Method for manufacturing instrument, photocurable composition, three-dimensional object and mold

Abstract

To provide a method for manufacturing an instrument for use in an oral cavity, which hardly causes a reduction of a dimensional accuracy when manufacturing the instrument for use in an oral cavity by using a mold produced by stereo-lithography.SOLUTION: There is provided a method for manufacturing an instrument for use in an oral cavity, comprising: a step 1 of curing a photocurable composition by stereo-lithography to manufacture a mold used for manufacturing the equipment for use in the oral cavity; and a step 2 of manufacturing the instrument by polymerizing a curable composition in the mold, wherein, in the step 1, the photocurable composition is irradiated with visible light having a wavelength of 405 nm at an irradiation dose of 11 mJ / cm2 to form a cured layer A1 having a thickness of 50 μm; the cured layer A1 is laminated in the thickness direction to form a rectangular plate-shaped object A1; when a rectangular plate-shaped test piece A1 is produced by stereo-lithography under the conditions of irradiating the modeled object A1 with ultraviolet rays with a wavelength of 365 nm at an irradiation dose of 3 J / cm2, a storage modulus of the test piece A1 at 25°C is 150 MPa or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a method for manufacturing an article, a photocurable composition, a three-dimensional object, and a mold. [Background technology]

[0002] In recent years, dental products such as dental prostheses, equipment used in the oral cavity, etc. have been studied. For example, from the viewpoint of the efficiency of molding these dental products, a method of manufacturing three-dimensional objects such as dental products by stereolithography using a 3D printer is known (for example, see Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 4160311 Summary of the Invention [Problem to be solved by the invention]

[0004] Meanwhile, there are conventional methods for producing dental prostheses, for example, devices to be used in the oral cavity, without using stereolithography such as a 3D printer. According to this method, for example, when manufacturing a removable denture among dental prostheses, first, a mold of the patient's oral cavity is taken directly from the patient using an impression material, and a model of the patient's oral cavity is made by referring to the impression material. A mold is then made from the model using silicone. The mold is used as a mold, and a hardenable composition is injected into it, allowing a removable denture to be manufactured by room temperature polymerization. As described above, conventional methods that do not use photolithography have the problem of requiring complicated processes such as creating a model of the patient's oral cavity and making a silicone mold.

[0005] In contrast, the above-mentioned complication is eliminated by a method of directly manufacturing a denture by stereolithography using a 3D printer. However, compared to conventional methods that do not use a 3D printer, the materials that can be properly hardened by stereolithography are very limited, so the characteristics of the resulting denture are also limited. For example, the conventional method uses room temperature polymerization using a mold, but this method allows the use of many materials that can improve aesthetics and physical properties. In contrast, such materials used in room temperature polymerization often cannot be used in stereolithography using a 3D printer. As a result, when stereolithography using a 3D printer is used, it is difficult to adjust the resulting denture to obtain the desired properties.

[0006] As described above, there is a demand for a method for manufacturing an oral cavity device that can easily produce an oral cavity device and that can easily be adjusted to obtain desired properties.

[0007] In order to achieve the above-mentioned objective, the inventors have discovered a method for producing a mold for manufacturing equipment to be used in the oral cavity, such as a removable denture, by stereolithography using a 3D printer, and using the mold to manufacture equipment to be used in the oral cavity, such as a removable denture.

[0008] On the other hand, when a mold for an intraoral appliance is made from a photocurable composition and the mold is used to manufacture the intraoral appliance, the dimensions of the intraoral appliance manufactured using the mold may be off. In other words, the above manufacturing method leaves room for improvement in terms of the dimensional accuracy of the intraoral appliance manufactured using the mold.

[0009] An object of one aspect of the present disclosure is to provide a method for manufacturing equipment to be used in the oral cavity, which does not result in a decrease in dimensional accuracy when the equipment is manufactured using a mold produced by photopolymerization, as well as a photocurable composition, a three-dimensional object, and a mold suitable for this manufacturing method. [Means for solving the problem]

[0010] Means for solving the above problems include the following aspects. <1> A step 1 of hardening the photocurable composition by photolithography to prepare a mold for use in manufacturing an instrument for use in the oral cavity; and step 2 of polymerizing the hardenable composition in the mold to produce a device for use in the oral cavity, In the step 1, The photocurable composition was irradiated with visible light having a wavelength of 405 nm at a dose of 11 mJ / cm 2 The cured layers A1 are laminated in the thickness direction to form a rectangular plate-shaped object A1 having a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm. The object A1 is irradiated with ultraviolet light having a wavelength of 365 nm at a dose of 3 J / cm. 2 When a rectangular plate-shaped test piece A1 with a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm was produced by photolithography under the condition of irradiation with A method for producing a device to be used in the oral cavity, wherein the storage modulus of the test piece A1 at 25°C is 150 MPa or more. <2> In the step 1, the photocurable composition contains a filler. <1> A method for producing an equipment used in the manufacture of the equipment described in claim 1 for use in the oral cavity. <3> In the step 1, the filler contained in the photocurable composition includes one or more selected from the group consisting of silica and organic fillers. <2> A method for producing an equipment used in the manufacture of the equipment described in claim 1 for use in the oral cavity. <4> In the step 1, the content of the filler contained in the photocurable composition is 5% by mass to 80% by mass relative to the total mass of the photocurable composition. <2> or <3> A method for producing an equipment used in the manufacture of the equipment described in claim 1 for use in the oral cavity. <5> In the step 1, the photocurable composition contains a (meth)acrylic monomer, a filler, and a photopolymerization initiator. <1> ~ <4> 1. A method for manufacturing an equipment used in the manufacture of an equipment for use in the oral cavity described in any one of the above. <6> In the step 1, the photocurable composition is A (meth)acrylic monomer (A) having one or more (meth)acryloyl groups and no siloxane bond; (B) a (meth)acrylic monomer having two or more (meth)acryloyl groups and a siloxane bond, and (C) a (meth)acrylic monomer having no (meth)acryloyl group and having a solubility parameter (SP value) of 7.00 to 15.00 (cal / cm 3 ) 1 / 2 and one or more compounds (C) selected from the group consisting of <1> ~ <5> 1. A method for manufacturing an equipment used in the manufacture of an equipment for use in the oral cavity described in any one of the above. <7> In the step 1, the photocurable composition contains the (meth)acrylic monomer (B) and a compound (C). <6> A method for producing an equipment used in the manufacture of the equipment described in claim 1 for use in the oral cavity. <8> The equipment to be manufactured for use in the oral cavity is a dental prosthesis. <1> ~ <7> 1. A method for manufacturing an equipment used in the manufacture of an equipment for use in the oral cavity described in any one of the above. <9> 1. A photocurable composition comprising: The photocurable composition is A (meth)acrylic monomer (A) having one or more (meth)acryloyl groups and no siloxane bond; (B) a (meth)acrylic monomer having two or more (meth)acryloyl groups and a siloxane bond, and (C) a copolymer having no (meth)acryloyl group and a solubility parameter (SP value) of 7.00 to 15.00 (cal / cm 3 ) 1 / 2 and one or more compounds (C) selected from the group consisting of A photopolymerization initiator, The photocurable composition was irradiated with visible light having a wavelength of 405 nm at a dose of 11 mJ / cm 2 The cured layers A1 are laminated in the thickness direction to form a rectangular plate-shaped object A1 having a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm. The object A1 is irradiated with ultraviolet light having a wavelength of 365 nm at a dose of 3 J / cm. 2When a rectangular plate-shaped test piece A1 with a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm was produced by photolithography under the condition of irradiation with The photocurable composition has a storage modulus at 25°C of 150 MPa or more for the test piece A1. <10> Contains fillers, <9> The photocurable composition according to claim 1. <11> The filler contained in the photocurable composition includes one or more selected from the group consisting of silica and organic fillers. <10> The photocurable composition according to claim 1. <12> The (meth)acrylic monomer (B) and the compound (C) are included. <9> ~ <11> 13. The photocurable composition according to claim 12, <13> The (meth)acrylic monomer (A), A di(meth)acrylic monomer (A-1) having at least one of a ring structure or a urethane bond, and two (meth)acryloyloxy groups, and having no siloxane bond; and a mono(meth)acrylic monomer (A-2) having one (meth)acryloyloxy group and an aromatic ring, and having no siloxane bond. <9> ~ <12> 13. The photocurable composition according to claim 12, <14> a total content of the di(meth)acrylic monomer (A-1), the mono(meth)acrylic monomer (A-2), the (meth)acrylic monomer (B) and the compound (C) contained in the photocurable composition is 20 mass% to 95 mass% with respect to the total mass of the photocurable composition; <13> The photocurable composition according to claim 1. <15> the content of the di(meth)acrylic monomer (A-1) in the photocurable composition is 3% by mass to 50% by mass based on the total content of the di(meth)acrylic monomer (A-1), the mono(meth)acrylic monomer (A-2), the (meth)acrylic monomer (B) and the compound (C) in the photocurable composition; <13> or <14> The photocurable composition according to claim 1. <16> the content of the mono(meth)acrylic monomer (A-2) in the photocurable composition is 20% by mass to 85% by mass based on the total content of the di(meth)acrylic monomer (A-1), the mono(meth)acrylic monomer (A-2), the (meth)acrylic monomer (B) and the compound (C) in the photocurable composition; <13> ~ <15> 13. The photocurable composition according to claim 12, <17> the content of the (meth)acrylic monomer (B) in the photocurable composition is 1 mass % to 35 mass % based on the total content of the di(meth)acrylic monomer (A-1), the mono(meth)acrylic monomer (A-2), the (meth)acrylic monomer (B) and the compound (C) in the photocurable composition; <13> ~ <16> 13. The photocurable composition according to claim 12, <18> the content of the compound (C) contained in the photocurable composition is 1 mass % to 30 mass % based on the total content of the di(meth)acrylic monomer (A-1), the mono(meth)acrylic monomer (A-2), the (meth)acrylic monomer (B) and the compound (C) contained in the photocurable composition; <13> ~ <17> 13. The photocurable composition according to claim 12, <19> Used in photolithography, <9> ~ <18> 13. The photocurable composition according to claim 12, <20> Used in the production of casting molds by stereolithography, <9> ~ <18> 13. The photocurable composition according to claim 12, <21> The mold is a mold used for manufacturing a device to be used in the oral cavity. <20> The photocurable composition according to claim 1. <22> The mold is a mold used for producing a dental prosthesis; <20> The photocurable composition according to claim 1. <23> <9> ~ <22> 13. A three-dimensional object comprising a cured product of the photocurable composition according to claim 12. <24> <23> A mold comprising the three-dimensional object described above. Effect of the Invention

