Resin composition, method for producing oral appliance, and oral appliance

Abstract

To provide a resin composition suitable for obtaining an intraoral appliance having high molding accuracy by three dimensional molding of a fused deposition modeling method.SOLUTION: A resin composition used for production of an oral appliance by fused deposition modeling three dimensional shaping, the resin composition comprising an acrylic resin.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a resin composition, a method for manufacturing an oral appliance, and an oral appliance. [Background technology]

[0002] In recent years, fused deposition modeling (also known as molten deposition modeling) has been attracting attention as a 3D printer method that can inexpensively model objects. For example, a resin composition containing polylactic acid as a constituent unit is used as a modeling material in this fused deposition modeling method (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-80369 Summary of the Invention [Problem to be solved by the invention]

[0004] Meanwhile, in recent years, attention has been focused on the use of 3D printers in the manufacture of intraoral appliances such as dental products. The manufacture of intraoral appliances using 3D printers mainly involves the use of stereolithography (i.e., three-dimensional modeling). Under these circumstances, the present inventors attempted to manufacture intraoral appliances by fused deposition modeling three-dimensional modeling rather than by stereolithography three-dimensional modeling. However, when polylactic acid, which is primarily used in fused deposition modeling of three-dimensional fabrication, is used to manufacture oral appliances using three-dimensional fabrication techniques, the fabrication precision of the resulting oral appliances is insufficient.

[0005] An object of one embodiment of the present disclosure is to provide a resin composition suitable for obtaining an oral appliance with high modeling accuracy by three-dimensional modeling using fused deposition modeling, as well as an oral appliance using this resin composition and a method for manufacturing the same. [Means for solving the problem]

[0006] Specific means for solving the above problems are as follows. <1> A resin composition containing an acrylic resin, used in the manufacture of oral appliances by fused deposition modeling three-dimensional modeling. <2> The acrylic resin includes a methyl (meth)acrylate resin. <1> The resin composition according to claim 1. <3> Used for manufacturing denture bases or dentures using fused deposition modeling. <1> or <2> The resin composition according to claim 1. <4> The melt flow rate measured in accordance with ISO1133-1:2022 at 230°C and a load of 3.8 kg is 0.1 g / 10 min to 100 g / 10 min. <1> ~ <3> The resin composition according to any one of the above. <5> Density measured in accordance with ISO 1183:2019 is 1.0 g / cm 3 ~1.4g / cm 3 That is, <1> ~ <4> The resin composition according to any one of the above. <6> The water absorption rate is 2.0% by mass or less when immersed in water at 23°C for 24 hours in accordance with ISO 62:2008. <1> ~ <5> The resin composition according to any one of the above. <7> The water content represented by the following formula (1) is 1.0 mass% or less. <1> ~ <6> The resin composition according to any one of the above. Moisture content (mass%)=((mass of resin composition before drying−mass of resin composition dried at 100°C for 24 hours) / mass of resin composition before drying)×100 ... Equation (1) <8> Coefficient of linear expansion measured in accordance with ISO 11359:2023 is 5 x 10 -4 (1 / ℃) or less, <1> ~ <7> The resin composition according to any one of the above. <9> The content of the acrylic resin is 80% by mass or more based on the total amount of the resin composition. <1> ~ <8> The resin composition according to any one of the above. <10> The form under a temperature condition of 25°C is in the form of pellets or filaments. <1> ~ <9> The resin composition according to any one of the above. <11> <1> ~ <10> 1. A method for manufacturing an oral appliance, comprising the step of manufacturing the oral appliance by fused deposition modeling three-dimensional modeling using the resin composition according to any one of claims 1 to 9. <12> <1> ~ <10> An oral appliance manufactured by three-dimensional fabrication using the resin composition according to any one of the above items 1 to 4, using a fused deposition modeling method. [Effects of the Invention]

[0007] According to one embodiment of the present disclosure, there is provided a resin composition suitable for obtaining oral appliances with high modeling accuracy by three-dimensional modeling using fused deposition modeling, as well as an oral appliance using this resin composition and a method for manufacturing the same. DETAILED DESCRIPTION OF THE INVENTION

[0008] In the present disclosure, a numerical range indicated using "to" means a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the present disclosure, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved. In the present disclosure, when there are multiple substances corresponding to each component, the amount of each component means the total amount of the multiple substances unless otherwise specified. In this disclosure, "(meth)acrylate" means acrylate or methacrylate.

