Photocurable composition, method for producing three-dimensional object, mold, and cured product, and method for producing plate denture

Abstract

This photosetting composition comprises a (meth)acrylic monomer component and a photoinitiator. When a cured layer A1 having a thickness of 50 µm is obtained by irradiating the photosetting composition with visible light having a wavelength of 405 nm at an irradiation quantity of 11 mJ / cm2, a rectangular plate-like shaped article A1 having a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm is obtained by layering the cured layer A1 in the thickness direction, and a rectangular plate-like test piece A1 having a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm is prepared through optical shaping by irradiating the shaped article A1 with ultraviolet rays having a wavelength of 365 nm at an irradiation quantity of 3 J / cm2, the storage modulus of the test piece A1 at 25°C is 10 MPa or more and the storage modulus of the test piece A1 at 37°C is 400 MPa or less.

Description

[Technical Field]

[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 plate denture. [Background technology]

[0002] In recent years, dental products such as dental prostheses, instruments used in the oral cavity, etc. have been studied. For example, from the viewpoint of the efficiency of manufacturing these dental products, a method of manufacturing three-dimensional objects such as dental products by stereolithography using a 3D printer is known (see, for example, Patent Document 1). [Patent Document 1] Patent No. 4160311 Summary of the Invention [Problem to be solved by the invention]

[0003] On the other hand, there have been methods for producing dental prostheses, dentures, etc. without using stereolithography such as 3D printers. According to this method, for example, when producing a removable denture, first, a mold of the patient's oral cavity is taken directly from the patient using an impression material, and a model that mimics the patient's oral cavity is created using the impression material. A mold is then made from the model using silicone. The mold is used as a mold, and a curable composition is poured into it, allowing it to polymerize at room temperature to produce a removable denture. As mentioned above, conventional methods that do not use stereolithography have the problem of requiring complicated processes such as creating a model of the patient's oral cavity and making a mold using silicone.

[0004] In contrast, the direct production of removable dentures using stereolithography with 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 characteristics of the resulting removable dentures. For example, conventional methods use room-temperature polymerization using a mold, which allows the use of many materials that can improve aesthetics and physical properties. However, materials used in such room-temperature polymerization are often not compatible with stereolithography using a 3D printer. As a result, stereolithography using a 3D printer makes it difficult to adjust the resulting removable dentures to achieve the desired properties.

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

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

[0007] On the other hand, when a mold for a denture is prepared using a photocurable composition and a denture is manufactured using the mold, depending on the type of polymerizable composition used to manufacture the denture, the mold itself may shrink and deform when the polymerizable composition poured into the mold during the manufacture of the denture is polymerized, which may result in deformation of the resulting denture.

[0008] When removing a denture obtained by polymerizing a polymerizable composition in a mold from the mold, the denture may become stuck in the mold due to the fact that the denture contains artificial teeth, making it physically difficult to remove.

[0009] An object of one aspect of the present disclosure is to provide a photocurable composition that can be used to create a mold that is suppressed from deforming during the production of a denture, or a mold that makes it easy to remove a denture from within when producing a denture using the mold, as well as a method for producing a three-dimensional object, mold, and cured product using this photocurable composition. Another object of the present disclosure is to provide a method for manufacturing a denture that allows for the production of a denture in a simple manner. [Means for solving the problem]

[0010] The means for solving the above problems include the following aspects. <1> A photocurable composition comprising a (meth)acrylic monomer component and 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 were 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 was then 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 stereolithography under the condition of irradiation with The storage modulus of the test piece A1 at 25°C is 10 MPa or more, The photocurable composition has a storage modulus at 37°C of 400 MPa or less in the test piece A1. <2> The (meth)acrylic monomer component is a mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring; a di(meth)acrylic monomer (Y) having at least one of a ring structure or a urethane bond and two (meth)acryloyloxy groups, and not having a siloxane bond; and a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond and two or more (meth)acryloyloxy groups. <1> The photocurable composition according to claim 1. <3> A photocurable composition comprising a (meth)acrylic monomer component and a photopolymerization initiator, The (meth)acrylic monomer component is a mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring; a di(meth)acrylic monomer (Y) having at least one of a ring structure or a urethane bond and two (meth)acryloyloxy groups, and not having a siloxane bond; A photocurable composition comprising: a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond and two or more (meth)acryloyloxy groups. <4> The molecular weight of the di(meth)acrylic monomer (Y) is 400 to 5000. <2> or <3> The photocurable composition according to claim 1. <5> The molecular weight of the polyfunctional (meth)acrylic monomer (Z) is 400 to 5000. <2> ~ <4> 1. The photocurable composition according to claim 1 . <6> the content of the mono(meth)acrylic monomer (X) is 30% by mass to 90% by mass based on the total amount of the (meth)acrylic monomer components; <2> ~ <5> 1. The photocurable composition according to claim 1 . <7> the content of the di(meth)acrylic monomer (Y) is 5% by mass to 55% by mass based on the total amount of the (meth)acrylic monomer components; <2> ~ <6> 1. The photocurable composition according to claim 1 . <8> the content of the polyfunctional (meth)acrylic monomer (Z) is 1% by mass to 60% by mass based on the total amount of the (meth)acrylic monomer components; <2> ~ <7> 1. The photocurable composition according to claim 1 . <9> The siloxane bond concentration in the composition is 0.100 mmol / g to 3,000 mmol / g. <2> ~ <8> 1. The photocurable composition according to claim 1 . <10> the aromatic ring concentration in the (meth)acrylic monomer component is 0.0015 mol / g to 0.0070 mol / g; <1> ~ <9> 1. The photocurable composition according to claim 1 . <11> the aromatic ring concentration in the (meth)acrylic monomer component is 0.0015 mol / g to 0.0042 mol / g; <1> ~ <9> The photocurable composition according to claim 1. <12> the (meth)acrylic monomer component includes a di(meth)acrylic monomer (A) having two (meth)acryloyloxy groups and an aromatic ring, wherein the distance between an oxygen atom forming an oxy group in one of the (meth)acryloyloxy groups and an oxygen atom forming an oxy group in the other (meth)acryloyloxy group is 25 Å or more and 80 Å or less; <1> 11> The photocurable composition according to any one of the above items. <13> Meet either of the following conditions (a) and (b): <1> ~ <12> 1. The photocurable composition according to claim 1 . (a) The (meth)acrylic monomer component contains two or more types of di(meth)acrylic monomers (A) each having two (meth)acryloyloxy groups and an aromatic ring, wherein the distance between the oxygen atom forming the oxy group in one (meth)acryloyloxy group and the oxygen atom forming the oxy group in the other (meth)acryloyloxy group is 25 Å or more and 80 Å or less. (b) the (meth)acrylic monomer component is a di(meth)acrylic monomer (A) having two (meth)acryloyloxy groups and an aromatic ring, wherein the distance between an oxygen atom forming an oxy group in one of the (meth)acryloyloxy groups and an oxygen atom forming an oxy group in the other (meth)acryloyloxy group is 25 Å or more and 80 Å or less; a di(meth)acrylic monomer (B-1) having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, wherein the distance between an oxygen atom forming an oxy group in one of the (meth)acryloyloxy groups and an oxygen atom forming an oxy group in the other (meth)acryloyloxy group is 10 Å or more and less than 25 Å; It has two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, and an oxygen atom forming an oxy group in one of the (meth)acryloyloxy groups and an oxygen atom forming an oxy group in the other (meth)acryloyloxy group. a di(meth)acrylic monomer (B-2) in which the distance between the oxygen atom forming the oxy group in one (meth)acryloyloxy group and the oxygen atom forming the oxy group in the other (meth)acryloyloxy group is more than 80 Å and less than 200 Å; and and one or more (meth)acrylic monomers (B) selected from the group consisting of mono(meth)acrylic monomers (B-3) having one (meth)acryloyloxy group and at least one of an aromatic ring and a hydroxy group. <14> (b) above is satisfied, and When the (meth)acrylic monomer (B) contains the di(meth)acrylic monomer (B-1), the molecular weight of the di(meth)acrylic monomer (B-1) is 400 or more and 800 or less; When the (meth)acrylic monomer (B) contains the di(meth)acrylic monomer (B-2), the molecular weight of the di(meth)acrylic monomer (B-2) is 900 or more and 3000 or less; When the (meth)acrylic monomer (B) contains the mono(meth)acrylic monomer (B-3), the molecular weight of the mono(meth)acrylic monomer (B-3) is 130 or more and 350 or less. <13> The photocurable composition according to claim 1. <15> (b) above is satisfied, and The content of the (meth)acrylic monomer (B) is 3% by mass to 80% by mass based on the total amount of the (meth)acrylic monomer components. <13> or <14> The photocurable composition according to claim 1. <16> The molecular weight of the di(meth)acrylic monomer (A) is 650 or more and 1300 or less. <12> ~ <15> 1. The photocurable composition according to claim 1 . <17> The content of the di(meth)acrylic monomer (A) is 30% by mass or more based on the total amount of the (meth)acrylic monomer components. <12> ~ <16> 1. The photocurable composition according to claim 1 . <18> The viscosity measured using an E-type viscometer at 25°C and 50 rpm is 5 mPa·s to 6000 mPa·s. <1> ~ <17> 1. The photocurable composition according to claim 1 . <19> A photocurable composition for stereolithography, <1> ~ <18> 1. The photocurable composition according to claim 1 . <20> A photocurable composition used in the manufacture of a mold by stereolithography, <1> ~ <19> 1. The photocurable composition according to claim 1 . <21> <1> ~ <20> 10. A three-dimensionally shaped object comprising a cured product of the photocurable composition according to any one of the above items. <22> <21> A mold comprising the three-dimensional object described in 1. <23> Used in the manufacture of removable dentures, <22> The template described in <24> <22> or <23> A method for producing a cured product, comprising the step of polymerizing a curable composition in the mold described in claim 1. <25> A step of hardening the photocurable composition by stereolithography to prepare a mold to be used in manufacturing a denture; A method for manufacturing a plate denture, comprising the step of polymerizing the hardenable composition in the mold to manufacture a plate denture. [Effects of the Invention]

[0011] According to one aspect of the present disclosure, there is provided a photocurable composition that can be used to create a mold that is suppressed from deforming during the production of a denture, or a mold that allows a denture to be easily removed from the mold when a denture is produced using the mold, as well as a method for producing a three-dimensional object, mold, or cured product using this photocurable composition, and a method for producing a denture. According to another aspect of the present disclosure, there is provided a method for manufacturing a denture that allows a denture to be produced in a simple manner. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 2 is a schematic diagram of a three-dimensional object A2 formed in an example. [Figure 2] FIG. 10 is a schematic diagram of a three-dimensional object A3 formed in an example. [Figure 3] FIG. 10 is a schematic diagram of a three-dimensional object A4 formed in an example. DETAILED DESCRIPTION OF THE INVENTION

[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 stages in this disclosure, 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. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value of that 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] Hereinafter, the photocurable composition of the present disclosure will be described with reference to a first embodiment and a second embodiment. The preferred embodiments of the first embodiment and the preferred embodiments of the second embodiment may be combined as appropriate. The preferred uses and physical properties of the photocurable composition of the second embodiment are the same as those of the photocurable composition of the first embodiment, unless otherwise specified.

