WO2023189780A1 - Photocurable composition, three-dimensional shaped object, and tool to be fit inside oral cavity - Google Patents

Abstract

Provided is a photocurable composition comprising: a (meth)acrylic monomer (A) that has two urethane bonds and two (meth)acryloyl groups, each of the two (meth)acryloyl groups being joined to each of the two urethane bonds via a C4-10 alkylene group having bonded thereto an oxygen atom or a nitrogen atom; a (meth)acrylic monomer (B) having one (meth)acryloyl group; and a photopolymerization initiator.

Description

Photocurable composition, three-dimensional molded object, and appliance installed in the oral cavity

The present disclosure relates to a photocurable composition, a three-dimensional molded object, and an appliance installed in the oral cavity.

In recent years, studies have been conducted on dental products such as dental prostheses and instruments used in the oral cavity. For example, from the viewpoint of the efficiency of modeling these dental products, a method of manufacturing three-dimensional objects such as dental products by stereolithography using a 3D printer is known (for example, see Patent Document 1).

Patent No. 4160311

When a three-dimensional object manufactured by stereolithography using a photocurable composition is used for a denture base, a splint, or other appliance installed in the oral cavity, in addition to a certain bending strength and bending elastic modulus, a certain toughness is required.
Further, a three-dimensional object manufactured by stereolithography may be washed with isopropyl alcohol after modeling, but the cleaning may reduce the toughness of the three-dimensional object, and sufficient toughness may not be obtained.

An object of one aspect of the present disclosure is to provide a photocurable composition that can produce a three-dimensional object that has high toughness even after cleaning with isopropyl alcohol, a three-dimensional object obtained from this photocurable composition, and a three-dimensional object that can be used in the oral cavity. The purpose is to provide a device to be worn.

Means for solving the above problems include the following aspects.
<1> It has two urethane bonds and two (meth)acryloyl groups, and each of the two (meth)acryloyl groups has an oxygen atom or a nitrogen atom for each of the two urethane bonds. (meth)acrylic monomer (A) connected via a bonded alkylene group having 4 to 10 carbon atoms;
(meth)acrylic monomer (B) having one (meth)acryloyl group,
A photocurable composition comprising a photopolymerization initiator.
<2> The photocurable composition according to <1>, wherein the (meth)acrylic monomer (A) is a compound represented by the following general formula (A-1).

(In formula (A-1), R ^1A is a divalent hydrocarbon group, R ^2A and R ^3A are each independently an alkylene group having 4 to 10 carbon atoms, and R ^4A and R ^5A are , each independently a methyl group or a hydrogen atom)
<3> The photocurable composition according to <2>, wherein R ^1A in the general formula (A-1) is a divalent hydrocarbon group having 5 to 20 carbon atoms.
<4> The photocuring according to <2>, wherein R ^1A in the general formula (A-1) is a group represented by any of the following general formulas (a-1) to (a-7). sexual composition.

(In formulas (a-1) to (a-7), * indicates the bonding position.)
<5> The (meth)acrylic monomer (B) is at least one of a compound represented by the following general formula (B-1) and a compound represented by the following general formula (B-2), <1> ~The photocurable composition according to any one of <4>.

(In formula (B-1), R ^1B1 is a monovalent organic group having one or more selected from the group consisting of an aromatic ring, a hydroxy group, and a carboxy group, and R ^2B1 is a methyl group or a hydrogen atom. In formula (B-2), R ^1B2 and R ^2B2 are each independently a monovalent organic group, R ^1B2 and R ^2B2 may be combined with each other to form a ring, and R ^3B2 is , a methyl group or a hydrogen atom)
<6> The photocurable composition according to any one of <1> to <5>, wherein the (meth)acrylic monomer (A) has a molecular weight of 440 to 650.
<7> The photocurable composition according to any one of <1> to <6>, wherein the (meth)acrylic monomer (B) has a molecular weight of 125 to 300.
<8> The content of the (meth)acrylic monomer (A) is 300 parts by mass to 950 parts by mass based on 1000 parts by mass of the (meth)acrylic monomer component contained in the photocurable composition, <1> ~The photocurable composition according to any one of <7>.
<9> The content of the (meth)acrylic monomer (B) is (
The photocurable composition according to any one of <1> to <8>, wherein the amount is 50 parts by mass to 700 parts by mass based on 1000 parts by mass of the meth)acrylic monomer component.
<10> The photocurable composition according to any one of <1> to <9>, which has a viscosity of 5 mPa·s to 6000 mPa·s as measured by an E-type viscometer at 25° C. and 50 rpm. thing.
<11> By irradiating the photocurable composition with visible light having a wavelength of 405 nm at a dose of 11 mJ/cm ² to form a cured layer A1 with a thickness of 50 μm, and by laminating the cured layer A1 in the thickness direction, A rectangular plate-shaped object A1 with a length of 64 mm, a width of 10 mm, and a thickness of 3.3 mm is formed, and by irradiating the object A1 with ultraviolet light with a wavelength of 365 nm at a dose of 10 J/ ^cm2 , the length is 64 mm. When a rectangular plate-shaped test piece A1 with a width of 10 mm and a thickness of 3.3 mm is produced, the bending strength of the test piece A1 is 50 Mpa or more, the bending elastic modulus is 1500 Mpa or more, and
A photocurable composition was irradiated with visible light with a wavelength of 405 nm at a dose of 11 mJ/cm ² to form a cured layer A2 with a thickness of 50 μm, and the cured layer A2 was laminated in the thickness direction to form a layer with a length of 39 mm. , a rectangular plate-shaped object A2 with a width of 8 mm and a thickness of 4 mm is formed, and by ^irradiating the object A2 with ultraviolet light with a wavelength of 365 nm at a dose of 10 J/cm2, the object A2 has a length of 39 mm, a width of 8 mm, and a thickness of 4 mm. The photocurable composition according to any one of <1> to <10>, wherein when a rectangular plate-shaped test piece A2 is produced, the total work of failure of the test piece A2 is 500 J/m ² or more. thing.
<12> The photocurable composition according to any one of <1> to <11>, which is used for stereolithography.
<13> The photocurable composition according to any one of <1> to <12>, which is used for manufacturing a device to be mounted in the oral cavity by stereolithography.
<14> A three-dimensional object comprising a cured product of the photocurable composition according to any one of <1> to <13>.
<15> An appliance to be worn in the oral cavity, including the three-dimensional structure according to <14>.

