Photocurable composition, three-dimensional shaped object, casting mold, method for producing cured object, and method for producing dental prosthesis

Abstract

A photocurable composition comprising: a (meth)acrylic monomer (A) having one or more (meth)acryloyl groups and having no siloxane bond; a (meth)acrylic monomer (B) having two or more (meth)acryloyl groups and a siloxane bond; a compound (C) having no (meth)acryloyl group and having a solubility parameter (SP value) of 7.00-15.00 (cal / cm3)1 / 2; and a photopolymerization initiator.

Description

Photocurable composition, method for producing three-dimensional object, mold, and cured product, and method for producing dental prosthesis

[0001] The present disclosure relates to a method for producing a photocurable composition, a three-dimensional object, a mold, a cured product, and a method for producing a dental prosthesis.

[0002] In recent years, dental products such as dental prostheses and instruments used in the oral cavity have been studied. For example, from the viewpoint of the efficiency of manufacturing these dental products, a method for manufacturing three-dimensional objects such as dental products by stereolithography using a 3D printer is known (see, for example, Japanese Patent No. 4160311).

[0003] Meanwhile, there have been conventional methods for producing dental prostheses such as removable dentures without using stereolithography such as a 3D printer. According to these methods, for example, when producing a dental prosthesis such as a removable denture, a mold of the patient's oral cavity is first obtained directly from the patient using an impression material, and a model simulating the patient's oral cavity is created using the impression material. A mold is then made from the model using silicone. Using the mold as a casting mold, a curable composition can be injected into the mold and polymerized at room temperature to produce a dental prosthesis such as a removable denture. As described above, conventional methods that do not use stereolithography have the problem of complicated processes, such as producing a model simulating the patient's oral cavity and making a mold using silicone.

[0004] In contrast, a method for directly manufacturing a removable denture by stereolithography using a 3D printer eliminates the above-mentioned complications. However, compared to conventional methods that do not use a 3D printer, the materials that can be properly cured by stereolithography are very limited, resulting in limited features of the resulting dental prostheses, such as removable dentures. For example, conventional methods use room-temperature polymerization using a mold, but this method allows the use of many materials that can improve aesthetics and physical properties. However, materials used in such room-temperature polymerization are often not usable in stereolithography using a 3D printer. As a result, stereolithography using a 3D printer makes it difficult to adjust the desired properties of the resulting dental prostheses, such as removable dentures.

[0005] As described above, there is a need for a method for manufacturing a dental prosthesis that allows for simple fabrication of the dental prosthesis and allows for easy adjustment to obtain desired properties.

[0006] In order to achieve the above object, the present inventors have discovered a method for producing a mold for manufacturing a dental prosthesis by stereolithography using a 3D printer, and then using the mold to manufacture the dental prosthesis.

[0007] When a dental prosthesis mold is prepared using a photocurable composition and then used to manufacture the dental prosthesis, it is desirable to improve the releasability of the dental prosthesis from the mold. The present inventors have discovered that a photocurable composition containing a (meth)acrylic monomer component having a siloxane bond can be used to improve the releasability of the dental prosthesis from the mold. However, the use of a (meth)acrylic monomer component having a siloxane bond can roughen the surface of a three-dimensional object such as a mold. Therefore, it is desirable to reduce the surface roughness from the viewpoint of, for example, the appearance of the three-dimensional object.

[0008] An object of one aspect of the present disclosure is to provide a photocurable composition capable of producing a three-dimensionally shaped object with reduced surface roughness, as well as a method for producing a three-dimensionally shaped object, a mold, or a cured product using the photocurable composition, and a method for producing a dental prosthesis.

[0009] Means for solving the above problems include the following aspects: <1> 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. <2> 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 ３ ) １／２The photocurable composition according to <1>, wherein the compound (C) has a cohesive energy density (cal / mol) of 10,000 or more. <3> The photocurable composition according to <1> or <2>, wherein the compound (C) has a cohesive energy density (cal / mol) of 10,000 or more. <4> The photocurable composition according to any one of <1> to <3>, wherein the (meth)acrylic monomer (A) includes: 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. <5> The photocurable composition according to <4>, wherein the di(meth)acrylic monomer (A-1) has a molecular weight of 400 to 8,000. <6> The photocurable composition according to <4> or <5>, wherein the molecular weight of the mono(meth)acrylic monomer (A-2) is 160 to 400. <7> The photocurable composition according to any one of <1> to <6>, wherein the molecular weight of the (meth)acrylic monomer (B) is 400 to 5,000. <8> The photocurable composition according to any one of <4> to <7>, wherein 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 (meth)acrylic monomer component and the compound (C) in the photocurable composition. <9> The photocurable composition according to any one of <4> to <8>, wherein 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 (meth)acrylic monomer component and the compound (C) in the photocurable composition. <10> The photocurable composition according to any one of <1> to <9>, wherein the content of the (meth)acrylic monomer (B) in the photocurable composition is 1% by mass to 35% by mass, based on the total content of the (meth)acrylic monomer component and the compound (C) in the photocurable composition. <11> The photocurable composition according to any one of <1> to <10>, wherein the content of the compound (C) in the photocurable composition is 1% by mass to 30% by mass, based on the total content of the (meth)acrylic monomer component and the compound (C) in the photocurable composition.<12> The photocurable composition according to any one of <1> to <11>, wherein the siloxane bond concentration in the photocurable composition is 0.100 mmol / g to 3.000 mmol / g. <13> The photocurable composition according to any one of <1> to <12>, wherein the aromatic ring concentration in the (meth)acrylic monomer component contained in the photocurable composition is 0.0015 mol / g to 0.0070 mol / g. <14> The photocurable composition according to any one of <1> to <13>, which is a photocurable composition for stereolithography. <15> The photocurable composition according to any one of <1> to <14>, which is a photocurable composition used in the production of a mold by stereolithography. <16> A three-dimensionally shaped object comprising a cured product of the photocurable composition according to any one of <1> to <15>. <17> A mold comprising the three-dimensionally shaped object according to <16>. <18> The mold according to <17>, used in the production of a dental prosthesis. <19> A method for producing a cured product, comprising the step of polymerizing a curable composition in the mold according to <17> or <18>. <20> A method for producing a dental prosthesis, comprising the steps of: curing the photocurable composition according to any one of <1> to <15> by stereolithography to prepare a mold to be used in the production of a dental prosthesis; and polymerizing the curable composition in the mold to produce the dental prosthesis.

[0010] According to one aspect of the present disclosure, there are provided a photocurable composition capable of producing a three-dimensional object with reduced surface roughness, as well as a method for producing a three-dimensional object, a mold, or a cured product using the photocurable composition, and a method for producing a dental prosthesis.

[0011] FIG. 2 is a schematic diagram of a three-dimensional object A1 formed in an example.

[0012] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. In the present disclosure, when a composition contains multiple substances corresponding to each component, the amount of each component contained in the composition means the total amount of the multiple substances present in the composition, unless otherwise specified. In the numerical ranges described in stages in the present disclosure, the upper or lower limit described in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in the numerical ranges described in the present disclosure, the upper or lower limit of that numerical range may be replaced with a value shown in the examples. In the present disclosure, "light" is a concept that includes active energy rays such as ultraviolet rays and visible light.

[0013] In this disclosure, "(meth)acrylate" means acrylate or methacrylate, "(meth)acryloyl" means acryloyl or methacryloyl, and "(meth)acrylic" means acrylic or methacrylic.

[0014] [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.

