Classifications

• • 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
  • B29C33/00—Moulds or cores; Details thereof or accessories therefor
  • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
  • B29C33/40—Plastics, e.g. foam or rubber
• • 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
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
  • A61C13/00—Dental prostheses; Making same
  • A61C13/01—Palates or other bases or supports for the artificial teeth; Making same
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
  • A61C13/00—Dental prostheses; Making same
  • A61C13/01—Palates or other bases or supports for the artificial teeth; Making same
  • A61C13/04—Palates or other bases or supports for the artificial teeth; Making same made by casting
• • 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
  • B29C33/00—Moulds or cores; Details thereof or accessories therefor
  • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
  • B29C33/3842—Manufacturing moulds, e.g. shaping the mould surface by machining
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y10/00—Processes of additive manufacturing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D 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 [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/062—Polyethers
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/067—Polyurethanes; Polyureas
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/0094—Condition, form or state of moulded material or of the material to be shaped having particular viscosity
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2833/00—Use of polymers of unsaturated acids or derivatives thereof as mould material
  • B29K2833/04—Polymers of esters
  • B29K2833/08—Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0037—Other properties
  • B29K2995/0046—Elastic
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0037—Other properties
  • B29K2995/0088—Molecular weight
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/753—Medical equipment; Accessories therefor
  • B29L2031/7532—Artificial members, protheses
  • B29L2031/7536—Artificial teeth

Definitions

• the present disclosure relates to a method of manufacturing a photocurable composition, a three-dimensional molded object, a mold, a cured product, and a method of manufacturing a denture.
• Patent Document 1 Patent No. 4160311
• the conventional method utilizes room temperature polymerization using a mold, but this method can use many materials that can improve aesthetics and physical properties.
• materials used in such room-temperature polymerization cannot often be used in stereolithography using a 3D printer. As a result, when stereolithography is performed using a 3D printer, it becomes difficult to make adjustments to obtain desired properties in the resulting denture.
• the present inventors manufactured a mold for manufacturing a denture with a 3D printer using stereolithography, and discovered a method of manufacturing a denture with a denture using the mold.
• the denture When removing a denture obtained by polymerizing a polymerizable composition in a mold from the mold, the denture may not fit into the mold due to the fact that the denture is equipped with artificial teeth. This may make it physically difficult to remove.
• An object of one aspect of the present disclosure is to make it possible to create a mold in which the denture can be easily removed from the mold when manufacturing the denture using a mold or a mold that suppresses deformation during the manufacture of the denture.
• An object of the present invention is to provide a photocurable composition, and a method for producing three-dimensional objects, molds, and cured products using this photocurable composition.
• An object of another aspect of the present disclosure is to provide a method for manufacturing a denture that can be manufactured by a simple method.
• the storage modulus of the test piece A1 at 25°C is 10 MPa or more
• a photocurable composition in which the storage modulus of the test piece A1 at 37° C. is 400 MPa or less.
• the (meth)acrylic monomer component is A mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring, A di(meth)acrylic monomer (Y) having at least one of a ring structure or a urethane bond and two (meth)acryloyloxy groups and having no siloxane bond;
• the photocurable composition according to ⁇ 1> comprising a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond and two or more (meth)acryloyloxy groups.
• a photocurable composition comprising a (meth)acrylic monomer component and a photopolymerization initiator,
• the (meth)acrylic monomer component is A mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring,
• a di(meth)acrylic monomer (Y) having at least one of a ring structure or a urethane bond and two (meth)acryloyloxy groups and having no siloxane bond;
• a photocurable composition comprising a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond and two or more (meth)acryloyloxy groups.
• ⁇ 4> The photocurable composition according to ⁇ 2> or ⁇ 3>, wherein the di(meth)acrylic monomer (Y) has a molecular weight of 400 to 5,000.
• ⁇ 5> The photocurable composition according to any one of ⁇ 2> to ⁇ 4>, wherein the polyfunctional (meth)acrylic monomer (Z) has a molecular weight of 400 to 5,000.
• ⁇ 6> Any one of ⁇ 2> to ⁇ 5>, wherein the content of the mono(meth)acrylic monomer (X) is 30% by mass to 90% by mass with respect to the total amount of the (meth)acrylic monomer component. 1.
• ⁇ 7> Any one of ⁇ 2> to ⁇ 6>, wherein the content of the di(meth)acrylic monomer (Y) is 5% by mass to 55% by mass with respect to the total amount of the (meth)acrylic monomer component. 1.
• the photocurable composition according to item 1. ⁇ 8> Any of ⁇ 2> to ⁇ 7>, wherein the content of the polyfunctional (meth)acrylic monomer (Z) is 1% by mass to 60% by mass with respect to the total amount of the (meth)acrylic monomer component.
• the (meth)acrylic monomer component has two (meth)acryloyloxy groups and an aromatic ring, and the oxygen atom forming the oxy group in one (meth)acryloyloxy group and the Any one of ⁇ 1> to 11>, comprising a di(meth)acrylic monomer (A) having a distance of 25 ⁇ or more and 80 ⁇ or less between the oxygen atom forming the oxy group in the (meth)acryloyloxy group
• the photocurable composition described in . ⁇ 13> The photocurable composition according to any one of ⁇ 1> to ⁇ 12>, which satisfies either of the following conditions (a) and (b).
• the (meth)acrylic monomer component has two (meth)acryloyloxy groups and an aromatic ring, and the oxygen atom forming the oxy group in one (meth)acryloyloxy group and the other Two or more types of di(meth)acrylic monomers (A) having a distance of 25 ⁇ or more and 80 ⁇ or less from the oxygen atom forming the oxy group in the (meth)acryloyloxy group are included.
• the (meth)acrylic monomer component is It has two (meth)acryloyloxy groups and an aromatic ring, and the oxygen atom forming the oxy group in one (meth)acryloyloxy group forms the oxy group in the other (meth)acryloyloxy group.
• ⁇ 17> Any one of ⁇ 12> to ⁇ 16>, wherein the content of the di(meth)acrylic monomer (A) is 30% by mass or more based on the total amount of the (meth)acrylic monomer component.
• ⁇ 18> The photocurable composition according to any one of ⁇ 1> to ⁇ 17>, 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.
• ⁇ 19> The photocurable composition according to any one of ⁇ 1> to ⁇ 18>, which is a photocurable composition for stereolithography.
• ⁇ 20> The photocurable composition according to any one of ⁇ 1> to ⁇ 19>, which is a photocurable composition used for manufacturing a mold by stereolithography.
• ⁇ 21> A three-dimensional object comprising a cured product of the photocurable composition according to any one of ⁇ 1> to ⁇ 20>.