According to one aspect of the present disclosure, there is provided a photocurable composition that can produce a three-dimensional structure that has high toughness even after cleaning with isopropyl alcohol, a three-dimensional structure obtained from this photocurable composition, and a three-dimensional structure that can be used in the oral cavity. You will be provided with a device to wear.

In the present disclosure, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as lower and upper limits.
In the present disclosure, if there are multiple substances corresponding to each component in the composition, the amount of each component contained in the composition is the total amount of the multiple substances present in the composition, unless otherwise specified. means quantity.
In the numerical ranges described step by step in this disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step. . Furthermore, in the numerical ranges described in this disclosure, the upper limit or lower limit of the numerical range may be replaced with the values shown in the Examples.
In the present disclosure, "light" is a concept that includes active energy rays such as ultraviolet rays and visible light.

In the present disclosure, "(meth)acrylate" means acrylate or methacrylate, "(meth)acryloyl" means acryloyl or methacryloyl, and "(meth)acrylic" means acrylic or methacrylic.

[Photocurable composition]
The photocurable composition of the present disclosure has two urethane bonds and two (meth)acryloyl groups, and each of the two (meth)acryloyl groups is attached to each of the two urethane bonds. , a (meth)acrylic monomer (A) connected via an alkylene group having 4 to 10 carbon atoms to which an oxygen atom or a nitrogen atom is bonded (hereinafter also referred to as "(meth)acrylic monomer (A)"). , a (meth)acrylic monomer (B) having one (meth)acryloyl group (hereinafter also referred to as "(meth)acrylic monomer (B)"), and a photopolymerization initiator.
In the photocurable composition of the present disclosure, by combining the (meth)acrylic monomer (A) and the (meth)acrylic monomer (B), it is possible to produce a three-dimensional object that has high toughness even after cleaning with isopropyl alcohol. .

The photocurable composition of the present disclosure is a composition that is cured by light irradiation, and a cured product can be obtained by curing this composition. A preferred manufacturing method for manufacturing 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, the cured product produced using the photocurable composition of the present disclosure is preferably a photocurable composition for stereolithography. (i.e., a cured product obtained by stereolithography).

Stereolithography is a method of stacking cured layers to obtain a cured product (i.e., a stereolithography) by repeating the operation of irradiating a photocurable composition with light to form a cured layer.
The stereolithography may be an inkjet stereolithography or a liquid bath stereolithography (that is, stereolithography using a liquid tank).

In inkjet stereolithography, droplets of a photocurable composition are ejected from an inkjet nozzle onto a substrate, and the droplets adhering to the substrate are irradiated with light to obtain a cured product.
In an example of stereolithography using an inkjet method, for example, a head including an inkjet nozzle and a light source is scanned in a plane, and a photocurable composition is discharged from the inkjet nozzle onto a base material, and the discharged photocurable composition is A cured layer is formed by irradiating the object with light, and these operations are repeated to sequentially stack the cured layers to obtain a cured product (that is, a stereolithographic object).

In liquid bath method stereolithography, a part of the photocurable composition (i.e., an uncured photocurable composition in a liquid state; the same applies hereinafter) contained in a liquid bath is cured by light irradiation. By forming layers and repeating this operation, cured layers are laminated to obtain a cured product (that is, a stereolithographic product). Liquid bath type stereolithography differs from inkjet type stereolithography in that a liquid bath is used.
Examples of liquid bath type stereolithography include DLP (Digital Light Processing) type stereolithography and SLA (Stereolithography) type stereolithography.
In the DLP method, a planar light is irradiated onto the photocurable composition in a liquid tank.
In the SLA method, a photocurable composition in a liquid tank is scanned with a laser beam.
From the viewpoint of more effectively achieving the effects of the photocurable composition of the present disclosure, the liquid bath type stereolithography is preferably DLP type stereolithography.

In an example of DLP stereolithography, for example,
A vertically movable build table,
A tray (i.e., a liquid tank) that is disposed below the build table (on the side in the gravity direction; the same applies hereinafter), includes a light-transmitting part, and contains 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 part of the tray;
A 3D printer (for example, "Cara Print 4.0" manufactured by Kulzer, "Max UV" manufactured by Asiga, etc.) is used.
In this example, a one-layer gap is first created between the build table and the tray, and the 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 part of the tray, and the area irradiated with light is cured to form the first layer. form a hardened layer. The gap between the build table and the tray is then widened by the next layer and the resulting space is filled with the photocurable composition. Next, the photocurable composition filling 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, the cured layers are laminated and a three-dimensional structure is manufactured. In this example, the manufactured three-dimensional structure may be further hardened by further irradiating the three-dimensional structure with light.
Regarding stereolithography using the DLP method, for example, the descriptions in Japanese Patent No. 5111880 and Japanese Patent No. 5235056 may be referred to.

<Application>
The use of the photocurable composition of the present disclosure is not particularly limited.
The photocurable composition of the present disclosure may be a photocurable composition used in the manufacture of dental products. Dental products manufactured using photocurable compositions have high toughness even after cleaning with isopropyl alcohol.
Examples of dental products include dental prostheses, intraoral appliances, dental models, investment casting models, and the like.
Examples of dental prostheses include inlays, crowns, bridges, temporary crowns, and temporary bridges.
Appliances installed in the oral cavity include dentures (e.g., complete dentures, partial dentures, etc.), mouthpieces, mouth guards, orthodontic appliances, occlusal splints, and temporomandibular joints. Examples include splints such as splints for medical treatment, trays for impression taking, surgical guides, etc.
Examples of the dental model include a tooth and jaw model.

The photocurable composition of the present disclosure is preferably a photocurable composition used for stereolithography, more preferably a photocurable composition used for manufacturing dental products by stereolithography, and More preferably, it is a photocurable composition used for manufacturing a molded appliance to be placed in the oral cavity.

<(meth)acrylic monomer (A)>
The photocurable composition of the present disclosure has two urethane bonds and two (meth)acryloyl groups, and each of the two (meth)acryloyl groups is attached to each of the two urethane bonds. , a (meth)acrylic monomer (A) connected via an alkylene group having 4 to 10 carbon atoms to which an oxygen atom or a nitrogen atom is bonded.
One type of (meth)acrylic monomer (A) may be used alone, or two or more types may be used in combination.

