Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
  • A61C19/00—Dental auxiliary appliances
  • A61C19/003—Apparatus for curing resins by radiation
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
  • A61K6/62—Photochemical radical initiators
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/70—Preparations for dentistry comprising inorganic additives
  • A61K6/71—Fillers
  • A61K6/74—Fillers comprising phosphorus-containing compounds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
  • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
  • B29C64/10—Processes of additive manufacturing
  • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
  • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y70/00—Materials specially adapted for additive manufacturing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y80/00—Products made by additive manufacturing
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light

Definitions

• the present disclosure relates to a photocurable composition, a three-dimensional object, a dental product, and a splint.
• dental products worn in the oral cavity are sometimes worn all the time, such as during the day, and are therefore required to be aesthetically pleasing.
• dental products may be made more transparent to improve aesthetics.
• a coloring component such as a coloring material
• transparency may be insufficient due to the coloring of the photocurable resin itself.
• it may be possible to improve transparency by reducing the thickness of the product itself.
• the mechanical strength tends to decrease, and the mechanical strength may be insufficient in applications that require a certain level of mechanical strength for use in the oral cavity, such as splints for treating temporomandibular joint disorders.
• An object of one aspect of the present disclosure is to provide a photocurable composition capable of producing a cured product that has both high mechanical strength and high transparency, and a three-dimensional molded article containing the cured product of this photocurable composition, a dental and Sprint products.
• a photocurable composition containing a photopolymerizable component and a photopolymerization initiator A cured layer A1 having a thickness of 50 ⁇ m is formed by irradiating the photocurable composition with visible light having a wavelength of 405 nm at a dose of 11 mJ/cm 2 , and by laminating the cured layer A1 in the thickness direction, the length A rectangular plate-shaped object A1 of 50 mm, width 40 mm, and thickness 4.5 mm is formed, and after irradiating the object A1 with ultraviolet light with a wavelength of 365 nm at a dose of 10 J/cm 2 , a 50 mm x 40 mm surface is coated on both sides.
• a cured layer A1 having a thickness of 50 ⁇ m is formed by irradiating the photocurable composition with visible light having a wavelength of 405 nm at a dose of 11 mJ/cm 2 , and by laminating the cured layer A1 in the thickness direction, the length A rectangular plate-shaped object A2 of 64 mm, width 10 mm, and thickness 3.3 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 length is 64 mm and the width is 10 mm.
• a photocurable composition wherein when a rectangular plate-shaped test piece A2 having a thickness of 3.3 mm is prepared, the bending strength of the test piece A2 is 50 MPa or more and the bending elastic modulus is 1500 MPa or more.
• the photopolymerizable component is A mono(meth)acrylic monomer (A-1) having one (meth)acryloyloxy group and having no cyclic structure, and a mono(meth)acrylic monomer (A-1) having two (meth)acryloyloxy groups and having no cyclic structure.
• the photocurable composition according to ⁇ 2> or ⁇ 3> which satisfies at least one of the following (1) or (2).
• the (meth)acrylic monomer (A) includes the mono(meth)acrylic monomer (A-1), and the mono(meth)acrylic monomer (A-1) has a molecular weight of 100 to 500.
• the molecular weight of the di(meth)acrylic monomer (A-2) is 400 to 1000.
• the (meth)acrylic monomer (B) contains the di(meth)acrylic monomer (B-1), and the di(meth)acrylic monomer (B-1) has a molecular weight of 200 to 800.
• the (meth)acrylic monomer (B) includes the di(meth)acrylic monomer (B-2), and the di(meth)acrylic monomer (B-2) has a molecular weight of 170 to 700.
• the (meth)acrylic monomer (B) includes the tri(meth)acrylic monomer (B-3), and the tri(meth)acrylic monomer (B-3) has a molecular weight of 200 to 1,500.
• ⁇ 8> Any one of ⁇ 2> to ⁇ 7>, wherein the content of the (meth)acrylic monomer (B) is 25% by mass to 90% by mass with respect to the total amount of the (meth)acrylic monomer component.
• the photocurable composition described in . ⁇ 9> Any one of ⁇ 2> to ⁇ 8>, wherein the content of the (meth)acrylic monomer (C) is 5% by mass to 70% by mass with respect to the total amount of the (meth)acrylic monomer component.
• the photocurable composition described in . ⁇ 10> The photocurable composition according to any one of ⁇ 1> to ⁇ 9>, wherein the photopolymerization initiator contains an acylphosphine oxide compound.
• a photocurable composition comprising a photopolymerizable component and a photopolymerization initiator, A photocurable composition, wherein the photopolymerization initiator contains an acylphosphine oxide compound and an alkyl benzoylformate compound.
• the photopolymerizable component is Di(meth)acrylic monomer (B-1) having two (meth)acryloyloxy groups and having a cyclic structure, having two (meth)acryloyloxy groups and one of the (meth)acryloyloxy groups A di(meth)acrylic monomer (B-2) in which the distance between an oxygen atom forming an oxy group and an oxygen atom forming an oxy group in the other (meth)acryloyloxy group is less than 25 ⁇ ( one or more (meth)acrylic monomers selected from the group consisting of (excluding di(meth)acrylic monomers (B-1)), and tri(meth)acrylic monomers (B-3) having three (meth)acryloyloxy groups); ) acrylic monomer (B); (meth)acrylic monomer (C) having one (meth)acryloyloxy group and having an aromatic structure;
• the (meth)acrylic monomer (B) includes the di(meth)acrylic monomer (B-1), and the di(meth)acrylic monomer (B-1) has a molecular weight of 200 to 800.
• the (meth)acrylic monomer (B) includes the di(meth)acrylic monomer (B-2), and the di(meth)acrylic monomer (B-2) has a molecular weight of 170 to 700.
• the (meth)acrylic monomer (B) includes the tri(meth)acrylic monomer (B-3), and the tri(meth)acrylic monomer (B-3) has a molecular weight of 200 to 1,500.
• ⁇ 17> The photocurable composition according to any one of ⁇ 1> to ⁇ 16>, 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.
• ⁇ 18> The photocurable composition according to any one of ⁇ 1> to ⁇ 17>, which is a photocurable composition for stereolithography.