• ⁇ 22> A mold including the three-dimensional structure according to ⁇ 21>.
• ⁇ 23> The mold according to ⁇ 22>, which is used for manufacturing a denture.
• a method for producing a cured product comprising a step of polymerizing the curable composition in the mold according to ⁇ 22> or ⁇ 23>.
• a step of curing the photocurable composition by stereolithography to produce a mold used for manufacturing a denture A method for producing a denture with a denture, comprising the step of polymerizing a curable composition in the mold to produce a denture with a denture.
• the present disclosure when producing a fixed denture using a mold or mold in which deformation during the production of a fixed denture is suppressed, it is possible to create a mold that allows easy removal of the fixed denture from within the mold.
• the present invention provides a photocurable composition, a method for producing a three-dimensional object, a mold, a cured product, and a method for producing a denture using the photocurable composition.
• a method for manufacturing a denture that can be manufactured by a simple method.
• FIG. 2 is a schematic configuration diagram of a three-dimensional structure A2 formed in an example.
• FIG. 3 is a schematic configuration diagram of a three-dimensional structure A3 formed in an example.
• FIG. 3 is a schematic configuration diagram of a three-dimensional structure A4 formed in an example.
• 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 compositions of the first embodiment and the second embodiment will be described.
• the preferred embodiment of the first embodiment and the preferred embodiment of the second embodiment may be combined as appropriate.
• Preferred uses and physical properties of the photocurable composition of the second embodiment are the same as those of the photocurable composition of the first embodiment, unless otherwise mentioned.
• the photocurable composition of the first embodiment of the present disclosure is a photocurable composition containing a (meth)acrylic monomer 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 with a width of 40 mm, a width of 10 mm, and a thickness of 1.0 mm is formed, and the object A1 is irradiated with ultraviolet light with a wavelength of 365 nm at a dose of 3 J/cm 2 to form a long object.
• the storage modulus of the test piece A1 at 25°C is 10 MPa or more
• the storage modulus of the test piece A1 at 37° C. is 400 MPa or less.
• the photocurable composition of the present disclosure includes a (meth)acrylic monomer component and a photopolymerization initiator, and the test piece A1 prepared under the above conditions has a storage modulus of 10 MPa or more at 25°C, and , the storage modulus of test piece A1 at 37° C. is 400 MPa or less.
• 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, and for example, it is preferably a photocurable composition used for manufacturing molds, dental products, etc. by stereolithography, and is suitable for manufacturing molds by stereolithography. It is more preferable that the photocurable composition is used.
• the mold examples include molds used for manufacturing dentures. For example, with artificial teeth arranged in a mold, a curable composition for making a denture base is injected into the mold, and the curable composition after injection is cured to produce a denture with a denture.
• 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 storage modulus of test piece A1 at 25° C. is 10 MPa or more, and from the viewpoint of suppressing mold deformation (for example, a mold made using the photocurable composition of the present disclosure).
• the pressure is preferably 15 MPa or more, more preferably 30 MPa or more, and 50 MPa or more. It is even more preferable that there be.
• the upper limit of the storage modulus of test piece A1 at 25°C is not particularly limited, and for example, from the viewpoint of ease of extraction from the mold (for example, to suppress damage to the mold, denture, etc. when pulling out the denture from the mold). viewpoint), the pressure may be 2000 MPa or less, 1000 MPa or less, or 500 MPa or less.
• the storage modulus of test piece A1 at 37° C. is 400 MPa or less, and from the viewpoint of ease of extraction from the mold, it is preferably 300 MPa or less, and more preferably 250 MPa or less. It is preferably 200 MPa or less, and more preferably 200 MPa or less.
• the lower limit of the storage modulus at 37°C of test piece A1 is not particularly limited, and for example, from the viewpoint of suppressing mold deformation during use, it may be 10 MPa or more, 30 MPa or more, 50 MPa or more. It may be.
• the aromatic ring concentration in the (meth)acrylic monomer component is preferably from 0.0015 mol/g to 0.0042 mol/g, and preferably from 0.0016 mol/g to 0.0041 mol/g. It is more preferable that the amount is 0.0017 mol/g to 0.0040 mol/g.
• the photocurable composition of the present disclosure satisfies any of the following conditions (1) to (3) from the viewpoint of being superior in extractability from a mold and suitably suppressing mold deformation during use. is preferred.
• the aromatic ring concentration in the (meth)acrylic monomer component is 0.0030 mol/g to 0.0042 mol/g.
• the aromatic ring concentration in the (meth)acrylic monomer component is 0.0015 mol/g to 0.0035 mol/g, and the urethane bond concentration in the (meth)acrylic monomer component is 0.0001 mol/g to 0.0020 mol /g.
• the aromatic ring concentration in the (meth)acrylic monomer component is 0.0015 mol/g to 0.0035 mol/g, and the hydroxyl group concentration in the (meth)acrylic monomer component is 0.0005 mol/g to 0.0030 mol/g. It is g.
• the urethane bond concentration in the (meth)acrylic monomer component may be 0.0001 mol/g to 0.0020 mol/g, or 0.0002 mol/g to 0.0018 mol/g, as described in (2) above. It may be 0.0004 mol/g to 0.0016 mol/g.
• the hydroxyl group concentration in the (meth)acrylic monomer component may be 0.0005 mol/g to 0.0030 mol/g, or 0.0006 mol/g to 0.0025 mol/g, as described in (3) above. It may be 0.0008 mol/g to 0.0022 mol/g.
• the photocurable composition of the present disclosure includes at least one (meth)acrylic monomer component.
• the content of the (meth)acrylic monomer component relative to the total amount of the photocurable composition of the present disclosure is preferably 60% by mass or more, more preferably 80% by mass or more. It is preferably 90% by mass or more, and more preferably 90% by mass or more.
• the upper limit of the content of the (meth)acrylic monomer component relative to the total amount of the photocurable composition of the present disclosure is not particularly limited, and may be less than 100% by mass, for example, may be 99.9% by mass or less. .
• the (meth)acrylic monomer component means a monomer having one or more (meth)acryloyloxy groups in the molecule.
• the photocurable composition of the present disclosure may or may not contain photopolymerizable components other than the (meth)acrylic monomer component.
• photopolymerizable components other than the (meth)acrylic monomer component include styrene, styrene derivatives, (meth)acrylonitrile, and the like.
• the content of photopolymerizable components other than the (meth)acrylic monomer component is 20% by mass or less based on the total amount of photopolymerizable components in the photocurable composition of the present disclosure. It may be 10% by mass or less, 5% by mass or less, or 1.0% by mass or less.