[0016] [First embodiment] [Photocurable composition] The photocurable composition according to the first embodiment of the present disclosure is a photocurable composition including a (meth)acrylic monomer component and a photopolymerization initiator, The photocurable composition was irradiated with visible light having a wavelength of 405 nm at a dose of 11 mJ / cm 2The cured layers A1 were 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 was then 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 stereolithography under the condition of irradiation with The storage modulus of the test piece A1 at 25°C is 10 MPa or more, The storage modulus of the test piece A1 at 37°C is 400 MPa or less.

[0017] The photocurable composition of the present disclosure contains a (meth)acrylic monomer component and a photopolymerization initiator, and test piece A1 prepared under the above conditions has a storage modulus of 10 MPa or more at 25° C. and a storage modulus of 400 MPa or less at 37° C. Use of such a photocurable composition makes it possible to prepare a mold that is suppressed from deforming during the production of a plate denture, or a mold that allows a plate denture to be easily removed from the mold when the plate denture is manufactured using the mold.

[0018] 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 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; 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 produced by stereolithography).

[0019] Stereolithography is a method of 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 optical shaping may be inkjet type optical shaping, or liquid tank type optical shaping (i.e. (i.e., photolithography using a liquid tank)

[0020] 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-based stereolithography, 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. These operations are repeated to sequentially stack the cured layers to obtain a cured product (i.e., a stereolithography product).

[0021] In liquid tank type stereolithography, a portion 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 it uses a liquid tank. Examples of liquid tank type stereolithography include DLP (Digital Light Processing) type stereolithography and SLA (Stereolithography) type stereolithography. In the DLP method, a photocurable composition in a liquid tank is irradiated with planar light. In the SLA method, a laser beam is scanned over a photocurable composition in a 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 the liquid tank type stereolithography.

[0022] In an example of DLP type stereolithography, for example, a build table that is movable in the vertical direction; a tray (i.e., a liquid tank) disposed below the build table (on the gravity direction side; 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 the light-transmitting portion of the tray; A 3D printer equipped with the above (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 this gap is filled with a 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 irradiated area 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 for curing the first layer, to form a second cured layer. By repeating the above operations, cured layers are stacked to produce a three-dimensional object. In this example, the produced three-dimensional object may be further cured by irradiating it with light. For information on DLP type stereolithography, reference may be made to the descriptions in Japanese Patent Nos. 5111880 and 5235056, for example.

[0023] <Application> The use 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, etc. by stereolithography, and more preferably a photocurable composition used in the production of molds by stereolithography.

[0024] 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.

[0025] Dental products include dental prostheses, medical instruments used in the oral cavity, dental models, and lost casts. Examples include construction models, etc. Dental prostheses include inlays, crowns, bridges, temporary crowns, temporary bridges, and the like. 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 occlusal splints and splints for treating temporomandibular joint disorders, impression trays, and surgical guides. Examples of dental models include tooth and jaw models.

[0026] In the photocurable composition of the present disclosure, the storage modulus of test piece A1 at 25°C is 10 MPa or more, and from the viewpoint of suppressing deformation of the mold (for example, from the viewpoint of suppressing deformation of the mold when a photocurable composition for producing a denture base or the like is injected into a mold prepared using the photocurable composition of the present disclosure and polymerized), the storage modulus is preferably 15 MPa or more, more preferably 30 MPa or more, and even more preferably 50 MPa or more. The upper limit of the storage modulus of test piece A1 at 25°C is not particularly limited, and may be, for example, 2000 MPa or less, 1000 MPa or less, or 500 MPa or less, from the viewpoint of ease of removal from the mold (for example, from the viewpoint of preventing damage to the mold, denture, etc. when removing the denture from the mold).

[0027] In the photocurable composition of the present disclosure, the storage modulus of test piece A1 at 37°C is 400 MPa or less, and from the viewpoint of ease of removal from a mold, it is preferably 300 MPa or less, more preferably 250 MPa or less, and even more preferably 200 MPa or less. The lower limit of the storage modulus of test piece A1 at 37°C is not particularly limited, and may be, for example, 10 MPa or more, 30 MPa or more, or 50 MPa or more, from the viewpoint of suppressing deformation of the mold during use.

[0028] 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 0.0042 mol / g, more preferably 0.0016 mol / g to 0.0041 mol / g, and even more preferably 0.0017 mol / g to 0.0040 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 be more excellent in terms of removability from a mold and for deformation of the mold during use to be suitably suppressed.

[0029] The photocurable composition of the present disclosure preferably satisfies any one of the following conditions (1) to (3), from the viewpoints of achieving superior removability from a mold and suitably suppressing deformation of the mold during use. (1) The aromatic ring concentration in the (meth)acrylic monomer component is 0.0030 mol / g to 0.0042 mol / g. (2) The aromatic ring concentration in the (meth)acrylic monomer component is 0.0015 mol / g to 0.0035 mol / g, and the urethane bond concentration in the (meth)acrylic monomer component is 0.0001 mol / g to 0.0020 mol / g. (3) The aromatic ring concentration in the (meth)acrylic monomer component is 0.0015 mol / g to 0.0035 mol / g, and the hydroxyl group concentration in the (meth)acrylic monomer component is 0.0005 mol / g to 0.0030 mol / g.

[0030] The urethane bond concentration in the (meth)acrylic monomer component may be 0.0001 mol / g to 0.0020 mol / g, as in the above-mentioned (2), or 0.0002 mol / g to 0.0018 mol / g, or 0.0004 mol / g to 0.0016 mol / g.

[0031] The hydroxyl group concentration in the (meth)acrylic monomer component may be 0.0005 mol / g to 0.0030 mol / g as in the above-mentioned (3), or may be 0.0006 mol / g to 0.0025 mol / g, or may be 0.0008 mol / g to 0.0022 mol / g.

[0032] <(Meth)acrylic monomer component> The photocurable composition of the present disclosure contains at least one (meth)acrylic monomer component.

[0033] 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 80% by mass or more, and even more preferably 90% by mass or more. The upper limit of the content of the (meth)acrylic monomer component relative to the total amount of the photocurable composition of the present disclosure is not particularly limited, and may be less than 100% by mass, for example, 99.9% by mass or less.

[0034] Here, the (meth)acrylic monomer component means a monomer having one or more (meth)acryloyloxy groups in the molecule.

[0035] 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% 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.

[0036] The (meth)acrylic monomer constituting the (meth)acrylic monomer component is not particularly limited as long as it is a monomer having one or more (meth)acryloyloxy groups in the molecule. The (meth)acrylic monomer may be a monofunctional (meth)acrylic monomer (i.e., a monomer having one (meth)acryloyloxy group in the molecule), a difunctional (meth)acrylic monomer (i.e., a monomer having two (meth)acryloyloxy groups in the molecule), or a polyfunctional (meth)acrylic monomer (i.e., a tri- or higher functional (meth)acrylic monomer; i.e., a monomer having three or more (meth)acryloyloxy groups in the molecule).

[0037] From the viewpoint of decreasing the storage modulus at 25°C and the storage modulus at 37°C of the test piece A1, the (meth)acrylic monomer component preferably contains a di(meth)acrylic monomer (A) having two (meth)acryloyloxy groups and an aromatic ring, in which the distance between the oxygen atom forming the oxy group in one of the (meth)acryloyloxy groups and the oxygen atom forming the oxy group in the other (meth)acryloyloxy group (hereinafter also referred to as distance d1) is 25 Å or more and 80 Å or less. The (meth)acrylic monomer component may contain one kind of di(meth)acrylic monomer (A) alone or two or more kinds thereof.

[0038] In the present disclosure, d1 (i.e., the distance between an oxygen atom forming an oxy group in one (meth)acryloyloxy group and an oxygen atom forming an oxy group in the other (meth)acryloyloxy group) means the linear distance between these two oxygen atoms. d1 refers to the value obtained using the "display distance measurement" function in PerkinElmer's "Chem 3D" (version 18.2.0.48).

[0039] The d1 of the di(meth)acrylic monomer (A) is 25 Å or more and 80 Å or less, and may be, for example, 30 Å or more and 60 Å or less, or 30 Å or more and 50 Å or less.

[0040] The di(meth)acrylic monomer (A) preferably contains a cyclic structure. Examples of the cyclic structure include an aromatic structure and an alicyclic structure. Among these, the di(meth)acrylic monomer (A) preferably contains an aromatic structure, and more preferably contains a bisphenol structure such as bisphenol A or bisphenol F.

[0041] The di(meth)acrylic monomer (A) may have at least one of an ethyleneoxy group and a propyleneoxy group.

[0042] The molecular weight of the di(meth)acrylic monomer (A) is preferably 650 or more and 1,300 or less, more preferably 700 or more and 1,200 or less, and even more preferably 750 or more and 1,000 or less.

[0043] The weight average molecular weight of the di(meth)acrylic monomer (A) is preferably 650 or more and 1,300 or less, more preferably 700 or more and 1,200 or less, and even more preferably 750 or more and 1,000 or less. In this disclosure, the weight average molecular weight is measured by gel permeation chromatography (GPC).

[0044] Examples of the di(meth)acrylic monomer (A) include ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol F di(meth)acrylate, and propoxylated bisphenol F di(meth)acrylate.

[0045] The content of the di(meth)acrylic monomer (A) is preferably 30% by mass or more, more preferably 40% by mass to 100% by mass, and even more preferably 50% by mass to 100% by mass, based on the total amount of the (meth)acrylic monomer components.