• ⁇ 19> The photocurable composition according to any one of ⁇ 1> to ⁇ 18>, which is used for manufacturing a splint by stereolithography.
• ⁇ 20> A three-dimensional object comprising a cured product of the photocurable composition according to any one of ⁇ 1> to ⁇ 19>.
• ⁇ 21> A dental product comprising the three-dimensional structure according to ⁇ 20>.
• ⁇ 22> A sprint including the three-dimensional structure according to ⁇ 20>.
• a photocurable composition capable of producing a cured product having both high mechanical strength and high transparency, a three-dimensional molded article containing the cured product of the photocurable composition, and a dental products and sprints.
• a numerical range expressed using “ ⁇ ” means a range that includes the numerical values written before and after " ⁇ " as lower and upper limits.
• 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.
• 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. .
• the upper limit or lower limit of the numerical range may be replaced with the values shown in the Examples.
• “light” is a concept that includes active energy rays such as ultraviolet rays and visible light.
• (meth)acrylate means acrylate or methacrylate
• (meth)acryloyl means acryloyl or methacryloyl
• (meth)acrylic means acrylic or methacrylic
• the photocurable composition of the present disclosure the photocurable composition of the first aspect and the photocurable composition of the second aspect will be explained.
• the configuration and preferred configuration described in the first aspect and the configuration and preferred configuration described in the second aspect may be combined as appropriate.
• descriptions of matters common to the first aspect will be omitted.
• the photocurable composition of the first aspect is a photocurable composition containing a photopolymerizable component and a photopolymerization initiator, A cured layer A1 having a thickness of 50 ⁇ m is formed by irradiating the photocurable composition with visible light having a wavelength of 405 nm at a dose of 11 mJ/cm 2 , and by laminating the cured layer A1 in the thickness direction, the length A rectangular plate-shaped object A1 of 50 mm, width 40 mm, and thickness 4.5 mm is formed, and after irradiating the object A1 with ultraviolet light with a wavelength of 365 nm at a dose of 10 J/cm 2 , a 50 mm x 40 mm surface is coated on both sides.
• a cured layer A1 having a thickness of 50 ⁇ m is formed by irradiating the photocurable composition with visible light having a wavelength of 405 nm at a dose of 11 mJ/cm 2 , and by laminating the cured layer A1 in the thickness direction, the length A rectangular plate-shaped object A2 of 64 mm, width 10 mm, and thickness 3.3 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 length is 64 mm and the width is 10 mm.
• the bending strength of the test piece A2 was 50 MPa or more, and the bending elastic modulus was 1500 MPa or more.
• test piece A1 and test piece A2 may be produced by the method described in Examples below.
• 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.
• 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).
• 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.
• 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).
• 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.
• the liquid bath type stereolithography is preferably DLP type stereolithography.
• a vertically movable build table for example, 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.
• a light source e.g., an LED light source
• a 3D printer for example, "Cara Print 4.0" manufactured by Kulzer, "Max UV” manufactured by Asiga, etc.
• a one-layer gap is first created between the build table and the tray, and the gap is filled with a photocurable composition.
• 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.
• 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.
• the manufactured three-dimensional structure may be further hardened by further irradiating the three-dimensional structure with light.
• stereolithography using the DLP method for example, the descriptions in Japanese Patent No. 5111880 and Japanese Patent No. 5235056 may be referred to.
• 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 both high mechanical strength and high transparency.
• dental products include dental prostheses, medical instruments used in the oral cavity, dental models, investment casting models, and the like.
• dental prostheses include inlays, crowns, bridges, temporary crowns, and temporary bridges.
• Medical devices used in the oral cavity include dentures (e.g., complete dentures, partial dentures, etc.), mouthpieces, mouth guards, orthodontic appliances, occlusal splints, and temporomandibular joints.
• splints such as splints for medical treatment, trays for impression taking, surgical guides, etc.
• the dental model include a tooth and jaw model.
• the photocurable composition of the present disclosure is preferably a photocurable composition for stereolithography, more preferably a photocurable composition used for manufacturing dental products by stereolithography, and is more preferably a photocurable composition for use in stereolithography. More preferably, it is a photocurable composition used in the production of splints.
• the photocurable composition of the present disclosure includes at least one photopolymerizable component.
• the photopolymerizable component include compounds containing an ethylenic double bond.
• compounds containing ethylenic double bonds include (meth)acrylic monomers, styrene, styrene derivatives, (meth)acrylonitrile, and the like.
• the photopolymerizable component As the photopolymerizable component, the photopolymerizable components described in paragraphs 0030 to 0059 of International Publication No. 2019/189652 may be used.
• 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, more preferably 80% by mass or more, More preferably, it is 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.
• the photopolymerizable component preferably contains at least one (meth)acrylic monomer.
• the (meth)acrylic monomer means a monomer having one or more (meth)acryloyl groups in the molecule.
• all the (meth)acrylic monomers contained in the photocurable composition may be referred to as "(meth)acrylic monomer components", and all the (meth)acrylic monomers contained in the photocurable composition of the present disclosure
• the total content of (meth)acrylic monomers may be referred to as "total content of (meth)acrylic monomer components.”
• the total content of (meth)acrylic monomer components based on the total amount of photopolymerizable components in the photocurable composition of the first aspect is preferably 80% by mass or more, more preferably 90% by mass or more. It is preferably 95% by mass or more, and more preferably 95% by mass or more.
• the upper limit of the total content of (meth)acrylic monomer components relative to the total amount of photopolymerizable components in the photocurable composition of the first aspect is not particularly limited, and may be 100% by mass or less.
• the total content of the (meth)acrylic monomer component with respect to the total amount of the photocurable composition of the first aspect is preferably 60% by mass or more, and 80% by mass or more. It is more preferable that the amount is 90% by mass or more.
• the upper limit of the total content of (meth)acrylic monomer components relative to the total amount of the photocurable composition of the first aspect is not particularly limited, and may be less than 100% by mass, for example, 99.9% by mass or less. It's okay.
• 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.
• a (meth)acrylic monomer may be a monofunctional (meth)acrylic monomer (i.e., a monomer having one (meth)acryloyloxy group in the molecule) or a difunctional (meth)acrylic monomer (i.e., a monomer having one (meth)acryloyloxy group in the molecule).