[0015] The photocurable composition of the present disclosure includes a (meth)acrylic monomer component containing the (meth)acrylic monomer (A) and the (meth)acrylic monomer (B), a compound (C) that satisfies the solubility parameter requirement, and a photopolymerization initiator, thereby enabling the production of a three-dimensional object with reduced surface roughness.

[0016] The photocurable composition of the present disclosure is a composition that cures upon irradiation with light, and a cured product is obtained by curing this composition. A preferred method for producing a cured product using the photocurable composition of the present disclosure is stereolithography. The photocurable composition of the present disclosure is preferably a photocurable composition for stereolithography, and in other words, a cured product produced using the photocurable composition of the present disclosure is preferably a stereolithography product (i.e., a cured product obtained by stereolithography).

[0017] Stereolithography is a method of repeatedly irradiating a photocurable composition with light to form cured layers, thereby laminating the cured layers and obtaining a cured product (i.e., a stereolithography product). Stereolithography may be inkjet-type stereolithography or liquid-vat-type stereolithography (i.e., stereolithography using a liquid vat).

[0018] 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 stereolithography, for example, a head equipped with an inkjet nozzle and a light source is scanned within a plane while the photocurable composition is ejected from the inkjet nozzle onto the substrate, and the ejected photocurable composition is irradiated with light to form a cured layer. These operations are repeated to sequentially stack cured layers to obtain a cured product (i.e., a stereolithography product).

[0019] In liquid tank-type stereolithography, a portion of a photocurable composition (i.e., an uncured photocurable composition in a liquid state; the same applies hereinafter) contained in a liquid tank is cured by irradiating it with light to form a cured layer, and this operation is repeated to stack 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) stereolithography and SLA (Stereolithography) stereolithography. In the DLP method, planar light is irradiated onto the photocurable composition in the liquid tank. In the SLA method, laser light is scanned onto the photocurable composition in the liquid tank. From the viewpoint of more effectively achieving the effects of the photocurable composition of the present disclosure, DLP-type stereolithography is preferred as liquid tank-type stereolithography.

[0020] An example of DLP-based stereolithography uses a 3D printer (e.g., Kulzer's "Cara Print 4.0," Asiga's "Max UV," etc.) equipped with: a build table movable in the vertical direction; a tray (i.e., liquid tank) disposed below the build table (on the gravity side; the same applies below) that includes a light-transmitting portion and contains a photocurable composition; and 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 the light-transmitting portion of the tray. In this example, a gap of one layer is first formed between the build table and the tray, and this gap is filled with photocurable composition. Next, planar light is irradiated from below through the light-transmitting portion of the tray onto the photocurable composition filled in the gap, curing the irradiated area 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 photocurable composition. Next, the photocurable composition filling the space is irradiated with light in the same manner as for curing the first layer, forming a second cured layer. By repeating the above operations, cured layers are stacked to produce a three-dimensional object. In this example, the three-dimensional object may be further cured by further irradiating the produced three-dimensional object with light. For details on DLP-based stereolithography, see, for example, Japanese Patent Publication No. 5111880 and Japanese Patent Publication No. 5235056.

[0021] <Application> The application of the photocurable composition of the present disclosure is not particularly limited. For example, it is preferably a photocurable composition used in the production of molds, dental products, and the like by stereolithography, and more preferably a photocurable composition used in the production of molds by stereolithography.

[0022] Examples of the mold include molds used for producing a plate denture. For example, a plate denture may be produced by injecting a hardenable composition for producing a denture base into the mold with artificial teeth arranged in the mold and then hardening the injected hardenable composition.

[0023] Examples of dental products include dental prostheses, medical instruments used in the oral cavity, dental models, and models for lost-loss casting. Examples of dental prostheses include inlays, crowns, bridges, temporary crowns, temporary bridges, and dentures (e.g., complete dentures, partial dentures, etc.). Examples of medical instruments used in the oral cavity include dentures (e.g., complete dentures, partial dentures, etc.), mouthpieces, mouthguards, orthodontic appliances, splints such as occlusal splints and splints for treating temporomandibular disorders, impression trays, and surgical guides. Examples of dental models include tooth and jaw models.

[0024] In the photocurable composition of the present disclosure, the aromatic ring concentration in the (meth)acrylic monomer component is preferably 0.0015 mol / g to 0.0070 mol / g, more preferably 0.0016 mol / g to 0.0065 mol / g, and even more preferably 0.0017 mol / g to 0.0052 mol / g. By adjusting the aromatic ring concentration in the (meth)acrylic monomer component as described above, there is a tendency for the composition to have better removability from the mold and to be able to suitably suppress deformation of the mold during use.

[0025] The photocurable composition of the present disclosure contains (meth)acrylic monomer components such as (meth)acrylic monomer (A) and (meth)acrylic monomer (B) described below. In the present disclosure, the (meth)acrylic monomer component refers to a compound having one or more (meth)acryloyl groups.

[0026] From the viewpoint of mechanical strength of the cured product, the content of the (meth)acrylic monomer component relative to the total amount of the photocurable composition of the present disclosure is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more. The content of the (meth)acrylic monomer component relative to the total amount of the photocurable composition of the present disclosure may be 99% by mass or less, 95% by mass or less, or 90% by mass or less.

[0027] <(Meth)acrylic Monomer (A)> The photocurable composition of the present disclosure contains at least one (meth)acrylic monomer (A) having one or more (meth)acryloyl groups and no siloxane bond.

[0028] 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, two (meth)acryloyloxy groups, and no siloxane bond Mono(meth)acrylic monomer (A-2): A compound having one (meth)acryloyloxy group and an aromatic ring, and no siloxane bond

[0029] (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 the mold during the production of a plate denture and improving the water resistance of the mold. Furthermore, when the ring structure contains an aromatic ring, the aromatic ring concentration in the (meth)acrylic monomer component increases, which tends to improve releasability and provide excellent toughness. The di(meth)acrylic monomer (A-1) having a urethane bond can suppress fracture when a plate denture is removed from the mold and tends to provide excellent toughness. The (meth)acrylic monomer (A) may contain one type of di(meth)acrylic monomer (A-1), or may contain two or more types of di(meth)acrylic monomer (A-1).

[0030] 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 the present disclosure, the weight average molecular weight is measured by gel permeation chromatography (GPC).

[0031] 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 rate.

[0032] 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 viscosity 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 more preferable that the solubility parameter (SP value) of the di(meth)acrylic monomer (A-1) is 8.50 (cal / cm ３ ) １／２ When the solubility parameter (SP value) of the di(meth)acrylic monomer (A-1) is 12.70 (cal / cm ３ ) １／２ When the above condition is satisfied, a three-dimensionally shaped object having excellent bending strength and toughness can be easily obtained.

[0033] 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. Examples of the ring structure include an aromatic ring structure and an alicyclic structure.

[0034] 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).

[0035]

[0036]

[0037] In formula (6-1), R １ are each independently a divalent organic group, and R ２ are each independently a divalent hydrocarbon group which may have a substituent, and R ３ are each independently a hydrogen atom or a methyl group, X is a divalent organic group, and n is an integer of 0 to 10. １ , R ２ , R ３ may be the same or different, and when there are a plurality of X's, they may be the same or different.

[0038] In formula (6-1), R １ Examples of R include a divalent hydrocarbon group, and a divalent organic group containing one or more bonds selected from the group consisting of an ether bond and an ester bond. １ The divalent hydrocarbon group as R may be, for example, a divalent chain hydrocarbon group or a divalent hydrocarbon group containing a ring structure (aromatic ring structure, alicyclic structure). １ When the divalent organic group represented by R contains an ether bond, the number of ether bonds is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. １ When the divalent organic group represented by R contains an ester bond, the number of ester bonds is preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 6. １ The number of carbon atoms in may be, for example, 2 to 60, preferably 2 to 40, and more preferably 2 to 30.