[0009] [Resin composition] The resin composition of the present disclosure is a resin composition used for producing oral appliances by three-dimensional fabrication using fused deposition modeling. The resin composition of the present disclosure contains an acrylic resin.

[0010] As mentioned above, conventionally, polylactic acid has been used as the resin material in fused deposition modeling three-dimensional modeling. However, when the inventors attempted to manufacture oral appliances (e.g., dental products) using polylactic acid as the material (resin) and fused deposition modeling three-dimensional modeling, the modeling precision of the resulting oral appliances was insufficient. In response to this problem, the resin composition of the present disclosure provides excellent molding precision for the resulting oral appliance when manufactured by three-dimensional modeling using fused deposition modeling. In other words, the resin composition of the present disclosure is suitable for obtaining oral appliances with high molding precision through three-dimensional modeling using fused deposition modeling. The reason for this effect is thought to be that the resin composition used as a material for three-dimensional modeling in the fused deposition modeling method contains an acrylic resin as the resin.

[0011] <Application> The resin composition of the present disclosure is used to manufacture oral appliances by three-dimensional fabrication using fused deposition modeling. The fused deposition modeling method is also called FDM (Fused Deposition Modeling) method. Three-dimensional modeling is also called 3D modeling. For three-dimensional fabrication using the fused deposition modeling method, known techniques can be used as appropriate.

[0012] The oral appliances include dental products, and more specifically, denture bases, dentures, dental splints, and the like. Examples of oral appliances include mouthpieces for sports.

[0013] The resin composition of the present disclosure is preferably used for producing a denture base or a denture by three-dimensional fabrication using a fused deposition modeling method.

[0014] <Acrylic resin> The resin composition of the present disclosure contains an acrylic resin. The resin composition of the present disclosure may contain only one type of acrylic resin, or two or more types of acrylic resins.

[0015] In the present disclosure, "acrylic resin" means a resin that includes structural units derived from (meth)acrylate (i.e., acrylate or methacrylate). The "acrylic resin" in this disclosure is Even if it is a homopolymer of one type of (meth)acrylate, Even if it is a copolymer of two or more (meth)acrylates, It may also be a copolymer of one or more (meth)acrylates with other monomers. The proportion of structural units derived from (meth)acrylate in the "acrylic resin" in the present disclosure is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

[0016] The acrylic resin preferably contains a methyl (meth)acrylate-based resin, and more preferably contains a methyl methacrylate-based resin (hereinafter also referred to as "PMMA"). Here, the methyl (meth)acrylate-based resin means a resin containing structural units derived from methyl (meth)acrylate, and the methyl methacrylate-based resin (PMMA) means a resin containing structural units derived from methyl methacrylate.