• the monomer has two (meth)acryloyloxy groups
• it is a polyfunctional (meth)acrylic monomer (i.e., a trifunctional or more functional (meth)acrylic monomer; i.e., a monomer with three or more (meth)acryloyl groups in the molecule.
• a monomer having an oxy group may also be used.
• the photopolymerizable component is A mono(meth)acrylic monomer (A-1) having one (meth)acryloyloxy group and having no cyclic structure, and a mono(meth)acrylic monomer (A-1) having two (meth)acryloyloxy groups and having no cyclic structure.
• 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 ⁇ or more.
• (meth)acrylic monomer (A), (meth)acrylic monomer (B), and (meth)acrylic monomer (C) it is possible to suitably produce a cured product that has both high mechanical strength and high transparency. It is. For example, using (meth)acrylic monomer (A) tends to increase the transparency of the cured product, and using (meth)acrylic monomer (B) tends to increase the mechanical strength of the cured product. There is a tendency that the transparency and mechanical strength of the cured product can be adjusted by using the (meth)acrylic monomer (C).
• the (meth)acrylic monomer (A) includes one or more selected from the group consisting of the aforementioned mono(meth)acrylic monomer (A-1) and the aforementioned di(meth)acrylic monomer (A-2). include.
• the mono(meth)acrylic monomer (A-1) and the di(meth)acrylic monomer (A-2) may be used individually, or in combination of two or more.
• the mono(meth)acrylic monomer (A-1) is a (meth)acrylic monomer component that has one (meth)acryloyloxy group and does not have a cyclic structure.
• the mono(meth)acrylic monomer (A-1) does not contain a cyclic structure.
• the cyclic structure include an aromatic structure and an alicyclic structure.
• the mono(meth)acrylic monomer (A-1) may contain a (meth)acrylic monomer component having one (meth)acryloyloxy group and a hydrocarbon group which may have a substituent.
• a hydrocarbon group which may have a substituent examples include a hydroxy group, an amino group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a carbonyl group, a carboxy group, an ethyleneoxy group, Examples include propyleneoxy group.
• the carbon number of the hydrocarbon group which may have a substituent may be 4 to 30, 5 to 20, or 6 to 18. Good too.
• the mono(meth)acrylic monomer (A-1) includes a (meth)acrylic monomer component having one (meth)acryloyloxy group and a hydrocarbon group, and a (meth)acrylic monomer component having one (meth)acryloyloxy group and a hydroxy group. It may contain one or more selected from the group consisting of meth)acrylic monomer components. From the viewpoint of toughness in the cured product, it is preferable to include a (meth)acrylic monomer component having one (meth)acryloyloxy group and one hydroxyl group.
• the molecular weight of the mono(meth)acrylic monomer (A-1) is preferably 100 to 500, more preferably 100 to 400, and preferably 100 to 300 from the viewpoint of mechanical strength in the cured product. More preferred.
• Alkyl (meth)acrylates such as octyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; Hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, EO-modified or PO-modified (meth)acrylates such as methoxy-polyethylene glycol (meth)acrylate, ethoxy-polyethylene glycol (meth)acrylate, and methoxypolypropylene glycol (meth)acrylate; Aminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate and diethylaminoethy
• the di(meth)acrylic monomer (A-2) has two (meth)acryloyloxy groups, does not have a cyclic structure, and has oxygen forming an oxy group in one (meth)acryloyloxy group.
• the di(meth)acrylic monomer (A-2) does not contain a cyclic structure.
• the cyclic structure include an aromatic structure and an alicyclic structure.
• the di(meth)acrylic monomer (A-2) may have at least one of an ethyleneoxy group and a propyleneoxy group.
• d1 i.e., 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
• d1 means the straight line distance between these two oxygen atoms.
• d1 means a value determined using the "display distance measurement" function in "Chem 3D” (version 18.2.0.48) manufactured by PerkinElmer.
• d1 of the di(meth)acrylic monomer (A-2) is not particularly limited as long as it is 25 ⁇ or more, and may be, for example, 30 ⁇ or more, or 35 ⁇ or more.
• the upper limit of d1 of the di(meth)acrylic monomer (A-2) is not particularly limited, and may be 50 ⁇ or less.
• the molecular weight of the di(meth)acrylic monomer (A-2) is preferably from 400 to 1000, more preferably from 400 to 800, and from 400 to 700, from the viewpoint of transparency and mechanical strength in the cured product. It is even more preferable that there be.
• di(meth)acrylic monomer (A-2) examples include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and the like.
• a higher content of (meth)acrylic monomer (A) tends to improve the transparency of the cured product, and a lower content of (meth)acrylic monomer (A) improves the bending strength of the cured product. There is a tendency. From the viewpoint of the balance between transparency and bending strength in the cured product, it is preferably 1% by mass to 20% by mass, and preferably 3% by mass to 18% by mass, based on the total amount of the (meth)acrylic monomer component. It is more preferably 5% by mass to 17% by mass, and particularly preferably 10% by mass to 15% by mass.
• the content of 4-hydroxybutyl (meth)acrylate is From the viewpoint of the balance between transparency and bending strength, it is preferably 1% by mass to 20% by mass, more preferably 5% by mass to 17% by mass, based on the total amount of the (meth)acrylic monomer component. , more preferably 10% by mass to 15% by mass.
• the content of the (meth)acrylic monomer (A) means the total content of the mono(meth)acrylic monomer (A-1) and the di(meth)acrylic monomer (A-2).
• the (meth)acrylic monomer (B) includes the aforementioned di(meth)acrylic monomer (B-1), the aforementioned di(meth)acrylic monomer (B-2), and the aforementioned tri(meth)acrylic monomer (B-3). ).
• the di(meth)acrylic monomer (B-1), the di(meth)acrylic monomer (B-2), and the tri(meth)acrylic monomer (B-3) may be used individually, You may use two or more types in combination.
• the di(meth)acrylic monomer (B-1) is a (meth)acrylic monomer component having two (meth)acryloyloxy groups and a cyclic structure.
• Examples of the cyclic structure in the di(meth)acrylic monomer (B-1) include aromatic structures and alicyclic structures.