The (meth)acrylic monomer (A) has two urethane bonds, and each of the two (meth)acryloyl groups and each of the two urethane bonds has a carbon number of 4 to which an oxygen atom or a nitrogen atom is bonded. It is a compound linked through ~10 alkylene groups. In addition, each of the two (meth)acryloyl groups in the (meth)acrylic monomer (A) is bonded to an oxygen atom or a nitrogen atom bonded to an alkylene group having 4 to 10 carbon atoms; It is preferably bonded to an oxygen atom or nitrogen atom bonded to an alkylene group, and more preferably bonded to an oxygen atom or nitrogen atom bonded to an alkylene group having 4 carbon atoms. By using this (meth)acrylic monomer (A), it is possible to obtain a three-dimensional structure having excellent bending modulus, bending strength, and toughness.

The (meth)acrylic monomer (A) has two urethane bonds, and each of the two (meth)acryloyl groups and each of the two urethane bonds have a carbon number of 4 to 10 to which an oxygen atom is bonded. A compound connected via an alkylene group is preferable, and a compound represented by the following general formula (A-1) is more preferable.

In formula (A-1), R ^1A is a divalent hydrocarbon group, R ^2A and R ^3A are each independently an alkylene group having 4 to 10 carbon atoms, and R ^4A and R ^5A are Each independently represents a methyl group or a hydrogen atom.

R ^1A in general formula (A-1) is preferably a divalent hydrocarbon group having 5 to 20 carbon atoms, a divalent chain hydrocarbon group having 5 to 10 carbon atoms, and a carbon having a cyclic structure. It is more preferably a divalent hydrocarbon group having 6 to 18 carbon atoms, and even more preferably a divalent hydrocarbon group having 8 to 16 carbon atoms and having a cyclic structure.

Examples of the divalent chain hydrocarbon group having 5 to 10 carbon atoms include pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, and the like.

Examples of the cyclic structure include aromatic ring structures and alicyclic structures. The cyclic structure also includes a combination of an aromatic ring structure and another linking group (for example, a divalent hydrocarbon group), such as a bisphenol A structure.

Examples of the aromatic ring structure include a benzene ring, a naphthalene ring, a bisphenol A structure, a phenylphenol structure, a phenoxybenzyl structure, a phenylalkylene structure, and an α-hydroxyphenyl structure.

Examples of the alicyclic structure include cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cyclohexenylene group, cycloheptylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, cycloundecylene group, Examples include cyclododecylene group, cyclotridecylene group, cyclotetradecylene group, cyclopentadecylene group, cyclooctadecylene group, cycloicosylene group, bicyclohexylene group, norbornylene group, isobornylene group, and adamantylene group. . Among these, norbornylene group and isobornylene group are preferred.

R ^1A in the general formula (A-1) is preferably a group represented by any of the following general formulas (a-1) to (a-7), and the following general formula (a-1) A group represented by any one of (a-4) is more preferable.

In formulas (a-1) to (a-7), * indicates the bonding position.

R ^2A and R ^3A each independently represent an alkylene group having 4 to 10 carbon atoms, preferably an alkylene group having 4 to 8 carbon atoms, and more preferably an alkylene group having 4 carbon atoms. Examples of the alkylene group having 4 to 10 carbon atoms include 1,4-butanediyl group, 1,2-dimethyl-1,2-ethanediyl group, 2-methyl-1,3-propanediyl group, 1,5-pentanediyl group, Examples include 1,6-hexanediyl group, 1,7-heptanediyl group, 1,8-octanediyl group, 1,9-nonanediyl group, 1,10-decanediyl group, 2,4,4-trimethylhexylene group, etc. It will be done. Both R ^2A and R ^3A are preferably 1,4-butanediyl groups.

The molecular weight of the (meth)acrylic monomer (A) is preferably 440 to 750, more preferably 440 to 650, even more preferably 450 to 600, particularly preferably 470 to 550. .

From the viewpoint of obtaining a three-dimensional object with excellent bending elastic modulus, bending strength, and toughness, the content of the (meth)acrylic monomer (A) is determined based on 1000 parts by mass of the (meth)acrylic monomer component contained in the photocurable composition. , is preferably from 300 parts by weight to 950 parts by weight, more preferably from 350 parts by weight to 900 parts by weight, even more preferably from 400 parts by weight to 900 parts by weight.

<(meth)acrylic monomer (B)>
The photocurable composition of the present disclosure includes a (meth)acrylic monomer (B) having one (meth)acryloyl group.
One type of (meth)acrylic monomer (B) may be used alone, or two or more types may be used in combination.

By combining this (meth)acrylic monomer (B) having one (meth)acryloyl group with the above-mentioned (meth)acrylic monomer (A), it is possible to produce a three-dimensional object that has high toughness even after cleaning with isopropyl alcohol. becomes.

The (meth)acrylic monomer (B) of the present disclosure is preferably at least one of a compound represented by the following general formula (B-1) and a compound represented by the following general formula (B-2).

In formula (B-1), R ^1B1 is a monovalent organic group having one or more selected from the group consisting of an aromatic ring, a hydroxy group, and a carboxy group, and R ^2B1 is a methyl group or a hydrogen atom. be.
The aforementioned monovalent organic group in R ^1B1 is preferably a monovalent organic group having 2 to 30 carbon atoms, more preferably a monovalent organic group having 4 to 20 carbon atoms.
In formula (B-2), R ^1B2 and R ^2B2 are each independently a monovalent organic group, R ^1B2 and R ^2B2 may be combined with each other to form a ring, and R ^3B2 is a methyl group. Or a hydrogen atom.
The aforementioned monovalent organic group in R ^1B2 and R ^2B2 is preferably a monovalent organic group having 2 to 10 carbon atoms, more preferably a monovalent organic group having 2 to 5 carbon atoms.
When R ^1B2 and R ^2B2 are bonded to each other to form a ring, the ring may be a ring consisting of a nitrogen atom and a carbon atom, and the ring may be a ring consisting of a nitrogen atom or a heteroatom other than a nitrogen atom (for example, an oxygen atom). ) and a carbon atom.
When R ^1B2 and R ^2B2 are bonded to each other to form a ring, the ring may be a 4- to 8-membered ring, a 5-membered ring, or a 6-membered ring.

The (meth)acrylic monomer (B) of the present disclosure may contain two or more compounds represented by general formula (B-1), and may contain two or more compounds represented by general formula (B-2). It may contain a compound represented by one or more types of general formula (B-1) and one or more types of compounds represented by general formula (B-2) in combination. .

