WO2021149520A1 - 光硬化性組成物、立体造形物、及び歯科用製品 - Google Patents

光硬化性組成物、立体造形物、及び歯科用製品 Download PDF

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Publication number
WO2021149520A1
WO2021149520A1 PCT/JP2021/000515 JP2021000515W WO2021149520A1 WO 2021149520 A1 WO2021149520 A1 WO 2021149520A1 JP 2021000515 W JP2021000515 W JP 2021000515W WO 2021149520 A1 WO2021149520 A1 WO 2021149520A1
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Prior art keywords
photocurable composition
condition
meth
mass
composition according
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English (en)
French (fr)
Japanese (ja)
Inventor
孝曉 林
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Mitsui Chemicals Inc
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Mitsui Chemicals Inc
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Priority to EP21745100.4A priority Critical patent/EP4079768A4/en
Priority to JP2021573067A priority patent/JP7762573B2/ja
Priority to US17/793,739 priority patent/US11873359B2/en
Publication of WO2021149520A1 publication Critical patent/WO2021149520A1/ja
Anticipated expiration legal-status Critical
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    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/20—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • A61C13/0003—Making bridge-work, inlays, implants or the like
    • A61C13/0006—Production methods
    • A61C13/0019—Production methods using three dimensional printing
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/15—Compositions characterised by their physical properties
    • A61K6/16—Refractive index
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments

Definitions

  • the present disclosure relates to photocurable compositions, three-dimensional objects, and dental products.
  • Patent Document 1 Japanese Patent No. 4160311
  • the desired modeling accuracy may not be obtained.
  • the thickness in the traveling direction of light at the time of stereolithography may be thicker than a desired thickness (that is, the thickness accuracy may be insufficient). Therefore, there is a demand for a photocurable composition capable of obtaining a three-dimensional model with excellent modeling accuracy.
  • An object of one aspect of the present disclosure is to provide a photocurable composition capable of obtaining a three-dimensional model with excellent modeling accuracy, a three-dimensional model obtained from the photocurable composition, and a dental product. ..
  • the means for solving the above problems include the following aspects.
  • the transmittance at a wavelength of 405 nm measured under the condition of an optical path length of 1 cm is 1.0% or more and 70.0% or less.
  • Condition (2) ...
  • the transmittance at a wavelength of 385 nm measured under the condition of an optical path length of 1 cm is 1.0% or more and 70.0% or less.
  • Equation (b) [In equation (a), x 1 represents a part by mass of the content of the dye compound with respect to 100 parts by mass of the photopolymerizable component contained in the photocurable composition. y 1 is the transmittance (%) at a wavelength of 405 nm, which is measured under the condition of an optical path length of 0.5 cm for a diluted solution (D2) diluted with ethanol so that the content of the dye compound is 0.01% by mass. Represents. In equation (b), x 2 represents the mass part of the content of the dye compound with respect to 100 parts by mass of the photopolymerizable component contained in the photocurable composition.
  • y 2 is the transmittance (%) at a wavelength of 385 nm, which is measured under the condition of an optical path length of 0.5 cm for a diluted solution (D2) diluted with ethanol so that the content of the dye compound is 0.01% by mass.
  • each dye compound contained in the photocurable composition satisfies the following condition (1-1).
  • each dye compound contained in the photocurable composition satisfies the condition (2-1) below.
  • Condition (1-1) Transmittance at a wavelength of 405 nm measured under the condition of an optical path length of 0.5 cm for a diluted solution (D2) diluted with ethanol so that the content of the dye compound is 0.01% by mass. However, it is 0.1% or more and 80.0% or less.
  • ⁇ 6> The photocurable composition according to any one of ⁇ 3> to ⁇ 5>, wherein the dye compound contains at least one of a dye and a pigment.
  • the photopolymerizable component contains a (meth) acrylic monomer.
  • the (meth) acrylic monomer contains at least one of a monofunctional (meth) acrylic monomer and a bifunctional (meth) acrylic monomer. The total amount of the bifunctional (meth) acrylic monomer and the monofunctional (meth) acrylic monomer with respect to the total amount of the (meth) acrylic monomer is 90% by mass or more.
  • ⁇ 9> The photocurable composition according to ⁇ 7> or ⁇ 8>, wherein the (meth) acrylic monomer contains a bifunctional (meth) acrylic monomer.