• the cyclic structure also includes a combination of an aromatic structure and another linking group, such as a bisphenol A structure.
• aromatic structure examples include a benzene ring, a naphthalene ring, a bisphenol A structure, a phenylphenol structure, a phenoxybenzyl structure, a phenylalkylene structure, and an ⁇ -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.
• the cyclic structure may be located in the main chain, or the cyclic structure may be located in the branched chain.
• the di(meth)acrylic monomer (B-1) contains one or more selected from the group consisting of a (meth)acrylic monomer component containing a bisphenol A structure and a (meth)acrylic monomer component containing a cyclic structure and a urethane bond. May contain.
• the di(meth)acrylic monomer (B-1) may have at least one of an ethyleneoxy group and a propyleneoxy group.
• a (meth)acrylic monomer component containing a bisphenol A structure has an ethyleneoxy group and a propyleneoxy group. It may have at least one propyleneoxy group.
• the molecular weight of the di(meth)acrylic monomer (B-1) is preferably 200 to 800, more preferably 300 to 700, and preferably 400 to 650 from the viewpoint of mechanical strength in the cured product. More preferred.
• the (meth)acrylic monomer component containing a cyclic structure and a urethane bond may include a compound represented by the following formula (1).
• R 1 is a divalent chain hydrocarbon group, a divalent hydrocarbon group having an aromatic structure, or a divalent hydrocarbon group having an alicyclic structure
• R 2 and R 3 are each independently 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.
• R 1 is a divalent chain hydrocarbon group
• R 2 and R 3 are each independently a divalent chain hydrocarbon group having a branched aromatic structure.
• the number of carbon atoms in the divalent chain hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 2 to 6.
• the divalent chain hydrocarbon group in R 1 may be linear or branched, saturated or unsaturated, and may have a substituent.
• the divalent chain hydrocarbon group in R 1 is preferably a straight chain or branched alkylene group having 1 to 20 carbon atoms, more preferably a straight chain or branched alkylene group having 1 to 12 carbon atoms, More preferably, it is a straight chain or branched alkylene group having 1 to 10 carbon atoms.
• linear or branched alkylene group having 1 to 20 carbon atoms include methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, heptanediyl group, octanediyl group, nonanediyl group, decanediyl group, undecanediyl group, dodecanediyl group, tridecanediyl group, tetradecanediyl group, pentadecanediyl group, octadecanediyl group, eicosylene group, vinylene group, propendiyl group, butenediyl group, pentendiyl group, ethynylene group, propynylene, A 2,4,4-trimethylhexylene group is mentioned.
• the divalent hydrocarbon group having an aromatic structure has 6 to 20 carbon atoms (more preferably 6 to 12 carbon atoms, even more preferably 6 to 12 carbon atoms, and even more preferably 6 to 12 carbon atoms), which may have a substituent.
• 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.
• arylene group examples include 1,3- or 1,4-phenylene group, 1,3- or 1,4-phenylene dimethylene group and 1,3- or 1,4-phenylene diethylene groups.
• the divalent hydrocarbon group having an alicyclic structure preferably has 3 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and more preferably 6 to 8 carbon atoms. It is even more preferable. Specific examples of the alicyclic structure are as described above.
• R 1 is a divalent hydrocarbon group having an alicyclic structure
• particularly preferred examples are as follows. * represents the bonding position.
• the divalent hydrocarbon group having an alicyclic structure in R 1 in formula (1) may have a substituent.
• substituents include straight chain or branched alkyl groups having 1 to 6 carbon atoms.
• R 2 and R 3 each independently represent a divalent chain hydrocarbon group which may have a substituent.
• the divalent chain hydrocarbon groups suitable as R 2 and R 3 are the same as the divalent chain hydrocarbon groups suitable as R 1 .
• the number of carbon atoms in the divalent chain hydrocarbon group which may have a substituent in R 2 and R 3 is preferably 2 to 6, more preferably 2 to 3.
• R 2 and R 3 are divalent chain hydrocarbon groups having a substituent
• substituents include; an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; Aryl group; Cycloalkyl groups having 3 to 6 carbon atoms such as cyclopentyl group and cyclohexyl group; tolyl group; xylyl group; Cumyl group; Styryl group; Alkoxyphenyl groups such as methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group; Examples include phenoxyalkyl groups such as phenoxymethyl group, phenoxyethyl group, and phenoxypropyl group.
• R 1 is a divalent chain hydrocarbon group
• R 2 and R 3 are each independently a divalent chain hydrocarbon group having an aromatic structure in a branched chain
• R 2 and R 3 are each independently a divalent chain hydrocarbon group having a branched aromatic structure
• a divalent chain hydrocarbon group having a branched group or a phenoxyalkyl group is preferable.
• the di(meth)acrylic monomer (B-2) has two (meth)acryloyloxy groups, 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.
• d1 of the di(meth)acrylic monomer (B-2) may be 3.0 ⁇ or more, 5.0 ⁇ or more, or 10 ⁇ or more.
• the upper limit of d1 of the di(meth)acrylic monomer (B-2) is less than 25 ⁇ , and may be 23 ⁇ or less.
• the molecular weight of the di(meth)acrylic monomer (B-2) is preferably 170 to 700, more preferably 200 to 600, and preferably 250 to 500 from the viewpoint of transparency in the cured product. More preferred.
• the di(meth)acrylic monomer (B-2) is selected from the group consisting of a (meth)acrylic monomer component having at least one of an ethyleneoxy group and a propyleneoxy group, and a (meth)acrylic monomer component containing a urethane bond. may include one or more.
• the di(meth)acrylic monomer (B-2) preferably does not contain a cyclic structure.
• Examples of the (meth)acrylic monomer component having at least one of an ethyleneoxy group and a propyleneoxy group include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and dipropylene glycol di(meth)acrylate.
• Examples of the (meth)acrylic monomer component containing a urethane bond include a compound represented by the following formula (2).
• R 6 is a divalent chain hydrocarbon group
• R 7 and R 8 are each independently a divalent chain hydrocarbon group which may have a substituent
• R 9 and R 10 are each independently a methyl group or a hydrogen atom.
• a preferred embodiment of the divalent chain hydrocarbon group for R 6 in formula (2) is the same as a preferred embodiment for the divalent chain hydrocarbon group for R 1 in formula (1).