R ^1B1 is preferably a monovalent organic group having an aromatic ring, a monovalent organic group having a hydroxy group, or a monovalent organic group having a carboxyl group. Incidentally, a monovalent organic group having an aromatic ring and a hydroxy group, and a monovalent organic group having an aromatic ring and a carboxyl group are classified as monovalent organic groups having an aromatic ring.
When R ^1B1 is a monovalent organic group having a hydroxy group or a monovalent organic group having a carboxy group, the flexibility of the three-dimensional structure tends to improve.
The monovalent organic group having an aromatic ring may be a monovalent organic group having an aromatic ring and a hydroxy group.

The monovalent organic group having an aromatic ring may have the aromatic ring structure shown below. In the aromatic ring structure shown below, * indicates a bonding position.

The molecular weight of the (meth)acrylic monomer (B) is preferably from 125 to 300, more preferably from 130 to 280, even more preferably from 130 to 270.

From the viewpoint of obtaining a three-dimensional object with excellent bending elastic modulus, bending strength, and toughness, the content of the (meth)acrylic monomer (B) is determined based on 1000 parts by mass of the (meth)acrylic monomer component contained in the photocurable composition. , is preferably from 50 parts by weight to 700 parts by weight, more preferably from 100 parts by weight to 650 parts by weight, even more preferably from 100 parts by weight to 600 parts by weight.

From the viewpoint of obtaining a three-dimensional structure with excellent bending modulus, bending strength, and toughness, the content ratio of (meth)acrylic monomer (A) and (meth)acrylic monomer (B) ((meth)acrylic monomer (A): The (meth)acrylic monomer (B)) may have a ratio of 40:60 to 95:5, or may have a ratio of 45:55 to 90:10.

The photocurable composition of the present disclosure may contain photopolymerizable components other than the (meth)acrylic monomer (A) and (meth)acrylic monomer (B) (hereinafter referred to as "other photopolymerizable components"). good.
Other photopolymerizable components include compounds containing ethylenic double bonds.
Examples of compounds containing ethylenic double bonds include (meth)acrylic monomers other than (meth)acrylic monomer (A) and (meth)acrylic monomer (B), styrene, styrene derivatives, (meth)acrylonitrile, etc. .
Hereinafter, the (meth)acrylic monomer (A), the (meth)acrylic monomer (B), and other photopolymerizable components used as necessary are also referred to as photopolymerizable components.

From the viewpoint of mechanical strength in the three-dimensional object, the content of the photopolymerizable component with respect to the total amount of the photocurable composition of the present disclosure is preferably 60% by mass or more, and more preferably 80% by mass or more. , more preferably 90% by mass or more.
The upper limit of the content of the photopolymerizable component with respect to the total amount of the photocurable composition of the present disclosure is not particularly limited, and may be less than 100% by mass, and may be, for example, 99.9% by mass or less.

From the viewpoint of obtaining a three-dimensional object with excellent bending modulus, bending strength, and toughness, the total content of (meth)acrylic monomer (A) and (meth)acrylic monomer (B) is determined based on the total mass of the photopolymerizable component. , is preferably 50% 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 total content of (meth)acrylic monomer (A) and (meth)acrylic monomer (B) is not particularly limited, and may be 100% by mass or less based on the total mass of the photopolymerizable component.

The (meth)acrylic monomer that is another photopolymerizable component may include a (meth)acrylic monomer (C) represented by general formula (C-1).

In formula (C-1), R ^1C is a divalent hydrocarbon group, R ^2C and R ^3C are each independently an alkylene group having 2 or 3 carbon atoms, and R ^4C and R ^5C are Each independently represents a methyl group or a hydrogen atom.
The preferred configuration of R ^1C is the same as the preferred configuration of R ^1A in formula (A-1) above.
R ^2C and R ^3C are each independently an alkylene group having 2 or 3 carbon atoms. Examples of the alkylene group having 2 or 3 carbon atoms include ethylene group, propylene group, and methylethylene group. Both R ^2C and R ^3C are preferably ethylene groups.

Other (meth)acrylic monomers that are photopolymerizable components include (meth)acrylic monomers that have two (meth)acryloyl groups and no urethane bond, and (meth)acrylic monomers that have three or more (meth)acryloyl groups. Examples include (meth)acrylic monomers.

The content of other photopolymerizable components (preferably (meth)acrylic monomer (C)) is preferably 50% by mass or less, and preferably 20% by mass or less based on the total mass of the photopolymerizable components. is more preferable, and even more preferably 10% by mass or less.
The lower limit of the content of other photopolymerizable components (preferably (meth)acrylic monomer (C)) is not particularly limited, and may be 0% by mass or more based on the total mass of the photopolymerizable components.

<Photopolymerization initiator>
The photocurable composition of the present disclosure includes a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it generates radicals when irradiated with light, and is preferably one that generates radicals at the wavelength of light used during stereolithography.
The wavelength of the light used during stereolithography is generally 365 nm to 500 nm, but is practically preferably 365 nm to 430 nm, and more preferably 365 nm to 420 nm.
As photopolymerization initiators, acylphosphine oxide compounds, alkyl benzoylformates, alkylphenone compounds, titanocene compounds, oxime ester compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, thioxanthone compounds, Examples include α-acyloxime ester compounds, phenylglyoxylate compounds, benzyl compounds, azo compounds, diphenyl sulfide compounds, organic dye compounds, iron-phthalocyanine compounds, benzoin ether compounds, anthraquinone compounds, etc. It will be done.
The photopolymerization initiator may contain only one type, or may contain two or more types.

As the photopolymerization initiator, from the viewpoint of reactivity, acylphosphine oxide compounds and alkylphenone compounds are more preferable, and as the photopolymerization initiator, one or more acylphosphine oxide compounds may be used, or It is more preferable to use a combination of one or more acylphosphine oxide compounds and one or more alkylphenone compounds.

Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. can be mentioned.

Examples of the alkylphenone compounds include 1-hydroxy-cyclohexyl-phenyl-ketone.

The total content of photopolymerization initiators in the photocurable composition of the present disclosure is preferably 0.1% by mass to 10% by mass, and 0.3% by mass based on the total amount of the photocurable composition. It is more preferably from 8% by weight, and even more preferably from 0.5% to 5% by weight.

<Other ingredients>
The photocurable composition of the present disclosure may contain one or more types of components other than the above-mentioned components, if necessary.
When the photocurable composition contains other components, the total mass of the (meth)acrylic monomer (A), (meth)acrylic monomer (B), and photopolymerization initiator is based on the total amount of the photocurable composition. , 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. It is even more preferable.