[0011] According to one aspect of the present disclosure, there is provided a method for producing equipment to be used in the oral cavity, which is unlikely to result in a decrease in dimensional accuracy of the resulting equipment to be used in the oral cavity when a mold produced by photopolymerization is used to produce the equipment, as well as a photocurable composition, a three-dimensional object, and a mold suitable for this production method. [Brief description of the drawings]

[0012] [Figure 1] FIG. 2 is a schematic diagram of a three-dimensional object B1 (frame) formed in an example. [Diagram 2] FIG. 13 is a schematic diagram of a three-dimensional object B2 (lid) formed in the example. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the present disclosure, when a plurality of substances corresponding to each component are present in the composition, the amount of each component contained in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified. In the numerical ranges described in the present disclosure in stages, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit value of the numerical range may be replaced with a value shown in the examples. In the present disclosure, the term "light" is a concept that encompasses active energy rays such as ultraviolet light and visible light.

[0014] In this disclosure, "(meth)acrylate" means acrylate or methacrylate, "(meth)acryloyl" means acryloyl or methacryloyl, and "(meth)acrylic" means acrylic or methacrylic.

[0015] <Equipment manufacturing method> The method for producing a device according to the present disclosure includes step 1 of hardening a photocurable composition by stereolithography to prepare a mold to be used in the production of a device to be used in the oral cavity, and step 2 of polymerizing the photocurable composition in the mold to produce a device to be used in the oral cavity. In step 1, the photocurable composition is irradiated with visible light having a wavelength of 405 nm at a dose of 11 mJ / cm. 2 The cured layers A1 are laminated in the thickness direction to form a rectangular plate-shaped object A1 having a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm. The object A1 is irradiated with ultraviolet light having a wavelength of 365 nm at a dose of 3 J / cm. 2 This method is used to manufacture equipment to be used in the oral cavity, in which when a rectangular plate-shaped test piece A1 with a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm is produced by photolithography under conditions of irradiation with light at a temperature of 100°C, the storage modulus of the test piece A1 at 25°C is 150 MPa or more.

[0016] In the manufacturing method of the disclosed device, when a mold manufactured by photolithography is used to manufacture a device to be used in the oral cavity, the dimensional accuracy of the obtained device to be used in the oral cavity is not likely to decrease.

[0017] [Process 1] The method for producing a device of the present disclosure includes step 1 of curing a photocurable composition by stereolithography to produce a mold to be used in producing a device to be used in the oral cavity.

[0018] Stereolithography is a method for obtaining a cured product (that is, a stereolithography product) by repeatedly irradiating a photocurable composition with light to form a cured layer, thereby laminating the cured layers. The photolithography may be an inkjet type photolithography, or a liquid tank type photolithography (i.e. In other words, photolithography using a liquid tank may be used.

[0019] In inkjet stereolithography, droplets of a photocurable composition are ejected from an inkjet nozzle onto a substrate, and the droplets attached to the substrate are irradiated with light to obtain a cured product. In one example of inkjet-type photofabrication, for example, a head equipped with an inkjet nozzle and a light source is scanned in a plane while a photocurable composition is ejected from the inkjet nozzle onto a substrate, and the ejected photocurable composition is irradiated with light to form a cured layer. By repeating these operations, the cured layers are stacked in sequence to obtain a cured product (i.e., a photofabricated product).

[0020] In liquid tank type stereolithography, a part of the photocurable composition (i.e., uncured photocurable composition in a liquid state; the same applies below) contained in a liquid tank is cured by irradiating it with light to form a cured layer, and this operation is repeated to stack the cured layers and obtain a cured product (i.e., a stereolithography product). Liquid tank type stereolithography differs from inkjet type stereolithography in that a liquid tank is used. Examples of liquid tank type stereolithography include DLP (Digital Light Processing) type stereolithography and SLA (Stereolithography) type stereolithography. In the DLP method, a surface of light is irradiated onto a photocurable composition in a liquid tank. In the SLA method, a laser beam is scanned over a photocurable composition in a liquid tank. From the viewpoint of more effectively exerting the effects of the photocurable composition of the present disclosure, the liquid tank type stereolithography is preferably DLP type stereolithography.

[0021] In an example of DLP type stereolithography, a build table that is vertically movable; a tray (i.e., liquid tank) disposed below the build table (on the side in the direction of gravity; the same applies below), including a light-transmitting portion, and containing a photocurable composition; a light source (e.g., an LED light source) disposed below the tray for irradiating the photocurable composition in the tray with planar light through a light-transmitting portion of the tray; A 3D printer equipped with this function (for example, "Cara Print4.0" manufactured by Kulzer, "Max UV" manufactured by Asiga, etc.) is used. In this example, first, a gap of one layer is provided between the build table and the tray, and the gap is filled with the photocurable composition. Next, the photocurable composition filled in the gap is irradiated with planar light from below through the light-transmitting portion of the tray, and the area irradiated with light is cured to form a first cured layer. Next, the gap between the build table and the tray is widened by the next layer, and the resulting space is filled with the photocurable composition. Next, the photocurable composition filled in the space is irradiated with light in the same manner as the curing of the first layer, and a second cured layer is formed. By repeating the above operations, the cured layers are stacked to manufacture a three-dimensional object. In this example, the manufactured three-dimensional object may be further cured by further irradiating the three-dimensional object with light. For information on DLP type stereolithography, the descriptions in Japanese Patent No. 5111880 and Japanese Patent No. 5235056 may be referred to, for example.

[0022] The equipment to be used in the oral cavity, which is manufactured by the method for manufacturing an equipment of the present disclosure, is preferably a medical instrument or a dental prosthesis to be used in the oral cavity, and more preferably a dental prosthesis. Examples of dental prostheses include inlays, crowns, bridges, temporary crowns, temporary bridges, composite resins, dentures (e.g., complete dentures, partial dentures, etc.). As the dental prostheses, dentures are preferred. Examples of medical devices used in the oral cavity include dentures (e.g., complete dentures, partial dentures, etc.), mouthpieces, mouthguards, orthodontic appliances, splints such as occlusion splints and splints for treating temporomandibular joint disorders, impression trays, and surgical guides.

[0023] The photocurable composition in step 1 is a composition that can be cured by photolithography and can be used to manufacture a mold for manufacturing equipment to be used in the oral cavity. Furthermore, the composition of the photocurable composition is not particularly limited as long as the storage modulus of test piece A1 at 25°C is 150 MPa or more when the test piece A1 is produced under the above-mentioned conditions. When the test piece A1 is prepared under the above-mentioned conditions, the photocurable composition may have a storage modulus at 25° C. of 200 MPa to 2000 MPa, or 250 MPa to 1500 MPa.

[0024] The photocurable composition in step 1 preferably contains a (meth)acrylic monomer and a photopolymerization initiator, and more preferably further contains a filler, which will be described later. Each component contained in the photocurable composition may be used alone or in combination of two or more kinds.

[0025] ((Meth)acrylic monomer) The (meth)acrylic monomer that may be contained in the photocurable composition in step 1 is not particularly limited as long as it is a compound having one or more (meth)acryloyl groups. Among them, the (meth)acrylic monomer preferably contains at least one of a (meth)acrylic monomer (A) having one or more (meth)acryloyl groups and no siloxane bond and a (meth)acrylic monomer (B) having two or more (meth)acryloyl groups and a siloxane bond, and more preferably contains both the (meth)acrylic monomer (A) and the (meth)acrylic monomer (B).

[0026] ((Meth)acrylic monomer (A)) The photocurable composition preferably contains a (meth)acrylic monomer (A) having one or more (meth)acryloyl groups and no siloxane bond.