[0039] In formula (6-1), R １ is represented by the following general formula (6-1-R １ ) is preferably a group represented by the formula (I).

[0040]

[0041] General formula (6-1-R １ ) Medium, R １Ａ is a divalent hydrocarbon group which may have a substituent, and R １Ｂ is a methylene group (-CH ２ -) or a carbonyl group (-C(=O)-), and R１Ｃ is a divalent hydrocarbon group, and m is an integer from 0 to 10. １Ｂ , R １Ｃ When there are multiple groups, they may be the same or different. * indicates the bonding position.

[0042] General formula (6-1-R １ ) in R １Ａ The divalent hydrocarbon group which may have a substituent as R 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. １Ａ The divalent chain hydrocarbon group as R may be branched and may be saturated or unsaturated. １Ａ The number of carbon atoms in the divalent chain hydrocarbon group as R is preferably 2 to 20, more preferably 2 to 15, and even more preferably 2 to 10. １Ａ The substituent that the divalent chain hydrocarbon group represented by R 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, with the phenoxy group being preferred. １Ａ The divalent hydrocarbon group containing an aromatic structure as R 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). 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. １Ａ The divalent hydrocarbon group containing an alicyclic structure as represented by 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.

[0043] General formula (6-1-R １ ) in R １ＣExamples of the divalent hydrocarbon group as R 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. １Ｃ The number of carbon atoms in the divalent chain hydrocarbon group as R is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. １Ｃ The divalent hydrocarbon group containing an aromatic structure as R 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). １Ｃ The divalent hydrocarbon group containing an alicyclic structure as is preferably a divalent hydrocarbon group having an alicyclic structure of 3 to 20 carbon atoms (more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms).

[0044] General formula (6-1-R １ In the formula (I), m is an integer of 0 to 10, preferably 0 to 8, and more preferably 0 to 6.

[0045] General formula (6-1-R １ ) in the left side * (i.e., R １Ａ The bonding position from R in general formula (6-1) １ It is preferable that the bond is made to the oxygen atom on the left side of the * (i.e., R １Ｃ The bonding position from R in general formula (6-1) １ It is preferable that the bond is with the oxygen atom on the right side of the group.

[0046] In formula (6-1), R ２ The divalent hydrocarbon group as R is, for example, a divalent chain hydrocarbon group or a divalent hydrocarbon group containing a ring structure. ２ The number of carbon atoms in the divalent chain hydrocarbon group represented by R is preferably 1 to 25, more preferably 1 to 20, and even more preferably 2 to 15. ２ The divalent hydrocarbon group containing a ring structure as R may contain an aromatic structure or an alicyclic structure. ２The carbon number of the divalent hydrocarbon group containing an aromatic structure represented by R is preferably 6 to 25, more preferably 6 to 20, and even more preferably 6 to 15. ２ The divalent hydrocarbon group containing an alicyclic structure as the aryl group preferably has 3 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms.

[0047] R ２ The divalent hydrocarbon group as the group is specifically represented by the following general formula (6-1-R ２ -1) ~ General formula (6-1-R ２ From the viewpoint of obtaining a three-dimensionally shaped object having excellent flexibility and toughness, a divalent hydrocarbon group represented by a structure selected from the following general formula (6-1-R ２ -4) ~ General formula (6-1-R ２ -13) is more preferred, and a divalent hydrocarbon group represented by the following general formula (6-1-R ２ -4) ~ General formula (6-1-R ２ Divalent hydrocarbon groups represented by structures selected from the following are more preferred:

[0048]

[0049] General formula (6-1-R ２ -1) ~ General formula (6-1-R ２ -13), * indicates the bond position.

[0050] In formula (6-1), X is a divalent organic group, 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 ether bonds is preferably 1 to 100, more preferably 2 to 90, and even more preferably 4 to 80. When the divalent organic group represented by X contains an ester bond, the number of ester bonds is preferably 1 to 100, more preferably 2 to 90, and even more preferably 4 to 80. The number of carbon atoms in the divalent organic group represented by X is preferably 2 to 500, more preferably 2 to 400, and even more preferably 2 to 300.

[0051] X in formula (6-1) is preferably a group represented by the following general formula (6-1-X).

[0052]

[0053] In general formula (6-1-X), R ＸＡ is a divalent hydrocarbon group, and R ＸＢ is a methylene group (-CH ２ -) or a carbonyl group (-C(=O)-), and R ＸＣ is a divalent hydrocarbon group, and k is an integer from 0 to 100. ＸＢ , R ＸＣ When a plurality of are present, they may be the same or different. * indicates the bonding position.

[0054] R in general formula (6-1-X) ＸＡ The divalent hydrocarbon group represented by R 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. ＸＡ The divalent chain hydrocarbon group as R may be branched and may be saturated or unsaturated. ＸＡ The number of carbon atoms in the divalent chain hydrocarbon group as R is preferably 2 to 20, more preferably 2 to 15, and even more preferably 2 to 10. ＸＡ The divalent hydrocarbon group containing an aromatic structure as R 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). ＸＡ The divalent hydrocarbon group containing an alicyclic structure as is preferably a divalent hydrocarbon group having an alicyclic structure of 3 to 20 carbon atoms (more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms).

[0055] R in general formula (6-1-X) ＸＣ Examples of the divalent hydrocarbon group as R include a divalent chain hydrocarbon group and a divalent hydrocarbon group containing a ring structure, with a divalent chain hydrocarbon group being preferred. ＸＣThe number of carbon atoms in the divalent chain hydrocarbon group as R is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. ＸＣ The divalent hydrocarbon group containing an aromatic structure as R 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). ＸＣ The divalent hydrocarbon group containing an alicyclic structure as is preferably a divalent hydrocarbon group having an alicyclic structure of 3 to 20 carbon atoms (more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms).

[0056] In the general formula (6-1-X), k is 0 to 100, preferably 2 to 90, and more preferably 4 to 80.

[0057] In formula (6-2), R ３ are each independently a hydrogen atom or a methyl group, and R ４ are each independently an alkylene group, an alkyleneoxy group, or a combination thereof, which may have a substituent; R ５ are each independently an oxygen atom or an ester bond (*1-O-C(=O)-*2, *1 is R ４ *2 is the bonding position with R ６ and R ６ is a divalent linking group containing a ring structure.

[0058] In formula (6-2), R ４ is an alkyleneoxy group, and R ５ may be an oxygen atom, or R ４ is an alkylene group, and R ５ is an ester bond (*1-O-C(=O)-*2, *1 is R ４ *2 is the bonding position with R ６ R ６ may be a phenylene group or a bisphenol skeleton (for example, a bisphenol A skeleton or a bisphenol F skeleton).

[0059] 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 component and the compound (C) in the photocurable composition.

[0060] (Mono(meth)acrylic monomer (A-2)) The (meth)acrylic monomer (A) preferably contains the mono(meth)acrylic monomer (A-2) described above. 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 plated denture from the mold (improved releasability) and tends to suppress fracture when removing the plated denture from the mold (excellent toughness). Furthermore, a mold that suppresses deformation during the manufacture of a plated denture can be suitably produced, and the use of a monofunctional monomer increases the flexibility of the mold, thereby improving 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 monomers (A-2).

[0061] The molecular weight or weight average molecular weight of the mono(meth)acrylic monomer (A-2) may be 160-400, or 180-300.