Examples of other components include monomers other than the (meth)acrylic monomer (A) and (meth)acrylic monomer (B) (for example, the above-mentioned (meth)acrylic monomer (C)).
When the photocurable composition contains monomers other than (meth)acrylic monomer (A) and (meth)acrylic monomer (B) as other components, the content of the monomers as other components is It is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less based on the total mass of monomer (A) and (meth)acrylic monomer (B). The content is preferably 10% by mass or less, particularly preferably 10% by mass or less.

Other ingredients include, for example, colorants, coupling agents such as silane coupling agents (for example, 3-acryloxypropyltrimethoxysilane), rubber agents, ion trapping agents, ion exchange agents, leveling agents, plasticizers, and erasers. Additives such as foaming agents, thermal polymerization initiators, etc. may also be mentioned.
When the photocurable composition of the present disclosure contains a thermal polymerization initiator, photocuring and thermal curing can be used together. Examples of the thermal polymerization initiator include thermal radical generators and amine compounds.

Other components include inorganic fillers.
However, from the viewpoint of further improving the modeling precision of the cured product, the photocurable composition of the present disclosure does not contain an inorganic filler (for example, silica, barium borosilicate glass, etc.; the same applies hereinafter), or When a filler is included, the content of the inorganic filler is 60% by mass or less (more preferably 40% by mass or less, still more preferably 20% by mass or less, particularly preferably 10% by mass or less) based on the total amount of the photocurable composition. It is preferable that

The method for preparing the photocurable composition of the present disclosure is not particularly limited.
A method for preparing the photocurable composition of the present disclosure includes, for example, a method of mixing a (meth)acrylic monomer (A), a (meth)acrylic monomer (B), a photopolymerization initiator, and other components as necessary. can be mentioned.
The means for mixing each component is not particularly limited, and includes means such as ultrasonic dissolution, a double-arm stirrer, a roll kneader, a twin-screw extruder, a ball mill kneader, and a planetary stirrer.
The photocurable composition of this embodiment may be prepared by mixing each component, filtering the mixture through a filter to remove impurities, and further performing a vacuum defoaming treatment.

<Preferred viscosity of photocurable composition>
The photocurable composition of the present disclosure preferably has a viscosity (hereinafter also simply referred to as "viscosity") measured by 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 from 5 mPa·s to 6000 mPa·s, the photocurable composition has excellent handling properties when producing a cured product (particularly a stereolithographic product).
The viscosity is more preferably 10 mPa·s to 5000 mPa·s, even more preferably 20 mPa·s to 5000 mPa·s, even more preferably 100 mPa·s to 4500 mPa·s.

In the photocurable composition of the present disclosure, a cured layer A1 having a thickness of 50 μm is formed by irradiating the photocurable composition with visible light having a wavelength of 405 nm at an irradiation amount of 11 mJ/cm ^{2 .} By laminating in the thickness direction, a rectangular plate-shaped object A1 with a length of 64 mm, a width of 10 mm, and a thickness of 3.3 mm is formed, and the object A1 is irradiated with ultraviolet light with a wavelength of 365 nm at a dose of 10 J/ ^cm2. By doing so, when a rectangular plate-shaped test piece A1 having a length of 64 mm, a width of 10 mm, and a thickness of 3.3 mm is produced, the bending strength of the test piece A1 is 50 Mpa or more and the bending elastic modulus is 1500 Mpa or more. It is preferable.

In the photocurable composition of the present disclosure, a cured layer A2 having a thickness of 50 μm is formed by irradiating the photocurable composition with visible light having a wavelength of 405 nm at an irradiation amount of 11 mJ/cm ^{2 .} By laminating in the thickness direction, a rectangular plate-shaped object A2 having a length of 39 mm, a width of 8 mm, and a thickness of 4 mm is formed, and the object A2 is irradiated with ultraviolet light with a wavelength of 365 nm at a dose of 10 J/cm2 ^. When a rectangular plate-shaped test piece A2 having a length of 39 mm, a width of 8 mm, and a thickness of 4 mm is prepared, the total destructive work of the test piece A2 is preferably 500 J/m ² or more.

The upper limit of the bending strength of the test piece A1 is not particularly limited, and may be, for example, 90 MPa or less.
The upper limit of the flexural modulus of the test piece A1 is not particularly limited, and may be, for example, 3000 MPa or less.
The upper limit of the total destructive work of test piece A2 is not particularly limited, and may be 2000 J/m ² or less.

Regarding the test piece A1 that has been cleaned using IPA, the bending strength of the test piece A1 and the bending elastic modulus of the test piece A1 may satisfy the above-mentioned numerical conditions.
Regarding the test piece A2 that has been cleaned using IPA, the total destructive work of the test piece A2 may satisfy the above-mentioned numerical conditions.
Examples of the cleaning method using IPA include the method described in Examples below.

When the test piece A1 obtained from the photocurable composition of the present disclosure satisfies the above-mentioned conditions of bending strength and bending elastic modulus, an appliance to be worn in the oral cavity with excellent mechanical strength tends to be obtained.
When the test piece A2 obtained from the photocurable composition of the present disclosure satisfies the above-mentioned total work of failure condition, an appliance that is worn in the oral cavity and has excellent toughness tends to be obtained.

[Three-dimensional object]
The three-dimensional structure of the present disclosure includes a cured product of the photocurable composition of the present disclosure.
Therefore, the three-dimensional structure of the present disclosure has high toughness even after cleaning with isopropyl alcohol.
It is preferable that the three-dimensional shaped article of the present disclosure includes a cured product obtained by stereolithography (i.e., a stereolithographic article).
The method for producing a cured product (for example, a stereolithographic product) is as described above.

[Appliances installed in the oral cavity]
The intraoral appliance of the present disclosure includes the three-dimensional structure of the present disclosure described above.
Therefore, the intraoral appliance of the present disclosure has high toughness even after cleaning with isopropyl alcohol.
Specific examples of appliances to be installed in the oral cavity are as described above, and include, for example, dentures, splints, and the like.

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

[Examples 1 to 19, Comparative Examples 1 to 3]
<Preparation of photocurable composition>
The components shown in Tables 1 to 4 below were mixed to obtain a photocurable composition.

<Measurement and evaluation>
The following measurements and evaluations were performed using the obtained photocurable composition. The results are shown in Tables 1 to 4.