[0027] The (meth)acrylic monomer (A) may contain at least one of the following di(meth)acrylic monomer (A-1) or mono(meth)acrylic monomer (A-2), and preferably contains both. Di(meth)acrylic monomer (A-1): a compound having at least one of a ring structure or a urethane bond, and two (meth)acryloyloxy groups, and having no siloxane bond. Mono(meth)acrylic monomer (A-2): a compound having one (meth)acryloyloxy group and an aromatic ring, and having no siloxane bond

[0028] (Di(meth)acrylic monomer (A-1)) The (meth)acrylic monomer (A) preferably contains the above-mentioned di(meth)acrylic monomer (A-1). The di(meth)acrylic monomer (A-1) having a ring structure favorably contributes to suppressing deformation of a mold during the manufacture of a plate denture and improving the water resistance of the mold. In addition, when the ring structure contains an aromatic ring, the aromatic ring concentration in the (meth)acrylic monomer component increases, and the mold releasability increases and the toughness tends to be excellent. The di(meth)acrylic monomer (A-1) having a urethane bond can suppress breakage when a plate denture is removed from a mold and tends to be excellent in toughness. The (meth)acrylic monomer (A) may contain one kind of di(meth)acrylic monomer (A-1), or may contain two or more kinds of di(meth)acrylic monomers (A-1).

[0029] The molecular weight or weight average molecular weight of the di(meth)acrylic monomer (A-1) may be 400 to 8000. The weight average molecular weight of the di(meth)acrylic monomer (A-1) may be 400 to 6000, or 400 to 5000. In this disclosure, the weight average molecular weight is measured by gel permeation chromatography (GPC).

[0030] Two types of di(meth)acrylic monomers (A-1) having different molecular weights may be used in combination, which tends to increase the dispersibility of the di(meth)acrylic monomer (A-1) in the polymer and improve the shape recovery speed.

[0031] The solubility parameter (SP value) of the di(meth)acrylic monomer (A-1) is 8.50 to 12.70 (cal / cm 3 ) 1 / 2 It is preferable that the density is 8.70 to 12.50 (cal / cm 3 ) 1 / 2 More preferably, it is 9.00 to 12.00 (cal / cm 3 ) 1 / 2 It is even more preferable that: The solubility parameter (SP value) of the di(meth)acrylic monomer (A-1) is 8.50 (cal / cm 3 ) 1 / 2 By satisfying the above, it becomes easier to obtain a three-dimensional object with less surface roughness and excellent appearance. The solubility parameter (SP value) of the di(meth)acrylic monomer (A-1) is 12.70 (cal / cm 3 ) 1 / 2 When the above ratio is satisfied, a three-dimensional object having excellent bending strength and toughness can be easily obtained.

[0032] The di(meth)acrylic monomer (A-1) is not particularly limited as long as it has at least one of a ring structure or a urethane bond, two (meth)acryloyloxy groups, and no siloxane bond. The ring structure may be an aromatic ring structure or an alicyclic structure.

[0033] When the di(meth)acrylic monomer (A-1) contains a urethane bond, it may be a compound represented by the following formula (6-1), and when it contains a ring structure, it may be a compound represented by the following formula (6-2). When the di(meth)acrylic monomer (A-1) contains both a urethane bond and a ring structure, it may be a compound represented by the following formula (6-1).

[0034] [ka]

[0035] [ka]

[0036] In formula (6-1), R1's are each independently a divalent organic group, R2's are each independently a divalent hydrocarbon group which may have a substituent, R3's are each independently a hydrogen atom or a methyl group, X's are a divalent organic group, and n is an integer of 0 to 10. A plurality of R1's, R2's, and R3's may be the same or different, and when a plurality of X's are present, they may be the same or different.

[0037] In formula (6-1), R1 is, for example, a divalent organic group containing one or more bonds selected from the group consisting of a divalent hydrocarbon group, an ether bond, and an ester bond. The divalent hydrocarbon group represented by R1 may be, for example, a divalent chain hydrocarbon group or a divalent hydrocarbon group containing a ring structure (aromatic ring structure, alicyclic structure). When the divalent organic group represented by R1 contains an ether bond, the number of the ether bonds is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 15. When the divalent organic group represented by R1 contains an ester bond, the number of the ester bonds is preferably 1 to 12, more preferably 1 to 8, and further preferably 1 to 6. In formula (6-1), R1 may have, for example, 2 to 60 carbon atoms, preferably 2 to 40 carbon atoms, and more preferably 2 to 30 carbon atoms.

[0038] In formula (6-1), R1 is preferably a group represented by the following general formula (6-1-R1).

[0039] [ka]

[0040] In general formula (6-1-R1), R 1A is a divalent hydrocarbon group which may have a substituent, R 1B is a methylene group (-CH-) or a carbonyl group (-C(=O)-), and R 1C is a divalent hydrocarbon group, and m is an integer of 0 to 10. 1B , R 1C When a plurality of are present, they may be the same or different. * indicates the bonding position.

[0041] R in formula (6-1-R1) 1A The divalent hydrocarbon group which may have a substituent as the substituent is, for example, a divalent chain hydrocarbon group or a divalent hydrocarbon group containing a ring structure, and is preferably a divalent chain hydrocarbon group. The ring structure contained in the divalent hydrocarbon group may be an aromatic structure or an alicyclic structure. R 1A The divalent chain hydrocarbon group as may be branched and may be saturated or unsaturated. R 1A The divalent chain hydrocarbon group as the alkyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and further preferably 2 to 10 carbon atoms. R 1A The substituent that the divalent chain hydrocarbon group may have is, for example, an alkoxy group having 2 to 10 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, preferably an aryloxy group. Examples of the aryloxy group include a phenoxy group and a naphthyloxy group, and preferably a phenoxy group. R 1A The divalent hydrocarbon group containing an aromatic structure as the aromatic group is preferably a divalent hydrocarbon group having an aromatic structure with 6 to 25 carbon atoms (more preferably with 6 to 20 carbon atoms, and even more preferably with 6 to 15 carbon atoms). Examples of the substituent that the divalent hydrocarbon group containing an aromatic structure may have include a linear or branched alkyl group having 1 to 6 carbon atoms. R 1AThe divalent hydrocarbon group containing an alicyclic structure as the above is preferably a divalent hydrocarbon group having an alicyclic structure having 3 to 20 carbon atoms (more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms). Examples of the substituent that the divalent hydrocarbon group containing an alicyclic structure may have include a linear or branched alkyl group having 1 to 6 carbon atoms.

[0042] R in formula (6-1-R1) 1C Examples of the divalent hydrocarbon group as include a divalent chain hydrocarbon group and a divalent hydrocarbon group containing a ring structure (aromatic structure or alicyclic structure), with a divalent chain hydrocarbon group being preferred. R 1C The divalent chain hydrocarbon group as the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 10 carbon atoms. R 1C The divalent hydrocarbon group containing an aromatic structure as the aromatic group is preferably a divalent hydrocarbon group having an aromatic structure with 6 to 25 carbon atoms (more preferably 6 to 20 carbon atoms, and even more preferably 6 to 15 carbon atoms). R 1C The divalent hydrocarbon group containing an alicyclic structure as the aryl group is preferably a divalent hydrocarbon group having an alicyclic structure having 3 to 20 carbon atoms (more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms).

[0043] In the general formula (6-1-R1), m is an integer of 0 to 10, preferably 0 to 8, and more preferably 0 to 6.

[0044] In the general formula (6-1-R1), the left * (i.e., R 1A The bonding position from R is preferably bonded to the oxygen atom on the left side of R in the general formula (6-1), and the bond from * on the right side (i.e., R 1C The bonding position from is preferably bonded to the oxygen atom on the right side of R1 in general formula (6-1).

[0045] In formula (6-1), the divalent hydrocarbon group as R2 is, for example, a divalent chain hydrocarbon group or a divalent hydrocarbon group containing a ring structure. The divalent chain hydrocarbon group represented by R2 preferably has 1 to 25 carbon atoms, more preferably has 1 to 20 carbon atoms, and further preferably has 2 to 15 carbon atoms. The divalent hydrocarbon group containing a ring structure represented by R2 may contain an aromatic structure or an alicyclic structure. The divalent hydrocarbon group containing an aromatic structure represented by R2 preferably has 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 15 carbon atoms. The divalent hydrocarbon group containing an alicyclic structure represented by R2 preferably has 3 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms.

[0046] Specifically, the divalent hydrocarbon group represented by R2 is preferably a divalent hydrocarbon group represented by a structure selected from the following general formulae (6-1-R2-1) to (6-1-R2-13). From the viewpoint of obtaining a three-dimensional object having excellent flexibility and toughness, a divalent hydrocarbon group represented by a structure selected from the following general formulae (6-1-R2-4) to (6-1-R2-13) is more preferred, and a divalent hydrocarbon group represented by a structure selected from the following general formulae (6-1-R2-4) to (6-1-R2-7) is even more preferred.

[0047] [ka]

[0048] In the general formulae (6-1-R2-1) to (6-1-R2-13), * indicates the bonding position.

