Classifications

• • 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
  • A61K6/80—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
• • 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
  • A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • A61K6/893—Polyurethanes
• • 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
• • 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

Definitions

• the present disclosure relates to a photocurable composition, a three-dimensional molded object, and an appliance installed in the oral cavity.
• a three-dimensional object manufactured by stereolithography using a photocurable composition is used for a denture base, a splint, or other appliance installed in the oral cavity, in addition to a certain bending strength and bending elastic modulus, a certain toughness is required. Further, a three-dimensional object manufactured by stereolithography may be washed with isopropyl alcohol after modeling, but the cleaning may reduce the toughness of the three-dimensional object, and sufficient toughness may not be obtained.
• An object of one aspect of the present disclosure is to provide a photocurable composition that can produce a three-dimensional object that has high toughness even after cleaning with isopropyl alcohol, a three-dimensional object obtained from this photocurable composition, and a three-dimensional object that can be used in the oral cavity.
• the purpose is to provide a device to be worn.
• Means for solving the above problems include the following aspects. ⁇ 1> It has two urethane bonds and two (meth)acryloyl groups, and each of the two (meth)acryloyl groups has an oxygen atom or a nitrogen atom for each of the two urethane bonds.
• R 1A is a divalent hydrocarbon group
• R 2A and R 3A are each independently an alkylene group having 4 to 10 carbon atoms
• R 4A and R 5A are , each independently a methyl group or a hydrogen atom
• R 4A in the general formula (A-1) is a group represented by any of the following general formulas (a-1) to (a-7). sexual composition.
• the (meth)acrylic monomer (B) is at least one of a compound represented by the following general formula (B-1) and a compound represented by the following general formula (B-2), ⁇ 1> ⁇ The photocurable composition according to any one of ⁇ 4>.
• R 1B1 is a monovalent organic group having one or more selected from the group consisting of an aromatic ring, a hydroxy group, and a carboxy group, and R 2B1 is a methyl group or a hydrogen atom.
• R 1B2 and R 2B2 are each independently a monovalent organic group, R 1B2 and R 2B2 may be combined with each other to form a ring, and R 3B2 is , a methyl group or a hydrogen atom) ⁇ 6>
• the photocurable composition according to any one of ⁇ 1> to ⁇ 5>, wherein the (meth)acrylic monomer (A) has a molecular weight of 440 to 650.
• ⁇ 7> The photocurable composition according to any one of ⁇ 1> to ⁇ 6>, wherein the (meth)acrylic monomer (B) has a molecular weight of 125 to 300.
• the content of the (meth)acrylic monomer (A) is 300 parts by mass to 950 parts by mass based on 1000 parts by mass of the (meth)acrylic monomer component contained in the photocurable composition, ⁇ 1> ⁇ The photocurable composition according to any one of ⁇ 7>.
• the content of the (meth)acrylic monomer (B) is ( The photocurable composition according to any one of ⁇ 1> to ⁇ 8>, wherein the amount is 50 parts by mass to 700 parts by mass based on 1000 parts by mass of the meth)acrylic monomer component.
• the photocurable composition according to any one of ⁇ 1> to ⁇ 9> which has a viscosity of 5 mPa ⁇ s to 6000 mPa ⁇ s as measured by an E-type viscometer at 25° C. and 50 rpm. thing.
• the bending strength of the test piece A1 is 50 Mpa or more
• the bending elastic modulus is 1500 Mpa or more
• a photocurable composition was irradiated with visible light with a wavelength of 405 nm at a dose of 11 mJ/cm 2 to form a cured layer A2 with a thickness of 50 ⁇ m, and the cured layer A2 was laminated in the thickness direction to form a layer with a length of 39 mm.
• a rectangular plate-shaped object A2 with a width of 8 mm and a thickness of 4 mm is formed, and by irradiating the object A2 with ultraviolet light with a wavelength of 365 nm at a dose of 10 J/cm2, the object A2 has a length of 39 mm, a width of 8 mm, and a thickness of 4 mm.