[0046] From the viewpoint of facilitating the formation of a mold that is easy to ensure removability and easy to suppress deformation, the (meth)acrylic monomer component preferably satisfies either of the following conditions (a) and (b): (a) The (meth)acrylic monomer component contains two or more types of the above-mentioned di(meth)acrylic monomer (A). (b) the (meth)acrylic monomer component is The di(meth)acrylic monomer (A) and a di(meth)acrylic monomer (B-1) having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, wherein the distance d1 is 10 Å or more and less than 25 Å; A di(meth)acrylic monomer (B-2) having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, wherein the distance d1 is more than 80 Å and less than 200 Å; and and one or more (meth)acrylic monomers (B) selected from the group consisting of mono(meth)acrylic monomers (B-3) having one (meth)acryloyloxy group and at least one of an aromatic ring and a hydroxy group.

[0047] When the (meth)acrylic monomer component satisfies the above-mentioned (a), the (meth)acrylic monomer component is sufficient as long as it contains two or more types of di(meth)acrylic monomer (A), and may or may not contain other (meth)acrylic monomer components. The (meth)acrylic monomer component containing two or more types of di(meth)acrylic monomer (A) not only reduces the storage modulus of test piece A1 at 25°C and at 37°C, but also makes it easier to control the reactivity than when using one type of di(meth)acrylic monomer (A), resulting in excellent operability during stereolithography.

[0048] When the (meth)acrylic monomer component satisfies the above-mentioned (a), the total content of the di(meth)acrylic monomer (A) 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, based on the total amount of the (meth)acrylic monomer component.

[0049] When the (meth)acrylic monomer component satisfies the above-mentioned (b), the (meth)acrylic monomer component contains the above-mentioned di(meth)acrylic monomer (A) and (meth)acrylic monomer (B). In this case, the (meth)acrylic monomer component may independently contain one kind of di(meth)acrylic monomer (A) and one kind of (meth)acrylic monomer, or may contain two or more kinds of di(meth)acrylic monomer (A) and one kind of (meth)acrylic monomer. The di(meth)acrylic monomer (B-1), di(meth)acrylic monomer (B-2) and mono(meth)acrylic monomer (B-3) classified as the (meth)acrylic monomer (B) will be described in detail below.

[0050] <Di(meth)acrylic monomer (B-1)> The di(meth)acrylic monomer (B-1) is a (meth)acrylic monomer component having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, and having a distance d1 of 10 Å or more and less than 25 Å. Use of the di(meth)acrylic monomer (B-1) tends to increase the storage modulus at 25°C and the storage modulus at 37°C of the test piece A1.

[0051] The d1 of the di(meth)acrylic monomer (B-1) may be 12 Å or more and 24 Å or less, or may be 14 Å or more and 22 Å or less.

[0052] The molecular weight of the di(meth)acrylic monomer (B-1) is preferably 400 or more and 800 or less, more preferably 400 or more and 700 or less, and even more preferably 400 or more and 650 or less.

[0053] The weight average molecular weight of the di(meth)acrylic monomer (B-1) is preferably 400 or more and 800 or less, more preferably 400 or more and 700 or less, and even more preferably 400 or more and 650 or less.

[0054] The di(meth)acrylic monomer (B-1) has at least one of an aromatic ring and a urethane bond. The di(meth)acrylic monomer (B-1) may contain only one of an aromatic ring and a urethane bond, or may contain both an aromatic ring and a urethane bond.

[0055] When the di(meth)acrylic monomer (B-1) contains an aromatic ring but does not contain a urethane bond, the di(meth)acrylic monomer (B-1) may have at least one of an ethyleneoxy group and a propyleneoxy group, or the di(meth)acrylic monomer (B-1) may have a bisphenol structure and at least one of an ethyleneoxy group and a propyleneoxy group.

[0056] When the di(meth)acrylic monomer (B-1) contains an aromatic ring but does not contain a urethane bond, specific examples of the di(meth)acrylic monomer (B-1) include ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol F di(meth)acrylate, and propoxylated bisphenol F di(meth)acrylate.

[0057] When the di(meth)acrylic monomer (B-1) contains a urethane bond, it is preferably a di(meth)acrylic monomer represented by the following formula (1): The compound may contain a compound that is

[0058] [ka]

[0059] In formula (1), R 1 is a divalent chain hydrocarbon group, R 2 and R 3each independently represents a divalent chain hydrocarbon group which may have a substituent, R 4 and R 5 are each independently a methyl group or a hydrogen atom.

[0060] R in formula (1) 1 In the formula (I), the divalent chain hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 2 to 6 carbon atoms. R 1 The divalent chain hydrocarbon group in may be linear or branched, saturated or unsaturated, and may have a substituent. R 1 The divalent chain hydrocarbon group in the formula (I) is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched alkylene group having 1 to 12 carbon atoms, and even more preferably a linear or branched alkylene group having 1 to 10 carbon atoms.

[0061] Specific examples of the linear or branched alkylene group having 1 to 20 carbon atoms include methylene, ethylene, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl, nonanediyl, decanediyl, undecanediyl, dodecanediyl, tridecanediyl, tetradecanediyl, pentadecanediyl, octadecanediyl, eicosylene, vinylene, propenediyl, butenediyl, pentanediyl, ethynylene, propynylene, and 2,4,4-trimethylhexylene. Of these, hexanediyl and 2,4,4-trimethylhexylene are preferred.

[0062] In formula (1), R 2 and R 3 are each independently a divalent chain hydrocarbon group which may have a substituent. R 2 and R 3 A divalent chain hydrocarbon group suitable as R 1 The divalent chain hydrocarbon groups are the same as those suitable for the alkyl group. However, R 2 and R 3 In the formula (I), the optionally substituted divalent chain hydrocarbon group preferably has 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms.

[0063] R 2 and R 3 When the group is a divalent chain hydrocarbon group having a substituent, examples of the substituent include: alkyl groups having 1 to 6 carbon atoms, such as methyl and ethyl groups; aryl groups; cycloalkyl groups having 3 to 6 carbon atoms, such as a cyclopentyl group and a cyclohexyl group; Tolyl group; Xylyl group; cumyl group; styryl group; alkoxyphenyl groups such as a methoxyphenyl group, an ethoxyphenyl group, and a propoxyphenyl group; Examples include phenoxyalkyl groups such as a phenoxymethyl group, a phenoxyethyl group, and a phenoxypropyl group.

[0064] <Di(meth)acrylic monomer (B-2)> The di(meth)acrylic monomer (B-2) is a (meth)acrylic monomer component having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, and having a distance d1 of more than 80 Å and less than 200 Å. Use of the di(meth)acrylic monomer (B-2) tends to decrease the storage modulus at 25°C and the storage modulus at 37°C of the test piece A1.

[0065] The d1 of the di(meth)acrylic monomer (B-2) may be 85 Å or more and 150 Å or less, or may be 90 Å or more and 120 Å or less.

[0066] The molecular weight of the di(meth)acrylic monomer (B-2) is preferably 900 or more and 3,000 or less, more preferably 1,200 or more and 2,500 or less, and even more preferably 1,500 or more and 2,000 or less.

[0067] The weight average molecular weight of the di(meth)acrylic monomer (B-2) is preferably 900 or more and 3,000 or less, more preferably 1,200 or more and 2,500 or less, and even more preferably 1,500 or more and 2,000 or less.

[0068] The di(meth)acrylic monomer (B-2) has at least one of an aromatic ring and a urethane bond. The di(meth)acrylic monomer (B-1) may contain either an aromatic ring or a urethane bond, or may contain both an aromatic ring and a urethane bond.

[0069] When the di(meth)acrylic monomer (B-2) contains a urethane bond, it may contain a compound represented by the following formula (2).

[0070] [ka]

[0071] In formula (2), R 6 are each independently a divalent chain hydrocarbon group, a divalent hydrocarbon group having an aromatic structure, or a divalent hydrocarbon group having an alicyclic structure, R 7 each independently represents a divalent chain hydrocarbon group which may have a substituent, R 8 is a divalent linking group, R 9 and R 10 are each independently a methyl group or a hydrogen atom.

[0072] In formula (2), R 6 When R is a divalent chain hydrocarbon group, 6 A preferred structure of R in formula (1) is 1 This is similar to the preferred configuration of

[0073] R in equation (2) 6In the formula (I), the divalent hydrocarbon group having an aromatic structure is preferably a divalent hydrocarbon group having an aromatic structure of 6 to 20 carbon atoms (more preferably 6 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms) which may have a substituent. Examples of the divalent hydrocarbon group having an aromatic structure include an arylene group, an alkylenearylene group, an alkylenearylenealkylene group, and an arylenealkylenearylene group. The divalent hydrocarbon group having an aromatic structure is preferably an alkylenearylene group or an alkylenearylenealkylene group.

[0074] Specific examples of the arylene group, alkylenearylene group, alkylenearylenealkylene group, alkylarylene group and arylenealkylenearylene group include a 1,3- or 1,4-phenylene group, a 1,3- or 1,4-phenylenedimethylene group, and a 1,3- or 1,4-phenylenediethylene group.

[0075] R in Equation (2) 6 In the formula (I), the divalent hydrocarbon group having an alicyclic structure preferably has 3 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms.

[0076] Examples of the alicyclic structure include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclohexenylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cycloundecylene group, a cyclododecylene group, a cyclotridecylene group, a cyclotetradecylene group, a cyclopentadecylene group, a cyclooctadecylene group, a cycloicosylene group, a bicyclohexylene group, a norbornylene group, an isobornylene group, an adamantylene group, and a methylenebiscyclohexylene group.

[0077] R in equation (2) 6The divalent hydrocarbon group having an alicyclic structure in the formula (I) may have a substituent, which may be a linear or branched alkyl group having 1 to 6 carbon atoms.

[0078] In formula (2), R 7 A preferred structure of R in formula (1) is 2 and R 3 This is similar to the preferred configuration of In formula (2), R 8 is a divalent linking group. Examples of the divalent linking group include a polyether group, an alkylene group, an arylene group, an alkylenearylene group, and an alkylenearylenealkylene group. Among these, a polyether group is preferred, and a polyether group composed of an ether group having 2 to 4 carbon atoms is more preferred.

[0079] <Mono(meth)acrylic monomer (B-3)> The mono(meth)acrylic monomer (B-3) is a (meth)acrylic monomer component having one (meth)acryloyloxy group and at least one of an aromatic ring and a hydroxy group. Use of the mono(meth)acrylic monomer (B-3) tends to decrease the viscosity of the photocurable composition while increasing the storage modulus at 25°C and 37°C of the test piece A1.

[0080] The molecular weight of the mono(meth)acrylic monomer (B-3) is preferably 130 or more and 350 or less, more preferably 130 or more and 320 or less, and even more preferably 130 or more and 300 or less.