[0049] In formula (6-1), X is a divalent organic group, and is preferably a divalent organic group containing one or more bonds selected from the group consisting of ether bonds and ester bonds. When the divalent organic group represented by X contains an ether bond, the number of the ether bonds is preferably 1-100, more preferably 2-90, and further preferably 4-80. When the divalent organic group represented by X contains an ester bond, the number of ester bonds is preferably 1-100, more preferably 2-90, and further preferably 4-80. The divalent organic group represented by X preferably has 2 to 500 carbon atoms, more preferably 2 to 400 carbon atoms, and further preferably 2 to 300 carbon atoms.

[0050] X in formula (6-1) is preferably a group represented by the following general formula (6-1-X).

[0051] [ka]

[0052] In general formula (6-1-X), R XA is a divalent hydrocarbon group, R XB is a methylene group (-CH-) or a carbonyl group (-C(=O)-), and R XC is a divalent hydrocarbon group, and k is an integer of 0 to 100. XB , R XC When a plurality of are present, they may be the same or different. * indicates the bonding position.

[0053] R in formula (6-1-X) XA The divalent hydrocarbon group as is, for example, a divalent chain hydrocarbon group or a divalent hydrocarbon group containing a ring structure, preferably a divalent chain hydrocarbon group. The ring structure contained in the divalent hydrocarbon group may be an aromatic structure or an alicyclic structure. R XA The divalent chain hydrocarbon group as may be branched and may be saturated or unsaturated. R XA The divalent chain hydrocarbon group as the alkyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and further preferably 2 to 10 carbon atoms. R XAThe divalent hydrocarbon group containing an aromatic structure as the aromatic group is preferably a divalent hydrocarbon group having an aromatic structure with 6 to 25 carbon atoms (more preferably 6 to 20 carbon atoms, and even more preferably 6 to 15 carbon atoms). R XA The divalent hydrocarbon group containing an alicyclic structure as the aryl group is preferably a divalent hydrocarbon group having an alicyclic structure having 3 to 20 carbon atoms (more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms).

[0054] R in formula (6-1-X) XC Examples of the divalent hydrocarbon group as include a divalent chain hydrocarbon group and a divalent hydrocarbon group containing a ring structure, with a divalent chain hydrocarbon group being preferred. R XC The divalent chain hydrocarbon group as the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 10 carbon atoms. R XC The divalent hydrocarbon group containing an aromatic structure as the aromatic group is preferably a divalent hydrocarbon group having an aromatic structure with 6 to 25 carbon atoms (more preferably 6 to 20 carbon atoms, and even more preferably 6 to 15 carbon atoms). R XC The divalent hydrocarbon group containing an alicyclic structure as the aryl group is preferably a divalent hydrocarbon group having an alicyclic structure having 3 to 20 carbon atoms (more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms).

[0055] In the general formula (6-1-X), k is 0 to 100, preferably 2 to 90, and more preferably 4 to 80.

[0056] In formula (6-2), R3 is independently a hydrogen atom or a methyl group, R4 is independently an alkylene group, an alkyleneoxy group, or a combination thereof, each of which may have a substituent, R5 is independently an oxygen atom or an ester bond (*1-O-C(=O)-*2, *1 is the bonding position to R4, and *2 is the bonding position to R6), and R6 is a divalent linking group containing a ring structure.

[0057] In formula (6-2), R4 may be an alkyleneoxy group and R5 may be an oxygen atom, or R4 may be an alkylene group and R5 may be an ester bond (*1-OC(=O)-*2, *1 is the bonding position with R4, *2 is the bonding position with R6). R6 may be a phenylene group or a bisphenol skeleton (e.g., a bisphenol A skeleton or a bisphenol F skeleton).

[0058] The content of the di(meth)acrylic monomer (A-1) in the photocurable composition is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 45% by mass, and even more preferably 10% by mass to 40% by mass, based on the total content of the (meth)acrylic monomer components (preferably the di(meth)acrylic monomer (A-1), the mono(meth)acrylic monomer (A-2), and the (meth)acrylic monomer (B)) and the compound (C) in the photocurable composition.

[0059] In the present disclosure, the (meth)acrylic monomer component refers to one or more compounds having one or more (meth)acryloyl groups. The (meth)acrylic monomer component preferably contains both the (meth)acrylic monomer (A) and the (meth)acrylic monomer (B), and more preferably contains the di(meth)acrylic monomer (A-1), the mono(meth)acrylic monomer (A-2), and the (meth)acrylic monomer (B).

[0060] The total content of the di(meth)acrylic monomer (A-1), the mono(meth)acrylic monomer (A-2) and the (meth)acrylic monomer (B) in the (meth)acrylic monomer component is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, even more preferably 90% by mass to 100% by mass, and particularly preferably 95% by mass to 100% by mass, based on the total amount of the (meth)acrylic monomer components.

[0061] (Mono(meth)acrylic monomer (A-2)) The (meth)acrylic monomer (A) preferably contains the above-mentioned mono(meth)acrylic monomer (A-2). By using the mono(meth)acrylic monomer (A-2), the aromatic ring concentration in the (meth)acrylic monomer component increases, which tends to make it easier to remove the denture from the mold (improved releasability), and tends to suppress breakage when removing the denture from the mold (excellent toughness). Furthermore, a mold that suppresses deformation during the manufacture of a denture can be suitably produced, and the flexibility of the mold can be increased by using a monofunctional monomer, which also improves the shape recovery of the mold. The (meth)acrylic monomer (A) may contain one type of mono(meth)acrylic monomer (A-2), or may contain two or more types of mono(meth)acrylic monomer (A-2).

[0062] The molecular weight or weight average molecular weight of the mono(meth)acrylic monomer (A-2) may be 160-400, or 180-300.

[0063] The solubility parameter (SP value) of the mono(meth)acrylic monomer (A-2) is 8.80 to 13.00 (cal / cm 3 ) 1 / 2 It is preferable that the calorific value is 9.00 to 12.50 (cal / cm 3 ) 1 / 2 More preferably, it is 9.50 to 12.00 (cal / cm 3 ) 1 / 2 It is even more preferable that: The solubility parameter (SP value) of the mono(meth)acrylic monomer (A-2) is 8.80 (cal / cm 3 ) 1 / 2 By satisfying the above, it becomes easier to obtain a three-dimensional object with less surface roughness and excellent appearance. The solubility parameter (SP value) of the mono(meth)acrylic monomer (A-2) is 13.00 (cal / cm 3 ) 1 / 2 When the above ratio is satisfied, a three-dimensional object having excellent bending strength and toughness can be easily obtained.

[0064] The mono(meth)acrylic monomer (A-2) is not particularly limited as long as it is a compound having one (meth)acryloyloxy group and an aromatic ring, and may be, for example, a compound represented by the following formula (5).

[0065] [ka]

[0066] In formula (5), R1 is a monovalent organic group having an aromatic ring, and R2 is a hydrogen atom or a methyl group.

[0067] In the formula (5), R1 preferably has 6 to 30 carbon atoms, and more preferably has 6 to 20 carbon atoms.

[0068] The monovalent organic group represented by R1 in formula (5) may have one or more aromatic rings, and preferably has one or two aromatic rings. The aromatic ring contained in the monovalent organic group represented by R1 in formula (5) may be either a single ring or a multiple ring. Examples of the monocyclic aromatic ring include a phenyl structure (phenyl group, phenylene group). The monocyclic aromatic ring may have a substituent, and examples of the substituent include an alkyl group, an aryloxy group (such as a phenoxy group), an arylalkylene group, and an aryl group. Examples of the polycyclic aromatic ring include a naphthyl structure (naphthyl group, naphthylene group). The polycyclic aromatic ring may have a substituent, and examples of the substituent include an alkyl group, an aryloxy group (such as a phenoxy group), an aryl alkylene group, and an aryl group.

[0069] R1 is preferably a monovalent organic group represented by a structure selected from the following general formulae (5-R1-1) to (5-R1-7).

[0070] [ka]

[0071] In the general formulae (5-R1-1) to (5-R1-7), * indicates the bonding position. In general formula (5-R1-7), R 1A represents an alkyl group having 1 to 10 carbon atoms.

[0072] [ka]

[0073] In formula (5-1), R 1A is a divalent linking group, R 2A is an alkyl group or an aryl group which may have a substituent, and R 3A is a hydrogen atom or a methyl group, n is an integer of 0 to 5, and m is 0 or 1.

[0074] In formula (5-1), R 1A may be an alkylene group, an arylene group, an alkylarylene group, an arylenealkyl group, an alkyleneoxy group, an aryleneoxy group, or a combination of two or more thereof. R 1A The number of carbon atoms is preferably 1 to 20, and more preferably 1 to 10. R 1A The hydrogen atoms contained in may be substituted with a hydroxy group, an alkyl group, an aryl group, an amino group, or the like.

[0075] In formula (5-1), n ​​is preferably 0 or 1. When n is 1 to 5, R2 is preferably a phenyl group which may have a substituent.

[0076] The content of the mono(meth)acrylic monomer (A-2) in the photocurable composition is preferably 20% by mass to 85% by mass, more preferably 30% by mass to 80% by mass, and even more preferably 40% by mass to 70% by mass, based on the total content of the (meth)acrylic monomer components (preferably the di(meth)acrylic monomer (A-1), the mono(meth)acrylic monomer (A-2), and the (meth)acrylic monomer (B)) and the compound (C) in the photocurable composition.