[0062] 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 viscosity 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 more preferable that the solubility parameter (SP value) of the mono(meth)acrylic monomer (A-2) is 8.80 (cal / cm ３ ) １／２When the solubility parameter (SP value) of the mono(meth)acrylic monomer (A-2) is 13.00 (cal / cm ３ ) １／２ When the above condition is satisfied, a three-dimensionally shaped object having excellent bending strength and toughness can be easily obtained.

[0063] 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):

[0064]

[0065] In formula (5), R １ is a monovalent organic group having an aromatic ring, and R ２ is a hydrogen atom or a methyl group.

[0066] R in formula (5) １ Preferably, has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms.

[0067] R in formula (5) １ The monovalent organic group represented by R may have one or more aromatic rings, but preferably has one or two aromatic rings. １ The aromatic ring of the monovalent organic group as may be monocyclic or polycyclic. Examples of monocyclic aromatic rings include phenyl structures (phenyl groups, phenylene groups). The monocyclic aromatic rings may have a substituent, and examples of the substituent include alkyl groups, aryloxy groups (phenoxy groups, etc.), aryl alkylene groups, and aryl groups. Examples of polycyclic aromatic rings include naphthyl structures (naphthyl groups, naphthylene groups). The polycyclic aromatic rings may have a substituent, and examples of the substituent include alkyl groups, aryloxy groups (phenoxy groups, etc.), aryl alkylene groups, and aryl groups.

[0068] R １ is represented by the following general formula (5-R １ -1) ~ General formula (5-R １It is preferable that the monovalent organic group is a monovalent organic group represented by a structure selected from the following:

[0069]

[0070] General formula (5-R １ -1) ~ General formula (5-R １ In formula (5-R-7), * indicates the bonding position. １ -7) Medium, R １Ａ represents an alkyl group having 1 to 10 carbon atoms.

[0071]

[0072] In formula (5-1), R １Ａ is a divalent linking group, and 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.

[0073] In formula (5-1), R １Ａ R 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. １Ａ The number of carbon atoms in R is preferably 1 to 20, and more preferably 1 to 10. 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.

[0074] In formula (5-1), n ​​is preferably 0 or 1. When n is 1 to 5, R ２ is preferably a phenyl group which may have a substituent.

[0075] 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 component and the compound (C) in the photocurable composition.

[0076] <(Meth)acrylic Monomer (B)> The photocurable composition of the present disclosure contains at least one (meth)acrylic monomer (B) having two or more (meth)acryloyl groups and a siloxane bond. By containing the (meth)acrylic monomer (B), the aromatic ring concentration in the (meth)acrylic monomer component increases, which tends to make it easier to remove a plate denture from a mold (improved releasability), and tends to provide excellent deformability and dimensional accuracy during the production of a plate denture.

[0077] 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), and more specifically, may contain a linear siloxane bond, a ladder-like siloxane bond including linear and branched siloxane bonds, a cage-like siloxane bond, or the like. The (meth)acrylic monomer (B) may contain two or three or more (meth)acryloyloxy groups.

[0078] Examples of the siloxane bond include a dimethylsiloxane bond, a methylphenylsiloxane bond, and a diphenylsiloxane bond, with the dimethylsiloxane bond being preferred.

[0079] 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.

[0080] The molecular weight of the (meth)acrylic monomer (B) may be 400 to 5000. The weight average molecular weight of the (meth)acrylic monomer (B) may be 400 to 4000.

[0081] Combining the (meth)acrylic monomer (B) with the compound (C) described below facilitates the production of a three-dimensionally shaped object with reduced surface roughness, which in turn facilitates the production of a three-dimensionally shaped object with excellent releasability, such as ease of demolding and toughness upon demolding, less surface roughness, and excellent appearance.

[0082] 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 viscosity 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 When the solubility parameter (SP value) of the (meth)acrylic monomer (B) is 9.50 (cal / cm ３ ) １／２ When the above condition is satisfied, a three-dimensional object having excellent releasability can be easily obtained.

[0083] The (meth)acrylic monomer (B) may be a compound represented by the following formula (7):

[0084]

[0085] In formula (7), R １ are each independently an alkylene group which may have a substituent, and R ２ are each independently an alkylene group which may have a substituent, and R ３ are each independently a hydrogen atom or a methyl group, and R ４ 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.

[0086] R １ is preferably a methylene group, an ethylene group, or a propylene group, and R ２ is more preferably a methylene group, an ethylene group, a propylene group or a butylene group. ４ is preferably a methyl group or a phenyl group, and more preferably a methyl group. m may be 1 to 30, or may be 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.

[0087] The content of the (meth)acrylic monomer (B) in the photocurable composition is preferably 1% by mass to 35% by mass, more preferably 5% by mass to 30% by mass, and even more preferably 10% by mass to 25% by mass, relative to the total content of the (meth)acrylic monomer component and the compound (C) in the photocurable composition.

[0088] In the (meth)acrylic monomer component, the total content of the (meth)acrylic monomer (A) and the (meth)acrylic monomer (B) is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass.

[0089] The siloxane bond concentration in the photocurable composition is preferably 0.100 mmol / g to 3.000 mmol / g, more preferably 0.300 mmol / g to 2.500 mmol / g, and even more preferably 0.400 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 fracture when a dental prosthesis such as a plate denture is removed from a mold, resulting in 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 photopolymerizable components other than the (meth)acrylic monomer component include styrene, styrene derivatives, (meth)acrylonitrile, and the like. In the photocurable composition of the present disclosure, the content of the photopolymerizable component other than the (meth)acrylic monomer component may be 20% by mass or less, 10% by mass or less, 5% by mass or less, or 1.0% by 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% by 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 is each independently 8.00 to 12.00 (cal / cm ３ ) １／２ and may be 8.50 to 11.50 (cal / cm ３ ) １／２ 9.00 to 11.00 (cal / cm ３ ) １／２ The solubility parameter (SP value) of the (meth)acrylic monomer component and the solubility parameter (SP value) of the photopolymerizable component each represent a weighted average value.

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

[0093] <Compound (C)> The photocurable composition of the present disclosure is a compound (C) that 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 The compound (C) includes a compound (C) having the formula:

[0094] The solubility parameter (SP value) of the 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 viscosity 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 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] The compound (C) has a solubility parameter (SP value) of 7.00 to 15.00 (cal / cm ３ ) １／２ There are no particular limitations on the compound as long as it satisfies the above conditions, 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 hydroxy group, or may be a linear alcohol compound having one hydroxy group. Specific examples of the higher alcohol include 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, and 1-dodecanol (lauryl alcohol).

[0099] Examples of the monoalcohol ester include a monoester containing one hydroxy group, a diester containing one hydroxy group, a triester containing one hydroxy group, etc. Specific examples of the monoalcohol ester include oxyacid esters such as diisostearyl malate, triethyl citrate, etc.

[0100] The polyhydric alcohol may be a compound containing two or more hydroxy groups and having no ester bond. The number of hydroxy groups in the polyhydric alcohol may be two or more, and may be two or three. Specific examples of the polyhydric alcohol include trimethylolpropane.

[0101] Examples of polyhydric alcohol esters include compounds containing two or more hydroxy groups and having an ester bond. The number of hydroxy 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, 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 ester compounds include monoesters, diesters, triesters, etc. of higher fatty acids having 5 or more carbon atoms. The ester compounds may also be fatty acid esters (fatty acid monoesters, fatty acid diesters, fatty acid triesters, etc.) synthesized from higher fatty acids and higher alcohols. Specific examples of ester compounds include ethyl laurate, isopropyl myristate, isopropyl palmitate, and glyceryl trioleate. Fatty acid esters synthesized from higher fatty acids and higher alcohols are prone to dimerization, so they may be dimers in the raw material stage, or may be derivatives of dimer diols such as di(isostearyl / phytosteryl) dimer dilinoleate.