[0081] The weight average molecular weight of the mono(meth)acrylic monomer (B-3) is preferably 130 or more and 350 or less, more preferably 130 or more and 320 or less, and even more preferably 130 or more and 300 or less.

[0082] The mono(meth)acrylic monomer (B-3) may contain a compound represented by the following formula (3).

[0083] [ka]

[0084] In formula (3), R 11 is a monovalent organic group having at least one of an aromatic structure and a hydroxy group.

[0085] R in equation (3) 11 The monovalent organic group having an aromatic structure in the formula (I) is preferably a monovalent organic group having 2 to 30 carbon atoms, and more preferably a monovalent organic group having 3 to 20 carbon atoms.

[0086] In formula (3), R 11 may be an organic group represented by the following formula (4):

[0087] [ka]

[0088] In formula (4), L1 is a single bond or a divalent chain hydrocarbon group having 1 to 30 carbon atoms which may have a heteroatom which is O or N, and A is a hydroxyalkyl group having 2 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms. * indicates the bonding position.

[0089] In formula (4), the divalent chain hydrocarbon group represented by L1 having 1 to 30 carbon atoms and optionally having a heteroatom of O or N may be linear or branched. The divalent chain hydrocarbon group represented by L1 has 1 to 30 carbon atoms and may have a heteroatom of O or N. The number of carbon atoms is more preferably 1 to 20, further preferably 1 to 10, and particularly preferably 1 to 8. When the divalent chain hydrocarbon group represented by L1 contains a heteroatom, the number of heteroatoms in L1 is preferably 1 to 3, and more preferably 1 or 2.

[0090] The divalent chain hydrocarbon group represented by L1 may have a substituent. Suitable examples of the substituent include an alkyl group having 1 to 3 carbon atoms, a hydroxy group, and an alkyl group having 1 to 3 carbon atoms in which one or two hydrogen atoms have been substituted with a hydroxy group. The divalent chain hydrocarbon group represented by L1 may contain a urethane bond. When the divalent chain hydrocarbon group represented by L1 contains a urethane bond, the number of urethane bonds in L1 may be 1 or 2.

[0091] Specific examples of the divalent chain hydrocarbon group represented by L1 in formula (4) include the following groups: In the following groups, * indicates the bonding position. [ka]

[0092] In the formula (4), when A is a hydroxyalkyl group having 2 to 10 carbon atoms, L1 is preferably a single bond. In this case, the mono(meth)acrylic monomer (B-3) is preferably 4-hydroxybutyl(meth)acrylate or 2-hydroxypropyl(meth)acrylate.

[0093] In formula (4), examples of the aromatic structure in the aryl group having 6 to 30 carbon atoms represented by A include a phenyl structure, a biphenyl structure, a naphthyl structure, and an anthryl structure.

[0094] The group represented by A in formula (4) may have a substituent. Suitable examples of the above substituents include: alkyl groups having 1 to 6 carbon atoms, such as methyl and ethyl groups; hydroxy groups; an alkyl group having 1 to 6 carbon atoms substituted with one or two hydroxy groups; aryl groups; cycloalkyl groups having 3 to 6 carbon atoms, such as a cyclopentyl group and a cyclohexyl group; Tolyl group; Xylyl group; cumyl group; styryl group; alkoxyphenyl groups such as a methoxyphenyl group, an ethoxyphenyl group, and a propoxyphenyl group; Examples include phenoxyalkyl groups such as a phenoxymethyl group, a phenoxyethyl group, and a phenoxypropyl group.

[0095] Examples of the group represented by A in formula (4) include the following: * represents the bonding position.

[0096] [ka]

[0097] The content of the (meth)acrylic monomer (B) is preferably 3% by mass to 80% by mass, more preferably 10% by mass to 70% by mass, and even more preferably 20% by mass to 60% by mass, based on the total amount of the (meth)acrylic monomer components.

[0098] The total content of the di(meth)acrylic monomer (A) and the (meth)acrylic monomer (B) 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 (meth)acrylic monomer components contained in the photocurable composition of the present disclosure. The upper limit of the total content of the di(meth)acrylic monomer (A) and the (meth)acrylic monomer (B) is not particularly limited, as long as it is 100% by mass or less.

[0099] In the photocurable composition of the present disclosure, by increasing the content of acrylic groups among the methacrylic groups and acrylic groups in the (meth)acrylic monomer component (for example, by increasing the content of acrylic monomer in the photocurable composition), the storage modulus of test piece A1 at 25° C. can be improved preferentially over the storage modulus at 37° C. Furthermore, by increasing the content of methacrylic groups among the methacrylic groups and acrylic groups in the (meth)acrylic monomer component (for example, by increasing the content of methacrylic monomer in the photocurable composition), the storage modulus of test piece A1 at 37° C. can be improved preferentially over the storage modulus at 25° C. Furthermore, by reducing the content of the acrylic groups among the methacrylic groups and acrylic groups in the (meth)acrylic monomer component (for example, by reducing the content of the acrylic monomer in the photocurable composition), the storage modulus of test piece A1 at 25°C can be reduced preferentially compared to the storage modulus at 37°C. Furthermore, by reducing the content of the methacrylic groups among the methacrylic groups and acrylic groups in the (meth)acrylic monomer component (for example, by reducing the content of the methacrylic monomer in the photocurable composition), the storage modulus of test piece A1 at 37°C can be reduced preferentially compared to the storage modulus at 25°C.

[0100] [Photopolymerization initiator] The photocurable compositions of the present disclosure include a photoinitiator. 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.

[0101] The photopolymerization initiator is not particularly limited as long as it generates radicals when irradiated with light, and it is preferable that it 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.

[0102] 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.

[0103] Examples of the acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0104] 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.

[0105] When the photopolymerization initiator contains an acylphosphine oxide compound, the content of the acylphosphine oxide 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.

[0106] When the above-mentioned (a) or (b) is satisfied, the total content of the two or more types of di(meth)acrylic monomers (A) and the photopolymerization initiator, or the total content of the di(meth)acrylic monomer (A), the (meth)acrylic monomer (B) and the photopolymerization initiator, is each independently preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, relative to the total amount of the photocurable composition of the present disclosure. The upper limit of the total content of the two or more di(meth)acrylic monomers (A) and the photopolymerization initiator, or the upper limit of the total content of the di(meth)acrylic monomer (A), the (meth)acrylic monomer (B) and the photopolymerization initiator is not particularly limited, as long as it is 100 mass% or less.

[0107] <Other ingredients> The photocurable composition of the present disclosure may contain one or more components other than the above-mentioned components, as needed. When the photocurable composition contains other components, the total mass of the (meth)acrylic monomer component and the photopolymerization initiator is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more, based on the total amount of the photocurable composition.

[0108] Examples of other components include coloring materials, coupling agents such as silane coupling agents (e.g., 3-acryloxypropyltrimethoxysilane), rubber agents, ion trapping agents, ion exchange agents, leveling agents, plasticizers, additives such as 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.

[0109] Other components include inorganic fillers. However, from the viewpoint of further improving the molding accuracy of the cured product, it is preferable that the photocurable composition of the present disclosure does not contain an inorganic filler (e.g., silica, barium borosilicate glass, etc.; the same applies below), or, if it contains an inorganic filler, the content of the inorganic filler relative to the total amount of the photocurable composition is 60 mass% or less (more preferably 40 mass% or less, even more preferably 20 mass% or less, and particularly preferably 10 mass% or less).

[0110] The method for preparing the photocurable composition of the present disclosure is not particularly limited. The photocurable composition of the present disclosure can be prepared, for example, by 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 examples include 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 this embodiment may be prepared by mixing the components, filtering the mixture to remove impurities, and then subjecting the mixture to a vacuum degassing treatment.

[0111] <Preferable Viscosity of Photocurable Composition> The photocurable composition of the present disclosure preferably has a viscosity (hereinafter simply referred to as "viscosity") measured using an E-type viscometer at 25°C and 50 rpm of 5 mPa·s to 6000 mPa·s. Here, rpm means revolutions per minute. When the viscosity is 5 mPa·s to 6000 mPa·s, the photocurable composition has excellent handleability when producing a cured product (particularly a photofabricated 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.

[0112] The photocurable composition of the second embodiment will be described below, with the explanation of the common points with the photocurable composition of the first embodiment being omitted.

[0113] [Second embodiment] [Photocurable composition] A photocurable composition according to a second embodiment of the present disclosure is a photocurable composition comprising a (meth)acrylic monomer component and a photopolymerization initiator, wherein the (meth)acrylic monomer component is The composition comprises a mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring, a di(meth)acrylic monomer (Y) having at least one of a ring structure or a urethane bond and two (meth)acryloyloxy groups and no siloxane bond, and a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond and two or more (meth)acryloyloxy groups.

[0114] The photocurable composition of the present disclosure comprises a (meth)acrylic monomer component and a photopolymerization initiator, and the (meth)acrylic monomer component comprises a mono(meth)acrylic monomer (X), a di(meth)acrylic monomer (Y), and a polyfunctional (meth)acrylic monomer (Z). Use of such a photocurable composition makes it possible to prepare a mold that is suppressed from deforming during the production of a denture, or a mold from which a denture can be easily removed when a denture is produced using the mold.

[0115] The photocurable composition of the present disclosure was exposed to visible light with a wavelength of 405 nm at an irradiation dose of 11 mJ / cm 2 The cured layers A1 were 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 was then 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 stereolithography under the condition of irradiation with The storage modulus of the test piece A1 at 25°C may be 10 MPa or more from the viewpoint of suppressing deformation of the mold (for example, from the viewpoint of suppressing deformation of the mold when a photocurable composition for producing a denture base, etc., is injected into a mold prepared using the photocurable composition of the present disclosure and polymerized), or may be 100 MPa or less from the viewpoint of ease of removal from the mold (for example, from the viewpoint of suppressing damage to the mold, the denture, etc., when the denture is removed from the mold). The storage modulus of the test piece A1 at 37° C. may be 400 MPa or less from the viewpoint of ease of removal from the mold, and may be 6 MPa or more from the viewpoint of suppressing deformation of the mold during use. By using a photocurable composition whose storage modulus at 25°C and storage modulus at 37°C fall within the above numerical ranges, it is possible to more suitably prepare a mold that is less likely to deform during the manufacture of a denture, or a mold that makes it easier to remove a denture from within when manufacturing a denture using the mold.