  • the content of the inorganic filler with respect to the total amount of the photocurable composition is The photocurable composition according to any one of ⁇ 1> to ⁇ 9>, which is 10% by mass or less.
  • ⁇ 12> The photocurable composition according to any one of ⁇ 1> to ⁇ 11>, which is a photocurable composition for stereolithography.
  • ⁇ 13> The photocurable composition according to any one of ⁇ 1> to ⁇ 12>, which is used in the production of dental products.
  • ⁇ 14> A three-dimensional model which is a cured product of the photocurable composition according to any one of ⁇ 1> to ⁇ 13>.
  • ⁇ 15> The three-dimensional model according to ⁇ 14>, which has at least one of a recess and a space.
  • ⁇ 16> A dental product containing the three-dimensional object according to ⁇ 14> or ⁇ 15>.
  • a photocurable composition capable of obtaining a three-dimensional model with excellent modeling accuracy, a three-dimensional model obtained from the photocurable composition, and a dental product are provided.
  • the numerical range represented by using “-” means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the term “process” is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. ..
  • the amount of each component contained in the composition is the total amount of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. Means.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. ..
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
  • light is a concept including active energy rays such as ultraviolet rays and visible rays.
  • the "(meth) acrylic monomer” means an acrylic monomer or a methacryl monomer
  • the "(meth) acryloyl group” means an acryloyl group or a methacryloyl group
  • the "(meth) acrylate” means an acrylate or a methacrylic monomer. It means methacrylate
  • (meth) acrylic acid means acrylic acid or methacrylic acid
  • “(meth) acrylonitrile” means acrylonitrile or methacrylonitrile.
  • the photocurable composition of the present disclosure is a photocurable composition containing a photopolymerizable component and a photopolymerization initiator.
  • a diluent (D1) obtained by diluting the photocurable composition with ethanol so that the ethanol content is 99% by mass satisfies the following condition (X). It is a photocurable composition.
  • the desired modeling accuracy may not be obtained.
  • the thickness in the traveling direction of light at the time of stereolithography becomes thicker than a desired thickness (that is, the thickness accuracy is insufficient).
  • a three-dimensional model can be obtained with excellent modeling accuracy (for example, excellent thickness accuracy).
  • a liquid tank type stereolithography that is, a stereolithography using a liquid tank
  • a part of the photocurable composition contained in the liquid tank that is, the uncured photocurable composition in a liquid state; the same applies hereinafter
  • a layer is formed, and by repeating this operation, the cured layers are laminated, whereby a three-dimensional model is obtained.
  • the liquid tank stereolithography differs from the inkjet stereolithography in that a liquid tank is used.
  • Liquid tank stereolithography is broadly divided into DLP (Digital Light Processing) stereolithography and SLA (Stereolithography) stereolithography.
  • DLP method Digital Light Processing
  • SLA Stepolithography
  • the photocurable composition in the liquid tank is irradiated with planar light.
  • SLA method the laser light is scanned against the photocurable composition in the liquid tank.
  • a build table that can be moved vertically, A tray (ie, a liquid tank) that is located below the build table (on the gravitational side; the same applies hereinafter), contains a light-transmitting portion, and contains a photocurable composition.
  • a light source for example, an LED light source
  • Cara Print 4.0 manufactured by Kulzer, "Max UV” manufactured by Asiga, etc.
  • a one-layer gap is provided between the build table and the tray, and this gap is filled with the photocurable composition.
  • the photocurable composition filled in the gap is irradiated with planar light from below through the light transmitting portion of the tray, and the light-irradiated region is cured to cure the first layer. Form a hardened layer.
  • the gap between the build table and the tray is widened by the next layer, and the resulting space is filled with the photocurable composition.
  • the photocurable composition filled in the space is irradiated with light in the same manner as in the case of curing the first layer to form a second cured layer. By repeating the above operation, the cured layers are laminated to produce a three-dimensional model.
  • FIG. 1 is a schematic perspective view showing an example of a three-dimensional model (three-dimensional model 10) in the present disclosure.
  • the three-dimensional model 10 includes a bottom surface portion 12 and a pair of side surface portions 14 and 16 facing each other.
  • the pair of side surface portions 14 and 16 are substantially perpendicular to the bottom surface portion 12.
  • the recess 20 is formed by the pair of side surface portions 14 and 16 and the bottom surface portion 12.
  • the gravitational direction G in FIG. 1 means the gravitational direction at the manufacturing stage of the three-dimensional model 10.