• ⁇ 12> The photocurable composition according to any one of ⁇ 1> to ⁇ 11>, which is used for stereolithography.
• ⁇ 13> The photocurable composition according to any one of ⁇ 1> to ⁇ 12>, which is used for manufacturing a device to be mounted in the oral cavity by stereolithography.
• ⁇ 14> A three-dimensional object comprising a cured product of the photocurable composition according to any one of ⁇ 1> to ⁇ 13>.
• ⁇ 15> An appliance to be worn in the oral cavity, including the three-dimensional structure according to ⁇ 14>.
• a photocurable composition that can produce a three-dimensional structure that has high toughness even after cleaning with isopropyl alcohol, a three-dimensional structure obtained from this photocurable composition, and a three-dimensional structure that can be used in the oral cavity. You will be provided with a device to wear.
• 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 has two urethane bonds and two (meth)acryloyl groups, and each of the two (meth)acryloyl groups is attached to each of the two urethane bonds.
• a (meth)acrylic monomer (A) connected via an alkylene group having 4 to 10 carbon atoms to which an oxygen atom or a nitrogen atom is bonded hereinafter also referred to as "(meth)acrylic monomer (A)"
• a (meth)acrylic monomer (B) having one (meth)acryloyl group hereinafter also referred to as "(meth)acrylic monomer (B)
• a photopolymerization initiator a photopolymerization initiator.
• the photocurable composition of the present disclosure by combining the (meth)acrylic monomer (A) and the (meth)acrylic monomer (B), it is possible to produce a three-dimensional object that has high toughness even after cleaning with isopropyl alcohol. .
• the photocurable composition of the present disclosure is a composition that is cured by light irradiation, and a cured product can be obtained by curing this composition.
• a preferred manufacturing method for manufacturing a cured product using the photocurable composition of the present disclosure is stereolithography.
• the photocurable composition of the present disclosure is preferably a photocurable composition for stereolithography.
• 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 high toughness even after cleaning with isopropyl alcohol.
• dental products include dental prostheses, intraoral appliances, dental models, investment casting models, and the like.
• dental prostheses include inlays, crowns, bridges, temporary crowns, and temporary bridges.
• Appliances installed in the oral cavity include dentures (e.g., complete dentures, partial dentures, etc.), mouthpieces, mouth guards, orthodontic appliances, occlusal splints, and temporomandibular joints.
• Examples include splints such as splints for medical treatment, trays for impression taking, surgical guides, etc.
• the dental model include a tooth and jaw model.
• the photocurable composition of the present disclosure is preferably a photocurable composition used for stereolithography, more preferably a photocurable composition used for manufacturing dental products by stereolithography, and More preferably, it is a photocurable composition used for manufacturing a molded appliance to be placed in the oral cavity.
• the photocurable composition of the present disclosure has two urethane bonds and two (meth)acryloyl groups, and each of the two (meth)acryloyl groups is attached to each of the two urethane bonds.
• One type of (meth)acrylic monomer (A) may be used alone, or two or more types may be used in combination.
• the (meth)acrylic monomer (A) has two urethane bonds, and each of the two (meth)acryloyl groups and each of the two urethane bonds has a carbon number of 4 to which an oxygen atom or a nitrogen atom is bonded. It is a compound linked through ⁇ 10 alkylene groups.
• each of the two (meth)acryloyl groups in the (meth)acrylic monomer (A) is bonded to an oxygen atom or a nitrogen atom bonded to an alkylene group having 4 to 10 carbon atoms; It is preferably bonded to an oxygen atom or nitrogen atom bonded to an alkylene group, and more preferably bonded to an oxygen atom or nitrogen atom bonded to an alkylene group having 4 carbon atoms.
• the (meth)acrylic monomer (A) has two urethane bonds, and each of the two (meth)acryloyl groups and each of the two urethane bonds have a carbon number of 4 to 10 to which an oxygen atom is bonded.