[0017] Methyl (meth)acrylate resins are Even if it is a homopolymer of one type of methyl (meth)acrylate, Even if it is a copolymer of methyl acrylate and methyl methacrylate, It may also be a copolymer of one or more types of methyl (meth)acrylate with other monomers. That is, a methyl(meth)acrylate-based resin (i.e., a resin containing a structural unit derived from methyl(meth)acrylate) may further contain a structural unit derived from a monomer other than methyl(meth)acrylate as a copolymerization component, or may not contain any copolymerization component. Examples of monomers other than methyl (meth)acrylate that can form copolymerization components include monofunctional (meth)acrylates such as ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, and dextran. Examples include sil(meth)acrylate, undecyl(meth)acrylate, dodecyl(meth)acrylate, tridecyl(meth)acrylate, tetradecyl(meth)acrylate, lauryl(meth)acrylate, stearyl(meth)acrylate, cyclohexyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate, and 2,3-dibromopropyl(meth)acrylate. Monomers other than methyl (meth)acrylate that can form copolymerization components include, for example, bifunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, meth)acrylate, polypropylene glycol di(meth)acrylate, propanediol di(meth)acrylate, glycerin di(meth)acrylate, dicyclopentanyl diacrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, bis(oxymethyl)tricyclo[5.2.2.0] 2,5 ]decane di(meth)acrylate, cyclohexanediol di(meth)acrylate, bis[(meth)acryloxymethyl]cyclohexane, diacrylate of acetal of trimethylolpropane and pivalaldehyde, hydroxypivalic acid neopentyl glycol ester diacrylate, bisphenol A-di(meth)acrylate, di(meth)acrylate of alkylene oxide adduct of bisphenol A, and the like. Examples of monomers other than methyl(meth)acrylate that can form copolymerization components include tri- to tetrafunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Examples of monomers other than methyl (meth)acrylate that can form copolymerization components include acrylic polymerizable oligomers such as epoxy (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, (meth)acrylate of polybutadiene oligomer, polyamide type (meth)acrylic oligomer, melamine (meth)acrylate, (meth)acrylate of cyclopentadiene oligomer, and (meth)acrylate of silicone oligomer.

[0018] The proportion of structural units derived from methyl (meth)acrylate in the "methyl (meth)acrylate-based resin" in the present disclosure is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 80% by mass or more, and still more preferably 90% by mass or more.

[0019] When the acrylic resin in the resin composition of the present disclosure contains a methyl(meth)acrylate-based resin (e.g., PMMA; the same applies hereinafter), the proportion of the methyl(meth)acrylate-based resin in the total amount of the acrylic resin is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

[0020] From the viewpoint of more stably ensuring the molding precision of the obtained oral appliance, the content of the acrylic resin relative to the total amount of the resin composition of the present disclosure is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more.

[0021] <Other ingredients> The resin composition of the present disclosure may contain components other than the acrylic resin (hereinafter also referred to as other components).

[0022] When the resin composition of the present disclosure contains other components, from the viewpoint of further improving the molding accuracy of the resulting oral appliance, the content of the other components is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and even more preferably 5% by mass or less, relative to the total amount of the resin composition. When the resin composition of the present disclosure contains other components, the content of the other components is, for example, 0.1 mass % or more relative to the total amount of the resin composition.

[0023] The other component is, for example, a resin other than an acrylic resin, more preferably a thermoplastic resin other than an acrylic resin. Examples of other thermoplastic resins include: Polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), and liquid crystal polyester; styrene-based resins; Polyamide (PA); Polycarbonate (PC); Polyphenylene sulfide (PPS); Polyphenylene ether (PPE); Modified PPE; Polyimide (PI); Polyamide-imide (PAI); Polyetherimide (PEI); Polysulfone (PSU); Modified PSU; Polyethersulfone (PES); Polyketone (PK); Polyetherketone (PEK); Polyetherketoneketone (PEKK); Polyarylate (PAR); Polyethernitrile (PEN); Modified polypropylene; Examples include:

[0024] The resin composition of the present disclosure may contain at least one inorganic filler as another component. Examples of inorganic fillers include: Fibrous fillers such as glass fibre, carbon fibre, asbestos fibre, silica fibre, alumina fibre, zirconia fibre, boron nitride fibre, silicon nitride fibre, boron fibre, fluorine-based resin fibre, potassium titanate fibre, etc.; Non-fibrous fillers (e.g., powdered fillers or flake fillers) such as mica, silica, talc, alumina, aluminosilicate glass, oline, calcium sulfate, calcium carbonate, titanium oxide, ferrite, clay, powdered glass, zinc oxide, nickel carbonate, iron oxide, quartz powder, magnesium carbonate, fluorine-based resin, graphite, carbon powder, nanotubes, hydroxyapatite, tricalcium phosphate, praseodymium compounds, erbium compounds, manganese compounds, titanium oxide, yellow iron oxide, and barium sulfate; etc. Furthermore, an inorganic filler may be included as a pigment. Examples of inorganic fillers used as pigments include inorganic pigments such as carbon black, cobalt blue, and titanium oxide pigments.