• a preferred embodiment of the optionally substituted divalent chain hydrocarbon group in R 7 and R 8 in formula (2) is a divalent chain hydrocarbon group that has substituents in R 2 and R 3 in formula (1).
• the preferred embodiments of the optional divalent chain hydrocarbon group are the same as those of the optional divalent chain hydrocarbon group (excluding cases containing a cyclic structure).
• (meth)acrylic monomer component containing a urethane bond 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (UDMA), 2,2,4-trimethylhexamethylenebis(2-carbamoyl (oxyethyl) diacrylate (UDA1) and the like.
• UDMA 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate
• UDA1 2,2,4-trimethylhexamethylenebis(2-carbamoyl (oxyethyl) diacrylate
• Tri(meth)acrylic monomer (B-3) The tri(meth)acrylic monomer (B-3) is a (meth)acrylic monomer component having three (meth)acryloyloxy groups.
• the molecular weight of the tri(meth)acrylic monomer (B-3) is preferably from 200 to 1,500, more preferably from 250 to 1,000, and preferably from 300 to 800, from the viewpoint of transparency in the cured product. More preferred.
• the content of the (meth)acrylic monomer (B) is preferably 25% by mass to 90% by mass, more preferably 30% by mass to 85% by mass, based on the total amount of the (meth)acrylic monomer component. , more preferably 35% to 80% by weight, particularly preferably 40% to 75% by weight.
• the content of (meth)acrylic monomer (B) refers to di(meth)acrylic monomer (B-1), di(meth)acrylic monomer (B-2), and tri(meth)acrylic monomer (B-3). ) means the total content of
• the content of the di(meth)acrylic monomer (B-1) is relative to the total amount of the (meth)acrylic monomer component. , may be 25% by mass to 90% by mass, or may be 40% by mass to 80% by mass.
• the content of the di(meth)acrylic monomer (B-2) is relative to the total amount of the (meth)acrylic monomer component. , 5% to 90% by weight, 5% to 20% by weight, or 40% to 80% by weight.
• the content of the tri(meth)acrylic monomer (B-3) is relative to the total amount of the (meth)acrylic monomer component. , may be 5% by mass to 70% by mass, or may be 10% by mass to 60% by mass.
• the (meth)acrylic monomer (C) has one (meth)acryloyloxy group and contains a (meth)acrylic monomer component having an aromatic structure.
• the (meth)acrylic monomer (C) may be used alone or in combination of two or more.
• the molecular weight of the (meth)acrylic monomer (C) is preferably from 140 to 500, more preferably from 140 to 400, even more preferably from 140 to 300.
• Examples of the (meth)acrylic monomer (C) include a compound represented by the following formula (3).
• R 11 is a monovalent organic group having an aromatic structure.
• the monovalent organic group having an aromatic structure in R 11 in formula (3) is preferably a monovalent organic group having 3 to 30 carbon atoms, and preferably a monovalent organic group having 6 to 20 carbon atoms. It is more preferable that there be.
• R 11 may be an organic group represented by formula (4) below.
• L 1 is a divalent chain hydrocarbon group which may have a single bond or a heteroatom which is O or N having 1 to 30 carbon atoms
• A is a divalent chain hydrocarbon group having 6 carbon atoms. ⁇ 30 aryl groups. * represents the bonding position.
• the divalent chain hydrocarbon group represented by L 1 which may have a hetero atom of O or N having 1 to 30 carbon atoms may be linear or branched. It may be chain-like.
• the carbon number of the divalent chain hydrocarbon group optionally having a hetero atom of O or N having 1 to 30 carbon atoms, represented by L 1 is more preferably 1 to 20, and 1 to 30 carbon atoms. It is more preferably from 1 to 10, and particularly preferably from 1 to 8.
• the divalent chain hydrocarbon group represented by L 1 contains a heteroatom, the number of heteroatoms in L 1 is preferably 1 to 3, more preferably 1 or 2.
• the divalent chain hydrocarbon group represented by L 1 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 of the hydrogen atoms are substituted with a hydroxy group.
• the divalent chain hydrocarbon group represented by L 1 may include a urethane bond. When the divalent chain hydrocarbon group represented by L 1 contains a urethane bond, the number of urethane bonds in L 1 may be 1 or 2.
• divalent chain hydrocarbon group represented by L 1 in formula (4) examples include the following groups.
• * represents the bonding position.
• the aromatic structure in the aryl group having 6 to 30 carbon atoms represented by A includes, for example, a phenyl structure, a biphenyl structure, a naphthyl structure, and an anthryl structure.
• the group represented by A in formula (4) may have a substituent.
• substituents include: an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; Hydroxy group; an alkyl group having 1 to 6 carbon atoms substituted with one or two hydroxy groups; Aryl group; Cycloalkyl groups having 3 to 6 carbon atoms such as cyclopentyl group and cyclohexyl group; tolyl group; xylyl group; Cumyl group; Styryl group; Alkoxyphenyl groups such as methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group; Examples include phenoxyalkyl groups such as phenoxymethyl group, phenoxyethyl group, and phenoxypropyl group.
• Examples of the group represented by A in formula (4) include the following examples. * represents the bonding position.
• the content of the (meth)acrylic monomer (C) is preferably 5% to 70% by mass, more preferably 8% to 60% by mass, based on the total amount of the (meth)acrylic monomer component. , more preferably 10% by mass to 55% by mass, particularly preferably 12% by mass to 50% by mass.
• the total content of (meth)acrylic monomer (A), (meth)acrylic monomer (B), and (meth)acrylic monomer (C) is 50% by mass to 100% by mass based on the total amount of (meth)acrylic monomer components. It is preferably 70% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass.
• the photocurable composition of the first aspect contains a photopolymerization initiator.
• the photocurable composition of the first aspect may contain only one kind of photopolymerization initiator, or may contain two or more kinds of photopolymerization initiators.
• 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.
• photopolymerization initiators include acylphosphine oxide compounds, alkyl benzoylformates, alkylphenone compounds, titanocene compounds, oxime ester compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, and thioxanthone compounds.