• a compound connected via an alkylene group is preferable, and a compound represented by the following general formula (A-1) is more preferable.
• R 1A is a divalent hydrocarbon group
• R 2A and R 3A are each independently an alkylene group having 4 to 10 carbon atoms
• R 4A and R 5A are Each independently represents a methyl group or a hydrogen atom.
• R 1A in general formula (A-1) is preferably a divalent hydrocarbon group having 5 to 20 carbon atoms, a divalent chain hydrocarbon group having 5 to 10 carbon atoms, and a carbon having a cyclic structure. It is more preferably a divalent hydrocarbon group having 6 to 18 carbon atoms, and even more preferably a divalent hydrocarbon group having 8 to 16 carbon atoms and having a cyclic structure.
• Examples of the divalent chain hydrocarbon group having 5 to 10 carbon atoms include pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, and the like.
• cyclic structure examples include aromatic ring structures and alicyclic structures.
• the cyclic structure also includes a combination of an aromatic ring structure and another linking group (for example, a divalent hydrocarbon group), such as a bisphenol A structure.
• aromatic ring 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.
• R 1A in the general formula (A-1) is preferably a group represented by any of the following general formulas (a-1) to (a-7), and the following general formula (a-1) A group represented by any one of (a-4) is more preferable.
• R 2A and R 3A each independently represent an alkylene group having 4 to 10 carbon atoms, preferably an alkylene group having 4 to 8 carbon atoms, and more preferably an alkylene group having 4 carbon atoms.
• the alkylene group having 4 to 10 carbon atoms include 1,4-butanediyl group, 1,2-dimethyl-1,2-ethanediyl group, 2-methyl-1,3-propanediyl group, 1,5-pentanediyl group, Examples include 1,6-hexanediyl group, 1,7-heptanediyl group, 1,8-octanediyl group, 1,9-nonanediyl group, 1,10-decanediyl group, 2,4,4-trimethylhexylene group, etc. It will be done. Both R 2A and R 3A are preferably 1,4-butanediyl groups.
• the molecular weight of the (meth)acrylic monomer (A) is preferably 440 to 750, more preferably 440 to 650, even more preferably 450 to 600, particularly preferably 470 to 550. .
• the content of the (meth)acrylic monomer (A) is determined based on 1000 parts by mass of the (meth)acrylic monomer component contained in the photocurable composition. , is preferably from 300 parts by weight to 950 parts by weight, more preferably from 350 parts by weight to 900 parts by weight, even more preferably from 400 parts by weight to 900 parts by weight.
• the photocurable composition of the present disclosure includes a (meth)acrylic monomer (B) having one (meth)acryloyl group.
• One type of (meth)acrylic monomer (B) may be used alone, or two or more types may be used in combination.
• the (meth)acrylic monomer (B) of the present disclosure is preferably at least one of a compound represented by the following general formula (B-1) and a compound represented by the following general formula (B-2).
• R 1B1 is a monovalent organic group having one or more selected from the group consisting of an aromatic ring, a hydroxy group, and a carboxy group
• R 2B1 is a methyl group or a hydrogen atom.
• the aforementioned monovalent organic group in R 1B1 is preferably a monovalent organic group having 2 to 30 carbon atoms, more preferably a monovalent organic group having 4 to 20 carbon atoms.
• R 1B2 and R 2B2 are each independently a monovalent organic group, R 1B2 and R 2B2 may be combined with each other to form a ring, and R 3B2 is a methyl group. Or a hydrogen atom.
• the aforementioned monovalent organic group in R 1B2 and R 2B2 is preferably a monovalent organic group having 2 to 10 carbon atoms, more preferably a monovalent organic group having 2 to 5 carbon atoms.
• the ring may be a ring consisting of a nitrogen atom and a carbon atom, and the ring may be a ring consisting of a nitrogen atom or a heteroatom other than a nitrogen atom (for example, an oxygen atom). ) and a carbon atom.
• the ring may be a 4- to 8-membered ring, a 5-membered ring, or a 6-membered ring.
• the (meth)acrylic monomer (B) of the present disclosure may contain two or more compounds represented by general formula (B-1), and may contain two or more compounds represented by general formula (B-2). It may contain a compound represented by one or more types of general formula (B-1) and one or more types of compounds represented by general formula (B-2) in combination. .