(IPA cleaning method)
Using a 3D printer (Kulzer, Cara Print 4.0), the obtained photocurable composition was irradiated with visible light with a wavelength of 405 nm at a dose of 11 mJ/cm ² to form a cured layer A1 with a thickness of 50 μm. By laminating the cured layers A1 in the thickness direction, a model having a length of 64 mm, a width of 10 mm, and a thickness of 3.3 mm was obtained to obtain a model A1. The obtained model A1 was immersed in isopropyl alcohol (IPA) and washed for 5 minutes using an ultrasonic cleaner with an output of 60 W. After drying the cleaned model A1 with air blow, the model A1 was subjected to stereolithography under the conditions of irradiating ultraviolet rays with a wavelength of 365 nm at an irradiation amount of 10 J/cm ² to a length of 64 mm, a width of 10 mm, A rectangular plate-shaped test piece A1 with a thickness of 3.3 mm was obtained.
Similarly, using a 3D printer (Kulzer, Cara Print 4.0), the photocurable composition was irradiated with visible light with a wavelength of 405 nm at a dose of 11 mJ/cm ² to form a cured layer A2 with a thickness of 50 μm. , the length was 39 mm, the width was 8 mm, and the thickness was 4 mm to obtain a model A2. The obtained model A2 was immersed in isopropyl alcohol and washed for 5 minutes using an ultrasonic cleaner with an output of 60 W. After drying the cleaned model A2 with air blow, the model A2 was subjected to stereolithography under the conditions of irradiating ultraviolet rays with a wavelength of 365 nm at an irradiation amount of 10 J/cm ² to a length of 39 mm, a width of 8 mm, A rectangular plate-shaped test piece A2 with a thickness of 4 mm was obtained.
The test pieces that were not washed with IPA were irradiated with ultraviolet rays with a wavelength of 365 nm without going through the above-mentioned isopropyl alcohol immersion step to obtain test pieces A1 and A2, respectively.
Note that the above-mentioned cleaning method using IPA is an example, and the cleaning method using IPA is not limited to the method described in the Examples.
In addition, for each of Examples 1 to 3 and each of Comparative Examples 1 to 3, with IPA cleaning (Example 1B to Example 3B, Comparative Example 1B to Comparative Example 3B) and without IPA cleaning (Example 1A to Example 3A, Comparisons with Comparative Examples 1A to 3A) are shown in Tables 1 to 4.
For Examples 4 to 19, only those with IPA washing (Example 4B to Example 19B) are shown.

(Viscosity of photocurable composition)
The viscosity of the photocurable composition was measured using an E-type viscometer at 25° C. and 50 rpm.

(Bending strength and bending elastic modulus of stereofabricated object)
The obtained test piece A1 (hereinafter referred to as "test piece") was stored in a constant temperature water bath at 37±1° C. for 50±2 hours.
Thereafter, the test piece was taken out from the constant temperature water bath, and the flexural strength and flexural modulus of the taken out test piece were measured in accordance with ISO20795-1:2008. These measurements were performed using a tensile testing device (manufactured by Intesco Co., Ltd.) at a tensile speed of 5±1 mm/min.

(Total fracture work in fracture toughness test by bending test)
The obtained test piece A2 (hereinafter referred to as "test piece") was notched in accordance with ISO20795-1:2008 and stored in a constant temperature water bath at 37±1° C. for 7 days±2 hours.
Thereafter, the test piece was taken out from the constant temperature water bath, and the taken out test piece was subjected to a fracture toughness test using a bending test in accordance with ISO20795-1:2008, and the total work of fracture (J/m ² ) was measured. The fracture toughness test (i.e., measurement of total fracture work) by bending test was performed using a tensile testing device (manufactured by Intesco Corporation) at an indentation speed of 1.0±0.2 mm/min.

In Tables 1 to 4, the numbers in the "Composition" column in each Example and Comparative Example mean parts by mass, and a blank column means that the corresponding component is not contained.

<(meth)acrylic monomer (A)>
In Tables 1 to 4, it has two urethane bonds and two (meth)acryloyl groups, and each of the two (meth)acryloyl groups has an oxygen atom for each of the two urethane bonds. The compounds classified as (meth)acrylic monomers (A) that are linked via an alkylene group having 4 to 10 carbon atoms to which a nitrogen atom is bonded are specifically the following UDA1 to 4.

UDA1: Compound produced in Production Example 1 UDA2: Compound produced in Production Example 2 UDA3: Compound produced in Production Example 3 UDA4: Compound produced in Production Example 4

<(meth)acrylic monomer (B)>
In Tables 1 to 4, the compounds classified as (meth)acrylic monomers (B) having one (meth)acryloyl group are specifically the following compounds.

BZA: Benzyl acrylate, manufactured by Osaka Organic Chemical Industry PO-A: Phenoxyethyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd. 4-HBA: 4-Hydroxybutyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. POB-A: m-phenoxybenzyl acrylate, manufactured by Kyoeisha Chemical Company A- LEN-10: Ethoxylated-o-phenylphenol acrylate, manufactured by Shin Nakamura Chemical Industries, Ltd. ACMO: 4-acryloylmorpholine, manufactured by KJ Chemicals M5700: 2-hydroxy-3-phenoxypropyl acrylate, manufactured by Toagosei HOMS: 2-methacryloyloxyethyl Succinic acid, manufactured by Kyoeisha Chemical HEMA: 2-hydroxyethyl acrylate, manufactured by Kyoeisha Chemical PO: Phenoxyethyl methacrylate, manufactured by Kyoeisha Chemical

<(meth)acrylic monomer (C)>
In Tables 1 to 4, the compounds classified as (meth)acrylic monomers (C) represented by the above-mentioned general formula (C-1) are specifically the following UDA5 to 7.

UDA5: Compound produced in Production Example 5 UDA6: Compound produced in Production Example 6 UDA7: Compound produced in Production Example 7

<Photopolymerization initiator>
In Tables 1 to 4, the compounds classified as photoinitiators are specifically the following photoinitiators 1 to 4.

Omnirad 819: Acylphosphine oxide compound (manufactured by IGM Resins B.V.)
Omnirad 184: Alkylphenone compound (manufactured by IGM Resins B.V.)
Omnirad TPO: Acylphosphine oxide compound (manufactured by IGM Resins B.V.)