[0104] The polyether compound may be a compound containing two or more ether bonds, and specifically may be a polyalkylene glycol (preferably having an alkylene group with 2 to 4 carbon atoms) such as polyethylene glycol or 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 The lower limit of the absolute value of the difference is preferably 0 (cal / cm ３ ) １／２ There are no particular limitations as long as it is equal to or greater than 0.10 (cal / cm ３ ) １／２ In the present disclosure, the average value of the solubility parameters (SP values) means the weighted average value of the SP values ​​of the corresponding components.

[0106] The difference (SP value 1-SP value 2) between the average value of the solubility parameters (SP value 1) of the (meth)acrylic monomer components contained in the photocurable composition and the average value of the solubility parameters (SP value 2) of the compound (C) contained in the photocurable composition is -0.50 (cal / cm) from the viewpoint of suppressing the surface roughness of the three-dimensionally shaped object and facilitating demolding. ３ ) １／２ It may be 0 (cal / cm ３ ) １／２ It may be 0.30 (cal / cm ３ ) １／２ The upper limit of SP value 1 - SP value 2 is not particularly limited, and may be, for example, 3.00 (cal / cm ３ ) １／２ It may be 2.00 (cal / cm ３ ) １／２ It may be the following:

[0107] 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.

[0108] The average value of the solubility parameter (SP value) of the components contained in the photocurable composition (excluding the photopolymerization initiator) is 8.00 to 12.00 (cal / cm ３ ) １／２It is preferable that the viscosity is 9.00 to 11.00 (cal / cm ３ ) １／２ More preferably, it is 9.00 to 10.30 (cal / cm ３ ) １／２ It is more preferable that:

[0109] 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.

[0110] 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 10,000 or more, and more preferably 11,000 or more. From the viewpoint of compatibility with the (meth)acrylic monomer component, the cohesive energy density (cal / mol) of the compound (C) is preferably 150,000 or less, and more preferably 110,000 or less.

[0111] The content of compound (C) in the photocurable composition is preferably 1% by mass to 30% by mass, more preferably 3% by mass to 20% by mass, and even more preferably 5% by mass to 15% by mass, relative to the total content of the (meth)acrylic monomer component and compound (C) in the photocurable composition.

[0112] [Photopolymerization initiator] The photocurable composition of the present disclosure contains a photopolymerization initiator. The photocurable composition of the present disclosure may contain only one type of photopolymerization initiator, or may contain two or more types of photopolymerization initiators.

[0113] The photopolymerization initiator is not particularly limited as long as it generates radicals upon irradiation with light, and is preferably one that generates radicals at the wavelength of light used in stereolithography. The wavelength of light used in stereolithography is generally 365 nm to 500 nm, but in practice it is preferably 365 nm to 430 nm, and more preferably 365 nm to 420 nm.

[0114] The photopolymerization initiator is preferably a compound that is not classified as a (meth)acrylic monomer component. For example, the photopolymerization initiator is preferably a compound that does not have a (meth)acryloyl group. The photopolymerization initiator has a solubility parameter (SP value) of 7.00 to 15.00 (cal / cm ３ ) １／２ In the present disclosure, compounds that are excited by light in a specific wavelength range (e.g., 365 nm to 500 nm) to generate radicals are classified as photopolymerization initiators. Compounds that are excited by light in a specific wavelength range (e.g., 365 nm to 500 nm) to generate radicals and have a solubility parameter (SP value) of 7.00 to 15.00 (cal / cm ３ ) １／２ A compound that satisfies the above condition is classified as a photopolymerization initiator, not as compound (C). That is, in the present disclosure, compound (C) is not a compound that is excited by light in a specific wavelength range (e.g., 365 nm to 500 nm) and generates radicals.

[0115] Examples of the photopolymerization initiator include acylphosphine oxide compounds, alkyl benzoylformate compounds, alkylphenone compounds, titanocene compounds, oxime ester compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, thioxanthone compounds, α-acyloxime ester compounds, phenyl glyoxylate compounds, benzyl compounds, azo compounds, diphenyl sulfide compounds, organic dye compounds, iron phthalocyanine compounds, benzoin ether compounds, and anthraquinone compounds.

[0116] Examples of the acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0117] The total content of the photopolymerization initiator in the photocurable composition of the present disclosure is preferably 0.1% by mass to 5% by mass, more preferably 0.5% by mass to 4% by mass, and even more preferably 0.5% by mass to 3% by mass, relative to the total amount of the photocurable composition.

[0118] When the photopolymerization initiator contains an acylphosphine oxide-based compound, the content of the acylphosphine oxide-based compound may be 50% by mass to 100% by mass, 70% by mass to 100% by mass, or 90% by mass to 100% by mass, relative to the total amount of the photopolymerization initiator.

[0119] The total content of the (meth)acrylic monomer component, compound (C), and photopolymerization initiator, or the total content of the (meth)acrylic monomer (A), (meth)acrylic monomer (B), compound (C), and photopolymerization initiator, is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the total amount of the photocurable composition of the present disclosure. The upper limit of the total content of the (meth)acrylic monomer component, compound (C), and photopolymerization initiator, or the total content of the (meth)acrylic monomer (A), (meth)acrylic monomer (B), compound (C), and photopolymerization initiator, is not particularly limited, as long as it is 100% by mass or less.

[0120] <Other Components> The photocurable composition of the present disclosure may contain one or more components other than the above-described components, as needed.

[0121] Examples of other components include coloring materials, coupling agents such as silane coupling agents, additives such as 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 thermal polymerization initiators include thermal radical generators and amine compounds.

[0122] However, from the viewpoint of further improving the molding accuracy of the cured product, the photocurable composition of the present disclosure does not contain an inorganic filler (e.g., silica, barium borosilicate glass, etc.; the same applies hereinafter), or if it contains an inorganic filler, the content of the inorganic filler relative to the total amount of the photocurable composition is preferably 60% by mass or less (more preferably 40% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less).

[0123] The method for preparing the photocurable composition of the present disclosure is not particularly limited. Examples of methods for preparing the photocurable composition of the present disclosure include a method of mixing a (meth)acrylic monomer component, a photopolymerization initiator, and, if necessary, other components. The means for mixing the components is not particularly limited, and includes, for example, ultrasonic dissolution, a twin-arm mixer, a roll mixer, a twin-screw extruder, a ball mill mixer, and a planetary mixer. The photocurable composition of the present embodiment may be prepared by mixing the components, filtering the mixture through a filter to remove impurities, and then subjecting the mixture to a vacuum degassing treatment.

[0124] <Preferred Viscosity of Photocurable Composition> The photocurable composition of the present disclosure preferably has a viscosity (hereinafter also simply referred to as "viscosity") measured at 25°C and 50 rpm using an E-type viscometer of 5 mPa·s to 6000 mPa·s. Here, rpm means revolutions per minute (revolutions per minute). When the viscosity is 5 mPa·s to 6000 mPa·s, the photocurable composition exhibits excellent handleability when producing a cured product (particularly a stereolithography product). The viscosity is more preferably 10 mPa·s to 5000 mPa·s, even more preferably 20 mPa·s to 5000 mPa·s, and even more preferably 100 mPa·s to 4500 mPa·s.