• R 1B1 is preferably a monovalent organic group having an aromatic ring, a monovalent organic group having a hydroxy group, or a monovalent organic group having a carboxyl group.
• a monovalent organic group having an aromatic ring and a hydroxy group, and a monovalent organic group having an aromatic ring and a carboxyl group are classified as monovalent organic groups having an aromatic ring.
• R 1B1 is a monovalent organic group having a hydroxy group or a monovalent organic group having a carboxy group, the flexibility of the three-dimensional structure tends to improve.
• the monovalent organic group having an aromatic ring may be a monovalent organic group having an aromatic ring and a hydroxy group.
• the monovalent organic group having an aromatic ring may have the aromatic ring structure shown below.
• * indicates a bonding position.
• the molecular weight of the (meth)acrylic monomer (B) is preferably from 125 to 300, more preferably from 130 to 280, even more preferably from 130 to 270.
• the content of the (meth)acrylic monomer (B) is determined based on 1000 parts by mass of the (meth)acrylic monomer component contained in the photocurable composition. , is preferably from 50 parts by weight to 700 parts by weight, more preferably from 100 parts by weight to 650 parts by weight, even more preferably from 100 parts by weight to 600 parts by weight.
• the content ratio of (meth)acrylic monomer (A) and (meth)acrylic monomer (B) ((meth)acrylic monomer (A):
• the (meth)acrylic monomer (B)) may have a ratio of 40:60 to 95:5, or may have a ratio of 45:55 to 90:10.
• the photocurable composition of the present disclosure may contain photopolymerizable components other than the (meth)acrylic monomer (A) and (meth)acrylic monomer (B) (hereinafter referred to as "other photopolymerizable components"). good.
• Other photopolymerizable components include compounds containing ethylenic double bonds. Examples of compounds containing ethylenic double bonds include (meth)acrylic monomers other than (meth)acrylic monomer (A) and (meth)acrylic monomer (B), styrene, styrene derivatives, (meth)acrylonitrile, etc. .
• the (meth)acrylic monomer (A), the (meth)acrylic monomer (B), and other photopolymerizable components used as necessary are also referred to as photopolymerizable components.
• the content of the photopolymerizable component with respect to the total amount of the photocurable composition of the present disclosure is preferably 60% by mass or more, and more preferably 80% by mass or more. , more preferably 90% by mass or more.
• the upper limit of the content of the photopolymerizable component with respect to the total amount of the photocurable composition of the present disclosure is not particularly limited, and may be less than 100% by mass, and may be, for example, 99.9% by mass or less.
• the total content of (meth)acrylic monomer (A) and (meth)acrylic monomer (B) is determined based on the total mass of the photopolymerizable component. , is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.
• the upper limit of the total content of (meth)acrylic monomer (A) and (meth)acrylic monomer (B) is not particularly limited, and may be 100% by mass or less based on the total mass of the photopolymerizable component.
• the (meth)acrylic monomer that is another photopolymerizable component may include a (meth)acrylic monomer (C) represented by general formula (C-1).
• R 1C is a divalent hydrocarbon group
• R 2C and R 3C are each independently an alkylene group having 2 or 3 carbon atoms
• R 4C and R 5C are Each independently represents a methyl group or a hydrogen atom.
• the preferred configuration of R 1C is the same as the preferred configuration of R 1A in formula (A-1) above.
• R 2C and R 3C are each independently an alkylene group having 2 or 3 carbon atoms. Examples of the alkylene group having 2 or 3 carbon atoms include ethylene group, propylene group, and methylethylene group. Both R 2C and R 3C are preferably ethylene groups.
• (meth)acrylic monomers that are photopolymerizable components include (meth)acrylic monomers that have two (meth)acryloyl groups and no urethane bond, and (meth)acrylic monomers that have three or more (meth)acryloyl groups. Examples include (meth)acrylic monomers.