• the lower limit of the content of photopolymerizable components other than the (meth)acrylic monomer component is not particularly limited, and may be, for example, 0% by mass or more.
• 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 (meth)acrylic monomer component has two (meth)acryloyloxy groups and an aromatic ring, and one
• the distance between an oxygen atom forming an oxy group in a (meth)acryloyloxy group and an oxygen atom forming an oxy group in the other (meth)acryloyloxy group (hereinafter also referred to as distance d1) is , preferably contains a di(meth)acrylic monomer (A) having a thickness of 25 ⁇ or more and 80 ⁇ or less.
• the (meth)acrylic monomer component may contain one type of di(meth)acrylic monomer (A) alone, or may contain two or more types of di(meth)acrylic monomer (A).
• 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.
• the d1 of the di(meth)acrylic monomer (A) is 25 ⁇ or more and 80 ⁇ or less, for example, may be 30 ⁇ or more and 60 ⁇ or less, or may be 30 ⁇ or more and 50 ⁇ or less.
• the di(meth)acrylic monomer (A) contains a cyclic structure.
• the cyclic structure include an aromatic structure and an alicyclic structure.
• the di(meth)acrylic monomer (A) preferably contains an aromatic structure, and preferably contains a bisphenol structure such as bisphenol A and bisphenol F.
• the di(meth)acrylic monomer (A) may have at least one of an ethyleneoxy group and a propyleneoxy group.
• the molecular weight of the di(meth)acrylic monomer (A) is preferably 650 or more and 1,300 or less, more preferably 700 or more and 1,200 or less, and even more preferably 750 or more and 1,000 or less.
• the weight average molecular weight of the di(meth)acrylic monomer (A) is preferably 650 or more and 1,300 or less, more preferably 700 or more and 1,200 or less, and even more preferably 750 or more and 1,000 or less. In this disclosure, weight average molecular weight is measured by gel permeation chromatography (GPC).
• di(meth)acrylic monomer (A) ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol F di(meth)acrylate, propoxylated bisphenol F di(meth)acrylate
• examples include acrylate.
• the content of the di(meth)acrylic monomer (A) is preferably 30% by mass or more, more preferably 40% to 100% by mass, and 50% by mass or more based on the total amount of the (meth)acrylic monomer component. More preferably, the amount is from % by mass to 100% by mass.
• the (meth)acrylic monomer component should satisfy either of the following conditions (a) and (b) from the viewpoint of making it easier to form a mold that can easily ensure extractability and easily suppress deformation. preferable.
• the (meth)acrylic monomer component contains two or more types of the aforementioned di(meth)acrylic monomers (A).
• the (meth)acrylic monomer component is The aforementioned di(meth)acrylic monomer (A), A di(meth)acrylic monomer (B-1) having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, and a distance d1 of 10 ⁇ or more and less than 25 ⁇ , A di(meth)acrylic monomer (B-2) having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, and having a distance d1 of more than 80 ⁇ and less than 200 ⁇ , and one ( one or more (meth)acrylic monomers (B) selected from the group consisting of mono(meth)acrylic monomers (B-3) having a meth)acryloyloxy group and at least one of an aromatic ring and a hydroxy group; ,including.
• the (meth)acrylic monomer component When the (meth)acrylic monomer component satisfies the above (a), the (meth)acrylic monomer component only needs to contain two or more types of di(meth)acrylic monomers (A), and other (meth)acrylic It may or may not contain a monomer component.
• the (meth)acrylic monomer component By containing two or more types of di(meth)acrylic monomers (A), the (meth)acrylic monomer component not only lowers the storage modulus at 25°C and the storage modulus at 37°C of test piece A1, but also It is easier to control the reactivity than when one type of di(meth)acrylic monomer (A) is used, and the operability during stereolithography is excellent.
• the total content of the di(meth)acrylic monomer (A) is 50% by mass to 100% by mass based on the total amount of the (meth)acrylic monomer component. It is preferably from 70% by mass to 100% by mass, even more preferably from 90% by mass to 100% by mass.
• the (meth)acrylic monomer component contains the above-mentioned di(meth)acrylic monomer (A) and (meth)acrylic monomer (B).
• the (meth)acrylic monomer component may each independently contain one type of di(meth)acrylic monomer (A) and (meth)acrylic monomer, or may contain two or more types thereof.
• di(meth)acrylic monomer (B-1), di(meth)acrylic monomer (B-2) and mono(meth)acrylic monomer (B-3) classified as (meth)acrylic monomer (B) are I will explain the details.
• the di(meth)acrylic monomer (B-1) has two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, and the distance d1 is 10 ⁇ or more and less than 25 ⁇ (meth) It is an acrylic monomer component.
• the use of di(meth)acrylic monomer (B-1) tends to increase the storage modulus at 25°C and the storage modulus at 37°C of test piece A1.
• d1 of the di(meth)acrylic monomer (B-1) may be 12 ⁇ or more and 24 ⁇ or less, or 14 ⁇ or more and 22 ⁇ or less.
• the molecular weight of the di(meth)acrylic monomer (B-1) is preferably 400 or more and 800 or less, more preferably 400 or more and 700 or less, and even more preferably 400 or more and 650 or less.
• the weight average molecular weight of the di(meth)acrylic monomer (B-1) is preferably 400 or more and 800 or less, more preferably 400 or more and 700 or less, and even more preferably 400 or more and 650 or less.
• the di(meth)acrylic monomer (B-1) has at least one of an aromatic ring and a urethane bond.
• the di(meth)acrylic monomer (B-1) may contain only one of an aromatic ring and a urethane bond, or may contain both an aromatic ring and a urethane bond.
• the di(meth)acrylic monomer (B-1) contains an aromatic ring and does not contain a urethane bond
• the di(meth)acrylic monomer (B-1) has at least one of an ethyleneoxy group and a propyleneoxy group.
• the di(meth)acrylic monomer (B-1) may have a bisphenol structure and at least one of an ethyleneoxy group and a propyleneoxy group.
• di(meth)acrylic monomer (B-1) contains an aromatic ring and does not contain a urethane bond
• specific examples of the di(meth)acrylic monomer (B-1) include ethoxylated bisphenol A di(meth)acrylate , propoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol F di(meth)acrylate, propoxylated bisphenol F di(meth)acrylate, and the like.
• the di(meth)acrylic monomer (B-1) may contain a compound represented by the following formula (1).
• R 1 is a divalent chain hydrocarbon group
• 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.
• 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.
• 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.
• ⁇ Di(meth)acrylic monomer (B-2) The di(meth)acrylic monomer (B-2) has two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, and the distance d1 is more than 80 ⁇ and less than 200 ⁇ (meth) It is an acrylic monomer component.