[0125] [Three-dimensionally shaped object] The three-dimensionally shaped object of the present disclosure includes a cured product of the photocurable composition of the present disclosure. Therefore, when the three-dimensionally shaped object of the present disclosure is a mold, deformation during the production of a dental prosthesis such as a plate denture can be suppressed, and when the dental prosthesis is produced using the mold, the dental prosthesis can be easily removed from the mold. The three-dimensionally shaped 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 (e.g., a stereolithography object) is as described above. A preferred embodiment of the three-dimensionally shaped object is a mold, more specifically, a mold used for producing a dental prosthesis.

[0126] [Method for Producing a Cured Product] The method for producing a cured product of the present disclosure includes a step of polymerizing the curable composition in the above-described mold. For example, a mold may be produced using the above-described photocurable composition of the present disclosure, and the curable composition may be injected into the mold and polymerized to produce a cured product. The curable composition injected into the mold is not particularly limited as long as it contains a polymerizable component that polymerizes by heat, light, or the like. For example, when preparing a dental prosthesis such as a plate denture by arranging artificial teeth in the mold, a conventionally known curable composition for producing a denture base may be injected into the mold and the injected curable composition for producing a denture base may be cured.

[0127] [Method for manufacturing a plate denture] The method for manufacturing a plate denture of the present disclosure includes the steps of hardening a photocurable composition by stereolithography to prepare a mold to be used in manufacturing a dental prosthesis, and polymerizing the hardenable composition in the mold to manufacture the dental prosthesis. The method for manufacturing a dental prosthesis of the present disclosure is a method for manufacturing a dental prosthesis through two steps, a step for preparing a mold and a step for manufacturing a dental prosthesis, and enables the manufacture of a plate denture by a method simpler than conventional methods for manufacturing dental prostheses using molds.

[0128] The process of creating a mold preferably includes, for example, a process of acquiring three-dimensional impression data of the oral cavity of a user of the dental prosthesis, a process of acquiring mold data from the acquired three-dimensional impression data, and a process of curing a photocurable composition by photo-molding based on the acquired mold data.

[0129] The step of manufacturing a dental prosthesis may be a step of manufacturing a plate denture. The step of manufacturing a plate denture preferably includes the steps of arranging artificial teeth in a mold, injecting a hardenable composition for denture base preparation into the mold with the artificial teeth arranged in the mold, hardening the injected hardenable composition, and removing the manufactured plate denture from the mold.

[0130] In the method for producing a dental prosthesis according to the present disclosure, the photocurable composition used to prepare the mold is not particularly limited. For example, from the viewpoint of suppressing deformation of the mold in the step of curing the curable composition after injection and suppressing damage to the dental prosthesis, the mold, etc. in the step of removing the produced dental prosthesis from the mold, it is preferable to use the photocurable composition according to the present disclosure as the photocurable composition used to prepare the mold.

[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 17, Comparative Examples 1 to 5 Preparation of Photocurable Compositions 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] <Measurements and Evaluations> The photocurable compositions obtained were subjected to the following measurements and evaluations. The results are shown in Tables 2 to 5.

[0134] (Releasability from denture) The obtained photocurable composition was irradiated with visible light having a wavelength of 405 nm at an irradiation dose of 11 mJ / cm ２ The cured layers A1 are laminated in the thickness direction to form the three-dimensional object A1 shown in FIG. 1 , and the object A1 is irradiated with ultraviolet light having a wavelength of 365 nm at an irradiation dose of 3 J / cm 2 . ２Test piece A1 shown in Figure 1 was prepared by stereolithography under irradiation conditions of 1000 Hz. As shown in Figure 1, test piece A1 had a shape with L 24 mm, L' 20 mm, W 2 mm, H 5 mm, H' 3 mm, D 14 mm, and D' 10 mm. A (meth)acrylate polymer powder for plate denture production and PalaXtreme (registered trademark, manufactured by Kulzer), a (meth)acrylate monomer liquid, were mixed in a ratio of 10 g powder to 6 g liquid. 30 seconds after mixing, the mixture was filled into the space of the prepared test piece A1, which was L' (20 mm) x D' (10 mm) x H' (3 mm), and polymerized at 55°C and a pressure of 2 bar for 30 minutes. Test piece A1 was then peeled off from the polymer for plate denture production. Thereafter, the surface of the polymer for making a plate denture that had been in contact with the test piece A1 was observed using a 3D shape measuring device (Keyence Corporation, VR-3200), and the area value of the test piece A1 that had been attached to the polymer for making a plate denture after removal was calculated. ２ The adhesion rate relative to the surface was calculated (Tables 2 to 5). The smaller the adhesion rate, the better the releasability. No surface adhesion was evaluated as "A," surface adhesion of less than 5% as "B," and adhesion of 5% or more as "C." The results are shown in Tables 2 to 5.

[0135] (Toughness at Demolding) The photocurable composition obtained 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 the three-dimensional object A1 shown in FIG. 1 , and the object A1 is irradiated with ultraviolet light having a wavelength of 365 nm at an irradiation dose of 3 J / cm 2 . ２Test piece A1 shown in Figure 1 was prepared by stereolithography under irradiation conditions of 1000 Hz. The size of test piece A1 used for the toughness evaluation was the same as that of test piece A1 used for the aforementioned demoldability evaluation. (Meth)acrylate polymer powder for plate denture production and PalaXtreme (registered trademark, manufactured by Kulzer), a (meth)acrylate monomer liquid, were mixed in a ratio of 10 g powder to 6 g liquid. 30 seconds after mixing, the space of the prepared test piece A1, consisting of L' (20 mm) x D' (10 mm) x H' (3 mm), was filled and polymerized at 55°C and 2 bar pressure for 30 minutes. Test piece A1 was then peeled off and removed from the polymer for plate denture production. The appearance of test piece A1 after removal was observed, and a grade of "A" was assigned for cases without fracture and a grade of "B" for cases with fracture. The results are shown in Tables 2 to 5.

[0136] (Surface Roughness) The obtained photocurable composition was printed using a 3D printer (Kulzer, Cara Print 4.0) with visible light having a wavelength of 405 nm and an illuminance of 8.0 mJ / cm. ２ A shaped object (layer width: 50 μm) was obtained by molding to a width of 20 mm, length of 20 mm, and thickness of 10 mm under the conditions of 10 J / cm. Note that the lamination was performed in the thickness direction. ２ A stereolithography object was obtained by irradiating the object with ultraviolet light having a wavelength of 365 nm under the above conditions and finally curing the object. The surface roughness (Rz) of the obtained stereolithography object (hereinafter referred to as "test piece") in the stacking surface direction (surface having a width of 20 mm and a length of 20 mm) and in the stacking height direction (surface having a width of 20 mm and a thickness of 10 mm) of the test piece was measured using a 3D shape measuring device (Keyence Corporation, VR-3200). The smaller the surface roughness Rz, the better the surface smoothness. Evaluation was based on the following criteria. The results are shown in Tables 2 to 5. A: Rz<30 μm B: 30 μm≦Rz<50 μm C: 50 μm≦Rz<70 μm D: 70 μm≦Rz

[0137] (Appearance Evaluation of Molded Article) The obtained photocurable composition was irradiated with visible light having a wavelength of 405 nm at an irradiation dose of 11 mJ / cm. ２The cured layers A1 are laminated in the thickness direction to form the three-dimensional object A1 shown in FIG. 1 , and the object A1 is irradiated with ultraviolet light having a wavelength of 365 nm at an irradiation dose of 3 J / cm 2 . ２ Test piece A1 shown in FIG. 1 was prepared by stereolithography under irradiation conditions of 1000 . Test piece A1 shown in FIG. 1 was prepared. The size of test piece A1 used for the appearance evaluation was the same as that of test piece A1 used for the aforementioned demoldability evaluation. (Meth)acrylate polymer powder for base denture production and PalaXtreme (registered trademark, manufactured by Kulzer), a (meth)acrylate monomer liquid, were mixed in a ratio of 10 g powder to 6 g liquid. 30 seconds after mixing, the space of the prepared test piece A1, consisting of L' (20 mm) x D' (10 mm) x H' (3 mm), was filled and polymerized at 55°C and 2 bar pressure for 30 minutes. Test piece A1 was then peeled off and removed from the polymer for base denture production. The surface of the polymer for base denture production that had been in contact with test piece A1 was then visually observed and evaluated based on the following criteria. The results are shown in Tables 2 to 5. A: The surface was smooth and not rough. B: The surface was rough and had uneven appearance.