[0116] In the photocurable composition of the second embodiment, the storage modulus of the test piece A1 at 25° C. may be less than 10 MPa, for example, 1 MPa to 10 MPa, or 2 MPa to 8 MPa.

[0117] In the photocurable composition of the second embodiment, the storage modulus of the test piece A1 at 37° C. may be, for example, 0.5 MPa to 20 MPa, 1 MPa to 10 MPa, or 1 MPa to 6 MPa.

[0118] When a cured product of the photocurable composition of the second embodiment is used as a mold, the releasability of a component (e.g., a denture) manufactured using the mold from the mold is improved, and the toughness at the time of mold release is improved, making the cured product less likely to break.

[0119] The (meth)acrylic monomer component contains a mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring. The use of the mono(meth)acrylic monomer (X) increases the aromatic ring concentration in the (meth)acrylic monomer component, which tends to facilitate removal of the denture from the mold (improved releasability) and tends to reduce fracture when removing the denture from the mold (excellent toughness). Furthermore, a mold that is less prone to deformation during the manufacture of a denture can be produced, and the use of a monofunctional monomer increases the flexibility of the mold, thereby improving the shape recovery of the mold. Furthermore, the mono(meth)acrylic monomer (X) is preferably used to adjust the storage modulus at 25°C and 37°C of the cured product of the photocurable composition to a low value.

[0120] The molecular weight of the mono(meth)acrylic monomer (X) may be 160-400, or 180-300.

[0121] The weight average molecular weight of the mono(meth)acrylic monomer (X) may be 160-400, or 180-300.

[0122] Two types of mono(meth)acrylic monomers (X) having different molecular weights may be used in combination, which tends to increase the dispersibility of the mono(meth)acrylic monomer (X) in the polymer and improve the shape recovery rate.

[0123] The mono(meth)acrylic monomer (X) 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):

[0124] [ka]

[0125] In formula (5), R1 is a divalent linking group, R2 is an alkyl group or aryl group which may have a substituent, R3 is a hydrogen atom or a methyl group, and n is an integer of 0-5.

[0126] In formula (5), R1 may be an alkylene group, an arylene group (e.g., a phenylene group), an alkylenearylene group (e.g., an alkylenephenylene group), an arylenealkylene group (e.g., a phenylenealkylene group), an alkyleneoxy group, an aryleneoxy group, or a combination of two or more of these. In addition, a hydrogen atom contained in R1 may be substituted with a hydroxy group, an alkyl group, an aryl group, an amino group, or the like. In formula (5), the number of atoms in the main chain of R1 may be 1 to 20, or may be 2 to 10. The number of carbon atoms in R1 may be 1 to 20, or may be 2 to 10.

[0127] In formula (5), n is preferably 0 or 1. When n is 1 to 5, R2 is preferably a phenyl group which may have a substituent. The number of carbon atoms in R2 may be 1 to 20, or may be 1 to 10. Examples of the substituent which the alkyl group or aryl group in R2 may have include a hydroxy group, an alkyl group, an aryl group, and an amino group.

[0128] The (meth)acrylic monomer component contains a di(meth)acrylic monomer (Y) having at least one of a ring structure or a urethane bond and two (meth)acryloyloxy groups, but no siloxane bond. The di(meth)acrylic monomer (Y) having a ring structure contributes favorably to suppressing mold deformation 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 (Y) having a urethane bond can suppress breakage when a plate denture is removed from the mold and tends to provide excellent toughness. Furthermore, the di(meth)acrylic monomer (Y) is favorably used to adjust the storage modulus at 25°C and 37°C of the cured product of the photocurable composition to a high value.

[0129] The di(meth)acrylic monomer (Y) 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.

[0130] In the di(meth)acrylic monomer (Y), the distance between the oxygen atom forming the oxy group in one (meth)acryloyloxy group and the oxygen atom forming the oxy group in the other (meth)acryloyloxy group may be 10 Å or more and 200 Å or less. The distance between the oxygen atoms may be 10 Å or more and less than 25 Å, 25 Å or more and 80 Å or less, or more than 80 Å and less than 200 Å. For example, by reducing the distance between the oxygen atoms, the elastic modulus of the mold tends to be increased, thereby favorably suppressing mold deformation during the production of a plate denture, and by increasing the distance between the oxygen atoms, the mold releasability tends to be improved.

[0131] The molecular weight of the di(meth)acrylic monomer (Y) may be 400 to 5,000. The weight average molecular weight of the di(meth)acrylic monomer (Y) may be 400-4,000.

[0132] Two types of di(meth)acrylic monomers (Y) having different molecular weights may be used in combination, which tends to increase the dispersibility of the di(meth)acrylic monomer (Y) in the polymer and improve the shape recovery rate.

[0133] When the di(meth)acrylic monomer (Y) 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 (Y) contains both a urethane bond and a ring structure, it may be a compound represented by the following formula (6-1).

[0134] [ka]

[0135] [ka]

[0136] In formula (6-1), R1's each independently represent an alkylene group which may have a substituent, an ester bond, an alkyleneoxy group, or a combination of at least two or more of these; R2's each independently represent an alkylene group which may have a substituent, a divalent ring structure, an ester bond, a urethane bond, an alkyleneoxy group, or a combination of at least two or more of these; and R3's each independently represent a hydrogen atom or a methyl group. In formula (6-2), R3's are each independently a hydrogen atom or a methyl group, R4's are each independently an alkylene group, an alkyleneoxy group, or a combination thereof, which may have a substituent, R5's are each independently an oxygen atom or an ester bond (*1-OC(=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.

[0137] In formula (6-1), when R1 is an alkylene group which may have a substituent or contains such an alkylene group, examples of the substituent include a phenyloxy group. When R1 is an alkyleneoxy group or contains an alkyleneoxy group, the alkyleneoxy group may be an ethyleneoxy group, a propyleneoxy group, etc. When R1 contains a plurality of alkyleneoxy groups, the plurality of alkyleneoxy groups may be a polyethyleneoxy group, a polypropyleneoxy group, etc. When R1 has an ester bond, R1 may contain a structural unit derived from ε-caprolactone, or may contain multiple structural units derived from ε-caprolactone. Furthermore, when R1 has an ester bond, it may be an alkylene group, -O-CO-alkylene group, in which the -O-CO-alkylene group may have a repeating structure (for example, 2 to 10). R1 may have 1 to 50 carbon atoms, or may have 2 to 25 carbon atoms. In formula (6-1), when R2 is an alkylene group (which may be linear or branched) which may have a substituent, examples of the substituent include a hydroxy group, an alkyl group, an aryl group, and an amino group. In formula (6-1), when R2 is a divalent ring structure or contains a divalent ring structure, examples of the ring structure include an aromatic ring or an alicyclic ring, specifically a phenylene group or a cyclohexylene group. R2 may also contain a group formed by a divalent ring structure and a divalent alkylene group (e.g., an isophorone group or a methylenebis(cyclohexylene) group). R2 may also be a divalent hydrocarbon group containing two ring structures, or a divalent linking group containing two urethane bonds and an alkyleneoxy group (for example, a divalent hydrocarbon group containing a ring structure-urethane bond-(poly)alkyleneoxy group-urethane bond-divalent hydrocarbon group containing a ring structure). R2 may have 1 to 200 carbon atoms, or may have 2 to 100 carbon atoms.

[0138] 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 to R4, and *2 is the bonding position to R6). R6 may be a phenylene group or a bisphenol skeleton (e.g., bisphenol A skeleton or bisphenol F skeleton). The number of carbon atoms in R4 may be 1 to 50, or may be 2 to 30. The number of carbon atoms in R6 may be 1 to 50, or may be 2 to 20.

[0139] The (meth)acrylic monomer component contains a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond (Si-O-Si) and two or more (meth)acryloyloxy groups. The inclusion of the polyfunctional (meth)acrylic monomer (Z) increases the aromatic ring concentration in the (meth)acrylic monomer component, which tends to make it easier to remove a denture from a mold (improved releasability), and tends to provide excellent deformability and dimensional accuracy during denture fabrication. The polyfunctional (meth)acrylic monomer (Z) is also suitable for adjusting the storage modulus at 25°C and 37°C of the cured product of the photocurable composition to a low value.

[0140] The polyfunctional (meth)acrylic monomer (Z) has a siloxane bond (Si-O-Si) and two or more (meth)acryloyloxy groups. The polyfunctional (meth)acrylic monomer (Z) may contain a plurality of siloxane bonds (Si-O-Si), more specifically, may contain linear siloxane bonds, ladder-type siloxane bonds including linear and branched siloxane bonds, cage-type siloxane bonds, etc. The polyfunctional (meth)acrylic monomer (Z) may contain two or more (meth)acryloyloxy groups.

[0141] Examples of the siloxane bond include a dimethylsiloxane bond, a methylphenylsiloxane bond, and a diphenylsiloxane bond, with the dimethylsiloxane bond being preferred.

[0142] The polyfunctional (meth)acrylic monomer (Z) 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.

[0143] The molecular weight of the polyfunctional (meth)acrylic monomer (Z) may be 400 to 5,000. The weight average molecular weight of the polyfunctional (meth)acrylic monomer (Z) may be 400 to 4,000.

[0144] The polyfunctional (meth)acrylic monomer (Z) may be a compound represented by the following formula (7):

[0145] [ka]

[0146] In formula (7), R1's each independently represent an alkylene group which may have a substituent, R2's each independently represent an alkylene group which may have a substituent, R3's each independently represent a hydrogen atom or a methyl group, R4's each independently represent an alkyl group, a hydrogen atom, or an aryl group, m is an integer of 0 or greater, n is an integer of 0 or greater, and 1 is an integer of 0 or greater.

[0147] 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 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. When n is 1 or more, n may be 1-30, or may be 1-20. l may be 0 or greater than 1. When l is greater than 1, l may be 1-30, or may be 1-20.

[0148] In the (meth)acrylic monomer component, the content of the mono(meth)acrylic monomer (X) is preferably 30% by mass to 90% by mass, and more preferably 40% by mass to 80% by mass, based on the total amount of the (meth)acrylic monomer component.

[0149] In the (meth)acrylic monomer component, the content of the di(meth)acrylic monomer (Y) is preferably 5% by mass to 55% by mass, and more preferably 10% by mass to 40% by mass, based on the total amount of the (meth)acrylic monomer component.

[0150] In the (meth)acrylic monomer component, the content of the polyfunctional (meth)acrylic monomer (Z) is preferably 1% by mass to 60% by mass, and more preferably 5% by mass to 50% by mass, based on the total amount of the (meth)acrylic monomer component.