[0077] ((Meth)acrylic monomer (B)) The (meth)acrylic monomer (B) is a compound having two or more (meth)acryloyl groups and a siloxane bond. When the photocurable composition contains the (meth)acrylic monomer (B), the aromatic ring concentration in the (meth)acrylic monomer component increases, which tends to make it easier to remove the denture from the mold (improved releasability), and tends to provide excellent deformability and dimensional accuracy during the production of the denture.

[0078] The (meth)acrylic monomer (B) has a siloxane bond (Si-O-Si) and two or more (meth)acryloyloxy groups. The (meth)acrylic monomer (B) may contain a plurality of siloxane bonds (Si-O-Si), more specifically, may contain linear siloxane bonds, ladder-shaped siloxane bonds including linear and branched siloxane bonds, cage-shaped siloxane bonds, etc. The (meth)acrylic monomer (B) may contain two or three or more (meth)acryloyloxy groups.

[0079] Examples of the siloxane bond include a dimethylsiloxane bond, a methylphenylsiloxane bond, and a diphenylsiloxane bond, with the dimethylsiloxane bond being preferred.

[0080] The (meth)acrylic monomer (B) may be a compound containing a siloxane bond (Si-O-Si) and three or more (meth)acryloyloxy groups, or may be a silsesquioxane containing three or more (meth)acryloyloxy groups.

[0081] The molecular weight of the (meth)acrylic monomer (B) may be 400-5,000. The (meth)acrylic monomer (B) may have a weight average molecular weight of 400-4,000.

[0082] By combining the (meth)acrylic monomer (B) with the compound (C) described later, it becomes easier to produce a three-dimensional object with reduced surface roughness. As a result, it becomes easier to obtain a three-dimensional object with excellent releasability, such as ease of demolding and toughness during demolding, less surface roughness, and excellent appearance.

[0083] The solubility parameter (SP value) of the (meth)acrylic monomer (B) is 6.50 to 9.50 (cal / cm 3 ) 1 / 2 It is preferable that the calorific value is 7.50 to 9.50 (cal / cm 3 ) 1 / 2 It is more preferable that: The solubility parameter (SP value) of the (meth)acrylic monomer (B) is 6.50 (cal / cm 3 ) 1 / 2 By satisfying the above, it becomes easier to obtain a three-dimensional object with less surface roughness and excellent appearance. The solubility parameter (SP value) of the (meth)acrylic monomer (B) is 9.50 (cal / cm 3 ) 1 / 2 When the content is equal to or less than 1, a three-dimensional object having excellent releasability can be easily obtained.

[0084] The (meth)acrylic monomer (B) may be a compound represented by the following formula (7):

[0085] [ka]

[0086] In formula (7), R1's are each independently an alkylene group which may have a substituent, R2's are each independently an alkylene group which may have a substituent, R3's are each independently a hydrogen atom or a methyl group, R4's are each independently an alkyl group, a hydrogen atom or an aryl group, m is an integer of 0 or more, and n is an integer of 0 or more.

[0087] R1 is preferably a methylene group, an ethylene group, or a propylene group, and R2 is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group. R4 is preferably a methyl group or a phenyl group, more preferably a methyl group. m may be an integer of 1 to 30, or may be an integer of 2 to 20. From the viewpoint of compatibility with other (meth)acrylic monomer components, m is preferably 30 or less, and more preferably 20 or less. n may be 0 or 1 or more.

[0088] The content of the (meth)acrylic monomer (B) in the photocurable composition is preferably 1 to 35 mass%, more preferably 5 to 30 mass%, and even more preferably 10 to 25 mass%, based on the total content of the (meth)acrylic monomer components (preferably the di(meth)acrylic monomer (A-1), the mono(meth)acrylic monomer (A-2), and the (meth)acrylic monomer (B)) and the compound (C) in the photocurable composition.

[0089] The siloxane bond concentration in the photocurable composition (preferably the siloxane bond concentration when the photocurable composition contains a (meth)acrylic monomer (B)) is preferably 0.100 mmol / g to 3,000 mmol / g, more preferably 0.150 mmol / g to 2,500 mmol / g, and even more preferably 0.200 mmol / g to 2,000 mmol / g. A siloxane bond concentration of 0.100 mmol / g or more tends to improve demolding properties, while a siloxane bond concentration of 3,000 mmol / g or less tends to suppress breakage when removing a dental prosthesis such as a plate denture from the mold and tends to have excellent toughness.

[0090] The photocurable composition of the present disclosure may or may not contain a photopolymerizable component other than the (meth)acrylic monomer component. Examples of the photopolymerizable component other than the (meth)acrylic monomer component include styrene, styrene derivatives, and (meth)acrylonitrile. In the photocurable composition of the present disclosure, the content of photopolymerizable components other than the (meth)acrylic monomer component may be 20 mass % or less, 10 mass % or less, 5 mass % or less, or 1.0 mass % or less, relative to the total amount of photopolymerizable components in the photocurable composition of the present disclosure. The lower limit of the content of the photopolymerizable component other than the (meth)acrylic monomer component is not particularly limited, and may be, for example, 0 mass % or more.

[0091] The solubility parameter (SP value) of the (meth)acrylic monomer component contained in the photocurable composition, or the solubility parameter (SP value) of the photopolymerizable component contained in the photocurable composition may each independently be 8.00 to 12.00, 8.50 to 11.50, or 9.00 to 11.00. The solubility parameter (SP value) of the (meth)acrylic monomer component and the solubility parameter (SP value) of the photopolymerizable component each mean a weighted average value.

[0092] The standard deviation of the solubility parameter (SP value) of the (meth)acrylic monomer component or the standard deviation of the solubility parameter (SP value) of the photopolymerizable component is preferably 1.3 or less, more preferably 1.1 or less, and even more preferably less than 1.0.

[0093] (Compound (C)) The compound (C) does not have a (meth)acryloyl group and has a solubility parameter (SP value) of 7.00 to 15.00 (cal / cm 3 ) 1 / 2 It is.

[0094] The solubility parameter (SP value) of compound (C) is 7.00 to 15.00 (cal / cm 3 ) 1 / 2 From the viewpoint of suppressing the surface roughness of the three-dimensional object and facilitating demolding, it is 8.00 to 13.00 (cal / cm 3 ) 1 / 2 It is preferable that the thickness is 8.30 to 11.00 (cal / cm 3 ) 1 / 2 More preferably, it is 8.30 to 10.70 (cal / cm 3 ) 1 / 2 It is even more preferable that: When the photocurable composition contains two or more types of compound (C), the solubility parameter (SP value) of the compound (C) means a weighted average value of the solubility parameters of the two or more types of compound (C).

[0095] The compound (C) is preferably not a compound that generates radicals when excited by light in a specific wavelength range (for example, 365 nm to 500 nm), and is preferably a compound that does not have a terminal unsaturated bond.

[0096] Compound (C) has a solubility parameter (SP value) of 7.00 to 15.00 (cal / cm 3 ) 1 / 2 As long as the compound satisfies the above requirements, it is not particularly limited, and examples thereof include alcohol compounds, carboxylic acids, ester compounds, and polyether compounds.

[0097] Examples of the alcohol compound include higher alcohols, monoalcohol esters, polyhydric alcohols, and polyhydric alcohol esters.

[0098] The higher alcohol is preferably an alcohol compound having 5 or more carbon atoms, more preferably an alcohol compound having 6 or more carbon atoms, and even more preferably an alcohol compound having 6 to 12 carbon atoms. The higher alcohol may be an alcohol compound having one hydroxyl group, or may be a linear alcohol compound having one hydroxyl group. Specific examples of higher alcohols include 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, and 1-dodecanol (lauryl alcohol).

[0099] Examples of monoalcohol esters include monoesters containing one hydroxy group, diesters containing one hydroxy group, and triesters containing one hydroxy group. Specific examples of monoalcohol esters include oxyacid esters such as diisostearyl malate, and triethyl citrate.

[0100] The polyhydric alcohol may be a compound having two or more hydroxyl groups and no ester bond. The number of hydroxyl groups in the polyhydric alcohol may be two or more, and may be two or three. A specific example of the polyhydric alcohol is trimethylolpropane.

[0101] The polyhydric alcohol ester may be a compound containing two or more hydroxyl groups and having an ester bond. The number of hydroxyl groups in the polyhydric alcohol ester may be two or more, and may be two or three. Specific examples of polyhydric alcohol esters include glycerin monoesters such as glycerol monostearate.

[0102] The carboxylic acid is preferably a higher fatty acid having 5 or more carbon atoms, and more preferably 6 or more carbon atoms. The carboxylic acid may be a higher fatty acid having 20 or less carbon atoms, or may be a higher fatty acid having 18 or less carbon atoms. Specific examples of the carboxylic acid include lauric acid, myristic acid, palmitic acid, and stearic acid.