[0025] From the viewpoint of further improving the molding accuracy of the resulting oral appliance, the resin composition of the present disclosure preferably does not contain an inorganic filler, or if it does contain an inorganic filler, the content of the inorganic filler is preferably less than 1 mass% relative to the total amount of the resin composition.

[0026] Other components that may be contained in the resin composition of the present disclosure include colorants, lubricants, plasticizers, flame retardants, nucleating agents, flow promoters, fluorescent agents, opalizing agents, antibacterial agents, X-ray contrast agents, opacifiers, antioxidants, anti-discoloration agents, stabilizers, and the like. Examples of colorants include organic pigments such as phthalocyanine, anthraquinone, isoindolinone, quinacridone, perylene, and azo pigments.

[0027] <Preferred physical properties> Preferred physical properties of the resin composition of the present disclosure or the acrylic resin in the resin composition of the present disclosure are shown below. Hereinafter, the preferred physical properties of the resin composition of the present disclosure may be the preferred physical properties of the acrylic resin in the resin composition of the present disclosure.

[0028] (Melt flow rate (MFR)) The resin composition of the present disclosure has a melt flow rate (MFR) measured in accordance with ISO1133-1:2022 at 230°C under a load of 3.8 kg of preferably 0.1 g / 10 min to 100 g / 10 min, more preferably 0.6 g / 10 min to 22 g / 10 min, and more preferably 0.8 g / 10 min to 22 g / 10 min. When the MFR is 0.1 g / 10 min, the phenomenon in which the next layer is drawn before solidification and the decrease in molding accuracy due to stringiness during molding are more effectively suppressed. When the MFR is 100 g / 10 min or less, the interlayer adhesion is further improved.

[0029] (Weight average molecular weight (Mw)) The acrylic resin (eg, PMMA) in the resin composition of the present disclosure preferably has a weight average molecular weight (Mw) of 1,000 to 2,000,000, more preferably 3,000 to 180,000, and even more preferably 3,000 to 110,000, calculated in terms of polystyrene, as determined by gel permeation chromatography (GPC).

[0030] (density) The resin composition of the present disclosure preferably has a density of 1.0 g / cm as measured in accordance with ISO 1183:2019. 3 ~1.4g / cm 3 , more preferably 1.14 g / cm 3 ~1.20g / cm 3 is.

[0031] (Water absorption rate) The resin composition of the present disclosure preferably has a water absorption rate of 2.0% by mass or less, and more preferably 1.5% by mass or less, when immersed in water at 23°C for 24 hours in accordance with ISO 62:2008. When the water absorption rate is 2.0% by mass or less, defects in appearance such as foaming due to moisture during shaping are further suppressed. There is no particular limitation on the lower limit of the water absorption rate, but examples of the lower limit include 0.001 mass %, 0.005 mass %, 0.008 mass %, and 0.01 mass %.

[0032] (moisture content) The resin composition of the present disclosure preferably has a water content represented by the following formula (1) of 1.0 mass % or less, and more preferably 0.5 mass % or less. When the moisture content is 1.0% by mass or less, defects in appearance such as foaming due to moisture during shaping are further suppressed. There is no particular limitation on the lower limit of the moisture content, but examples of the lower limit include 0.001 mass %, 0.005 mass %, 0.008 mass %, and 0.01 mass %. Moisture content (mass%)=((mass of resin composition before drying−mass of resin composition dried at 100°C for 24 hours) / mass of resin composition before drying)×100 ... Equation (1)

[0033] The resin composition of the present disclosure has a linear expansion coefficient measured in accordance with ISO 11359:2023 of preferably 7×10 -4 (1 / ℃) or less, more preferably 5×10 -4 (1 / °C) or less, more preferably 3 x 10 -4 (1 / ℃) or less. The lower limit of the linear expansion coefficient is not particularly limited, but the lower limit is, for example, 1.1 × 10 -4 (1 / ℃), 0.6×10 -4 (1 / ℃), 0.5×10 -4 (1 / ℃) etc.