• compounds, ⁇ -acyloxime ester compounds, phenylglyoxylate compounds, benzyl compounds, azo compounds, diphenyl sulfide compounds, organic dye compounds, iron-phthalocyanine compounds, benzoin ether compounds, anthraquinone compounds, etc. can be mentioned.
• the photopolymerization initiator preferably contains at least one of an acylphosphine oxide compound and an alkyl benzoylformate compound, and more preferably contains an acylphosphine oxide compound.
• Two or more photopolymerization initiators may be used in combination, and from the viewpoint of transparency in the cured product, the photopolymerization initiator may include an acylphosphine oxide compound and an alkyl benzoylformate compound.
• acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. can be mentioned.
• alkyl benzoylformate compounds examples include methyl benzoylformate, ethyl benzoylformate, propyl benzoylformate, and butyl benzoylformate.
• the total content of photopolymerization initiators in the photocurable composition of the first aspect is preferably 0.1% by mass to 5% by mass, and 0.5% by mass based on the total amount of the photocurable composition. It is more preferably from 0.5% to 3% by weight, and even more preferably from 0.5% to 3% by weight.
• the content of the acylphosphine oxide compound may be 50% by mass to 100% by mass, and 70% by mass based on the total amount of the photopolymerization initiator. % to 100% by mass, or 90% to 100% by mass.
• the content of 2,4,6-trimethylbenzoyldiphenylphosphine oxide is 1 mass based on the total amount of the photocurable composition. % to 5% by weight, more preferably 1.5% to 3% by weight.
• the content of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide depends on the photocurable composition. It is preferably 0.1% by mass to 2% by mass, more preferably 0.5% by mass to 1% by mass, based on the total amount of the product.
• the photocurable composition of the first aspect may contain one or more types of components other than the above-mentioned components, if necessary.
• the total mass of the photopolymerizable component and the photopolymerization initiator is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the photocurable composition. It is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more.
• the upper limit of the total mass of the photopolymerizable component and the photopolymerization initiator is not particularly limited, and may be 100% by mass or less, for example, 99.9% by mass or less.
• the photocurable composition includes monomers other than the (meth)acrylic monomer (A), (meth)acrylic monomer (B), and (meth)acrylic monomer (C), components other than the monomer and the photopolymerization initiator, etc. (hereinafter referred to as (also referred to as other ingredients) may be included.
• the photocurable composition contains monomers other than (meth)acrylic monomer (A), (meth)acrylic monomer (B), and (meth)acrylic monomer (C) as other components, the monomers as other components It is preferable that the content of % or less, even more preferably 20% by mass or less, particularly preferably 10% by mass or less.
• 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.
• the photocurable composition of the first aspect contains a thermal polymerization initiator, it is possible to use photocuring and thermal curing together.
• the thermal polymerization initiator include thermal radical generators and amine compounds.
• the photocurable composition of the first aspect does not contain an inorganic filler (for example, silica, barium borosilicate glass, etc., the same applies hereinafter), or When containing an inorganic filler, 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) based on the total amount of the photocurable composition. below) is preferred.
• an inorganic filler for example, silica, barium borosilicate glass, etc., the same applies hereinafter
• 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) based on the total amount of the photocurable composition. below) is preferred.
• the photocurable composition according to the modification of the first aspect is a photocurable composition containing a photopolymerizable component and a photopolymerization initiator,
• the photopolymerizable component is one or more (meth)acrylic monomers (A) selected from the group consisting of mono(meth)acrylic monomers (A-1) and di(meth)acrylic monomers (A-2); Di(meth)acrylic monomer (B-1), di(meth)acrylic monomer (B-2) (excluding di(meth)acrylic monomer (B-1)), and tri(meth)acrylic monomer (B-3) ) one or more (meth)acrylic monomers (B) selected from the group consisting of; (meth)acrylic monomer (C), including.
• the photocurable composition according to the modification of the first aspect it is possible to produce a cured product that has both high mechanical strength and high transparency.
• the photocurable composition according to the modified example may or may not satisfy the condition that ⁇ E*ab of the above-mentioned test piece A1 is 6.0 or less.
• the photocurable composition according to this modification may or may not satisfy the above-mentioned condition that the bending strength of test piece A2 is 50 MPa or more.
• the photocurable composition according to this modification may or may not satisfy the condition that the flexural modulus of the test piece A2 described above is 1500 MPa or more.
• the photocurable composition of the second aspect is a photocurable composition containing a photopolymerizable component and a photopolymerization initiator, wherein the photopolymerization initiator contains an acylphosphine oxide compound, an alkyl benzoylformate compound.
• the photocurable composition of the second aspect has high mechanical strength and high transparency by containing a photopolymerizable component and a photopolymerization initiator containing an acylphosphine oxide compound and an alkyl benzoylformate compound. It is possible to produce a cured product that is compatible with the above.
• the photopolymerizable component in the second aspect has the following properties from the viewpoint of mechanical strength in the cured product: Di(meth)acrylic monomer (B-1), di(meth)acrylic monomer (B-2) (excluding di(meth)acrylic monomer (B-1)), and tri(meth)acrylic monomer (B-3) ) one or more (meth)acrylic monomers (B) selected from the group consisting of; (meth)acrylic monomer (C), It is preferable to include.
• the di(meth)acrylic monomer (B-1) is the same as the di(meth)acrylic monomer (B-1) used in the first embodiment described above.
• the di(meth)acrylic monomer (B-2) is the same as the di(meth)acrylic monomer (B-2) used in the first embodiment described above.
• the tri(meth)acrylic monomer (B-3) is the same as the tri(meth)acrylic monomer (B-3) used in the first embodiment described above.
• the (meth)acrylic monomer (C) is the same as the (meth)acrylic monomer (C) used in the first embodiment described above.
• the content of the (meth)acrylic monomer (B) is preferably 25% by mass to 95% by mass, more preferably 30% by mass to 90% by mass, based on the total amount of the (meth)acrylic monomer component. , more preferably 40% to 90% by weight, particularly preferably 50% to 85% by weight.
• the content of (meth)acrylic monomer (B) refers to di(meth)acrylic monomer (B-1), di(meth)acrylic monomer (B-2), and tri(meth)acrylic monomer (B-3). ) means the total content of
• the content of the di(meth)acrylic monomer (B-1) is relative to the total amount of the (meth)acrylic monomer component. , may be 25% by mass to 95% by mass, or may be 50% by mass to 90% by mass.
