably one or more compounds selected from ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol diacrylate, and diethylene glycol dimethacrylate.

[0047] The above crosslinking agent may be included in an amount of 0.1 to 20 parts by weight per 100 parts by weight of the acrylate monomer, preferably 1 to 10 parts by weight, and more preferably 3 to 7 parts by weight.

[0048] The composition for dental materials of the present invention may be formed by mixing the first composition and the second composition in a weight ratio of 1:0.5 to 2, preferably in a weight ratio of 1:0.6 to 1, and more preferably in a weight ratio of 1:0.7 to 0.8.

[0049]

[0050] Meanwhile, the method for manufacturing the dental material of the present invention is,

[0051] A step of mixing methyl methacrylate, ethyl methacrylate, 2-hexylethyl methacrylate, and a polymerization initiator, and proceeding with a polymerization reaction to produce acrylate copolymer particles;

[0052] A step of preparing a liquid composition comprising an acrylate-based monomer and a crosslinking agent; and

[0053] The method includes the step of mixing the above acrylate copolymer particles with the above liquid composition to polymerize.

[0054] First, methyl methacrylate, ethyl methacrylate, 2-hexylethyl methacrylate, and a polymerization initiator are mixed to carry out the polymerization reaction.

[0055] At this time, methoxymethyl methacrylate, methoxymethyl acrylate, or a mixture thereof may be further included in the polymerization.

[0056] The above polymerization initiator may include peroxide-based compounds such as benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, and t-butyl hydroperoxide; and azo-based compounds such as 2,2'-azobis-isobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, and 2,2'-azobis-2-methylisobutyronitrile, but preferably benzoyl peroxide is used.

[0057] The above polymerization initiator may be used in an amount of 0.001 to 1 weight part per 100 weight parts of methyl methacrylate, preferably 0.01 to 0.5 weight parts, and more preferably 0.05 to 0.1 weight parts.

[0058] The above polymerization can be carried out through a suspension polymerization process in a solvent such as water, and the water can be used in an amount of 1 to 10 times the weight of methyl methacrylate.

[0059] In addition, the polymerization can be carried out at 50 to 90 ℃ for 0.5 to 10 hours, and preferably at 65 to 75 ℃ for 1 to 5 hours.

[0060] Through the above process, powder-form acrylate copolymer particles can be manufactured.

[0061] Next, a liquid composition comprising an acrylate-based monomer and a crosslinking agent is prepared.

[0062] A final dental material can be manufactured by mixing and polymerizing the above acrylate copolymer particles with the above liquid composition.

[0063] When mixing the above acrylate copolymer particles and the liquid composition, a polymerization initiator may be added, and the aforementioned peroxide-based or azo-based compounds, etc., may be used as polymerization initiators.

[0064] Polymerization resulting from the mixing of the above acrylate copolymer particles and the liquid composition can be carried out at 50 to 100°C for 0.5 to 2 hours.

[0065]

[0066] Hereinafter, the present invention will be described in detail through examples and experimental examples to specifically explain the invention. However, the embodiments according to the present invention may be modified in various different forms, and the scope of the present invention should not be interpreted as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the invention to those with average knowledge in the art.

[0067]

[0068] Example 1: Preparation of dental materials

[0069] 1,500 g of water, 400 g of methyl methacrylate (MMA), 85 g of ethyl methacrylate (EMA), 15 g of 2-hexylethyl methacrylate (HEMA), 15 g of methoxymethyl methacrylate (MEMA), 0.25 g of benzoyl peroxide, and 1 g of polyvinyl alcohol were added to a 2 L round-bottom flask equipped with a stirrer, and then polymerization was carried out for 5 hours in a constant temperature water bath at a temperature of 70 ℃ to produce acrylate copolymer particles.

[0070] Next, a liquid composition was prepared by mixing 40g of methyl methacrylate and 2g of ethylene glycol dimethacrylate.

[0071] 60 g of the above acrylate copolymer particles, 42 g of the liquid composition, and 0.8 g of benzoyl peroxide were mixed, injected into an analytical mold, and then polymerized in a hot press (80 degrees, 30 minutes) to produce a final dental material.

[0072]

[0073] Example 2: Preparation of dental materials

[0074] A dental material was prepared in the same manner as in Example 1 above, except that 15g of methoxymethyl methacrylate was replaced with 5g of methoxymethyl methacrylate.

[0075]

[0076] Example 3: Preparation of dental materials

[0077] A dental material was prepared in the same manner as in Example 1 above, except that 15g of methoxymethyl methacrylate was replaced with 25g of methoxymethyl methacrylate.

[0078]

[0079] Example 4: Preparation of dental materials

[0080] A dental material was prepared in the same manner as in Example 1 above, except that 25g of methoxymethyl acrylate (MEA) was used instead of 15g of methoxymethyl acrylate.

[0081]

[0082] Example 5: Preparation of dental materials

[0083] A dental material was prepared in the same manner as in Example 1 above, except that 0.5 g of Ag with a size of 50 nm was added to a 2 L round flask to prepare acrylate copolymer particles.

[0084]

[0085] Example 6: Preparation of dental materials

[0086] A dental material was prepared in the same manner as in Example 1 above, except that 0.5 g of Ga with a size of 50 nm was added to a 2 L round flask to prepare acrylate copolymer particles.