[0034] (glass transition temperature (Tg)) The resin composition of the present disclosure has a glass transition temperature (Tg) measured in accordance with ISO 11357-1:2023 and ISO 11357 / -3:2018 of preferably 60°C or higher, more preferably 70°C or higher, from the viewpoint of further suppressing scorching during thermal fusion molding. The upper limit of Tg is, for example, 200°C, 150°C, or the like.

[0035] (tensile strength) The tensile strength (ISO 527:2012) of the resin composition of the present disclosure is preferably 38 MPa to 78 MPa.

[0036] (tensile modulus) The tensile modulus (ISO 527:2012) of the resin composition of the present disclosure is preferably 1500 MPa to 3300 MPa.

[0037] (bending strength) The flexural strength (ISO 527:2012) of the resin composition of the present disclosure is preferably 51 MPa to 140 MPa.

[0038] (flexural modulus) The resin composition of the present disclosure preferably has a flexural modulus (ISO 527:2012) of 1400 MPa to 3300 MPa.

[0039] <Preferred form> Preferred embodiments of the resin composition of the present disclosure will be described below. The resin composition of the present disclosure is preferably in the form of pellets or filaments at room temperature (for example, at a temperature of 25°C).

[0040] When the resin composition of the present disclosure is in the form of a filament, the diameter of the filament is preferably 1.00 mm to 10.00 mm, from the viewpoint of further improving the molding precision of the obtained intraoral appliance. The lower limit of the filament diameter is more preferably 1.50 mm, and even more preferably 1.60 mm. The upper limit of the filament diameter is more preferably 4.00 mm, even more preferably 3.50 mm, and even more preferably 3.00 mm.

[0041] When the resin composition of the present disclosure is in the form of filaments, the circularity of the filaments is preferably 1.000 to 1.200, and more preferably 1.000 to 1.100, in order to easily obtain three-dimensionally shaped articles with excellent appearance and surface properties.

[0042] [Method for manufacturing oral appliances] The method for manufacturing an oral appliance of the present disclosure includes a step of manufacturing an oral appliance by three-dimensional fabrication using the resin composition of the present disclosure described above by fused deposition modeling. The method for manufacturing an oral appliance of the present disclosure may include other steps as needed. The method for manufacturing an oral appliance according to the present disclosure uses the resin composition according to the present disclosure described above, and therefore can manufacture an oral appliance with excellent molding precision.

[0043] The manufacture of oral appliances by three-dimensional fused deposition modeling may be carried out according to known techniques.

[0044] Prior to three-dimensional modeling, the resin composition of the present disclosure is preferably pre-dried. This makes it possible to suppress the generation of bubbles during molding, and further improve the aesthetics of the resulting intraoral appliance. The temperature for pre-drying the resin composition is preferably 130°C or lower, more preferably 120°C or lower, and even more preferably 70°C to 100°C. The temperature for pre-drying the resin composition is preferably 2 hours to 14 hours.

[0045] Three-dimensional modeling by fused deposition modeling is carried out by melting the resin composition of the present disclosure and extruding the molten resin composition from an extruder. Fused deposition modeling three-dimensional modeling can be performed using a fused deposition modeling 3D printer.

[0046] The extruder temperature of the 3D printer is preferably 170°C to 300°C, and more preferably 190°C to 300°C. When the extruder temperature is 170°C to 300°C, the amount of resin discharged from the extruder becomes more stable, and the molding accuracy is further improved.