[0138]

[0139]

[0140]

[0141]

[0142]

[0143] In Tables 2 to 5, the numbers in the "Composition" column for each Example and Comparative Example mean parts by mass, and blank spaces mean that the corresponding component is not contained. Compound (C) etc. in Table 5 means compound (C) or other compounds.

[0144] <Mono(meth)acrylic monomer (A-2)> In Tables 1 to 5, the structures of the compounds classified as mono(meth)acrylic monomer (A-2) are as follows:

[0145]

[0146] PO-A: Phenoxyethyl acrylate (Kyoeisha Chemical Co., Ltd.) PO: Phenoxyethyl methacrylate (Kyoeisha Chemical Co., Ltd.) P2H-A: Phenoxydiethylene glycol acrylate (Kyoeisha Chemical Co., Ltd.) M-600A: 2-hydroxy-3-phenoxypropyl acrylate (Kyoeisha Chemical Co., Ltd.) POB-A: m-phenoxybenzyl acrylate (Kyoeisha Chemical Co., Ltd.) A-LEN-10: Ethoxylated o-phenylphenol acrylate (Shin-Nakamura Chemical Co., Ltd.)

[0147] <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.

[0148]

[0149] SUA-001: Compound produced by the method described in Production Example 1A below. AH-600: Bifunctional urethane acrylate (Kyoeisha Chemical Co., Ltd.). SUA-002: Compound produced by the method described in Production Example 2A below. SU-003: Compound produced by the method described in Production Example 3A below. SU-004: Compound produced by the method described in Production Example 4A below.

[0150] [Production Example 1A: Production of SUA-1] Into a 1-liter four-neck flask equipped with a thoroughly dried stirring blade and a thermometer, 372 g (3.20 mol) of HEA (2-hydroxyethyl acrylate), 0.71 g (0.1% by mass relative to the total mass of HEA and TMHDI) of DBTDL (dibutyltin dilaurate), and 0.35 g (0.05% by mass relative to the total mass of HEA and TMHDI) of MEHQ (4-methoxyphenol) were added, stirred until homogeneous, and then heated to 60°C. Subsequently, 337 g (1.60 mol) of TMHDI (trimethylhexamethylene diisocyanate) was added dropwise over 1 hour. During the dropwise addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled so that the temperature remained below 80°C. After the entire amount was added dropwise, the reaction temperature was maintained at 80°C, and the reaction was carried out for 10 hours. The reaction progress was monitored by HPLC analysis to confirm the end point of the reaction. The product was discharged from the reactor to obtain 680 g of a bifunctional urethane acrylate (SUA-1). The viscosity at 25°C was 7100 mPa s.

[0151] [Production Example 2A: Production of SUA-2] Into a 1-liter four-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 the reaction was carried out at 80°C for 12 hours. The progress of the reaction was monitored by HPLC analysis, and the end point of the reaction was confirmed. The product was discharged from the reactor, yielding 451 g of a bifunctional urethane acrylate (SUA-2). The viscosity at 25°C was 12,000 mPa·s.

[0152] [Production Example 3A: Production of SUA-3] Into a 1-liter four-neck flask equipped with a thoroughly dried stirring blade and a thermometer, 222 g (1.00 mol) of IPDI (isophorone diisocyanate), 0.84 g (0.1% by mass relative to the total mass of IPDI, PTMG1000, and HEA) of DBTDL (dibutyltin dilaurate), and 0.42 g (0.05% by mass relative to the total mass of IPDI, PEG-1000, and HEA) of MEHQ (4-methoxyphenol) were added, stirred until homogeneous, and then heated to 60°C. Subsequently, 500 g (0.50 mol) of PTMG1000 (molecular weight 1000, manufactured by Mitsubishi Chemical Corporation) was added dropwise over 1 hour. Since the internal temperature rose due to the heat of reaction during the addition, the amount added was controlled so that the temperature remained below 80°C. After the entire amount was added dropwise, the reaction temperature was maintained at 80°C and the reaction was carried out for 5 hours. Subsequently, the internal temperature of the flask was maintained at 60°C, and 116 g (1.00 mol) of HEA (2-hydroxyethyl acrylate) added to a separate dropping funnel was added dropwise over 1 hour. Since the internal temperature rose due to the heat of reaction during the addition, the amount added was controlled so that the temperature remained below 80°C. After the entire amount was added dropwise, the reaction temperature was maintained at 80°C and the reaction was carried out for 5 hours. During this time, the progress of the reaction was tracked by HPLC analysis to confirm the end point of the reaction. By discharging the product from the reactor, 840 g of a multifunctional urethane acrylate (SUA-3) was obtained. The viscosity at 25°C was 63,000 mPa·s.

[0153] [Production Example 4A: Production of SUA-4] Into a 1-liter four-neck flask equipped with a thoroughly dried stirring blade and a thermometer, 222 g (1.00 mol) of IPDI (isophorone diisocyanate), 2.34 g (0.1% by mass relative to the total mass of IPDI, polypropylene glycol 4000, and HEA) of DBTDL (dibutyltin dilaurate), and 1.17 g (0.05% by mass relative to the total mass of IPDI, polypropylene glycol 4000, and HEA) of MEHQ (4-methoxyphenol) were added, stirred until homogeneous, and then heated to 60°C. Subsequently, 2000 g (0.50 mol) of polypropylene glycol 4000 (molecular weight 4000, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour. Since the internal temperature rose due to the heat of reaction during the addition, the amount added was controlled so that the temperature remained below 80°C. After the entire amount was added dropwise, the reaction temperature was maintained at 80°C and the reaction was carried out for 5 hours. Subsequently, the internal temperature of the flask was maintained at 60°C, and 116 g (1.00 mol) of HEA (2-hydroxyethyl acrylate) added to a separate dropping funnel was added dropwise over 1 hour. Since the internal temperature rose due to the heat of reaction during the addition, the amount added was controlled so that the temperature remained below 80°C. After the entire amount was added dropwise, the reaction temperature was maintained at 80°C and the reaction was carried out for 5 hours. During this time, 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 2,410 g of a multifunctional urethane acrylate (SUA-4). The viscosity at 25°C was 43,000 mPa·s.

[0154] <(Meth)acrylic Monomer (B)> In Tables 1 to 5, the structures of the compounds classified as (meth)acrylic monomer (B) are as follows:

[0155]

[0156] SiA-001: Compound produced by the method described in Production Example 1B below. SiA-002: Compound produced by the method described in Production Example 2B below. SiA-003: Compound produced by the method described in Production Example 3B below.