  • the traveling direction of light at the manufacturing stage of the three-dimensional model 10 is opposite to the gravitational direction G.
  • the three-dimensional model 10 is manufactured by DLP stereolithography, by laminating the cured layers, for example, from the upper side (opposite side to the gravity direction G) to the lower side (gravity direction) of the pair of side surface portions 14 and 16. It may be formed in order toward the G side), and finally the bottom surface portion 12 may be formed.
  • the entire three-dimensional model 10 is arranged between the build table and the tray, and the upper surfaces of the pair of side surface portions 14 and 16 are in contact with the build table.
  • the portion of the photocurable composition arranged in the gap between the build table and the tray is cured to form a one-layer cured layer, and this operation is performed.
  • the cured layers are laminated, thereby forming the bottom surface portion 12. That is, at the stage of forming the cured layer constituting the bottom surface portion 12, the photocurable composition is also present in the region corresponding to the recess 20, but the photocurable composition in the region corresponding to the recess 20 is not cured. , Only the photocurable composition in the region corresponding to the cured layer constituting the bottom surface portion 12 is cured in layers.
  • the conventional photocurable composition when the bottom surface portion 12 is formed, the one-layer cured layer becomes too thicker than the desired thickness, and as a result, the cured layers are laminated.
  • the thickness of the bottom surface portion 12 formed may be too thicker than the desired thickness (that is, the set value).
  • the thickness referred to here is the thickness in the traveling direction of light.
  • the reason why the one-layer cured layer is too thicker than the desired thickness is that the light transmission of the photocurable composition is too high, which is necessary for the formation of the cured layer in this photocurable composition. It is considered that this is because not only the thick portion but also the portion that should not be cured (that is, the region corresponding to the recess 20) is cured.
  • the curing may be insufficient. This may cause molding defects.
  • the phenomenon that the bottom surface portion 12 formed is too thick can be suppressed. That is, the thickness accuracy of the formed bottom surface portion 12 can be improved.
  • the reason why such an effect is exhibited is that the diluted solution (D1) of the photocurable composition of the present disclosure satisfies the condition (X), so that insufficient and excessive light transmission of the photocurable composition is suppressed. It is thought that it will be done. By suppressing the lack of light transmission of the photocurable composition, insufficient curing is suppressed, and thus molding defects are suppressed. By suppressing the excessive light transmission of the photocurable composition, it is possible to prevent the cured layer from becoming too thick.
  • Satisfaction of the condition (X) with the diluent (D1) of the photocurable composition of the present disclosure means that the photocurable composition of the present disclosure is transmitted at at least one wavelength included in the wavelength range of 365 nm to 405 nm. It means that the rate is within a specific range without excess or deficiency.
  • the wavelength included in the wavelength range of 365 nm to 405 nm is a typical wavelength of light in a 3D printer.
  • the diluent (D1) is a diluent obtained by diluting the photocurable composition of the present disclosure with ethanol so that the content of ethanol is 99% by mass.
  • the problem of the thickness accuracy of the bottom surface portion 12 of the three-dimensional modeled object 10 described above is not limited to the bottom surface portion 12 of the three-dimensional modeled object 10, but is not limited to the three-dimensional modeled object having at least one of a recess and a space (for example, a dental product). This is a problem that can occur in a portion where the traveling direction of light (that is, the vertical direction) is the thickness direction.
  • the concept of a recess includes a recess (for example, a recess 20) formed by a bottom and at least a pair of side surfaces, a hole with a bottom, and the like.
  • the concept of space includes an internal space completely surrounded by a wall surface of a three-dimensional object, a through hole, and the like.
  • the use of the photocurable composition of the present disclosure is not particularly limited.
  • the photocurable composition of the present disclosure is preferably a photocurable composition for stereolithography from the viewpoint of more effectively exerting the effect of improving the molding accuracy of the three-dimensional model.
  • the photocurable composition of the present disclosure is from the viewpoint of more effectively exerting the effect of improving the thickness accuracy of the three-dimensional modeled object (particularly, improving the accuracy of the thickness in the traveling direction of light during stereolithography). More preferably, it is a photocurable composition for stereolithography of a liquid tank method (for example, a DLP method or an SLA method, preferably a DLP method). It is more preferable that the photocurable composition is used for producing a three-dimensional model having at least one of a recess and a space by the liquid tank type stereolithography. The recesses and spaces are as described above.