[0047] The bed temperature of the 3D printer is preferably 10°C to 130°C, more preferably 10°C to 120°C, and even more preferably 10°C to 110°C. When the bed temperature is 10°C to 130°C, warping due to thermal shrinkage during modeling can be further suppressed.

[0048] The temperature inside the 3D printer is preferably 10°C to 130°C, and more preferably 10°C to 100°C. When the temperature inside the chamber is 10°C to 130°C, molding defects due to softening during molding can be further suppressed.

[0049] The intraoral appliance of the present disclosure is an intraoral appliance manufactured by three-dimensional fabrication using the resin composition of the present disclosure described above using fused deposition modeling. The oral appliance of the present disclosure is manufactured using the resin composition of the present disclosure described above, and therefore has excellent molding precision. [Example]

[0050] Examples of the present disclosure will be shown below, but the present disclosure is not limited to the following examples.

[0051] [Creating model data (1)] Pure Scan Powder (manufactured by Quest) was applied to a clasp / non-clasp denture comparison model (manufactured by Quest) (hereinafter simply referred to as the "model") onto which a partial denture could be fitted. The model was then fixed to a scan plate using Blu Tack (Bostik) as a fixing clay. Next, "Copy denture" was selected in the S-WAVE Dental System (manufactured by Shofusha), and the model was scanned using an S-WAVE Scanner E4 (manufactured by Shofusha) to create model data (1).

[0052] [Creating non-clasp partial denture data (2)] Non-clasp partial denture data (2) for three missing teeth (hereinafter also referred to as "data (2)") that fits the model in the obtained model data (1) was created using dental CAD software "3Shape Dental Designer" manufactured by 3Shape.

[0053] Example 1 <Preparing the filament> A pellet-shaped resin composition containing methyl methacrylate resin (PMMA) called "Acrypellets" manufactured by Yamahachi Dental Materials Industries Co., Ltd. was prepared. The PMMA contained in "Acrypellets" is hereinafter referred to as "PMMA1." The "Acrypellets" were pre-dried at 80°C for 8 hours, then placed in the hopper of a co-rotating twin-screw extruder Process 11 (manufactured by Thermo Fisher Scientific) and extruded under the following conditions: rotation speed 200 rpm, discharge rate 700 g / h, extruder diameter φ2.5 mm, cylinder 4 temperature 150°C, cylinder 5 temperature 200°C, cylinder 6 temperature 240°C, cylinder 7 temperature 240°C, cylinder 8 temperature 240°C, and extruder temperature 240°C. After air drying, a filament (hereinafter referred to as "filament 1") was obtained as a resin composition containing PMMA1 as the resin.

[0054] The physical properties of PMMA1 in filament 1 were as follows. The conditions for measuring the physical properties were as described above. The melt flow rate was in the range of 0.1 g / 10 min to 100 g / 10 min. The density is 1.0 g / cm 3 ~1.4g / cm 3 The range was. The water absorption rate was 2.0% by mass or less. The moisture content was 1.0% by mass or less. The linear expansion coefficient is 5 x 10 -4 (1 / ℃) or less.

[0055] <Loading data (2)> The data (2) obtained above was loaded into Simplify3D, a 3D printer slicer software made by Simplify3D, and sliced ​​to obtain "sliced ​​data (2)," which is data that can be 3D printed. The reading was performed with the following settings: The angle was adjusted so that the support material during modeling would stand on the occlusal surface (x, y, z = (90, 0, 0)). The height from the bed was set to 5.00 mm. The thickness of the support material was 1.00 mm. The maximum overhang angle was set to 20 degrees. Support materials were automatically placed.