[0151] In the (meth)acrylic monomer component, the total content of the mono(meth)acrylic monomer (X), the di(meth)acrylic monomer (Y) and the polyfunctional (meth)acrylic monomer (Z) 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.

[0152] The concentration of siloxane bonds in the composition is preferably 0.100 mmol / g to 3,000 mmol / g, and more preferably 0.300 mmol / g to 2,500 mmol / g. A siloxane bond concentration of 0.100 mmol / g or higher tends to improve demolding properties, while a concentration of 3,000 mmol / g or lower tends to reduce fracture when removing a denture from the mold and to have excellent toughness.

[0153] The aromatic ring concentration in the (meth)acrylic monomer component is preferably 0.0015 mol / g to 0.0070 mol / g, and more preferably 0.0020 mol / g to 0.0065 mol / g.

[0154] From the viewpoint of mold releasability and toughness, it is preferable that the siloxane bond concentration in the composition and the aromatic ring concentration in the (meth)acrylic monomer component each satisfy the above-mentioned numerical ranges.

[0155] The total content of the mono(meth)acrylic monomer (X), the di(meth)acrylic monomer (Y), the polyfunctional (meth)acrylic monomer (Z), and the 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 mono(meth)acrylic monomer (X), di(meth)acrylic monomer (Y), polyfunctional (meth)acrylic monomer (Z) and photopolymerization initiator is not particularly limited, as long as it is 100% by mass or less.

[0156] [Three-dimensional 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 mold, deformation during the manufacture of a denture can be suppressed, and when a denture is manufactured using the mold, the denture can be easily removed from the mold. 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 in the production of a denture.

[0157] [Method for producing cured product] The method for producing a cured product of the present disclosure includes a step of polymerizing the curable composition in the aforementioned mold. For example, a mold may be prepared using the photocurable composition of the present disclosure, the curable composition may be injected into the mold, and the injected curable composition may be 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 denture with a base by arranging artificial teeth in the mold, a conventionally known curable composition for preparing a denture base may be injected into the mold, and the injected curable composition for preparing a denture base may be cured.

[0158] [Method for manufacturing a plate denture] The method for manufacturing a plate-mounted denture disclosed herein includes a step of hardening a photocurable composition by photopolymerization to prepare a mold to be used in manufacturing the plate-mounted denture, and a step of polymerizing the hardenable composition in the mold to manufacture the plate-mounted denture. The method for manufacturing a plate denture disclosed herein is a method for manufacturing a plate denture by going through two steps: a step for making a mold and a step for manufacturing a plate denture, and it is possible to manufacture a plate denture in a simpler manner than the conventional method for manufacturing a plate denture using a mold.

[0159] 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 a denture, a process of acquiring mold data from the acquired three-dimensional impression data, and a process of curing a photocurable composition by photopolymerization based on the acquired mold data.

[0160] The process for producing a denture preferably includes the steps of arranging artificial teeth in a mold, injecting a hardenable composition for producing a denture base into the mold with the artificial teeth arranged in the mold, hardening the hardenable composition after injection, and removing the manufactured denture from the mold.

[0161] In the method for producing a plate denture of 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 hardening the hardenable composition after injection and suppressing damage to the plate denture, the mold, etc. in the step of removing the produced plate denture from the mold, it is preferable to use the photocurable composition of the present disclosure as the photocurable composition used to prepare the mold. [Example]

[0162] Examples of the present disclosure will be described below, but the present disclosure is not limited to the following examples.

[0163] [Examples 1 to 19, Comparative Examples 1 to 3] <Preparation of Photocurable Composition> Photocurable compositions were obtained by mixing the components shown in Tables 1 to 3. Table 1 shows the details of each component, and Tables 2 and 3 show the mixing ratios of each component.

[0164] <Measurement and Evaluation> The photocurable compositions thus obtained were subjected to the following measurements and evaluations. The results are shown in Tables 2 and 3.

[0165] (storage modulus) The resulting 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 were 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 was then irradiated with ultraviolet light having a wavelength of 365 nm at an irradiation dose of 3 J / cm. 2 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 stereolithography under the condition of irradiation with light. The prepared test piece A1 was subjected to dynamic viscoelasticity measurement under conditions of a temperature increase range of 25°C to 200°C at a temperature increase rate of 3°C / min at a measurement frequency of 1 Hz, and the storage modulus at 25°C and 37°C was determined. The test piece A1 was prepared using a DLP 3D printer (Kulzer, Cara Print 4.0), and the storage modulus was measured using a dynamic viscoelasticity measuring device (Hitachi High-Tech Science Corporation, DMA7100).

[0166] (viscosity) The viscosity of the resulting photocurable composition was measured using an E-type viscometer at 25° C. and 50 rpm. As a result, the viscosities of the photocurable compositions of Examples 1 to 19 were all in the range of 50 mPa·s to 3000 mPa·s.

[0167] (deformable) The resulting photocurable composition was irradiated with visible light having a wavelength of 405 nm at a dose of 11 mJ / cm. 2The cured layers A1 are laminated in the thickness direction to form a three-dimensional object A2 shown in FIG. 1, and the object A2 is irradiated with ultraviolet light having a wavelength of 365 nm at an irradiation dose of 3 J / cm. 2 Test piece A2 shown in FIG. 1 was fabricated by stereolithography under the condition of irradiation with . As shown in Figure 1, test piece A2 had dimensions of 28 mm L, 20 mm L', 2 mm W, 2 mm H, 24 mm H', and 22 mm H', with a gap width (D) of 2 mm. Palapress® Vario (Kulzer), a (meth)acrylate polymer powder for plate denture fabrication, and a (meth)acrylate monomer liquid, were mixed in a ratio of 10 g powder to 7 mL liquid. After the expansion phase (approximately 2 minutes at 23°C), the resulting test piece A2 was filled into the 2 mm gap and polymerized at 55°C and 2 bar pressure for 30 minutes. The length L of test piece A2 was then measured using a micrometer (Mitutoyo MDC-25PX), and the deviation (mm) from the design value (28 mm) was calculated. The smaller the deviation from the design value, the better the deformability and dimensional accuracy during plate denture fabrication. Deviations from the design value of less than 0.05 mm were evaluated as "A," deviations of 0.05 mm to 0.10 mm were evaluated as "B," and deviations of more than 0.10 mm were evaluated as "C."

[0168] (Shape recovery in a 37°C desorption test) The resulting 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 were laminated in the thickness direction to form a three-dimensional object A3 shown in FIG. 2, and ultraviolet light having a wavelength of 365 nm was irradiated onto the object A3 at an irradiation dose of 3 J / cm. 2 Test piece A3 shown in FIG. 2 was fabricated by stereolithography under the condition of irradiation with . As shown in FIG. 2, test piece A3 has a shape in which L is 15 mm, L' is 2 mm, H is 12 mm, H' is 2 mm, R is 4 mm, and the thickness (D) is 10 mm. An iron ball (10 mm in diameter) was inserted and removed between the two semi-cylinders of the obtained test piece A3 at a speed of 120.0 ± 2.0 mm / min to conduct a detachment test. After 10 cycles of insertion and removal, the test piece was observed and rated as follows: "A" if there was no change in shape or cracking after the test, "B" if there was a change in shape or no cracking after the test, and "C" if cracking occurred after the test.

[0169] [Table 1]

[0170] [Table 2]

[0171] [Table 3]

[0172] In Tables 2 and 3, 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.

[0173] <Di(meth)acrylic monomer (A)> In Tables 1 to 3, the compounds classified as di(meth)acrylic monomer (A) are specifically the following photopolymerizable components 1 and 2.

[0174] Photopolymerizable component 1: Ethoxylated bisphenol A diacrylate (A-BPE-10, Shin-Nakamura Chemical Co., Ltd.) Photopolymerizable component 2: ethoxylated bisphenol A dimethacrylate (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0175] [ka]

[0176] <(Meth)acrylic monomer (B)> In Tables 1 to 3, the compounds classified as the (meth)acrylic monomer (B) are specifically the following photopolymerizable components 3 to 17. Photopolymerizable components 3 to 9 are classified as di(meth)acrylic monomers (B-1) having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, and having a distance d1 of 10 Å or more and less than 25 Å. The photopolymerizable component 10 is classified as a di(meth)acrylic monomer (B-2) having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, and having a distance d1 of more than 80 Å and less than 200 Å. Photopolymerizable components 11 to 17 are classified as mono(meth)acrylic monomers (B-3) having one (meth)acryloyloxy group and at least one of an aromatic ring and a hydroxy group.

[0177] Photopolymerizable component 3: Ethoxylated bisphenol A diacrylate (BP-4EAL, Kyoeisha Chemical Co., Ltd.) Photopolymerizable component 4: Ethoxylated bisphenol A dimethacrylate (SR540, Sartomer Corporation) Photopolymerizable component 5: Ethoxylated bisphenol F diacrylate (M-208, Toagosei Co., Ltd.) Photopolymerizable component 6: Ethoxylated bisphenol A dimethacrylate (SR348, Sartomer Corporation) Photopolymerizable component 7: urethane diacrylate (SUA-1 (UDA in the table), a compound produced according to Production Example 1A below) Photopolymerizable component 8: urethane dimethacrylate (SUA-2 (UDMA in the table), a compound prepared according to Preparation Example 1B below) Photopolymerizable component 9: Difunctional urethane acrylate (AH-600, Kyoeisha Chemical Co., Ltd.) Photopolymerizable component 10: Multifunctional urethane acrylate (SUA-3 (UA1 in the table), a compound produced by the method described in Production Example 1C below) Photopolymerizable component 11: Phenoxyethyl acrylate (PO-A, Kyoeisha Chemical Co., Ltd.) Photopolymerizable component 12: Phenoxyethyl methacrylate (PO, Kyoeisha Chemical Co., Ltd.) Photopolymerizable component 13: m-phenoxybenzyl acrylate (POB-A, Kyoeisha Chemical Co., Ltd.) Photopolymerizable component 14: Ethoxylated o-phenylphenol acrylate (A-LEN-10, Shin-Nakamura Chemical Co., Ltd.) Photopolymerizable component 15: 4-hydroxybutyl acrylate (4-HBA) Photopolymerizable component 16: 2-hydroxypropyl acrylate (HOP-A, Kyoeisha Chemical Co., Ltd.) Photopolymerizable component 17: 2-hydroxy-3-phenoxypropyl acrylate (M600-A, Kyoeisha Chemical Co., Ltd.)