• the content of other photopolymerizable components is preferably 50% by mass or less, and preferably 20% by mass or less based on the total mass of the photopolymerizable components. is more preferable, and even more preferably 10% by mass or less.
• the lower limit of the content of other photopolymerizable components (preferably (meth)acrylic monomer (C)) is not particularly limited, and may be 0% by mass or more based on the total mass of the photopolymerizable components.
• the photocurable composition of the present disclosure includes a photopolymerization initiator.
• the photopolymerization initiator is not particularly limited as long as it generates radicals when irradiated with light, and is preferably one that generates radicals at the wavelength of light used during stereolithography.
• the wavelength of the light used during stereolithography is generally 365 nm to 500 nm, but is practically preferably 365 nm to 430 nm, and more preferably 365 nm to 420 nm.
• acylphosphine oxide compounds As photopolymerization initiators, acylphosphine oxide compounds, alkyl benzoylformates, alkylphenone compounds, titanocene compounds, oxime ester compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, thioxanthone compounds, Examples include ⁇ -acyloxime ester compounds, phenylglyoxylate compounds, benzyl compounds, azo compounds, diphenyl sulfide compounds, organic dye compounds, iron-phthalocyanine compounds, benzoin ether compounds, anthraquinone compounds, etc. It will be done.
• the photopolymerization initiator may contain only one type, or may contain two or more types.
• acylphosphine oxide compounds and alkylphenone compounds are more preferable, and as the photopolymerization initiator, one or more acylphosphine oxide compounds may be used, or It is more preferable to use a combination of one or more acylphosphine oxide compounds and one or more alkylphenone compounds.
• acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. can be mentioned.
• alkylphenone compounds examples include 1-hydroxy-cyclohexyl-phenyl-ketone.
• the total content of photopolymerization initiators in the photocurable composition of the present disclosure is preferably 0.1% by mass to 10% by mass, and 0.3% by mass based on the total amount of the photocurable composition. It is more preferably from 8% by weight, and even more preferably from 0.5% to 5% by weight.
• 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 (A), (meth)acrylic monomer (B), and photopolymerization initiator is based on the total amount of the photocurable composition. , preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more. It is even more preferable.
• Examples of other components include monomers other than the (meth)acrylic monomer (A) and (meth)acrylic monomer (B) (for example, the above-mentioned (meth)acrylic monomer (C)).
• the content of the monomers as other components is It is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less based on the total mass of monomer (A) and (meth)acrylic monomer (B).
• the content is preferably 10% by mass or less, particularly preferably 10% by mass or less.
• 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.
• a method for preparing the photocurable composition of the present disclosure includes, for example, a method of mixing a (meth)acrylic monomer (A), a (meth)acrylic monomer (B), a photopolymerization initiator, and other components as necessary. can be mentioned.
• the means for mixing each component is not particularly limited, and includes means such as ultrasonic dissolution, a double-arm stirrer, a roll kneader, a twin-screw extruder, a ball mill kneader, and a planetary stirrer.
• the photocurable composition of this embodiment may be prepared by mixing each component, filtering the mixture through a filter to remove impurities, and further performing a vacuum defoaming treatment.
• 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.
• 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 64 mm, a width of 10 mm, and a thickness of 3.3 mm is formed, and the object A1 is irradiated with ultraviolet light with a wavelength of 365 nm at a dose of 10 J/ cm2.
• the bending strength of the test piece A1 is 50 Mpa or more and the bending elastic modulus is 1500 Mpa or more. It is preferable.