  • the photocurable composition of the present disclosure is preferably a photocurable composition used in the production of dental products from the viewpoint of more effectively exerting the effect of improving the molding accuracy of the three-dimensional modeled object.
  • Dental products preferably include a three-dimensional object having at least one of a recess and a space.
  • dental products include dentures (that is, artificial teeth), denture bases, dental prostheses, medical instruments used in the oral cavity, dental models, vanishing casting models, and the like.
  • Dental prostheses include inlays, crowns, bridges, temporary crowns, temporary bridges and the like.
  • medical devices used in the oral cavity include mouthpieces, mouth guards, orthodontic appliances, occlusal sprints, impression trays, surgical guides, and the like.
  • Examples of the dental model include a tooth jaw model and the like.
  • the diluent (D1) satisfies at least one of the condition (1) and the condition (2).
  • Condition (1) ...
  • the transmittance at a wavelength of 405 nm measured under the condition of an optical path length of 1 cm is 1.0% or more and 70.0% or less.
  • Condition (2) ...
  • the transmittance at a wavelength of 385 nm measured under the condition of an optical path length of 1 cm is 1.0% or more and 70.0% or less.
  • the photocurable composition in which the diluent (D1) satisfies the condition (1) may be hereinafter referred to as the photocurable composition according to the first embodiment, and the diluent (D1) is referred to as the photocurable composition.
  • the photocurable composition in an embodiment that satisfies the condition (2) may be referred to as a photocurable composition according to the second embodiment.
  • the fact that the diluent (D1) of the photocurable composition satisfies the condition (1) means that the transmittance of the photocurable composition at a wavelength of 405 nm is within a specific range without excess or deficiency. Satisfying the condition (2) with the diluted solution (D1) of the photocurable composition means that the transmittance of the photocurable composition at a wavelength of 385 nm is within a specific range without excess or deficiency.
  • the wavelengths of 405 nm and 385 nm are typical wavelengths of light in a 3D printer, respectively.
  • the photocurable composition according to the first embodiment and the photocurable composition according to the second embodiment will be described separately.
  • the photocurable composition of one of the first embodiment and the second embodiment may satisfy the requirements of the photocurable composition of the other embodiment.
  • the photocurable composition according to the first embodiment satisfies the requirements for the photocurable composition according to the second embodiment (that is, the diluent (D1) satisfies the condition (2)).
  • the photocurable composition of the present disclosure is not limited to the following first and second embodiments.
  • the photocurable composition of the present disclosure contains a photopolymerizable component and a photopolymerization initiator, and the diluent (D1) is the condition (X) (that is, the optical path length is 1 cm).
  • the transmittance at at least one wavelength included in the measured wavelength range of 365 nm to 405 nm is 1.0% or more and 70.0% or less), and there are no other particular restrictions. do not have. Further, even if the photocurable composition of the present disclosure is of an embodiment other than the first embodiment and the second embodiment, the photocurable composition of the first embodiment or the second embodiment shown below May meet the requirements of.
  • the photocurable composition according to the first embodiment is a photocurable composition containing a photopolymerizable component and a photopolymerization initiator, and the above-mentioned photocurable composition has an ethanol content of ethanol.
  • the diluent (D1) diluted with ethanol so as to be 99% by mass is a photocurable composition that satisfies the following condition (1).
  • the transmittance at a wavelength of 405 nm measured under the condition of an optical path length of 1 cm is 1.0% or more and 70.0% or less.
  • the photocurable composition according to the first embodiment when the diluent (D1) satisfies the condition (1), insufficient and excessive light transmittance at a wavelength of 405 nm with respect to the photocurable composition is suppressed. NS. As a result, the curing of the photocurable composition according to the first embodiment becomes insufficient (leading to the occurrence of molding defects), and the thickness of the cured region in the photocurable composition according to the first embodiment. It is suppressed that (that is, the thickness in the traveling direction of light) becomes too thick, and as a result, a cured layer having a desired thickness is obtained.
  • the transmittance of the diluent (D1) at a wavelength of 405 nm is 1.0% or more, it is possible to prevent the photocurable composition according to the first embodiment from being sufficiently cured. As a result, molding defects are suppressed. Further, when the transmittance of the diluted solution (D1) at a wavelength of 405 nm is 70.0% or less, it is possible to prevent the thickness of the cured region in the photocurable composition according to the first embodiment from becoming too thick.