[0178] [ka]

[0179] [ka]

[0180] [ka]

[0181] <Other monomers> In Tables 1 to 3, compounds classified as other monomers are specifically photopolymerizable components 18 and 19 shown below. Photopolymerizable component 18: Ethoxylated hydrogenated bisphenol A dimethacrylate (HBPEM-10, Daiichi Kogyo Seiyaku Co., Ltd.) Photopolymerizable component 19: Ethoxylated hydrogenated bisphenol A diacrylate (HBPE-4, Daiichi Kogyo Seiyaku Co., Ltd.)

[0182] [ka]

[0183] <Photopolymerization initiator> In Tables 1 to 3, compounds classified as photopolymerization initiators are specifically photopolymerization initiators 1 and 2 shown below.

[0184] Photopolymerization initiator 1: acylphosphine oxide compound (Omnirad 819: "Omnirad 819" manufactured by IGM Resins BV) Photopolymerization initiator 2: acylphosphine oxide compound (Omnirad TPO: "Omnirad TPO" manufactured by IGM Resins BV)

[0185] [ka]

[0186] [Production Example 1A: Production of SUA-1] In 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 and stirred until homogeneous. The mixture was then heated to 60°C. Subsequently, 337 g (1.60 mol) of TMHDI (trimethylhexamethylene diisocyanate) was added dropwise over 1 hour. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 80°C. After the entire amount was added, the reaction temperature was maintained at 80°C and the reaction was allowed to proceed for 10 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 to obtain 680 g of a bifunctional urethane acrylate (SUA-1), whose viscosity at 25°C was 7100 mPa·s.

[0187] [Production Example 1B: Production of SUA-2] A 1-liter, four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 416 g (3.20 mol) of HEMA (hydroxyethyl methacrylate), 0.75 g (0.1% by mass relative to the total mass of HEA and TMHDI), and 0.38 g (0.05% by mass relative to the total mass of HEA and TMHDI). The mixture was stirred until homogeneous and then heated to 60°C. Subsequently, 337 g (1.60 mol) of TMHDI was added dropwise over 1 hour. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 80°C. After the entire amount was added, the reaction temperature was maintained at 80°C and the reaction was continued for 10 hours. The reaction progress was monitored by HPLC analysis to confirm the end point. The product was discharged from the reactor, yielding 720 g of a bifunctional urethane acrylate (SUA-2). Its viscosity at 25°C was 8200 mPa·s.

[0188] [Production Example 1C: 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 of DBTDL (0.1% by mass relative to the total mass of IPDI, PEG-1000, and HEA), and 0.42 g of MEHQ (0.05% by mass relative to the total mass of IPDI, PEG-1000, and HEA) 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. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 80°C. After the entire amount was added, the reaction temperature was maintained at 80°C and the reaction was carried out for 5 hours. Next, the internal temperature of the flask was maintained at 60°C, and 116 g (1.00 mol) of HEA from a separate dropping funnel was added dropwise over 1 hour. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 80°C. After the entire amount was added, the reaction temperature was maintained at 80°C and the reaction was carried out for 5 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 840 g of urethane acrylate (SUA-3). The viscosity at 40°C was 41,000 mPa·s.

[0189] As shown in Tables 2 and 3, in the examples, cured products with excellent deformability and shape recovery properties were obtained. On the other hand, the cured products obtained in Comparative Examples 1 and 2 were easily deformed, and the cured product obtained in Comparative Example 3 did not recover its shape.

[0190] Example 20 <Production of removable dentures> Plaster casts of the upper and lower jaws were scanned using a laboratory dental scanner (Kulzer, Cara Scan 4.0) to create 3D impression data. Each 3D impression data was then uploaded to commercially available CAD software (3D Systems, Geomagic Design X). A mold for the production of removable dentures was designed using the CAD software, the mold thickness was set to 2.0 mm, and 3D modeling data was obtained. The photocurable composition of Example 1 was irradiated with visible light having a wavelength of 405 nm at a dose of 11 mJ / cm 2 The cured layers were stacked in the thickness direction and molded using the 3D modeling data of the mold obtained above to obtain a molded article for the production of a plate denture. 2 The molded object was irradiated with ultraviolet light at a wavelength of 365 nm under the above conditions to completely harden it, thereby obtaining a mold for manufacturing a removable denture.

[0191] Artificial teeth were arranged in the mold for making a plate denture obtained above, and (meth)acrylate polymer powder and (meth)acrylate monomer liquid for making plate denture (Palapress® Vario, manufactured by Kulzer) were mixed in a specified ratio and poured into the mold with the artificial teeth arranged. The mixture was then covered with a plaster model and polymerized at 55°C and 2 bar pressure for 30 minutes. After polymerization, the mold and plaster model were removed, and a plate denture was obtained. At this time, it was confirmed that both the mold and the plate denture were not damaged. Furthermore, this method allows for easier production of dentures than conventional manual methods using wax dentures or silicone, and is suitable for obtaining desired physical properties because denture resins that are unsuitable for photopolymerization can be used to produce dentures.

[0192] [Examples 20 to 43, Comparative Examples 4 to 8] <Preparation of Photocurable Composition> Photocurable compositions were obtained by mixing the components shown in Tables 4 to 7. Table 4 shows the details of each component, and Tables 5 to 7 show the mixing ratios of each component.

[0193] <Measurement and Evaluation> The photocurable composition thus obtained was subjected to the following measurements and evaluations: The methods for measuring and evaluating physical properties, etc., which have already been described, will be omitted here. The results are shown in Tables 5 to 7.

[0194] (Releasability for dentures) The resulting 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 were laminated in the thickness direction to form a three-dimensional object A4 shown in FIG. 3, and ultraviolet rays having a wavelength of 365 nm were irradiated onto the object A4 at an irradiation dose of 3 J / cm. 2 Test piece A4 shown in FIG. 3 was fabricated by stereolithography under the condition of irradiation with . As shown in Figure 3, test piece A4 had dimensions of 24 mm L, 20 mm L', 2 mm W, 5 mm H, 3 mm H', 14 mm D, and 10 mm D'. (Meth)acrylate polymer powder for denture fabrication and Palapress® Vario (Kulzer), a (meth)acrylate monomer liquid, were mixed in a ratio of 10 g powder to 7 mL liquid. 15 seconds after mixing, the mixture was filled into the space of test piece A4, measuring L' (20 mm), D' (10 mm), and H' (3 mm), and polymerized at 55°C and 2 bar pressure for 30 minutes. Test piece A4 was then peeled off the denture polymer. Thereafter, the surface of the polymer for making a plate denture that had been in contact with the test piece A4 was observed using a 3D shape measuring device (Keyence Corporation, VR-3200), and the area value of the test piece A4 that had been attached to the polymer for making a plate denture after removal was calculated, and the area (200 mm 2 The adhesion rate was calculated based on the surface adhesion rate. The smaller the adhesion rate, the better the release properties. 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.

[0195] (Toughness when demolding (ease of removal)) The resulting 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 were laminated in the thickness direction to form a three-dimensional object A4 shown in FIG. 3, and ultraviolet rays having a wavelength of 365 nm were irradiated onto the object A4 at an irradiation dose of 3 J / cm. 2 Test piece A4 shown in FIG. 3 was fabricated by stereolithography under the condition of irradiation with . As shown in Figure 3, test piece A4 had dimensions of 24 mm L, 20 mm L', 2 mm W, 5 mm H, 3 mm H', 14 mm D, and 10 mm D'. (Meth)acrylate polymer powder for plate denture fabrication and Palapress® Vario (Kulzer), a (meth)acrylate monomer liquid, were mixed in a ratio of 10 g powder to 7 mL liquid. 15 seconds after mixing, the mixture was filled into the space of the resulting test piece A4, consisting of L' (20 mm), D' (10 mm), and H' (3 mm), and polymerized at 55°C and 2 bar pressure for 30 minutes. Test piece A4 was then peeled off the plate denture fabrication polymer. The appearance of test piece A4 after removal was observed and rated as "A" if no fractures were present and "B" if fractures were present.

[0196] (Shape recovery speed) The obtained photocurable composition was printed using a 3D printer (Kulzer, Cara Print 4.0) with visible light at a wavelength of 405 nm and an illuminance of 8.0 mJ / cm. 2 Under the above conditions, a molded object (layer width 50 μm) measuring 8 mm in length, 39 mm in width, and 4 mm in thickness was obtained. 10J / cm for the resulting object 2 The object was irradiated with ultraviolet light having a wavelength of 365 nm under the above conditions to effect final curing, thereby obtaining a photo-fabricated object. The obtained stereolithography object (hereinafter referred to as "test piece") was bent by applying stress so that both ends of the test piece in the longitudinal (horizontal) direction were in contact with each other, and the test piece was held for 10 seconds. After that, the stress was released and the change in shape of the test piece was observed and evaluated according to the following criteria. A: After stress release, it returned to its original shape within 1 second B: After stress release, it took more than 1 second to return to its original shape.

[0197] [Table 4]

[0198] [Table 5]

[0199] [Table 6]

[0200] [Table 7]

[0201] In Tables 5 to 7, 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. In Tables 5 to 7, the details of each component are as follows:

[0202] <Mono(meth)acrylic monomer (X)> The structures of the mono(meth)acrylic monomers (X) listed in Tables 4 to 7 are as follows: PO-A manufactured by Kyoeisha Chemical Co., Ltd. PO Kyoeisha Chemical Co., Ltd. P2H-A Kyoeisha Chemical Co., Ltd. M-600A Kyoeisha Chemical Co., Ltd. POB-A manufactured by Kyoeisha Chemical Co., Ltd. A-LEN-10 Shin-Nakamura Chemical Co., Ltd.

[0203] [ka]

[0204] <Di(meth)acrylic monomer (Y)> The structures of the di(meth)acrylic monomers (Y) listed in Tables 4 to 7 are as follows: SUA-1: A compound (UDA in the table) prepared by the method described in Preparation Example 1A below. ABE-300 Shin-Nakamura Chemical Co., Ltd. A-BPE-10 Shin-Nakamura Chemical Co., Ltd. SA-001: Compound prepared by the method described in Preparation Example 2A below AH-600 Kyoeisha Chemical Co., Ltd. SA-002 Compound prepared by the method described in Preparation Example 2B below SUA-3: A compound (UA1 in the table) prepared by the method described in Preparation Example 1C below.