• the use of di(meth)acrylic monomer (B-2) tends to reduce the storage modulus at 25°C and the storage modulus at 37°C of test piece A1.
• d1 of the di(meth)acrylic monomer (B-2) may be 85 ⁇ or more and 150 ⁇ or less, or 90 ⁇ or more and 120 ⁇ or less.
• the molecular weight of the di(meth)acrylic monomer (B-2) is preferably 900 or more and 3000 or less, more preferably 1200 or more and 2500 or less, and even more preferably 1500 or more and 2000 or less.
• the weight average molecular weight of the di(meth)acrylic monomer (B-2) is preferably 900 or more and 3000 or less, more preferably 1200 or more and 2500 or less, and even more preferably 1500 or more and 2000 or less.
• the di(meth)acrylic monomer (B-2) has at least one of an aromatic ring and a urethane bond.
• the di(meth)acrylic monomer (B-1) may contain only one of an aromatic ring and a urethane bond, or may contain both an aromatic ring and a urethane bond.
• di(meth)acrylic monomer (B-2) contains a urethane bond, it may contain a compound represented by the following formula (2).
• R 6 is each independently a divalent chain hydrocarbon group, a divalent hydrocarbon group having an aromatic structure, or a divalent hydrocarbon group having an alicyclic structure.
• R 7 is each independently a divalent chain hydrocarbon group which may have a substituent
• R 8 is a divalent linking group
• R 9 and R 10 are each independently a methyl group or a hydrogen atom.
• R 6 when R 6 is a divalent chain hydrocarbon group, the preferred configuration of R 6 is the same as the preferred configuration of R 1 in formula (1).
• 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.
• 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, Cyclododecylene group, cyclotridecylene group, cyclotetradecylene group, cyclopentadecylene group, cyclooctadecylene group, cycloicosylene group, bicyclohexylene group, norbornylene group, isobornylene group, adamantylene group, methylenebiscyclo Examples include xylene group.
• the divalent hydrocarbon group having an alicyclic structure in R 6 in formula (2) may have a substituent.
• substituents include straight chain or branched alkyl groups having 1 to 6 carbon atoms.
• R 7 is the same as the preferred configuration of R 2 and R 3 in formula (1).
• R 8 is a divalent linking group.
• the divalent linking group include a polyether group, an alkylene group, an arylene group, an alkylenearylene group, an alkylenearylenealkylene group, and the like. Among these, polyether groups are preferred, and polyether groups constituted by ether groups having 2 to 4 carbon atoms are more preferred.
• the mono(meth)acrylic monomer (B-3) is a (meth)acrylic monomer component having one (meth)acryloyloxy group and at least one of an aromatic ring and a hydroxy group.
• the molecular weight of the mono(meth)acrylic monomer (B-3) is preferably 130 or more and 350 or less, more preferably 130 or more and 320 or less, and even more preferably 130 or more and 300 or less.
• the weight average molecular weight of the mono(meth)acrylic monomer (B-3) is preferably 130 or more and 350 or less, more preferably 130 or more and 320 or less, and even more preferably 130 or more and 300 or less.
• the mono(meth)acrylic monomer (B-3) may contain a compound represented by the following formula (3).
• R 11 is a monovalent organic group having at least one of an aromatic structure and a hydroxy group.
• the monovalent organic group having an aromatic structure in R 11 in formula (3) is preferably a monovalent organic group having 2 to 30 carbon atoms, and preferably a monovalent organic group having 3 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 2 to 30 carbon atoms. ⁇ 10 hydroxyalkyl group or an aryl group having 6 to 30 carbon atoms. * 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.
• L 1 is preferably a single bond.
• the mono(meth)acrylic monomer (B-3) is preferably 4-hydroxybutyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.
• 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 (B) is preferably 3% by mass to 80% by mass, more preferably 10% by mass to 70% by mass, based on the total amount of the (meth)acrylic monomer component.
• the content is preferably 20% by mass to 60% by mass, more preferably 20% by mass to 60% by mass.
• the total content of the di(meth)acrylic monomer (A) and the (meth)acrylic monomer (B) is 80% by mass or more based on the total amount of the (meth)acrylic monomer component contained in the photocurable composition of the present disclosure.
• the content is preferably 90% by mass or more, and even more preferably 95% by mass or more.
• the upper limit of the total content of di(meth)acrylic monomer (A) and (meth)acrylic monomer (B) is not particularly limited, and may be 100% by mass or less.
• the photocurable composition of the present disclosure by increasing the content of acrylic groups among the methacrylic groups and acrylic groups of the (meth)acrylic monomer component (for example, increasing the content of the acrylic monomer in the photocurable composition). ), it is possible to improve the storage modulus of the test piece A1 at 25°C more preferentially than the storage modulus at 37°C.
• the test The storage modulus of piece A1 at 37°C can be improved more preferentially than the storage modulus at 25°C.
• the test The storage modulus at 25°C of piece A1 can be reduced more preferentially than the storage modulus at 37°C, and the content of methacrylic groups among the methacrylic groups and acrylic groups of the (meth)acrylic monomer component can be reduced.
• the storage modulus of test piece A1 at 37°C is preferentially reduced over the storage modulus at 25°C. be able to.
• the photocurable composition of the present disclosure includes a photopolymerization initiator.
• the photocurable composition of the present disclosure 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.
• acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. can be mentioned.
• the total content of the photopolymerization initiator in the photocurable composition of the present disclosure is preferably 0.1% by mass to 5% by mass, and 0.5% by mass based on the total amount of the photocurable composition. It is more preferably 4% by mass, and even more preferably 0.5% by mass to 3% by mass.
• 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 total content of two or more di(meth)acrylic monomers (A) and a photopolymerization initiator, or the total content of di(meth)acrylic monomers (A), (meth) ) is preferably 80% by mass or more, and preferably 90% by mass or more, each independently of the total amount of the photocurable composition of the present disclosure. It is more preferable that the amount is 95% by mass or more.
• the upper limit of the total content of two or more types of di(meth)acrylic monomers (A) and photopolymerization initiator, or di(meth)acrylic monomer (A), (meth)acrylic monomer (B), and photopolymerization initiator is not particularly limited, and may be 100% by mass or less.
• the photocurable composition of the present disclosure may contain one or more types of components other than the above-mentioned components, if necessary.
• the total mass of the (meth)acrylic monomer component and the photopolymerization initiator is preferably 30% by mass or more based on the total amount of the photocurable composition, It is 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.
• 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.
• thermal polymerization initiator include thermal radical generators and amine compounds.
• 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.