• the content of the di(meth)acrylic monomer (B-2) is relative to the total amount of the (meth)acrylic monomer component. , 10% to 95% by weight, 10% to 30% by weight, or 50% to 90% by weight.
• the content of the tri(meth)acrylic monomer (B-3) is relative to the total amount of the (meth)acrylic monomer component. , may be 5% by mass to 70% by mass, or may be 10% by mass to 60% by mass.
• the content of the (meth)acrylic monomer (C) is preferably 5% by mass to 75% by mass, more preferably 10% by mass to 70% by mass, based on the total amount of the (meth)acrylic monomer component. , more preferably 10% by mass to 60% by mass, particularly preferably 15% by mass to 50% by mass.
• the total content of (meth)acrylic monomer (B) and (meth)acrylic monomer (C) with respect to the total amount of photopolymerizable components in the photocurable composition of the second aspect may be 80% by mass or more. It is preferably 90% by mass or more, more preferably 95% by mass or more.
• the upper limit of the total content of the above-mentioned (meth)acrylic monomer (B) and (meth)acrylic monomer (C) with respect to the total amount of photopolymerizable components in the photocurable composition of the second aspect is not particularly limited, It may be 100% by mass or less.
• the photocurable composition of the second aspect contains a photopolymerization initiator.
• the photopolymerization initiator includes an acylphosphine oxide compound and an alkyl benzoylformate compound.
• Photopolymerization initiators such as acylphosphine oxide compounds and alkyl benzoylformate compounds are not particularly limited as long as they generate radicals when irradiated with light. It is preferable that it generates.
• Preferred examples of the acylphosphine oxide compound and the alkyl benzoylformate compound are the same as the compounds described in the first embodiment above.
• the photocurable composition of the second aspect may contain only one type of acylphosphine oxide compound and an alkyl benzoylformate compound, or may contain two or more types of the acylphosphine oxide compound and the alkyl benzoylformate compound.
• the photocurable composition of the second aspect may contain a photopolymerization initiator other than the acylphosphine oxide compound and the alkyl benzoylformate compound (hereinafter also referred to as "other photopolymerization initiator").
• photopolymerization initiators examples include alkylphenone compounds, titanocene compounds, oxime ester compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, thioxanthone compounds, ⁇ -acyloxime ester compounds, phenyl Examples include glyoxylate compounds, benzyl compounds, azo compounds, diphenyl sulfide compounds, organic dye compounds, iron-phthalocyanine compounds, benzoin ether compounds, and anthraquinone compounds.
• the total content of photopolymerization initiators in the photocurable composition of the second aspect is preferably 0.1% by mass to 10% by mass, and 0.5% by mass based on the total amount of the photocurable composition. It is more preferably from 1% to 8% by weight, and even more preferably from 1% to 5% by weight.
• the total content of the acylphosphine oxide compound and the alkyl benzoylformate compound may be 50% by mass to 100% by mass, or 70% by mass to 100% by mass, based on the total amount of the photopolymerization initiator. It may be 90% by mass to 100% by mass.
• the mass ratio of the acylphosphine oxide compound and the alkyl benzoylformate compound may be 1:0.1 to 1:10, and may be 1:0.
• the ratio may be 2 to 1:5, or 1:0.25 to 1:2.
• the photocurable composition of the second aspect may contain one or more types of components other than the above-mentioned components, if necessary.
• the total mass of the (meth)acrylic monomer (B), (meth)acrylic monomer (C), and photoinitiator 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.
• the upper limit of the total mass of the (meth)acrylic monomer (B), (meth)acrylic monomer (C), and photopolymerization initiator is not particularly limited, and may be 100% by mass or less, for example, 99.9% by mass or less It may be.
• Examples of other components include monomers other than the (meth)acrylic monomer (B) and (meth)acrylic monomer (C).
• 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 (B) and (meth)acrylic monomer (C).
• the content is preferably 10% by mass or less, particularly preferably 10% by mass or less.
• a cured layer A1 having a thickness of 50 ⁇ m 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 .
• a rectangular plate-shaped object A1 with a length of 50 mm, a width of 40 mm, and a thickness of 4.5 mm was formed, and the object A1 was irradiated with ultraviolet rays with a wavelength of 365 nm at a dose of 10 J/cm.
• ⁇ E * ab of the test piece A1 may be 6.0 or less.
• a cured layer A1 having a thickness of 50 ⁇ m 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 .
• a rectangular plate-shaped object A2 with a length of 64 mm, a width of 10 mm, and a thickness of 3.3 mm is formed, and the object A2 is irradiated with ultraviolet rays with a wavelength of 365 nm at a dose of 10 J/cm.
• the bending strength of the test piece A2 is 50 MPa or more, and the bending elastic modulus is 1500 MPa or more. It may be a photocurable composition.
• the photocurable composition of the second aspect may satisfy at least one of the numerical conditions of ⁇ E * ab , flexural strength, and flexural modulus described above, and preferably may satisfy all of the numerical conditions.
• the lower limit of ⁇ E * ab of test piece A1 is not particularly limited, and may be, for example, 2.0 or more.
• the upper limit of the bending strength of the test piece A2 is not particularly limited, and may be, for example, 90 MPa or less.
• the upper limit of the flexural modulus of test piece A2 is not particularly limited, and may be, for example, 3000 MPa or less.
• the method for preparing the photocurable composition of the present disclosure is not particularly limited.
• methods for preparing the photocurable composition of the present disclosure include a method of mixing a photopolymerizable component, a photopolymerization initiator, and other components as necessary.
• 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.
• 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. .
• rpm means revolutions per minute.
• 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.
• 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 both high mechanical strength and high transparency. 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 is as described above.
• the dental product of the present disclosure includes the three-dimensional structure of the present disclosure described above. Therefore, the dental product of the present disclosure has both high mechanical strength and high transparency. Specific examples of dental products are as described above, and one example is a splint.
• the obtained test piece was irradiated with ultraviolet rays with a wavelength of 365 nm at 10 J/cm 2 to fully cure the photocurable composition, thereby obtaining a cured product of the test piece.