[0205] [ka]

[0206] [Production Example 2A: Production of SA-001] A 2-liter, four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 170.81 g (1.64 mol) of pentanediol, 120.8 g (0.82 mol) of phthalic anhydride, 3.6 g of p-toluenesulfonic acid, 0.5 g of phenothiazine, and 300 g of toluene. The mixture was heated to 150-200°C under a nitrogen atmosphere and reacted for 5 hours. Then, 122.50 g (1.70 mol) of acrylic acid was added, and the mixture was further heated and reacted for 10 hours. The reaction product was dissolved in 500 g of toluene, neutralized with 10% aqueous NaOH, and washed with 150 g of 5% aqueous ammonium sulfate. The toluene was distilled under reduced pressure to obtain 390 g of di(meth)acrylic monomer (SA-001). The viscosity at 25°C was 410 mPa·s.

[0207] [Production Example 2B: Production of SA-002] A four-neck flask equipped with a stirrer, air inlet, and thermometer was charged with 344 g (1.00 mol) of caprolactone-modified 2-hydroxyethyl acrylate (trade name "Placcel FA2D" manufactured by Daicel Corporation, average caprolactone addition moles: 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), and the mixture was reacted at 80°C for 12 hours. The reaction progress was monitored by HPLC analysis, and the end point was confirmed. The product was discharged from the reactor, yielding 451 g of di(meth)acrylic monomer (SA-002). The viscosity at 25°C was 12,000 mPa·s.

[0208] <Polyfunctional (meth)acrylic monomer (Z)> The structures of the polyfunctional (meth)acrylic monomers (Z) listed in Tables 4 to 7 are as follows: SiA-001: A compound prepared by the method described in Preparation Example 2C below. SiA-002: A compound prepared by the method described in Preparation Example 2D below. SiA-003: A compound prepared by the method described in Preparation Example 2E below.

[0209] [ka]

[0210] [Production Example 2C: Production of SiA-001] In a 1-liter, four-neck flask equipped with a thoroughly dried stirring blade and thermometer, 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 and stirred until homogeneous. The mixture was then heated to 70°C. Subsequently, 181 g (2.00 mol) of acryloyl chloride was added dropwise over 1 hour. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 70°C. After the entire amount was added, the reaction temperature was maintained at 70°C and the reaction was continued for 5 hours. The reaction solution was then neutralized with 10% aqueous NaOH solution and washed with 150 g of 5% aqueous ammonium sulfate solution. The ethyl acetate was distilled under reduced pressure to obtain 440 g of a polyfunctional (meth)acrylic monomer (SiA-001). The viscosity at 25°C was 110 mPa·s.

[0211] [Production Example 2D: Production of SiA-002] In a 1-liter four-neck flask equipped with a thoroughly dried stirring blade and 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 and stirred until homogeneous. The mixture was then heated to 60°C. Subsequently, 593 g (2.00 mol) of octamethylcyclotetrasiloxane was added dropwise over 1 hour. After the entire amount was added, the reaction temperature was maintained at 60°C and the reaction was carried out for 6 hours. Subsequently, 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 addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 60°C. After the entire amount was added, the reaction temperature was maintained at 60°C and the reaction was carried out for 5 hours. The reaction solution was then neutralized with a 10% aqueous solution of NaOH and 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-003). The viscosity at 25°C was 310 mPa·s.

[0212] [Production Example 2E: Production of SiA-003] In a 1-liter, four-necked flask equipped with a thoroughly dried stirring blade and thermometer, 667 g (3.00 mol) of hexamethylcyclotrisiloxane, 100 mL of toluene, 200 mL of tetrahydrofuran, and 100 mL of hexane were added and stirred until homogeneous. Then, under ice cooling, 2 mL of butyllithium (approximately 15% hexane solution) was added dropwise over 1 hour. After the entire amount was added, the reaction temperature was maintained at room temperature and the reaction was allowed to proceed for 2 hours. Subsequently, 207 g (1.00 mol) of 3-(chlorodimethylsilyl)propyl acrylate from a separate dropping funnel was added dropwise over 1 hour. After the entire amount was added, the reaction temperature was maintained at 30°C and the reaction was allowed to proceed for 24 hours. The progress of the reaction was monitored by HPLC analysis to confirm the end point. 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), whose viscosity at 25°C was 280 mPa·s.

[0213] <Other monomers> The structures of the other monomers listed in Tables 4 to 7 are as follows: LA manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 9EG-A manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[0214] [ka]

[0215] <Photopolymerization initiator> As the photopolymerization initiators shown in Tables 4 to 7, the above-mentioned photopolymerization initiator 1 (acylphosphine oxide compound, Omnirad 819: "Omnirad 819" manufactured by IGM Resins BV) was used.

[0216] As shown in Tables 4 to 7, in Examples 20 to 43, cured products with excellent deformability and shape recovery properties were obtained. On the other hand, the cured products obtained in Comparative Examples 4 to 8 were inferior to those obtained in Examples 20 to 43 in terms of deformability and shape recovery. Furthermore, in Examples 20 to 43, the evaluations of the mold releasability and toughness were also good.

[0217] The disclosures of Japanese Patent Application No. 2022-052228, filed on March 28, 2022, and Japanese Patent Application No. 2023-036051, filed on March 8, 2023, are incorporated herein by reference in their entirety. All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A photocurable composition comprising a (meth)acrylic monomer component and a photopolymerization initiator, The 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 were 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 was then 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 stereolithography under the condition of irradiating with The storage modulus of the test piece A1 at 25°C is 10 MPa or more, The storage modulus of the test piece A1 at 37 ° C. is 400 MPa or less, A photocurable composition that satisfies either of the following conditions (a) and (b): (a) The (meth)acrylic monomer component contains two or more types of di(meth)acrylic monomers (A) each having two (meth)acryloyloxy groups and an aromatic ring, wherein the distance between an oxygen atom forming an oxy group in one of the (meth)acryloyloxy groups and an oxygen atom forming an oxy group in the other (meth)acryloyloxy group is 25 Å or more and 80 Å or less, and the total content of the di(meth)acrylic monomers (A) is 90% by mass to 100% by mass based on the total amount of the (meth)acrylic monomer component. (b) the (meth)acrylic monomer component is a di(meth)acrylic monomer (A) having two (meth)acryloyloxy groups and an aromatic ring, wherein the distance between an oxygen atom forming an oxy group in one of the (meth)acryloyloxy groups and an oxygen atom forming an oxy group in the other (meth)acryloyloxy group is 25 Å or more and 80 Å or less; a di(meth)acrylic monomer (B-1) having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, wherein the distance between an oxygen atom forming an oxy group in one of the (meth)acryloyloxy groups and an oxygen atom forming an oxy group in the other (meth)acryloyloxy group is 10 Å or more and less than 25 Å; A di(meth)acrylic monomer (B-2) having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, wherein the distance between an oxygen atom forming an oxy group in one of the (meth)acryloyloxy groups and an oxygen atom forming an oxy group in the other (meth)acryloyloxy group is more than 80 Å and less than 200 Å; and one or more (meth)acrylic monomers (B) selected from the group consisting of mono(meth)acrylic monomers (B-3) having one (meth)acryloyloxy group and at least one of an aromatic ring and a hydroxy group, the total content of the di(meth)acrylic monomer (A) and the (meth)acrylic monomer (B) is 95% by mass or more based on the total amount of the (meth)acrylic monomer components, and the total content of the photopolymerization initiators is 0.1% by mass to 5% by mass based on the total amount of the photocurable composition; The mono(meth)acrylic monomer (B-3) includes a compound represented by the following formula (3): 【Chemistry 1】 (In formula (3), R 11 is a monovalent organic group having at least one of an aromatic structure and a hydroxy group.)

2. A photocurable composition comprising a (meth)acrylic monomer component and a photopolymerization initiator, The (meth)acrylic monomer component is a mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring; a di(meth)acrylic monomer (Y) having at least one of a ring structure or a urethane bond and two (meth)acryloyloxy groups, but not having a siloxane bond; a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond and two or more (meth)acryloyloxy groups, a content of the mono(meth)acrylic monomer (X) in a photocurable composition is 40% by mass to 80% by mass, based on the total amount of the (meth)acrylic monomer components, and a content of the polyfunctional (meth)acrylic monomer (Z) in a photocurable composition is 10% by mass to 60% by mass, based on the total amount of the (meth)acrylic monomer components.

3. 3. The photocurable composition according to claim 2, wherein the di(meth)acrylic monomer (Y) has a molecular weight of 400 to 5,000.

4. 4. The photocurable composition according to claim 2, wherein the polyfunctional (meth)acrylic monomer (Z) has a molecular weight of 400 to 5,000.

5. 4. The photocurable composition according to claim 2, wherein the content of the mono(meth)acrylic monomer (X) is 30% by mass to 90% by mass based on the total amount of the (meth)acrylic monomer components.

6. 4. The photocurable composition according to claim 2, wherein the content of the di(meth)acrylic monomer (Y) is 5% by mass to 55% by mass based on the total amount of the (meth)acrylic monomer components.

7. 4. The photocurable composition according to claim 2, wherein the content of the polyfunctional (meth)acrylic monomer (Z) is 1% by mass to 60% by mass based on the total amount of the (meth)acrylic monomer components.

8. 4. The photocurable composition according to claim 2, wherein the siloxane bond concentration in the composition is 0.100 mmol / g to 3.000 mmol / g.

9. 4. The photocurable composition according to claim 2, wherein the (meth)acrylic monomer component has an aromatic ring concentration of 0.0015 mol / g to 0.0070 mol / g.

10. 4. The photocurable composition according to claim 1, wherein the viscosity of the composition measured at 25° C. and 50 rpm using an E-type viscometer is 5 mPa·s to 6000 mPa·s.

11. The photocurable composition according to any one of claims 1 to 3, which is a photocurable composition for stereolithography.

12. The photocurable composition according to any one of claims 1 to 3, which is a photocurable composition used for producing a mold by stereolithography.

13. A three-dimensional object comprising a cured product of the photocurable composition according to any one of claims 1 to 3.

14. A mold comprising the three-dimensional object according to claim 13.

15. The mold according to claim 14, which is used in the manufacture of a denture base.

16. A method for producing a cured product, comprising polymerizing a curable composition in the mold of claim 14.

17. A process of hardening the photocurable composition according to any one of claims 1 to 3 by photolithography to prepare a mold to be used in the manufacture of a plate-mounted denture; A method for manufacturing a plate denture, comprising the step of polymerizing the hardenable composition in the mold to manufacture a plate denture.

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