Production Examples 1 to 7 will be explained below.
In addition, explanations of abbreviations in the following production examples are shown below.
HEA: 2-hydroxyethyl acrylate 2-HPA: 2-hydroxypropyl acrylate 4-HBA: 4-hydroxybutyl acrylate DBTDL: dibutyltin dilaurate MEHQ: 4-methoxyphenol TMXDI: 1,3-tetramethylxylylene diisocyanate XDI: m-xylylene diisocyanate NBDI: norbornane-2,6-diylbis(methylene) diisocyanate H6XDI: 1,3-bis(isocyanatomethyl)cyclohexane

(Production example 1: Production of UDA1)
In a 1 liter 4-necked flask equipped with a sufficiently dried stirring blade and a thermometer, 288 g (2.00 mol) of 4-HBA and 0.48 g (0.4 g of DBTDL based on the total mass of 4-HBA and XDI) were placed. .1% by mass) and 0.24 g of MEHQ (0.05% by mass based on the total mass of 4-HBA and XDI) were added, stirred until homogeneous, and then heated to 60°C. Subsequently, 188 g (1.00 mol) of XDI was added dropwise over 1 hour. During the dropping, the internal temperature rose due to the heat of reaction, so the amount of dropping was controlled to keep it below 80°C. After dropping the entire amount, the reaction temperature was maintained at 80°C and the reaction was carried out for 10 hours. At this time, the progress of the reaction was followed by HPLC analysis to confirm the end point of the reaction. By discharging the product from the reactor, 445 g of urethane acrylate (UDA1) was obtained. The viscosity at 65°C was 430 mPa·s.

(Production example 2: Production of UDA2)
In a 1 liter 4-necked flask equipped with a sufficiently dried stirring blade and a thermometer, 288 g (2.00 mol) of 4-HBA and 0.48 g of DBTDL (based on the total mass of 4-HBA and TMXDI) were added. 0.1% by mass) and 0.24 g of MEHQ (0.05% by mass based on the total mass of 4-HBA and TMXDI) were added, stirred until homogeneous, and then heated to 60°C. Subsequently, 244 g (1.00 mol) of TMXDI was added dropwise over 1 hour. During the dropping, the internal temperature rose due to the heat of reaction, so the amount of dropping was controlled to keep it below 80°C. After dropping the entire amount, the reaction temperature was maintained at 80°C and the reaction was carried out for 10 hours. At this time, the progress of the reaction was followed by HPLC analysis to confirm the end point of the reaction. By discharging the product from the reactor, 510 g of urethane acrylate (UDA2) was obtained. The viscosity at 65°C was 1600 mPa·s.

(Production example 3: Production of UDA3)
In a 1 liter 4-necked flask equipped with a sufficiently dried stirring blade and a thermometer, 390 g (2.70 mol) of 4-HBA and 0.67 g of DBTDL (based on the total mass of 4-HBA and NBDI) were added. 0.1% by mass) and 0.34g of MEHQ (0.05% by mass based on the total mass of 4-HBA and NBDI) were added, stirred until homogeneous, and then heated to 60°C. Subsequently, 278 g (1.35 mol) of NBDI was added dropwise over 1 hour. During the dropping, the internal temperature rose due to the heat of reaction, so the amount of dropping was controlled to keep it below 80°C. After dropping the entire amount, the reaction temperature was maintained at 80°C and the reaction was carried out for 10 hours. At this time, the progress of the reaction was followed by HPLC analysis to confirm the end point of the reaction. By discharging the product from the reactor, 630 g of urethane acrylate (UDA3) was obtained. The viscosity at 65°C was 360 mPa·s.

(Production example 4: Production of UDA4)
In a 1 liter 4-necked flask equipped with a sufficiently dried stirring blade and a thermometer, 288 g (2.00 mol) of 4-HBA and 0.48 g of DBTDL (based on the total mass of 4-HBA and H6XDI) were added. 0.1% by mass) and 0.24 g of MEHQ (0.05% by mass based on the total mass of 4-HBA and H6XDI) were added, stirred until homogeneous, and then heated to 60°C. Subsequently, 194 g (1.00 mol) of H6XDI was added dropwise over 1 hour. During the dropping, the internal temperature rose due to the heat of reaction, so the amount of dropping was controlled to keep it below 80°C. After dropping the entire amount, the reaction temperature was maintained at 80°C and the reaction was carried out for 10 hours. At this time, the progress of the reaction was followed by HPLC analysis to confirm the end point of the reaction. By discharging the product from the reactor, 450 g of urethane acrylate (UDA4) was obtained. The viscosity at 65°C was 340 mPa·s.

(Production example 5: Production of UDA5)
In a 1 liter 4-necked flask equipped with a sufficiently dried stirring blade and a thermometer, 232 g (2.00 mol) of HEA and 0.48 g of DBTDL (0.1 mass relative to the total mass of HEA and TMXDI) were placed. %) and 0.24 g of MEHQ (0.05% by mass based on the total mass of HEA and TMXDI) were added, stirred until homogeneous, and then heated to 60°C. Subsequently, 244 g (1.00 mol) of TMXDI was added dropwise over 1 hour. During the dropping, the internal temperature rose due to the heat of reaction, so the amount of dropping was controlled to keep it below 80°C. After dropping the entire amount, the reaction temperature was maintained at 80°C and the reaction was carried out for 10 hours. At this time, the progress of the reaction was followed by HPLC analysis to confirm the end point of the reaction. By discharging the product from the reactor, 455 g of urethane acrylate (UDA5) was obtained. The viscosity at 65°C was 2200 mPa·s.

(Production example 6: Production of UDA6)
In a 1 liter 4-necked flask equipped with a sufficiently dried stirring blade and a thermometer, 418 g (3.21 mol) of 2HPA and 0.72 g (0.72 g of DBTDL based on the total mass of 2-HPA and XDI) were placed. 1% by mass) and 0.36 g of MEHQ (0.05% by mass based on the total mass of 2-HPA and XDI) were added, stirred until homogeneous, and then heated to 60°C. Subsequently, 303 g (1.61 mol) of XDI was added dropwise over 1 hour. During the dropping, the internal temperature rose due to the heat of reaction, so the amount of dropping was controlled to keep it below 80°C. After dropping the entire amount, the reaction temperature was maintained at 80°C and the reaction was carried out for 10 hours. At this time, the progress of the reaction was followed by HPLC analysis to confirm the end point of the reaction. By discharging the product from the reactor, 690 g of urethane acrylate (UDA7) were obtained. The viscosity at 65°C was 570 mPa·s.