• Examples of the method for preparing the photocurable composition of the present disclosure include a method of mixing a (meth)acrylic monomer 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 photocurable composition of the second embodiment of the present disclosure is a photocurable composition containing a (meth)acrylic monomer component and a photopolymerization initiator, wherein the (meth)acrylic monomer component is A mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring, at least one of a ring structure or a urethane bond, and two (meth)acryloyloxy groups, a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond and two or more (meth)acryloyloxy groups; including.
• the (meth)acrylic monomer component is A mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring, at least one of a ring structure or a urethane bond, and two (meth)acryloyloxy groups, a polyfunctional (meth)acrylic monomer (Z) having a silox
• the photocurable composition of the present disclosure includes a (meth)acrylic monomer component and a photopolymerization initiator, and the (meth)acrylic monomer component includes a mono(meth)acrylic monomer (X) and a di(meth)acrylic monomer (X). It includes an acrylic monomer (Y) and a polyfunctional (meth)acrylic monomer (Z).
• a rectangular plate-shaped object A1 with a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm is formed, and the object A1 is irradiated with ultraviolet rays with a wavelength of 365 nm at an irradiation amount of 3 J/cm 2 by stereolithography.
• the storage modulus of the test piece A1 at 25° C. is determined from the viewpoint of suppressing deformation of the mold (for example, applying a photocurable composition for making a denture base to a mold prepared using the photocurable composition of the present disclosure).
• the pressure may be 10 MPa or more, and from the viewpoint of ease of extraction from the mold (for example, from the viewpoint of removing the denture from the mold, the mold when removing the denture from the mold, the denture, etc.) 100 MPa or less may be sufficient from the viewpoint of suppressing damage to
• the storage modulus of the test piece A1 at 37° C. may be 400 MPa or less from the viewpoint of ease of extraction from the mold, and may be 6 MPa or more from the viewpoint of suppressing mold deformation during use.
• the storage modulus of the test piece A1 at 25°C may be less than 10 MPa, for example, 1 MPa to 10 MPa, or 2 MPa to 8 MPa. Good too.
• the storage modulus of the test piece A1 at 37° C. may be, for example, 0.5 MPa to 20 MPa, 1 MPa to 10 MPa, or 1 MPa to 6 MPa. It may be.
• the releasability of a member manufactured using the mold (for example, a denture) from the mold is improved, and when the mold is released, The toughness of the cured product is improved and the cured product is less likely to break.
• the (meth)acrylic monomer component includes a mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring.
• a mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring.
• the concentration of aromatic rings in the (meth)acrylic monomer component increases, which tends to make it easier to remove the denture from the mold (improving mold releasability). It tends to prevent breakage when the denture is taken out from inside (it has excellent toughness).
• the mono(meth)acrylic monomer (X) is suitably used when adjusting the storage modulus at 25° C. and the storage modulus at 37° C. of the cured product of the photocurable composition to
• the molecular weight of the mono(meth)acrylic monomer (X) may be from 160 to 400, or from 180 to 300.
• the weight average molecular weight of the mono(meth)acrylic monomer (X) may be from 160 to 400, or from 180 to 300.
• Two types of mono(meth)acrylic monomers (X) having different molecular weights may be used together. This tends to increase the dispersibility of the mono(meth)acrylic monomer (X) in the polymer and improve the shape recovery speed.
• the mono(meth)acrylic monomer (X) is not particularly limited as long as it is a compound having one (meth)acryloyloxy group and an aromatic ring, and for example, a compound represented by the following formula (5). There may be.
• R 1 is a divalent linking group
• R 2 is an alkyl group or aryl group that may have a substituent
• R 3 is a hydrogen atom or a methyl group
• n is It is an integer from 0 to 5.
• R 1 is an alkylene group, an arylene group (phenylene group, etc.), an alkylene arylene group (alkylene phenylene group, etc.), an arylene alkylene group (phenylene alkylene group, alkyleneoxy group, aryleneoxy group, or two thereof) A combination of the above may be used.Furthermore, the hydrogen atom contained in R1 may be substituted with a hydroxy group, an alkyl group, an aryl group, an amino group, or the like. In formula (5), the number of atoms in the main chain of R 1 may be from 1 to 20, or from 2 to 10. The number of carbon atoms in R 1 may be from 1 to 20, or from 2 to 10.
• n is preferably 0 or 1.
• R 2 is preferably a phenyl group which may have a substituent.
• the number of carbon atoms in R 2 may be from 1 to 20, or from 1 to 10.
• substituents that the alkyl group or aryl group in R 2 may have include a hydroxy group, an alkyl group, an aryl group, and an amino group.
• the (meth)acrylic monomer component is a di(meth)acrylic monomer (Y) that has at least one of a ring structure or a urethane bond and two (meth)acryloyloxy groups and does not have a siloxane bond.
• the di(meth)acrylic monomer (Y) having a ring structure suitably contributes to suppressing deformation of a mold during the production of a denture and improving the water resistance of the mold. Further, when the ring structure includes an aromatic ring, the concentration of the aromatic ring in the (meth)acrylic monomer component tends to increase, the mold releasability increases, and the toughness tends to be excellent.
• the di(meth)acrylic monomer (Y) having a urethane bond can suppress breakage when the denture is taken out from the mold, and tends to have excellent toughness. Further, the di(meth)acrylic monomer (Y) is suitably used when adjusting the storage modulus at 25° C. and the storage modulus at 37° C. of the cured product of the photocurable composition to be high.
• the di(meth)acrylic monomer (Y) is not particularly limited as long as it is a compound that has at least one of a ring structure or a urethane bond and two (meth)acryloyloxy groups and does not have a siloxane bond.
• Examples of the ring structure include an aromatic ring structure and an alicyclic structure.
• the di(meth)acrylic monomer (Y) has 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.
• the distance between them may be 10 ⁇ or more and 200 ⁇ or less.
• the distance between the aforementioned oxygen atoms may be 10 ⁇ or more and less than 25 ⁇ , 25 ⁇ or more and 80 ⁇ or less, or more than 80 ⁇ and less than 200 ⁇ .
• the elastic modulus of the mold can be increased and the deformation of the mold during the manufacture of dentures can be suppressed. This tends to improve mold releasability.
• the molecular weight of the di(meth)acrylic monomer (Y) may be 400 to 5,000.
• the weight average molecular weight of the di(meth)acrylic monomer (Y) may be from 400 to 4,000.
• di(meth)acrylic monomers (Y) Two types of di(meth)acrylic monomers (Y) with different molecular weights may be used together. This tends to increase the dispersibility of the di(meth)acrylic monomer (Y) in the polymer and improve the shape recovery speed.