• a cured layer A2 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 having a length of 39 mm, a width of 8 mm, and a thickness of 4 mm is formed, and the object A2 is irradiated with ultraviolet light with a wavelength of 365 nm at a dose of 10 J/cm2 .
• the total destructive work of the test piece A2 is preferably 500 J/m 2 or more.
• the upper limit of the bending strength of the test piece A1 is not particularly limited, and may be, for example, 90 MPa or less.
• the upper limit of the flexural modulus of the test piece A1 is not particularly limited, and may be, for example, 3000 MPa or less.
• the upper limit of the total destructive work of test piece A2 is not particularly limited, and may be 2000 J/m 2 or less.
• the bending strength of the test piece A1 and the bending elastic modulus of the test piece A1 may satisfy the above-mentioned numerical conditions.
• the total destructive work of the test piece A2 may satisfy the above-mentioned numerical conditions. Examples of the cleaning method using IPA include the method described in Examples below.
• test piece A1 obtained from the photocurable composition of the present disclosure satisfies the above-mentioned conditions of bending strength and bending elastic modulus, an appliance to be worn in the oral cavity with excellent mechanical strength tends to be obtained.
• test piece A2 obtained from the photocurable composition of the present disclosure satisfies the above-mentioned total work of failure condition, an appliance that is worn in the oral cavity and has excellent toughness tends to be obtained.
• the three-dimensional structure of the present disclosure includes a cured product of the photocurable composition of the present disclosure. Therefore, the three-dimensional structure of the present disclosure has high toughness even after cleaning with isopropyl alcohol. It is preferable that the three-dimensional shaped article of the present disclosure includes a cured product obtained by stereolithography (i.e., a stereolithographic article).
• stereolithography i.e., a stereolithographic article.
• the method for producing a cured product for example, a stereolithographic product is as described above.
• the intraoral appliance of the present disclosure includes the three-dimensional structure of the present disclosure described above. Therefore, the intraoral appliance of the present disclosure has high toughness even after cleaning with isopropyl alcohol.
• Specific examples of appliances to be installed in the oral cavity are as described above, and include, for example, dentures, splints, and the like.
• the obtained photocurable composition was irradiated with visible light with a wavelength of 405 nm at a dose of 11 mJ/cm 2 to form a cured layer A1 with a thickness of 50 ⁇ m.
• a model having a length of 64 mm, a width of 10 mm, and a thickness of 3.3 mm was obtained to obtain a model A1.
• the obtained model A1 was immersed in isopropyl alcohol (IPA) and washed for 5 minutes using an ultrasonic cleaner with an output of 60 W.
• IPA isopropyl alcohol
• the model A1 was subjected to stereolithography under the conditions of irradiating ultraviolet rays with a wavelength of 365 nm at an irradiation amount of 10 J/cm 2 to a length of 64 mm, a width of 10 mm, A rectangular plate-shaped test piece A1 with a thickness of 3.3 mm was obtained.
• the photocurable composition was irradiated with visible light with a wavelength of 405 nm at a dose of 11 mJ/cm 2 to form a cured layer A2 with a thickness of 50 ⁇ m.
• model A2 was immersed in isopropyl alcohol and washed for 5 minutes using an ultrasonic cleaner with an output of 60 W. After drying the cleaned model A2 with air blow, the model A2 was subjected to stereolithography under the conditions of irradiating ultraviolet rays with a wavelength of 365 nm at an irradiation amount of 10 J/cm 2 to a length of 39 mm, a width of 8 mm, A rectangular plate-shaped test piece A2 with a thickness of 4 mm was obtained.
• test pieces that were not washed with IPA were irradiated with ultraviolet rays with a wavelength of 365 nm without going through the above-mentioned isopropyl alcohol immersion step to obtain test pieces A1 and A2, respectively.
• the above-mentioned cleaning method using IPA is an example, and the cleaning method using IPA is not limited to the method described in the Examples.
• Example 1B to Example 3B Comparative Example 1B to Comparative Example 3B