[0103] Examples of the ester compound include monoesters, diesters, triesters, etc. of higher fatty acids having 5 or more carbon atoms. The ester compound may be a fatty acid ester (fatty acid monoester, fatty acid diester, fatty acid triester, etc.) synthesized from a higher fatty acid and a higher alcohol. Specific examples of the ester compounds include ethyl laurate, isopropyl myristate, isopropyl palmitate, and glyceryl trioleate. Since fatty acid esters synthesized from higher fatty acids and higher alcohols are easily dimerized, they may be in the form of a dimer at the raw material stage, or may be derivatives of dimer diols such as di(isostearyl / phytosteryl) dimer dilinoleate.

[0104] The polyether compound includes a compound containing two or more ether bonds. Specific examples of the polyether compound include polyalkylene glycols (the alkylene group preferably has 2 to 4 carbon atoms), such as polyethylene glycol and polypropylene glycol.

[0105] The absolute value of the difference between the average value of the solubility parameters (SP values) of the (meth)acrylic monomer components contained in the photocurable composition and the average value of the solubility parameters (SP values) of the compound (C) contained in the photocurable composition is 4.00 (cal / cm) from the viewpoint of suppressing the surface roughness of the three-dimensional object and facilitating demolding. 3 ) 1 / 2 It is preferable that the calorie content is 3.00 (cal / cm 3 ) 1 / 2 More preferably, it is 2.00 (cal / cm 3 ) 1 / 2 It is even more preferable that: The lower limit of the absolute value of the above difference is 0(cal / cm 3 ) 1 / 2There is no particular limitation as long as it is equal to or greater than 0.10 (cal / cm 3 ) 1 / 2 It may be more than that. In the present disclosure, the average value of the solubility parameter (SP value) means the weighted average value of the SP values ​​of the corresponding components.

[0106] When the photocurable composition contains two or more types of compound (C), the standard deviation of the solubility parameters (SP values) of the compounds (C) is preferably 3.5 or less, more preferably 2.0 or less, and even more preferably less than 1.0.

[0107] The average value of the solubility parameter (SP value) of the components contained in the photocurable composition (excluding the photopolymerization initiator) is preferably 8.00 to 12.00, more preferably 9.00 to 11.00, and even more preferably 9.00 to 10.30.

[0108] The standard deviation of the solubility parameters (SP values) of the components contained in the photocurable composition (excluding the photopolymerization initiator) is preferably 1.3 or less, more preferably 1.1 or less, and even more preferably less than 1.0.

[0109] The cohesive energy density (cal / mol) of the compound (C) is preferably 10,000 or more, and more preferably 11,000 or more, from the viewpoints of preventing volatilization of the compound (C) and suppressing the surface roughness of the three-dimensionally shaped object. The cohesive energy density (cal / mol) of the compound (C) is preferably 150,000 or less, and more preferably 110,000 or less, from the viewpoint of compatibility with the (meth)acrylic monomer component.

[0110] The content of compound (C) contained in the photocurable composition is preferably 1 mass % to 30 mass %, more preferably 3 mass % to 20 mass %, and even more preferably 5 mass % to 15 mass %, based on the total content of (meth)acrylic monomer components (preferably di(meth)acrylic monomer (A-1), mono(meth)acrylic monomer (A-2), and (meth)acrylic monomer (B)) and compound (C) contained in the photocurable composition.

[0111] The photocurable composition in step 1 is A (meth)acrylic monomer (A), (B) one or more selected from the group consisting of a (meth)acrylic monomer and a compound (C); Preferably, A (meth)acrylic monomer (A), (Meth)acrylic monomer (B) and compound (C), It is more preferred that the composition comprises:

[0112] The total content of the (meth)acrylic monomer (A), the (meth)acrylic monomer (B) and the compound (C) contained in the photocurable composition, preferably the total content of the di(meth)acrylic monomer (A-1), the mono(meth)acrylic monomer (A-2), the (meth)acrylic monomer (B) and the compound (C) contained in the photocurable composition, is preferably 20% by mass to 95% by mass, more preferably 30% by mass to 90% by mass, and even more preferably 40% by mass to 85% by mass, based on the total mass of the photocurable composition.

[0113] (Filler) In the method for producing the article of the present disclosure, in step 1, the photocurable composition preferably contains a filler. As the filler, inorganic fillers, organic fillers, etc. are preferred. The fillers may be used alone or in combination of two or more kinds.

[0114] Examples of inorganic fillers include various glasses such as silica and alumina (containing silicon dioxide as the main component and, as necessary, oxides of heavy metals, boron, aluminum, etc.), various ceramics, diatomaceous earth, kaolin, clay minerals (montmorillonite, etc.), activated clay, synthetic zeolite, mica, calcium fluoride, ytterbium fluoride, calcium phosphate, barium sulfate, zirconium dioxide, titanium dioxide, and fine powders of hydroxyapatite, etc. Specific examples of such inorganic fillers include barium borosilicate glass (Kimble Raysorb T3000, Schott 8235, Schott GM27884, Schott GM39923, etc.), strontium boroaluminosilicate glass (Raysorb T4000, Schott G018-093, Schott GM32087, etc.), lanthanum glass (Schott GM31684, etc.), fluoroaluminosilicate glass (Schott G018-091, Schott G018-117, etc.), and boroaluminosilicate glass containing zirconium, cesium, etc. (Schott G018-307, G018-308, G018-310, etc.).

[0115] Examples of the organic filler include fine powders of polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, and the like.

[0116] The filler contained in the photocurable composition preferably includes one or more selected from the group consisting of silica and organic fillers.

[0117] The content of the filler in the photocurable composition is preferably 5% by mass to 80% by mass, more preferably 10% by mass to 70% by mass, and even more preferably 15% by mass to 60% by mass, relative to the total mass of the photocurable composition.

[0118] (Other Ingredients) In the method for producing the article of the present disclosure, in step 1, the photocurable composition may contain one or more components other than the above-mentioned components, as necessary.

[0119] Examples of other components include additives such as coloring materials, coupling agents such as silane coupling agents, rubber agents, ion trapping agents, ion exchange agents, leveling agents, plasticizers, and antifoaming agents, and thermal polymerization initiators. When the photocurable composition of the present disclosure contains a thermal polymerization initiator, photocuring and thermal curing can be performed in combination. Examples of the thermal polymerization initiator include a thermal radical generator and an amine compound.

[0120] [Process 2] The method for producing the appliance of the present disclosure includes step 2 of polymerizing the hardenable composition in the mold to produce an appliance to be used in the oral cavity.

[0121] In step 2, a curable composition is poured into the mold and polymerized in the mold. The curable composition is not particularly limited as long as it contains a polymerizable component that is polymerized by heat, light, a chemical polymerization initiator, or the like.

[0122] As the equipment to be used in the oral cavity, a dental prosthesis is preferable, and a plate denture is more preferable.

[0123] Step 2 may be carried out in a manner appropriate for the equipment to be manufactured. For example, when manufacturing an appliance to be used in the oral cavity by combining other components with the hardenable composition in a mold, the appliance can be manufactured by injecting the hardenable composition into the mold with the other components arranged in the mold and hardening the hardenable composition after injection.For example, a denture with a plate can be manufactured by injecting a hardenable composition for making a denture base into the mold with artificial teeth arranged in the mold and hardening the hardenable composition after injection. On the other hand, when no other components are combined, the hardenable composition may be injected alone into a mold and then hardened to produce an article.

[0124] Step 2 may be a step of producing a denture with a base. The step of producing a denture with a base preferably includes a step of arranging artificial teeth in a mold, a step of injecting a hardenable composition for producing a denture base into the mold with the artificial teeth arranged in the mold, a step of hardening the hardenable composition after injection, and a step of removing the produced denture with a base from the mold.

[0125] When step 2 is a step of manufacturing a denture, step 1 preferably includes, for example, a step of acquiring three-dimensional impression data of the oral cavity of a user of the denture, a step of acquiring mold data from the acquired three-dimensional impression data, and a step of hardening a photocurable composition by photolithography based on the acquired mold data to create a mold to be used in manufacturing the denture.

[0126] <Photocurable composition> The photocurable composition of the present disclosure comprises a (meth)acrylic monomer (A) having one or more (meth)acryloyl groups and no siloxane bond, a (meth)acrylic monomer (B) having two or more (meth)acryloyl groups and a siloxane bond, and a (meth)acrylic monomer (C) having no (meth)acryloyl group and having a solubility parameter (SP value) of 7.00 to 15.00 (cal / cm 3 ) 1 / 2 and a photopolymerization initiator, and the photocurable composition is irradiated with visible light having a wavelength of 405 nm at a dose of 11 mJ / cm. 2 The cured layers A1 are laminated in the thickness direction to form a rectangular plate-shaped object A1 having a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm. The object A1 is irradiated with ultraviolet light having a wavelength of 365 nm at a dose of 3 J / cm. 2 When a rectangular plate-shaped test piece A1 having a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm is produced by stereolithography under conditions of irradiation with light at 400 nm, the storage modulus of the test piece A1 at 25° C. is 150 MPa or more.

[0127] The photocurable composition of the present disclosure is a composition that is cured by irradiation with light, and a cured product is obtained by curing the composition. The method for producing a cured product using the photocurable composition of the present disclosure is preferably the above-mentioned stereolithography. The photocurable composition of the present disclosure is preferably a photocurable composition for photolithography. In other words, a cured product produced using the photocurable composition of the present disclosure is preferably a photolithography product (i.e., a cured product produced by photolithography).