• the cured product of the obtained test piece was polished at 150 rpm using a rotary polisher (manufactured by Buehler, Ecomet 30) on both sides of 50 mm x 40 mm, and with No. 400 abrasive paper on one side of 0.15 mm, and with No. 800 abrasive paper. Polished 0.07 mm on one side with abrasive paper, 0.02 mm on one side with No. 1000 abrasive paper, and 0.01 mm on one side with No.
• the flexural strength and flexural modulus of cured products obtained using the photocurable compositions prepared in each Example and Comparative Example were measured by the following methods. Using a 3D printer (Kulzer, Cara Print 4.0), a test piece of 64 mm x 10 mm x 3.3 mm was made using the photocurable composition to be measured, with a lamination width of 50 ⁇ m, and each layer was exposed to visible light with a wavelength of 405 nm. Modeling was performed by irradiating at 11 mJ/cm 2 .
• the obtained test piece was irradiated with ultraviolet rays with a wavelength of 365 nm at 10 J/cm 2 to fully cure the curable composition, thereby obtaining a cured product of the test piece.
• the obtained test piece was stored in a constant temperature water bath at 37 ⁇ 1° C. for 50 ⁇ 2 hours. After that, the test piece was taken out from the constant temperature water bath, and the bending strength and bending elastic modulus of the taken out test piece were measured using a universal testing machine (manufactured by Intesco Corporation, UNIVERSAL TESTER 210X) in accordance with ISO20795-2:2013. The measurement was carried out under conditions of water at 37 ⁇ 1° C. and a test speed of 5 ⁇ 1 mm/min.
• the compounds classified as (meth)acrylic monomers (A) are specifically the following photopolymerizable components 1 to 7.
• photopolymerizable components 1 to 7 photopolymerizable components 1 to 5 have one (meth)acryloyloxy group and are classified as mono(meth)acrylic monomers (A-1) that do not have a cyclic structure. be done.
• photopolymerizable components 6 and 7 have two (meth)acryloyloxy groups, do not have a cyclic structure, and have one of the (meth)acryloyloxy groups in A di(meth)acrylic monomer (A-2) in which the distance between an oxygen atom forming an oxy group and an oxygen atom forming an oxy group in the other (meth)acryloyloxy group is 25 ⁇ or more. being classified.
• Photopolymerizable component 1 2-hydroxyethyl methacrylate (HO-250, Kyoeisha Chemical Co., Ltd.)
• Photopolymerizable component 2 2-hydroxypropyl methacrylate (HOP(N), Kyoeisha Chemical Co., Ltd.)
• Photopolymerizable component 3 2-hydroxypropyl acrylate (HOP-A(N), Kyoeisha Chemical Co., Ltd.)
• Photopolymerizable component 4 4-hydroxybutyl acrylate (4HBA, Osaka Organic Chemical Industry Co., Ltd.)
• Photopolymerizable component 5 lauryl acrylate (LA, Kyoeisha Chemical Co., Ltd.)
• Photopolymerizable component 7 Polypropylene glycol (700) diacrylate (APG-700, Shin Nakamura Chemical
• the compounds classified as (meth)acrylic monomers (B) are specifically the following photopolymerizable components 8 to 17.
• photopolymerizable components 8 to 17 photopolymerizable components 8 to 10, 13 and 14 are di(meth)acrylic monomers (B-1) having two (meth)acryloyloxy groups and having a cyclic structure. are categorized.
• photopolymerizable components 8 to 17 photopolymerizable components 11, 12, 15 to 17 have two (meth)acryloyloxy groups, and form an oxy group in one (meth)acryloyloxy group.
• Di(meth)acrylic monomer (B-2) (di(meth)acrylic (excluding monomer (B-1)).
• Photopolymerizable component 8 Ethoxylated bisphenol A diacrylate (ABE-300, Shin Nakamura Chemical Co., Ltd.)
• Photopolymerizable component 9 Ethoxylated bisphenol A diacrylate (A-BPE-4, Shin Nakamura Chemical Co., Ltd.)
• Photopolymerizable component 10 Ethoxylated bisphenol A dimethacrylate (SR540, Sartomer Co., Ltd.)
• Photopolymerizable component 13 Bifunctional urethane acrylate (AH-600, Kyoeisha Chemical Co., Ltd.)
• Photopolymerizable component 14 difunctional urethane acrylate (UDA
• Photopolymerizable component 18 Benzyl methacrylate (BZ, Kyoeisha Chemical Co., Ltd.)
• Photopolymerizable component 19 Phenoxyethyl methacrylate (PO, Kyoeisha Chemical Co., Ltd.)
• Photopolymerizable component 20 Phenoxyethyl acrylate (PO-A, Kyoeisha Chemical Co., Ltd.)
• Photopolymerizable component 21 m-phenoxybenzyl acrylate (POB-A, Kyoeisha Chemical Co., Ltd.)
• Photopolymerizable component 22 2-(o-phenylphenoxy)ethyl acrylate (HRD-0 1. Nissho Technofine Chemical Co., Ltd.)
• Photopolymerizable component 23 2-hydroxy-3-phenoxypropyl acrylate (M600-A, Kyoeisha Chemical Co., Ltd.)
• Photoinitiator 1 Acylphosphine oxide compound (Omnirad TPO: “Omnirad TPO” manufactured by IGM Resins B.V.)
• Photoinitiator 2 Acyl phosphine oxide compound (Omnirad 819: “Omnirad 819” manufactured by IGM Resins B.V.)
• HEA Hydroxyethyl acrylate
• DBTDL Dibutyltin dilaurate
• MEHQ 4-methoxyphenol
• TMHDI Mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate
• TMXDI 1,3-tetramethylxyly Range isocyanate
• Photoinitiator 1 Acylphosphine oxide compound (Omnirad TPO: “Omnirad TPO” manufactured by IGM Resins B.V.)
• Photoinitiator 2 Acylphosphine oxide compound (Omnirad 819: “Omnirad 819” manufactured by IGM Resins B.V.)
• Photoinitiator 3 Alkyl benzoylformate compound (MBF, BASF)
• Photoinitiator 4 Alkyl benzoylformate compound (EBF, Tokyo Chemical Industry Co., Ltd.)

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