• Example 1A to Example 3A Comparisons with Comparative Examples 1A to 3A
• Tables 1 to 4 For Examples 4 to 19, only those with IPA washing (Example 4B to Example 19B) are shown.
• Viscosity of photocurable composition The viscosity of the photocurable composition was measured using an E-type viscometer at 25° C. and 50 rpm.
• test piece (Bending strength and bending elastic modulus of stereofabricated object)
• the obtained test piece A1 (hereinafter referred to as "test piece") was stored in a constant temperature water bath at 37 ⁇ 1° C. for 50 ⁇ 2 hours. Thereafter, the test piece was taken out from the constant temperature water bath, and the flexural strength and flexural modulus of the taken out test piece were measured in accordance with ISO20795-1:2008. These measurements were performed using a tensile testing device (manufactured by Intesco Co., Ltd.) at a tensile speed of 5 ⁇ 1 mm/min.
• test piece Total fracture work in fracture toughness test by bending test
• the obtained test piece A2 (hereinafter referred to as "test piece") was notched in accordance with ISO20795-1:2008 and stored in a constant temperature water bath at 37 ⁇ 1° C. for 7 days ⁇ 2 hours. Thereafter, the test piece was taken out from the constant temperature water bath, and the taken out test piece was subjected to a fracture toughness test using a bending test in accordance with ISO20795-1:2008, and the total work of fracture (J/m 2 ) was measured.
• the fracture toughness test i.e., measurement of total fracture work) by bending test was performed using a tensile testing device (manufactured by Intesco Corporation) at an indentation speed of 1.0 ⁇ 0.2 mm/min.
• ⁇ (meth)acrylic monomer (A)> In Tables 1 to 4, it has two urethane bonds and two (meth)acryloyl groups, and each of the two (meth)acryloyl groups has an oxygen atom for each of the two urethane bonds.
• the compounds classified as (meth)acrylic monomers (A) that are linked via an alkylene group having 4 to 10 carbon atoms to which a nitrogen atom is bonded are specifically the following UDA1 to 4.
• UDA1 Compound produced in Production Example 1
• UDA2 Compound produced in Production Example 2
• UDA3 Compound produced in Production Example 3
• UDA4 Compound produced in Production Example 4
• BZA Benzyl acrylate, manufactured by Osaka Organic Chemical Industry
• PO-A Phenoxyethyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd.
• 4-HBA 4-Hydroxybutyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.
• POB-A m-phenoxybenzyl acrylate, manufactured by Kyoeisha Chemical Company
• A- LEN-10 Ethoxylated-o-phenylphenol acrylate, manufactured by Shin Nakamura Chemical Industries, Ltd.
• ACMO 4-acryloylmorpholine, manufactured by KJ Chemicals M5700: 2-hydroxy-3-phenoxypropyl acrylate, manufactured by Toagosei HOMS: 2-methacryloyloxyethyl Succinic acid, manufactured by Kyoeisha Chemical HEMA: 2-hydroxyethyl acrylate, manufactured by Kyoeisha Chemical PO: Phenoxyethyl methacrylate, manufactured by Kyoeisha Chemical
• UDA5 Compound produced in Production Example 5
• UDA6 Compound produced in Production Example 6
• UDA7 Compound produced in Production Example 7
• Omnirad 819 Acylphosphine oxide compound (manufactured by IGM Resins B.V.)
• Omnirad 184 Alkylphenone compound (manufactured by IGM Resins B.V.)
• Omnirad TPO Acylphosphine oxide compound (manufactured by IGM Resins B.V.)

Landscapes

• Health & Medical Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Oral & Maxillofacial Surgery (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Public Health (AREA)
• Manufacturing & Machinery (AREA)
• General Health & Medical Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• Epidemiology (AREA)
• Veterinary Medicine (AREA)
• Plastic & Reconstructive Surgery (AREA)
• Organic Chemistry (AREA)
• Optics & Photonics (AREA)
• Mechanical Engineering (AREA)
• Physics & Mathematics (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Biophysics (AREA)
• Polymerisation Methods In General (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=88200992

Family Applications (1)

Country Status (2)

Citations (5)

• 2023
  • 2023-03-17 JP JP2024511848A patent/JPWO2023189780A1/ja active Pending
  • 2023-03-17 WO PCT/JP2023/010758 patent/WO2023189780A1/ja active Application Filing

Patent Citations (5)

Also Published As

Similar Documents

Legal Events