[0128] By preparing a mold for an instrument to be used in the oral cavity using the photocurable composition of the present disclosure and manufacturing the instrument to be used in the oral cavity using the mold, the dimensional accuracy of the instrument to be manufactured to be used in the oral cavity is improved. Therefore, the photocurable composition of the present disclosure is preferably used for manufacturing a mold by stereolithography. The mold manufactured using the photocurable composition of the present disclosure is preferably a mold used for manufacturing an instrument to be used in the oral cavity, and more preferably a mold used for manufacturing a dental prosthesis.

[0129] A preferred form of the photocurable composition of the present disclosure is the same as the preferred form of the photocurable composition used in step 1 of the above-described method for producing an article of the present disclosure.

[0130] <3D object> The three-dimensional object of the present disclosure includes a cured product of the photocurable composition of the present disclosure. Therefore, when the three-dimensional object of the present disclosure is a casting mold, the dimensional accuracy of equipment used in the oral cavity, such as a dental prosthesis, produced using the casting mold is improved. The three-dimensional object of the present disclosure preferably includes a cured product obtained by stereolithography (i.e., a stereolithography object). The method for producing a cured product (for example, a photofabricated product) is as described above. A preferred embodiment of the three-dimensional object is a mold, more specifically, a mold used for producing a denture plate. EXAMPLES

[0131] Examples of the present disclosure will be described below, but the present disclosure is not limited to the following examples.

[0132] [Examples 1 to 20, Comparative Examples 1 to 3] <Preparation of Photocurable Composition> Photocurable compositions were obtained by mixing the components shown in Tables 1 to 5. Table 1 shows the details of each component, and Tables 2 to 5 show the mixing ratios of each component.

[0133] <Measurement and Evaluation> The photocurable compositions thus obtained were subjected to the following measurements and evaluations. The results are shown in Tables 2 to 5.

[0134] (Storage modulus at 25℃) The storage modulus at 25° C. of the cured products obtained using the photocurable compositions prepared in the Comparative Examples and Examples was measured by the following method. The results are shown in Tables 2 to 5. Using a 3D printer (Kulzer, Cara Print 4.0 PRO), a test piece of 40 mm in length, 10 mm in width, and 1 mm in thickness was printed using the curable composition to be measured, with a layer width of 50 μm. Each layer was exposed to 11 mJ / cm of visible light with a wavelength of 385 nm. 2 The resulting test piece was irradiated with 10 J / cm2 of ultraviolet light with a wavelength of 365 nm. 2 The photocurable composition was fully cured by irradiation under the above conditions to obtain a cured product of test piece A1. The storage modulus of the obtained cured test piece A1 was measured at a measurement frequency of 1 Hz while heating the test piece from 25°C to 100°C at a rate of 3°C / min using a dynamic viscoelasticity measuring device (DMA-7100, manufactured by Hitachi High-Tech Corporation), and the storage modulus at 25°C was read.

[0135] (Releasability for dentures) Using the photocurable compositions prepared in the Comparative Examples and Examples, a 3D printer (Kulzer, Cara Print 4.0 PRO) was used to print the three-dimensional objects shown in Figures 1 and 2 using the photocurable compositions to be measured. The three-dimensional objects were printed to a layer width of 50 μm, and each layer was exposed to visible light with a wavelength of 385 nm at 11 mJ / cm. 2Each test piece was irradiated with 10 J / cm2 of ultraviolet light with a wavelength of 365 nm. 2 The photocurable composition was fully cured by irradiation under the above conditions, thereby obtaining cured products of three-dimensional objects B1 (frame) and B2 (lid). As shown in FIG. 1, the three-dimensional object B1 has a shape with L of 24 mm, L' of 20 mm, W of 2 mm, H of 4 mm, H' of 2 mm, D of 14 mm, and D' of 10 mm. As shown in FIG. 2, the three-dimensional object B2 has a shape with L of 24 mm, H of 2 mm, and D of 14 mm. Using the obtained cured products of the three-dimensional objects B1 and B2, a (meth)acrylate polymer powder for making dentures with a plate and Palapress (registered trademark) Vario (manufactured by Kulzer), which is a (meth)acrylate monomer liquid, were mixed in a ratio of 10 g powder: 7 mL liquid, and 15 seconds after mixing, the mixture was filled into the space of the three-dimensional object B1 consisting of L' (20 mm) x D' (10 mm) x H' (2 mm), and the mixture was covered with the three-dimensional object B2, and polymerized for 30 minutes at 55°C and a pressure of 2 bar. Then, the three-dimensional objects B1 and B2 were peeled off from the polymer for making dentures with a plate. Then, the 200 mm of L' (20 mm) x D' (10 mm) of the polymer for making dentures with a plate that was in contact with the three-dimensional object B2 was removed. 2 The surface consisting of L' and D' was observed with a 3D shape measuring device (Keyence Corporation, VR-3200), and the area value of the three-dimensional object B2 attached to the polymer for making the denture after removal was calculated, and the surface consisting of L' and D' (200 mm 2 The adhesion rate was calculated based on the surface adhesion rate. The smaller the adhesion rate, the better the releasability. The evaluation was performed as follows: "A" for no surface adhesion, "B" for surface adhesion of less than 5%, and "C" for surface adhesion of 5% or more.

[0136] (Accuracy evaluation) Using the photocurable compositions prepared in the Comparative Examples and Examples, a 3D printer (Kulzer, Cara Print 4.0 PRO) was used to print the three-dimensional objects shown in Figures 1 and 2 using the photocurable compositions to be measured. The three-dimensional objects were printed to a layer width of 50 μm, and each layer was exposed to visible light with a wavelength of 385 nm at 11 mJ / cm. 2Each test piece was irradiated with 10 J / cm2 of ultraviolet light with a wavelength of 365 nm. 2 The photocurable composition was fully cured by irradiation under the above conditions, thereby obtaining cured products of three-dimensional objects B1 (frame) and B2 (lid). Using the obtained cured products of the three-dimensional objects B1 and B2, a (meth)acrylate polymer powder for making dentures and a (meth)acrylate monomer liquid, Palapress (registered trademark) Vario (manufactured by Kulzer), were mixed in a ratio of 10 g powder to 7 mL liquid, and 15 seconds after mixing, the mixture was filled into the space of the three-dimensional object B1 consisting of L' (20 mm) x D' (10 mm) x H' (2 mm), and the mixture was covered with the three-dimensional object B2 and polymerized for 30 minutes at 55°C and a pressure of 2 bar. Then, the three-dimensional objects B1 and B2 were peeled off from the polymer for making dentures. The length M' of the long side of the obtained polymer for making a plate denture was measured with a Mitutoyo micrometer (MDQ-30), and the dimensional difference (accuracy of the formula below) from the design value L' (20 mm) was calculated using the formula below. Precision (mm) = Absolute value (M'-L') The obtained accuracy (mm) was evaluated as "A" when it was less than 0.2, "B" when it was between 0.2 and 0.3, "C" when it was between 0.3 and 0.5, and "D" when it was 0.5 or more.

[0137] [Table 1]

[0138] [Table 2]

[0139] [Table 3]

[0140] [Table 4]

[0141] [Table 5]

[0142] In Tables 2 to 5, the numbers in the "Composition" column for each Example and Comparative Example mean parts by mass, and a blank space means that the corresponding component is not contained.

[0143] <Di(meth)acrylic monomer (A-1)> In Tables 1 to 5, the structures of the compounds classified as di(meth)acrylic monomer (A-1) are as follows.

[0144] [ka]

[0145] AH-600: Bifunctional urethane acrylate (Kyoeisha Chemical Co., Ltd.) SUA-002: A compound prepared by the method described in Preparation Example 1A below.

[0146] [Production Example 1A: Production of SUA-002] In a 1-liter 4-neck flask equipped with a thoroughly dried stirring blade and a thermometer, 344 g (1.00 mol) of caprolactone-modified 2-hydroxyethyl acrylate (trade name "Placcel FA2D", manufactured by Daicel Corporation, average number of moles of caprolactone added: 2), 131 g (0.50 mol) of dicyclohexylmethane 4,4'-diisocyanate, 0.84 g of DBTDL (dibutyltin dilaurate), and 0.42 g of MEHQ (4-methoxyphenol) were added and reacted at 80°C for 12 hours. The progress of the reaction was tracked by HPLC analysis to confirm the end point of the reaction. The product was discharged from the reactor to obtain 451 g of bifunctional urethane acrylate (SUA-002). The viscosity at 25°C was 12,000 mPa·s.

[0147] <Mono(meth)acrylic monomer (A-2)> In Tables 1 to 5, the structures of the compounds classified as mono(meth)acrylic monomers (A-2) are as follows.

[0148] [ka]

[0149] POB-A: m-Phenoxybenzyl acrylate (Kyoeisha Chemical Co., Ltd.) A-LEN-10: Ethoxylated o-phenylphenol acrylate (Shin-Nakamura Chemical Co., Ltd.)

[0150] <(Meth)acrylic monomer (B)> In Tables 1 to 5, the structures of the compounds classified as (meth)acrylic monomers (B) are as follows.