• the di(meth)acrylic monomer (Y) may be a compound represented by the following formula (6-1) when it contains a urethane bond, and it may be a compound represented by the following formula (6-1) when it contains a ring structure. It may also be a compound represented by 2). When the di(meth)acrylic monomer (Y) contains both a urethane bond and a ring structure, it may be a compound represented by the following formula (6-1).
• R 1 is an alkylene group, an ester bond, an alkyleneoxy group, or a combination of at least two of these, each of which may independently have a substituent
• R 2 is a substituted an alkylene group which may have a group, a divalent ring structure, an ester bond, a urethane bond, an alkyleneoxy group, or a combination of at least two of these
• R 3 is each independently a hydrogen atom or a methyl It is the basis.
• R 3 is each independently a hydrogen atom or a methyl group
• R 4 is each independently an optionally substituted alkylene group, alkyleneoxy group, or a combination thereof.
• R 1 when R 1 is an alkylene group which may have a substituent or contains the alkylene group, examples of the substituent include a phenyloxy group.
• the alkyleneoxy group may be an ethyleneoxy group, a propyleneoxy group, or the like.
• the plurality of alkyleneoxy groups when a plurality of alkyleneoxy groups are included, the plurality of alkyleneoxy groups may be a polyethyleneoxy group, a polypropyleneoxy group, or the like.
• R 1 when R 1 has an ester bond, R 1 may contain a structural unit derived from ⁇ -caprolactone, or may contain a plurality of structural units derived from ⁇ -caprolactone.
• R 1 when R 1 has an ester bond, it may be an alkylene group -O-CO-alkylene group, and among these, the -O-CO-alkylene group may have a repeating structure (for example, 2 to 10). .
• the number of carbon atoms in R 1 may be from 1 to 50, or from 2 to 25.
• R 2 when R 2 is an alkylene group (which may be linear or branched) that may have a substituent, examples of the substituent include a hydroxy group, an alkyl group, aryl group, amino group, etc.
• R 2 when R 2 is a divalent ring structure or includes a divalent ring structure, examples of the ring structure include an aromatic ring or an alicyclic ring, and specifically, a phenylene group. , cyclohexylene group. Furthermore, R 2 may include a group formed by a divalent ring structure and a divalent alkylene group (eg, an isophorone group, a methylenebis(cyclohexylene) group). In addition, R 2 is a divalent hydrocarbon group containing two ring structures, two urethane bonds, and a divalent linking group containing an alkyleneoxy group (for example, a divalent hydrocarbon group containing a ring structure - a urethane bond). - (poly)alkyleneoxy group - urethane bond - divalent hydrocarbon group containing a ring structure). The number of carbon atoms in R 2 may be from 1 to 200, or from 2 to 100.
• R 4 is an alkyleneoxy group
• R 5 may be an oxygen atom
• R 4 is an alkylene group
• R 6 may be a phenylene group or a bisphenol skeleton (eg, a bisphenol A skeleton or a bisphenol F skeleton).
• the number of carbon atoms in R 4 may be from 1 to 50, or from 2 to 30.
• the number of carbon atoms in R 6 may be from 1 to 50, or from 2 to 20.
• the (meth)acrylic monomer component includes a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond (Si-O-Si) and two or more (meth)acryloyloxy groups.
• a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond (Si-O-Si) and two or more (meth)acryloyloxy groups.
• the aromatic ring concentration in the (meth)acrylic monomer component increases, which tends to make it easier to remove the denture from the mold (improving mold releasability), It has excellent deformability when manufacturing dentures, and tends to have excellent dimensional accuracy.
• the polyfunctional (meth)acrylic monomer (Z) is suitably used when adjusting the storage modulus at 25° C. and the storage modulus at 37° C. of the cured product of the photocurable composition to be low.
• the polyfunctional (meth)acrylic monomer (Z) has a siloxane bond (Si-O-Si) and two or more (meth)acryloyloxy groups.
• the polyfunctional (meth)acrylic monomer (Z) may contain a plurality of siloxane bonds (Si-O-Si), and more specifically, a linear siloxane bond, a ladder-like siloxane containing a linear chain and a branch. It may contain bonds, cage-type siloxane bonds, and the like.
• the polyfunctional (meth)acrylic monomer (Z) may contain two or more (meth)acryloyloxy groups.
• siloxane bond examples include a dimethylsiloxane bond, a methylphenylsiloxane bond, a diphenylsiloxane bond, and the like, with a dimethylsiloxane bond being preferred.
• the polyfunctional (meth)acrylic monomer (Z) may be a compound containing a siloxane bond (Si-O-Si) and three or more (meth)acryloyloxy groups, and three or more (meth)acryloyloxy groups. It may also be a silsesquioxane containing an acryloyloxy group.
• the polyfunctional (meth)acrylic monomer (Z) may have a molecular weight of 400 to 5,000.
• the weight average molecular weight of the polyfunctional (meth)acrylic monomer (Z) may be from 400 to 4,000.
• the polyfunctional (meth)acrylic monomer (Z) may be a compound represented by the following formula (7).
• R 1 is an alkylene group that may each independently have a substituent
• R 2 is an alkylene group that may each independently have a substituent
• R 3 are each independently a hydrogen atom or a methyl group
• R4 is each independently an alkyl group, a hydrogen atom, or an aryl group
• m is an integer of 0 or more
• n is an integer of 0 or more
• l is an integer greater than or equal to 0.
• R 1 is preferably a methylene group, ethylene group or propylene group
• R 2 is more preferably a methylene group, ethylene group, propylene group or butylene group.
• R 4 is preferably a methyl group or a phenyl group, more preferably a methyl group.
• m may be from 1 to 30, or from 2 to 20. From the viewpoint of compatibility with other (meth)acrylic monomer components, m is preferably 30 or less, more preferably 20 or less.
• n may be 0 or 1 or more. When n is 1 or more, n may be from 1 to 30, or from 1 to 20.
• l may be 0 or 1 or more. When l is 1 or more, l may be from 1 to 30, or from 1 to 20.
• the content of the mono(meth)acrylic monomer (X) is preferably from 30% by mass to 90% by mass, and from 40% by mass to the total amount of the (meth)acrylic monomer component. More preferably, it is 80% by mass.
• the content of the di(meth)acrylic monomer (Y) is preferably from 5% by mass to 55% by mass, and from 10% by mass to the total amount of the (meth)acrylic monomer component. More preferably, it is 40% by mass.
• the content of the polyfunctional (meth)acrylic monomer (Z) is preferably 1% by mass to 60% by mass, and 5% by mass based on the total amount of the (meth)acrylic monomer component. % to 50% by mass is more preferable.