(Production example 7: Production of UDA7)
In a 1 liter 4-neck flask equipped with a sufficiently dried stirring blade and a thermometer, 372 g (3.20 mol) of HEA and 0.70 g of DBTDL (0.1 mass relative to the total mass of HEA and NBDI) %) and 0.35 g of MEHQ (0.05% by mass based on the total mass of HEA and NBDI) were added, stirred until homogeneous, and then heated to 60°C. Subsequently, 330 g (1.60 mol) of NBDI was added dropwise over 1 hour. During the dropping, the internal temperature rose due to the heat of reaction, so the amount of dropping was controlled to keep it below 80°C. After dropping the entire amount, the reaction temperature was maintained at 80°C and the reaction was carried out for 10 hours. At this time, the progress of the reaction was followed by HPLC analysis to confirm the end point of the reaction. By discharging the product from the reactor, 670 g of urethane acrylate (UDA7) was obtained. The viscosity at 65°C was 930 mPa·s.

As shown in Table 1, by using the photocurable compositions of Examples 1 to 3, no particular change in total fracture work was observed in the fracture toughness test by bending test before and after IPA cleaning.
On the other hand, as shown in Table 4, when the photocurable compositions of Comparative Examples 1 to 3 were used, it was confirmed that the total fracture work was significantly reduced in the fracture toughness test by bending test after IPA cleaning.
From the above results, by using the photocurable compositions of Examples 1 to 3, it was possible to obtain three-dimensional objects that had high toughness even after cleaning with isopropyl alcohol.
In each of Examples 4 to 19, after IPA cleaning, the value of total fracture work in the fracture toughness test by bending test was obtained which was comparable to that when using the photocurable composition of each of Examples 1 to 3. . Furthermore, after IPA cleaning, the total work of fracture was much larger than the value of the total work of fracture in the fracture toughness test by bending test when the photocurable compositions of Comparative Examples 1 to 3 were used. Therefore, by using the photocurable compositions of Examples 4 to 19, it was possible to obtain three-dimensional objects that had high toughness even after cleaning with isopropyl alcohol.

The disclosure of Japanese Patent Application No. 2022-054222 filed on March 29, 2022 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards mentioned herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference. Incorporated herein by reference.

Claims (15)

It has two urethane bonds and two (meth)acryloyl groups, and each of the two (meth)acryloyl groups has a carbon atom to which an oxygen atom or a nitrogen atom is bonded to each of the two urethane bonds. (meth)acrylic monomer (A) connected via several 4 to 10 alkylene groups,
(meth)acrylic monomer (B) having one (meth)acryloyl group,
A photocurable composition comprising a photopolymerization initiator. The photocurable composition according to claim 1, wherein the (meth)acrylic monomer (A) is a compound represented by the following general formula (A-1).


(In formula (A-1), R ^1A is a divalent hydrocarbon group, R ^2A and R ^3A are each independently an alkylene group having 4 to 10 carbon atoms, and R ^4A and R ^5A are , each independently a methyl group or a hydrogen atom) The photocurable composition according to claim 2, wherein R ^1A in the general formula (A-1) is a divalent hydrocarbon group having 5 to 20 carbon atoms. The photocurable composition according to claim 2, wherein R ^1A in the general formula (A-1) is a group represented by any of the following general formulas (a-1) to (a-7). .

(In formulas (a-1) to (a-7), * indicates the bonding position.) The (meth)acrylic monomer (B) is at least one of a compound represented by the following general formula (B-1) and a compound represented by the following general formula (B-2). 4. The photocurable composition according to any one of 4.

(In formula (B-1), R ^1B1 is a monovalent organic group having one or more selected from the group consisting of an aromatic ring, a hydroxy group, and a carboxy group, and R ^2B1 is a methyl group or a hydrogen atom. In formula (B-2), R ^1B2 and R ^2B2 are each independently a monovalent organic group, R ^1B2 and R ^2B2 may be combined with each other to form a ring, and R ^3B2 is , a methyl group or a hydrogen atom) The photocurable composition according to any one of claims 1 to 5, wherein the (meth)acrylic monomer (A) has a molecular weight of 440 to 650. The photocurable composition according to any one of claims 1 to 6, wherein the (meth)acrylic monomer (B) has a molecular weight of 125 to 300. The content of the (meth)acrylic monomer (A) is 300 parts by mass to 950 parts by mass based on 1000 parts by mass of the (meth)acrylic monomer component contained in the photocurable composition. 7. The photocurable composition according to any one of 7. The content of the (meth)acrylic monomer (B) is 50 parts by mass to 700 parts by mass based on 1000 parts by mass of the (meth)acrylic monomer component contained in the photocurable composition. 8. The photocurable composition according to any one of 8. The photocurable composition according to any one of claims 1 to 9, which has a viscosity of 5 mPa·s to 6000 mPa·s as measured by an E-type viscometer at 25° C. and 50 rpm. A photocurable composition was irradiated with visible light with a wavelength of 405 nm at a dose of 11 mJ/cm ² to form a cured layer A1 with a thickness of 50 μm, and the cured layer A1 was laminated in the thickness direction to form a cured layer A1 with a length of 64 mm. By forming a rectangular plate-shaped object A1 with a width of 10 mm and a thickness of 3.3 mm, and irradiating the object A1 with ultraviolet light with a wavelength of 365 nm at a dose of 10 J/cm ² , a length of 64 mm and a width of 10 mm, When a rectangular plate-shaped test piece A1 with a thickness of 3.3 mm is produced, the bending strength of the test piece A1 is 50 Mpa or more, the bending elastic modulus is 1500 Mpa or more, and
A photocurable composition was irradiated with visible light with a wavelength of 405 nm at a dose of 11 mJ/cm ² to form a cured layer A2 with a thickness of 50 μm, and the cured layer A2 was laminated in the thickness direction to form a layer with a length of 39 mm. , a rectangular plate-shaped object A2 with a width of 8 mm and a thickness of 4 mm is formed, and by irradiating the object A2 with ultraviolet light with a wavelength of 365 nm at a dose of 10 J/cm2, the object ^A2 has a length of 39 mm, a width of 8 mm, and a thickness of 4 mm. The photocurable composition according to any one of claims 1 to 10, wherein when a rectangular plate-shaped test piece A2 is produced, the total work of fracture of the test piece A2 is 500 J/m ² or more. thing. The photocurable composition according to any one of claims 1 to 11, which is used for stereolithography. The photocurable composition according to any one of claims 1 to 12, which is used for manufacturing a device to be mounted in the oral cavity by stereolithography. A three-dimensional object comprising a cured product of the photocurable composition according to any one of claims 1 to 13. An appliance to be worn in the oral cavity, comprising the three-dimensional structure according to claim 14.