[0087]

[0088] Experimental Example 1: Confirmation of Physical Properties of Acrylate-Based Copolymer Particles

[0089] The composition, particle size, and molecular weight of the acrylate-based copolymer particles in the above examples were measured and are shown in Table 1 below.

[0090] The above average particle size was measured using a MARVERN Mastersizer 2000s according to the ASTM D1705 or ASTM D2921 method.

[0091] In addition, the weight-average molecular weight (Mw) was analyzed using gel permeation chromatography (Viscotek Corp., USA). The eluent used was tetrahydrofuran (THF), and the column was maintained at 40°C with the eluent flowing at a rate of 1 ml / min. GPC was calibrated using homogeneous polydisperse polystyrene standard samples of known molecular weight.

[0092] Composition Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Monomer (g) MMA 400 400 400 400 400 EMA 85 85 85 85 85 85 HEMA 15 15 15 15 15 15 MEMA 15 5 25 15 15 MEA 15 15 15 Inorganic (g) Ag 5 Ga 5 Analysis Results Average Particle Size (㎛) 67 71 12 16 47 269 Molecular Weight (Mw X 1,000) 82 18 31 76 48 01 45 3364

[0093] It was confirmed that the acrylate copolymer particles prepared in the above example had an average particle size of 64 to 121 μm and a weight-average molecular weight in the range of 364,000 to 831,000.

[0094]

[0095] Experimental Example 2: Evaluation of Flexural Strength and Antibacterial Properties

[0096] The dental material manufactured according to the above example was cut into specimens of 25 mm (L) X 10 mm (W) X 2 mm (T) size according to the ISO 20795 method, and the flexural strength was measured using a Shimadzu AGS-X instrument.

[0097] In addition, a diluted fungal solution of fibrous bacteria primarily found in the oral cavity was added to the specimen prepared according to the above example, and incubation was carried out for 24 hours. Subsequently, the fungal solution was spread onto an agar plate and incubated at 37°C for 24 hours to [per unit area] (1 cm²). 2 The number of bacteria per ) was measured.

[0098]

[0099] The above measurement results are shown in Table 2 below.

[0100] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Flexural Strength (Mpa) 999 496 95 9491 Antibacterial Properties 212 43 211 12 52 18 51 38

[0101] As shown in Table 2 above, it was confirmed that all materials of the examples exhibited high flexural strength of 90 MPa or higher and excellent antibacterial properties.

[0102]

[0103] Experimental Example 3: Evaluation of Long-term Preservation

[0104] In the above example, the acrylate copolymer particles and the liquid composition were stored in a 60°C oven for 45 days.

[0105] After 45 days, there was no difference in the appearance and physical properties of the above acrylate copolymer particles and liquid composition.

Claims

1. A first composition comprising acrylate copolymer particles copolymerized with methyl methacrylate, ethyl methacrylate, and 2-hexylethyl methacrylate; and A composition for dental materials characterized by comprising a second composition including an acrylate-based monomer and a crosslinking agent.

2. In Paragraph 1, A composition for a dental material characterized in that the above acrylate-based monomer is one or more compounds selected from methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, hydroxyethyl methacrylate, acrylic acid, and methacrylic acid.

3. In Paragraph 1, A composition for dental materials characterized in that the crosslinking agent is one or more compounds selected from ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol dimethacrylate, dipropylene glycol diacrylate, and dipropylene glycol dimethacrylate.

4. In Paragraph 1, A dental material composition characterized in that the above acrylate copolymer particles are copolymerized with 1 to 50 parts by weight of ethyl methacrylate and 0.1 to 10 parts by weight of 2-hexylethyl methacrylate per 100 parts by weight of methyl methacrylate.

5. In Paragraph 1, A dental material composition characterized in that the above acrylate copolymer particles are copolymerized by further including 0.1 to 10 parts by weight of methoxymethyl methacrylate, methoxymethyl acrylate, or a mixture thereof per 100 parts by weight of methyl methacrylate.

6. In Paragraph 1, A dental material composition characterized by the first composition further comprising one or more inorganic materials selected from Ag, Zn, and Ga.

7. In Paragraph 1, A dental material composition characterized in that the above acrylate copolymer particles have a weight-average molecular weight in the range of 100,000 to 1,000,000.

8. In Paragraph 1, A composition for dental materials characterized in that the above acrylate copolymer particles exhibit an average particle size of 10 to 200 μm.

9. In Paragraph 1, A dental material composition characterized by the first composition and the second composition being mixed in a weight ratio of 1:0.5 to 2.

10. A step of mixing methyl methacrylate, ethyl methacrylate, 2-hexylethyl methacrylate, and a polymerization initiator, and proceeding with a polymerization reaction to produce acrylate copolymer particles; A step of preparing a liquid composition comprising an acrylate-based monomer and a crosslinking agent; and A method for manufacturing a dental material characterized by including the step of mixing the above-mentioned acrylate copolymer particles and the above-mentioned liquid composition to polymerize.

11. In Paragraph 10, A method for manufacturing a dental material characterized by mixing the above acrylate copolymer particles and the above liquid composition, and then polymerizing at 50 to 100 ℃.