• the total content of mono(meth)acrylic monomer (X), di(meth)acrylic monomer (Y), and polyfunctional (meth)acrylic monomer (Z) is 50% by mass to 100% by mass. %, more preferably 70% to 100% by weight, even more preferably 90% to 100% by weight.
• the siloxane bond concentration in the composition is preferably 0.100 mmol/g to 3.000 mmol/g, more preferably 0.300 mmol/g to 2.500 mmol/g.
• the siloxane bond concentration is 0.100 mmol/g or more, mold release properties tend to improve, and when it is 3.000 mmol/g or less, it is possible to suppress breakage when taking out the denture from the mold, and improve toughness. They tend to be excellent at
• the aromatic ring concentration in the (meth)acrylic monomer component is preferably 0.0015 mol/g to 0.0070 mol/g, more preferably 0.0020 mol/g to 0.0065 mol/g.
• the siloxane bond concentration in the composition and the aromatic ring concentration in the (meth)acrylic monomer component each satisfy the aforementioned numerical ranges.
• the total content of the mono(meth)acrylic monomer (X), the di(meth)acrylic monomer (Y), the polyfunctional (meth)acrylic monomer (Z), and the photopolymerization initiator is the same as that of the photocurable composition of the present disclosure. It is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the total amount.
• the upper limit of the total content of mono(meth)acrylic monomer (X), di(meth)acrylic monomer (Y), polyfunctional (meth)acrylic monomer (Z), and photopolymerization initiator is not particularly limited, and is 100% by mass. The following is sufficient.
• the three-dimensional structure of the present disclosure includes a cured product of the photocurable composition of the present disclosure. Therefore, when the three-dimensional molded object of the present disclosure is a mold, deformation during the production of the denture can be suppressed, and when the denture is manufactured using the mold, the denture is removed from the mold. It becomes easier. 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.
• a preferred embodiment of the three-dimensional structure includes a mold, and more specifically, a mold used for manufacturing a denture.
• the method for producing a cured product of the present disclosure includes the step of polymerizing the curable composition in the mold described above.
• a mold is produced using the photocurable composition of the present disclosure described above, the curable composition is injected into the produced mold, and the injected curable composition is polymerized to produce a cured product. do it.
• the curable composition injected into the mold is not particularly limited as long as it contains a polymerizable component that is polymerized by heat, light, or the like.
• a conventionally known curable composition for making a denture base is injected into the mold, and the curable composition for making a denture base after injection is injected into the mold. may be cured.
• the method for manufacturing a denture with a denture of the present disclosure includes a step of curing a photocurable composition by stereolithography to produce a mold used for manufacturing the denture with a denture, polymerizing the curable composition in the mold, A step of manufacturing a fixed denture.
• the method for manufacturing a denture with a backing according to the present disclosure is a method of manufacturing a denture with a backing through two steps: a step of making a mold and a step of manufacturing a denture with a backing, and a method of manufacturing a denture with a backing using a conventional mold.
• a denture with a backing can be manufactured using a method that is simpler than a method for manufacturing a denture.
• the process of producing a mold includes, for example, a process of acquiring three-dimensional impression data in the oral cavity of a denture user, a process of acquiring mold data from the acquired three-dimensional impression data, and a process of acquiring mold data. It is preferable to include a step of curing the photocurable composition by stereolithography based on.
• the process of manufacturing dentures includes the steps of arranging artificial teeth in a mold, injecting a curable composition for making a denture base into the mold with the artificial teeth arranged in the mold, and post-injection steps. It is preferable to include the steps of curing the curable composition and removing the manufactured denture from the mold.
• the photocurable composition used to create the mold is not particularly limited.
• the photocurable composition of the present disclosure is preferable to use as a photocurable composition used for producing a mold.
• a rectangular plate-shaped object A1 with a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm is formed, and the object A1 is irradiated with ultraviolet rays with a wavelength of 365 nm at an irradiation amount of 3 J/cm 2 by stereolithography.
• a rectangular plate-shaped test piece A1 having a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm was prepared.
• the produced test piece A1 was measured by dynamic viscoelasticity measurement under the conditions of a measurement frequency of 1 Hz while increasing the temperature in a temperature range of 25°C to 200°C and a heating rate of 3°C/min.
• the storage modulus and the storage modulus at 37°C were determined.
• the test piece A1 was prepared using a DLP 3D printer (Kulzer, Cara Print 4.0), and the storage modulus was measured using a dynamic viscoelasticity measurement device (DMA7100, Hitachi High-Tech Science Co., Ltd.). This was done using
• viscosity The viscosity of the obtained photocurable composition was measured using an E-type viscometer at 25° C. and 50 rpm. As a result, the viscosities of the photocurable compositions of Examples 1 to 19 were all in the range of 50 mPa ⁇ s to 3000 mPa ⁇ s.
• test piece A2 has L of 28 mm, L' of 20 mm, W of 2 mm, H of 24 mm, H' of 22 mm, and width (D) of 2 mm.
• the shape has a gap of .
• a deviation from the design value was evaluated as "A”
• B a deviation of 0.05 mm or more and 0.10 mm or less
• C a deviation larger than 0.10 mm
• test piece A3 has L of 15 mm, L' of 2 mm, H of 12 mm, H' of 2 mm, R of 4 mm, and thickness (D) of 10 mm. It has the shape of An attachment/detachment test was conducted by inserting and removing an iron ball (diameter 10 mm) between the two semicircular columns of the obtained test piece A3 at a moving speed of 120.0 ⁇ 2.0 mm/min. Observe the test piece after moving it in and out 10 times, and evaluate it as "A” if there is no shape change and no cracking after the test, "B” if there is shape change and no cracking after the test, and "C” if cracking occurs after the test. did.
• Photopolymerizable component 1 Ethoxylated bisphenol A diacrylate (A-BPE-10, Shin Nakamura Chemical Co., Ltd.)
• Photopolymerizable component 2 Ethoxylated bisphenol A dimethacrylate (BPE-500, manufactured by Shin Nakamura Chemical Co., Ltd.)
• Photopolymerizable components 3 to 9 are di(meth)acrylic monomers (meth)acrylic monomers having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, and a distance d1 of 10 ⁇ or more and less than 25 ⁇ . Classified as B-1).
• the photopolymerizable component 10 is a di(meth)acrylic monomer (B- It is classified as 2).
• Photopolymerizable components 11 to 17 are classified as mono(meth)acrylic monomers (B-3) having one (meth)acryloyloxy group and at least one of an aromatic ring and a hydroxy group.