[0056] The slicer modeling parameters were set as follows: The default settings were used except for the following points. Extruder diameter: 0.40mm -Injection amount adjustment (power) … 1.00 Injection width: Automatic (0.48mm) Retraction use: Yes Retraction distance: 1.50mm Excess restart distance: 0.00mm Vertical lift retraction: 0.00mm Retraction speed: 1800.0 mm / min Height of one layer: 0.1500mm Top solid layer... 4 Bottom solid layer: 4 Outline... 2 First layer height: 200 First layer width: 300 First layer speed: 38% Outline printing order: from inside to outside Skirt / brim used... Yes Skirt layer... 1 Skirt offset distance from model: 5.50mm Skirt outline... 1 -Internal infill pattern: linear Internal pattern rotation: 0 degrees Infill rate: 100% ·Injection width … 100% Combined infill layers... 1 Outline overlap…25 Minimum infill length: 0.0mm External infill pattern: linear Rotation pattern rotation: 0 degrees Solid infill threshold area: 25.0mm 2 Solid infill extra extension: 0.0mm Top layer expansion … 1.00 Top layer extrusion modifier: 100% Infill pattern: grid Support rotation: 0 degrees Support infill ratio: 15% · Support base layer... 1 Inflate support generation... 0.5mm ·Combined support layer … 1 - High density support material layers... 5 Low-density support layer: 1 High-density support infill rate: 60% Offset on the horizontal plane of the model: 0.80mm Upper vertical separation layer: 1 Lower isolation layer: 1 Extruder temperature: 270℃ Bed temperature: 90℃ · Temperature inside the cabinet: No setting Cooling fan output: 25% for the first layer, 100% for the second layer and above Default print speed: 2400mm / min Outline speed: 50% Inner boundary speed: 50% ·Top layer speed…50% Solid infill rate: 80% Support generation speed: 80% -Speed ​​of generating high density support material: 70% ·XY movement speed … 4800mm / min ·Z movement speed … 500mm / min

[0057] <Manufacturing of dentures (2A)> CreatBot's fused deposition modeling 3D printer "PEEK-300" and The filament 1 containing PMMA1 prepared above, was prepared.

[0058] Filament 1 was pre-dried at 80°C for 8 hours, and the pre-dried filament 1 was used as the material to manufacture a denture (2A) using the above-mentioned 3D printer by three-dimensional modeling using fused deposition modeling. The above three-dimensional modeling was performed using No. 5000NS (manufactured by NITTO) fixing tape on the bed part of the 3D printer. The above three-dimensional modeling was performed using the “sliced ​​data (2)” obtained by the aforementioned slicer software “Simplify3D.” After the above three-dimensional modeling, the support material was removed with nippers to obtain the denture (2A).

[0059] <Creating denture (2A) data> Pure Scan Powder (Quest) was applied to the denture (2A) obtained above. The denture (2A) was then fixed to a scan plate using Blu Tack (Bostik) as a fixing agent. Next, "Copy denture" was selected in the S-WAVE Dental System (manufactured by Shofusha), and the denture (2A) was scanned with an S-WAVE Scanner E4 (manufactured by Shofusha) to obtain denture (2A) data.

[0060] <Confirming modeling accuracy> Using the reverse engineering software "Geomagic Design X" manufactured by 3D Systems, the accuracy of the denture (2A) modeling was confirmed by overlaying the aforementioned data (2) with the aforementioned denture (2A) data. In detail, the data (2) and the denture (2A) data were loaded, and "Align scans and scan data in scan group" was selected in the "Coordinate Alignment" tab. Next, data (2) was selected as the reference data and denture (2A) data as the movement data, and automatic alignment was performed with quality 5. Next, optimization was performed, and in the Accuracy Analyzer, the maximum deviation option was set to 2 mm, and the histogram confirmed that the build accuracy (%) was within ±0.2 mm. The results are shown in Table 1. Here, "modeling accuracy within ±0.2 mm (%)" means the percentage (%) of the entire surface area of ​​the denture (2A) in the denture (2A) data where the positional deviation from the data (2) is within ±0.2 mm. The closer the "modeling accuracy within ±0.2 mm (%)" is to 100%, the better the modeling accuracy of the denture (2A).