[0157] [Production Example 1B: Production of SiA-001] 324 g (1.00 mol) of 3,3'-(1,1,3,3,5,5-Hexamethyl-1,5-trisiloxanediyl)bis[1-propanol], 0.30 g of BHT, and 500 g of ethyl acetate were added to a 1-liter four-neck flask equipped with a thoroughly dried stirring blade and a thermometer, and the mixture was stirred until homogeneous, after which the temperature was raised to 70°C. Subsequently, 181 g (2.00 mol) of acryloyl chloride was added dropwise over 1 hour. During the dropwise addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled so that the temperature remained below 70°C. After the entire amount was added dropwise, the reaction temperature was maintained at 70°C, and the reaction was carried out for 5 hours. Thereafter, the reaction solution was neutralized with a 10% aqueous NaOH solution and then washed with 150 g of a 5% aqueous ammonium sulfate solution. Ethyl acetate was distilled under reduced pressure to obtain 440 g of a polyfunctional (meth)acrylic monomer (SiA-001), which had a viscosity of 110 mPa·s at 25°C.

[0158] [Production Example 2B: Production of SiA-002] 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 to a 1-liter four-neck flask equipped with a thoroughly dried stirring blade and a thermometer, and the mixture was stirred until homogeneous, after which the temperature was raised to 60°C. Subsequently, 593 g (2.00 mol) of octamethylcyclotetrasiloxane was added dropwise over 1 hour. After the entire amount was added dropwise, the reaction temperature was maintained at 60°C and the reaction was carried out for 6 hours. Thereafter, 740 g (2.00 mol) of octaethylene glycol was added to the reaction vessel, and the reaction was carried out for an additional 1 hour. Subsequently, 181 g (2.00 mol) of acryloyl chloride was added dropwise over 1 hour. During the dropwise addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled so that the temperature remained below 60°C. After the entire amount was added dropwise, the reaction temperature was maintained at 60°C and the reaction was carried out for 5 hours. Thereafter, the reaction solution was neutralized with a 10% aqueous solution of NaOH and then washed with 150 g of a 5% aqueous solution of ammonium sulfate. 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.

[0159] [Production Example 3B: Production of SiA-003] 667 g (3.00 mol) of hexamethylcyclotrisiloxane, 100 mL of toluene, 200 mL of tetrahydrofuran, and 100 mL of hexane were added to a 1-liter four-neck flask equipped with a thoroughly dried stirring blade and a thermometer, and the mixture was stirred until homogeneous. Subsequently, 2 mL of butyllithium (approximately 15% hexane solution) was added dropwise over 1 hour under ice cooling. After the entire amount was added, the reaction temperature was maintained at room temperature and the reaction was carried out for 2 hours. Subsequently, 207 g (1.00 mol) of 3-(chlorodimethylsilyl)propyl acrylate added to a separate dropping funnel was added dropwise over 1 hour. After the entire amount was added dropwise, the reaction temperature was maintained at 30°C and the reaction was carried out for 24 hours. The progress of the reaction was monitored by HPLC analysis, and the end point of the reaction was confirmed. The reaction solution was then neutralized with 10% aqueous NaOH solution and washed with 150 g of 5% aqueous ammonium sulfate solution. The solvent was distilled off under reduced pressure to obtain 812 g of a polyfunctional (meth)acrylic monomer (SiA-003), which had a viscosity of 280 mPa·s at 25°C.

[0160] <Compound (C)> In Tables 1 to 5, the compounds classified as compound (C) have the following structures.

[0161]

[0162]

[0163]

[0164] (C-1): Lauryl alcohol (Fujifilm Wako Pure Chemical Industries, Ltd.) (C-2): Myristic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) (C-3): Ethyl laurate (Fujifilm Wako Pure Chemical Industries, Ltd.) (C-4): Isopropyl myristate (Fujifilm Wako Pure Chemical Industries, Ltd.) (C-5): Isopropyl palmitate (Fujifilm Wako Pure Chemical Industries, Ltd.) (C-6): Glycerol monostearate (Fujifilm Wako Pure Chemical Industries, Ltd.) (C-7): Glyceryl trioleate (Sigma-Aldrich) (C-8): Diisostearyl malate (Kyoto Alcohol Kogyo Co., Ltd.) (C-9): Polypropylene glycol (Sigma-Aldrich) (C-10): Triethyl citrate (Fujifilm Wako Pure Chemical Industries, Ltd.) (C-11): Trimethylolpropane (Tokyo Chemical Industry Co., Ltd.) (C-12): 1-Hexanol (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0165] <Other Compounds> In Tables 1 to 5, the structures of the compounds classified as other compounds are as follows:

[0166] (1): Octafluorodecane (Sigma-Aldrich) (2): Sorbitol (Tokyo Chemical Industry Co., Ltd.)

[0167] <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 B.V.)

[0168]

[0169] As shown in Tables 2 to 5, three-dimensionally molded objects with reduced surface roughness could be produced by using the photocurable compositions of Examples 1 to 17. On the other hand, the three-dimensionally molded objects obtained using the photocurable compositions of Comparative Examples 1 to 5 had inferior surface roughness compared to Examples 1 to 20. Furthermore, Examples 1 to 17 were also evaluated as having good releasability, toughness, and appearance.

[0170] The disclosure of Japanese Patent Application No. 2023-111074, filed on July 5, 2023, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. 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 a solubility parameter (SP value) of 7.00 to 15.00 (cal / cm ３ ) １／２ and a photopolymerization initiator.

2. 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 ３ ) １／２ 2. The photocurable composition of claim 1, wherein:

3. The photocurable composition according to claim 1, wherein the cohesive energy density (cal / mol) of the compound (C) is 10,000 or more.

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

5. The photocurable composition according to claim 4, wherein the di(meth)acrylic monomer (A-1) has a molecular weight of 400 to 8,000.

6. The photocurable composition according to claim 4, wherein the molecular weight of the mono(meth)acrylic monomer (A-2) is 160 to 400.

7. The photocurable composition according to claim 1, wherein the molecular weight of the (meth)acrylic monomer (B) is 400 to 5,000.

8. The photocurable composition according to claim 4, 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 (meth)acrylic monomer component and the compound (C) in the photocurable composition.

9. The photocurable composition according to claim 4, wherein 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 (meth)acrylic monomer component and the compound (C) in the photocurable composition.

10. The photocurable composition according to claim 1, 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 (meth)acrylic monomer component and the compound (C) in the photocurable composition.

11. The photocurable composition according to claim 1, wherein the content of compound (C) in the photocurable composition is 1 mass % to 30 mass % based on the total content of the (meth)acrylic monomer component and compound (C) contained in the photocurable composition.

12. The photocurable composition according to claim 1, wherein the concentration of siloxane bonds in the photocurable composition is 0.100 mmol / g to 3.000 mmol / g.

13. The photocurable composition according to claim 1, wherein the (meth)acrylic monomer component contained in the photocurable composition has an aromatic ring concentration of 0.0015 mol / g to 0.0070 mol / g.

14. The photocurable composition according to claim 1, which is a photocurable composition for stereolithography.

15. The photocurable composition according to claim 1, which is used for producing a mold by stereolithography.

16. A three-dimensional object comprising a cured product of the photocurable composition according to any one of claims 1 to 15.

17. A mold comprising the three-dimensional object according to claim 16.

18. The mold of claim 17 for use in producing a dental prosthesis.

19. A method for producing a cured product, comprising the step of polymerizing a curable composition in the mold of claim 17.

20. A method for producing a dental prosthesis, comprising: a step of hardening the photocurable composition according to any one of claims 1 to 15 by photolithography to prepare a mold to be used in producing the dental prosthesis; and a step of polymerizing the hardenable composition in the mold to produce the dental prosthesis.

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