[0151] [ka]

[0152] SiA-002: A compound prepared by the method described in Preparation Example 1B below.

[0153] [Production Example 1B: Production of SiA-002] In a 1-liter 4-neck flask equipped with a thoroughly dried stirring blade and a thermometer, 287 g (1.00 mol) of 1,3-Bis(3-chloropropyl)-1,1,3,3-tetramethyldisiloxane, 0.30 g of BHT, and 500 g of toluene were added, stirred until homogenized, and then heated to 60°C. Then, 593 g (2.00 mol) of octamethylcyclotetrasiloxane was added dropwise over 1 hour. After the entire amount was added, the reaction temperature was kept at 60°C and the reaction was carried out for 6 hours. Then, 740 g (2.00 mol) of octaethylene glycol was added to the reaction vessel, and the reaction was carried out for another 1 hour. Then, 181 g (2.00 mol) of acryloyl chloride was added dropwise over 1 hour. During the drop, the internal temperature rose due to the heat of reaction, so the amount of dropwise addition was controlled so that it was 60°C or less. After the entire amount was added, the reaction temperature was kept at 60°C and the reaction was carried out for 5 hours. The reaction solution was then neutralized with a 10% NaOH aqueous solution and washed with 150 g of a 5% ammonium sulfate aqueous solution. Toluene was distilled under reduced pressure to obtain 440 g of a polyfunctional (meth)acrylic monomer (SiA-002). The viscosity at 25°C was 310 mPa·s.

[0154] <Compound (C)> In Tables 1 to 5, the structures of the compounds classified as compound (C) are as follows.

[0155] [ka]

[0156] (C-1): Isopropyl myristate (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0157] <Filler> SC4500-SMJ: Silica particles manufactured by Admatechs with an average particle size of 1.0 μm J-4P: PMMA beads with average particle size of 2.2 μm manufactured by Negami Chemical Industries, Ltd.

[0158] <Photopolymerization initiator> In Tables 1 to 5, the compounds classified as photopolymerization initiators are specifically the following compounds. Acylphosphine oxide compound (Omnirad 819: "Omnirad 819" manufactured by IGM Resins BV)

[0159] [ka]

[0160] As shown in Tables 2 to 5, by using the photocurable compositions of Examples 1 to 20, when a polymer for making dentures was produced using a three-dimensional object, which was a mold produced by stereolithography, the dimensional accuracy of the resulting polymer for making dentures was good. On the other hand, when the photocurable compositions of Comparative Examples 1 to 3 were used, the dimensional accuracy of the obtained polymers for producing dentures was poor. Furthermore, by using the photocurable compositions of Examples 6 to 20 containing the (meth)acrylic monomer (B), the releasability from the denture was better than when the photocurable compositions of Examples 1 to 5 containing no (meth)acrylic monomer (B) were used.

Claims

1. Step 1 of hardening the photocurable composition by photolithography to prepare a mold for use in manufacturing an instrument for use in the oral cavity; Step 2 of polymerizing the hardenable composition in the mold to produce a device to be used in the oral cavity, In the step 1, The photocurable composition was irradiated with visible light having a wavelength of 405 nm at a dose of 11 mJ / cm ２ The cured layers A1 are laminated in the thickness direction to form a rectangular plate-shaped object A1 having a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm. The object A1 is irradiated with ultraviolet light having a wavelength of 365 nm at an irradiation dose of 3 J / cm. ２ When a rectangular plate-shaped test piece A1 having a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm was produced by photolithography under the condition of irradiating with A method for producing a device to be used in the oral cavity, wherein the storage modulus of the test piece A1 at 25°C is 150 MPa or more.

2. The method for producing a device for use in the manufacture of a device for use in the oral cavity according to claim 1 , wherein in step 1, the photocurable composition contains a filler.

3. 3. The method for producing equipment used in the manufacture of equipment to be used in the oral cavity as described in claim 2, wherein in step 1, the filler contained in the photocurable composition includes one or more selected from the group consisting of silica and organic fillers.

4. 3. The method for manufacturing equipment used in the manufacture of equipment to be used in the oral cavity according to claim 2, wherein in step 1, the content of the filler contained in the photocurable composition is 5% by mass to 80% by mass relative to the total mass of the photocurable composition.

5. The method for manufacturing a device used in the manufacture of a device to be used in the oral cavity as described in claim 1, wherein in step 1, the photocurable composition contains a (meth)acrylic monomer, a filler, and a photopolymerization initiator.

6. In the step 1, the photocurable composition is A (meth)acrylic monomer (A) having one or more (meth)acryloyl groups and no siloxane bond; (B) a (meth)acrylic monomer having two or more (meth)acryloyl groups and a siloxane bond, and (C) a (meth)acrylic monomer having no (meth)acryloyl group and having a solubility parameter (SP value) of 7.00 to 15.00 (cal / cm ３ ) １／２ and one or more compounds (C) selected from the group consisting of:

7. The method for producing a device used in the manufacture of a device to be used in the oral cavity according to claim 6, wherein in step 1, the photocurable composition contains the (meth)acrylic monomer (B) and the compound (C).

8. 2. The method for producing an equipment used in the production of an equipment to be used in the oral cavity according to claim 1, wherein the equipment to be produced is a dental prosthesis.

9. 1. A photocurable composition comprising: The photocurable composition is A (meth)acrylic monomer (A) having one or more (meth)acryloyl groups and no siloxane bond; (B) a (meth)acrylic monomer having two or more (meth)acryloyl groups and a siloxane bond, and (C) a (meth)acrylic monomer not having a (meth)acryloyl group and having a solubility parameter (SP value) of 7.00 to 15.00 (cal / cm ３ ) １／２ and one or more compounds (C) selected from the group consisting of A photopolymerization initiator, The photocurable composition was irradiated with visible light having a wavelength of 405 nm at a dose of 11 mJ / cm ２ The cured layers A1 are laminated in the thickness direction to form a rectangular plate-shaped object A1 having a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm. The object A1 is irradiated with ultraviolet light having a wavelength of 365 nm at an irradiation dose of 3 J / cm. ２ When a rectangular plate-shaped test piece A1 having a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm was produced by photolithography under the condition of irradiating with The photocurable composition, wherein the storage modulus of the test piece A1 at 25°C is 150 MPa or more.

10. The photocurable composition of claim 9 comprising a filler.

11. The photocurable composition according to claim 10, wherein the filler contained in the photocurable composition comprises one or more selected from the group consisting of silica and organic fillers.

12. The photocurable composition according to claim 9 , comprising the (meth)acrylic monomer (B) and the compound (C).

13. The (meth)acrylic monomer (A) is A di(meth)acrylic monomer (A-1) having at least one of a ring structure or a urethane bond, and two (meth)acryloyloxy groups, and having no siloxane bond; The photocurable composition according to claim 10, comprising a mono(meth)acrylic monomer (A-2) having one (meth)acryloyloxy group and an aromatic ring, and having no siloxane bond.

14. The photocurable composition according to claim 13, wherein a total content of the di(meth)acrylic monomer (A-1), the mono(meth)acrylic monomer (A-2), the (meth)acrylic monomer (B) and the compound (C) contained in the photocurable composition is 20% by mass to 95% by mass with respect to the total mass of the photocurable composition.

15. The photocurable composition according to claim 13, wherein the content of the di(meth)acrylic monomer (A-1) in the photocurable composition is 3 mass % to 50 mass % based on the total content of the di(meth)acrylic monomer (A-1), the mono(meth)acrylic monomer (A-2), the (meth)acrylic monomer (B) and the compound (C) in the photocurable composition.

16. The photocurable composition according to claim 13, wherein the content of the mono(meth)acrylic monomer (A-2) contained in the photocurable composition is 20% by mass to 85% by mass, based on the total content of the di(meth)acrylic monomer (A-1), the mono(meth)acrylic monomer (A-2), the (meth)acrylic monomer (B) and the compound (C) contained in the photocurable composition.

17. The photocurable composition according to claim 13, wherein the content of the (meth)acrylic monomer (B) in the photocurable composition is 1 mass % to 35 mass % based on the total content of the di(meth)acrylic monomer (A-1), the mono(meth)acrylic monomer (A-2), the (meth)acrylic monomer (B) and the compound (C) contained in the photocurable composition.

18. The photocurable composition according to claim 13, wherein the content of the compound (C) contained in the photocurable composition is 1 mass % to 30 mass % based on the total content of the di(meth)acrylic monomer (A-1), the mono(meth)acrylic monomer (A-2), the (meth)acrylic monomer (B), and the compound (C) contained in the photocurable composition.

19. The photocurable composition according to claim 9 , which is used for stereolithography.

20. The photocurable composition according to claim 9, which is used for producing a mold by stereolithography.

21. The photocurable composition according to claim 20 , wherein the mold is a mold used for producing an appliance to be used in the oral cavity.

22. 21. The photocurable composition of claim 20, wherein the mold is a mold used in the manufacture of a dental prosthesis.

23. A three-dimensional object comprising a cured product of the photocurable composition according to claim 9.

24. A mold comprising the three-dimensional object according to claim 23.

Images