• Photopolymerizable component 3 Ethoxylated bisphenol A diacrylate (BP-4EAL, Kyoeisha Chemical Co., Ltd.)
• Photopolymerizable component 4 Ethoxylated bisphenol A dimethacrylate (SR540, Sartomer Co., Ltd.)
• Photopolymerizable component 5 Ethoxylated bisphenol F diacrylate (M-208, Toagosei Co., Ltd.)
• Photopolymerizable component 6 Ethoxylated bisphenol A dimethacrylate (SR348, Sartomer Co., Ltd.)
• Photopolymerizable component 7 Urethane diacrylate (SUA-1 (UDA in the table), compound produced according to Production Example 1A below)
• Photopolymerizable component 8 Urethane dimethacrylate (SUA-2 (UDMA in the table), compound produced according to Production Example 1B below)
• Photopolymerizable component 9 Bifunctional urethane acrylate (AH-600, Kyoeisha
• Photopolymerizable component 18 Ethoxylated hydrogenated bisphenol A dimethacrylate (HBPEM-10, Daiichi Kogyo Seiyaku Co., Ltd.)
• Photopolymerizable component 19 Ethoxylated hydrogenated bisphenol A diacrylate (HBPE-4, Daiichi Kogyo Seiyaku Co., Ltd.)
• Photoinitiator 1 Acylphosphine oxide compound (Omnirad 819: “Omnirad 819” manufactured by IGM Resins B.V.)
• Photoinitiator 2 Acylphosphine oxide compound (Omnirad TPO: “Omnirad TPO” manufactured by IGM Resins B.V.)
• TMHDI trimethylhexamethylene diisocyanate
• reaction temperature was maintained at 80°C and the reaction was carried out for 5 hours. At this time, the progress of the reaction was followed by HPLC analysis to confirm the end point of the reaction.
• HPLC analysis By discharging the product from the reactor, 840 g of urethane acrylate (SUA-3) was obtained.
• the viscosity at 40°C was 41000 mPa ⁇ s.
• Example 20 ⁇ Manufacture of dentures> A plaster model of the upper or lower jaw was used as three-dimensional impression data using a laboratory dental scanner (Kulzer, Cara Scan 4.0). Each three-dimensional impression data was uploaded to commercially available CAD software (3D Systems, Geomagic Design X). A mold for manufacturing dentures was designed on CAD software, the thickness of the mold was set to 2.0 mm, and three-dimensional modeling data was obtained.
• CAD software 3D Systems, Geomagic Design X
• the photocurable composition of Example 1 was irradiated with visible light with a wavelength of 405 nm at a dose of 11 mJ/cm 2 to form a cured layer with a thickness of 50 ⁇ m, and the cured layers were laminated in the thickness direction, and the above
• a molded article for manufacturing dentures with a base was obtained.
• the resulting molded article was irradiated with ultraviolet rays with a wavelength of 365 nm under conditions of 3 J/cm 2 to fully cure the article, thereby obtaining a mold for manufacturing dentures.
• this method allows for the creation of dentures more easily than conventional wax dentures, manual methods using silicone, etc., and the use of denture resin, which is unsuitable for stereolithography, for the production of dentures. Therefore, it is suitable for obtaining desired physical properties.
• L is 24 mm
• L' is 20 mm
• W is 2 mm
• H is 5 mm
• H' is 3 mm
• D is 14 mm. It has a shape in which D' is 10 mm.
• test piece A4 is peeled off from the denture manufacturing polymer.
• the surface of the polymer for making dentures that was in contact with test piece A4 was observed using a 3D shape measuring machine (Keyence Corporation, VR-3200), and the surface that was in contact with the polymer for making dentures after being removed was observed.
• the area value of test piece A4 was calculated, and the adhesion rate to the surface (200 mm 2 ) consisting of L' and D' was calculated. The smaller the adhesion rate, the better the mold releasability.
• the evaluation was made as "A" when there was no surface adhesion, "B” when surface adhesion was less than 5%, and "C” when surface adhesion was 5% or more.
• the obtained photocurable composition was printed using a 3D printer (Kulzer, Cara Print 4.0) to a size of 8 mm long x 39 mm wide under the conditions of a visible light wavelength of 405 nm and a visible light illuminance of 8.0 mJ/ cm2.
• a molded article (layer width 50 ⁇ m) was obtained by molding to a thickness of 4 mm.
• An optically shaped article was obtained by irradiating the obtained article with ultraviolet rays with a wavelength of 365 nm under conditions of 10 J/cm 2 to fully cure the article.
• test piece stress was applied to curve the test piece so that both ends of the test piece in the longitudinal direction (horizontal direction) were in contact with each other, and the test piece was held for 10 seconds. Thereafter, the stress was released and changes in the shape of the test piece were observed and evaluated based on the following criteria. A: It returned to its original shape within 1 second after stress was released. B: It took more than 1 second to return to its original shape after stress was released.
• ⁇ Mono(meth)acrylic monomer (X)> The structure of each mono(meth)acrylic monomer (X) listed in Tables 4 to 7 is as follows.
• PO-A manufactured by Kyoeisha Chemical Co., Ltd. PO manufactured by Kyoeisha Chemical Co., Ltd.
• ⁇ Di(meth)acrylic monomer (Y)> The structure of each di(meth)acrylic monomer (Y) listed in Tables 4 to 7 is as follows.
• SUA-1 Compound produced by the method described in Production Example 1A below (UDA in the table) ABE-300 A-BPE-10 manufactured by Shin Nakamura Chemical Co., Ltd. SA-001 manufactured by Shin Nakamura Chemical Co., Ltd.
• Compound produced by the method described in Production Example 1C below U1 in the table
• reaction product was dissolved in 500 g of toluene, neutralized with 10% NaOH aqueous solution, and then washed with 150 g of 5% ammonium sulfate aqueous solution. Toluene was distilled under reduced pressure to obtain 390 g of di(meth)acrylic monomer (SA-001). The viscosity at 25°C was 410 mPa ⁇ s.
• reaction temperature was maintained at 70°C and the reaction was carried out for 5 hours. Thereafter, the reaction solution was neutralized with a 10% NaOH aqueous solution, and then washed with 150 g of a 5% ammonium sulfate aqueous solution. Ethyl acetate was distilled under reduced pressure to obtain 440 g of polyfunctional (meth)acrylic monomer (SiA-001). The viscosity at 25°C was 110 mPa ⁇ s.
• Photopolymerization initiator As the photopolymerization initiator listed in Tables 4 to 7, the aforementioned photopolymerization initiator 1 (acylphosphine oxide compound, Omnirad 819: “Omnirad 819" manufactured by IGM Resins B.V.) was used.

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