[0061] Example 2 The same procedure as in Example 1 was carried out, except that a PMMA filament manufactured by YINGJI Co., Ltd. was used in place of Filament 1. The results are shown in Table 1. The PMMA filament manufactured by YINGJI is a filament-shaped resin composition containing a methyl methacrylate resin (PMMA). The PMMA contained in the PMMA filament manufactured by YINGJI is hereinafter referred to as "PMMA2."

[0062] The physical properties of PMMA2 in the PMMA filament manufactured by YINGJI were as follows. The measurement conditions for each property were as described above. The melt flow rate was in the range of 0.1 g / 10 min to 100 g / 10 min. The density is 1.0 g / cm 3 ~1.4g / cm 3 The range was. The water absorption rate was 2.0% by mass or less. The moisture content was 1.0% by mass or less. The linear expansion coefficient is 5 x 10 -4 (1 / ℃) or less.

[0063] Comparative Example 1 The same operations as in Example 1 were performed except that the filament 1 used in the production of denture (2A) was changed to ULTRAFUSE (registered trademark) PLA Pro1 Natural White Filament (manufactured by BASF) containing polylactic acid (PLA) as the resin, the extruder temperature was changed to 220°C, the bed temperature was changed to 60°C, the pre-drying of the filament was changed to "8 hours at 60°C", and the cooling fan output was changed to 0%. The results are shown in Table 1.

[0064] [Table 1]

[0065] As shown in Table 1, in Examples 1 and 2, in which dentures were manufactured by fused deposition modeling three-dimensional modeling using a resin composition (more specifically, filaments) containing acrylic resin (PMMA1, PMMA2) as the resin, the molding accuracy of the resulting dentures was superior to that of Comparative Example 1, in which dentures were manufactured by fused deposition modeling three-dimensional modeling using a resin composition (more specifically, filaments) containing polylactic acid (PLA) as the resin.

Claims

1. A resin composition containing an acrylic resin, used in the manufacture of oral appliances by fused deposition modeling three-dimensional modeling.

2. The resin composition according to claim 1 , wherein the acrylic resin comprises a methyl (meth)acrylate-based resin.

3. The resin composition according to claim 1, which is used for producing a denture base or a denture by three-dimensional fabrication using a fused deposition modeling method.

4. The resin composition according to claim 1, wherein the melt flow rate measured in accordance with ISO 1133-1: 2022 at 230 ° C. under a load of 3.8 kg is 0.1 g / 10 min to 100 g / 10 min.

5. The density measured in accordance with ISO 1183:2019 is 1.0 g / cm ３ ~1.4g / cm ３ The resin composition according to claim 1,

6. The resin composition according to claim 1, wherein the resin composition has a water absorption rate of 2.0 mass% or less when immersed in water at 23°C for 24 hours in accordance with ISO 62:2008.

7. The resin composition according to claim 1, wherein the water content represented by the following formula (1) is 1.0 mass% or less. Moisture content (mass%)=((mass of resin composition before drying−mass of resin composition dried at 100° C. for 24 hours) / mass of resin composition before drying)×100 Formula (1)

8. The linear expansion coefficient measured in accordance with ISO 11359:2023 is 5 x 10 －４ The resin composition according to claim 1, wherein the thermal expansion coefficient is 1 / °C or less.

9. The resin composition according to claim 1 , wherein the content of the acrylic resin is 80% by mass or more based on the total amount of the resin composition.

10. The resin composition according to claim 1, which is in the form of pellets or filaments at a temperature of 25°C.

11. A method for manufacturing an intraoral appliance, comprising a step of manufacturing an intraoral appliance by fused deposition modeling three-dimensional modeling using the resin composition according to any one of claims 1 to 10.

12. An oral appliance manufactured by three-dimensional fused deposition modeling using the resin composition according to any one of claims 1 to 10.

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