  • the transmittance at a wavelength of 405 nm is preferably 3.0% or more and 65.0% or less, and more preferably 5.0% or more and 60.0% or less.
  • the diluent (D1) of the photocurable composition can be adjusted so as to satisfy the condition (1).
  • the diluent (D1) satisfies the condition (1) by adjusting the content of the photopolymerization initiator. Can be adjusted as follows.
  • the photocurable composition according to the first embodiment preferably further contains a dye compound. This makes it easier to adjust the diluent (D1) so that it satisfies the condition (1).
  • the dye compound contained in the photocurable composition according to the first embodiment may be only one kind or two or more kinds.
  • the dye compound preferably contains at least one of a dye and a pigment.
  • a dye for example Anthraquinone dyes (eg, quinizarin, alizanin, etc.), Sudan-based dyes (eg, Sudan II, Sudan III, Sudan IV, etc.), Solvent Yellow dyes (eg, Solvent Yellow 2, Solvent Yellow 7, Solvent Yellow 11, etc.), Solvent Green dyes (eg, Solvent Green 3, Solvent Green 5, etc.), Solvent Orange dyes (eg, Solvent Orange 2, etc.), Solvent Blue dyes (eg, Solvent Blue 59, etc.), Basic Green dyes (eg, Basic Green 1, etc.), Acid Yellow dyes (eg Acid Yellow 3, etc.), Indophenol blue dye, And so on.
  • Anthraquinone dyes eg, quinizarin, alizanin, etc.
  • Sudan-based dyes eg, Sudan II, Sudan III, Sudan IV, etc.
  • Solvent Yellow dyes eg, Solvent Yellow 2, Solvent Yellow 7,
  • the pigment may be an organic pigment (eg, phthalocyanine blue, phthalocyanine green, ultramarine blue, carmine pigment, etc.) or an inorganic pigment (eg, titanium oxide, carbon black, aluminum powder, caramel, iron oxide, gunjo, konjo). , Chromium hydroxide, etc.).
  • organic pigment eg, phthalocyanine blue, phthalocyanine green, ultramarine blue, carmine pigment, etc.
  • an inorganic pigment eg, titanium oxide, carbon black, aluminum powder, caramel, iron oxide, gunjo, konjo.
  • Chromium hydroxide etc.
  • the dye compound a dye compound satisfying the condition (1-1) described later is preferable.
  • the sum of the values (A) defined by the following formula (a) for each of the contained dye compounds is 0.01. It is preferably 3.00 or less. This makes it easier to adjust the diluent (D1) so that it satisfies the condition (1).
  • the total value (A) defined by the following formula (a) for each of the contained dye compounds is more preferably 0.04 or more and 3.00 or less.
  • Equation (a) (x 1 / y 1 ) x 100 ... Equation (a)
  • x 1 represents a part by mass of the content of the dye compound with respect to 100 parts by mass of the photopolymerizable component contained in the photocurable composition.
  • y 1 is the transmittance (%) at a wavelength of 405 nm, which is measured under the condition of an optical path length of 0.5 cm for a diluted solution (D2) diluted with ethanol so that the content of the dye compound is 0.01% by mass. Represents.
  • D2 diluted solution
  • the total value (A) is a value that correlates with the total content of the dye compound contained in the photocurable composition according to the first embodiment.
  • the formula (a) defining a value (A) considering the different preferred content by transmittance (%) at a wavelength of 405nm of the dye compound, the values with x 1 and y 1 a (A) It is defined.
  • a dye compound having a low transmittance at a wavelength of 405 nm preferably has a lower content than a dye compound having a high transmittance at a wavelength of 405 nm.
  • the transmittance of the diluted solution (D2) of the dye compound is specified, not the transmittance of the dye compound itself.
  • each dye compound contained in the photocurable composition satisfies the following condition (1-1). This makes it easier to adjust the diluent (D1) so that it satisfies the condition (1).
  • the transmittance of the diluent (D2) at a wavelength of 405 nm is preferably 0.3% or more and 75.0% or less.
  • condition (1-1) in the first embodiment in order to strictly specify the range of the transmittance of the dye compound, not the transmittance of the dye compound itself but the transmittance of the diluted solution (D2) of the dye compound is used. I have specified. The same applies to the condition (2-1) in the second embodiment described later.
  • the photocurable composition according to the first embodiment contains at least one photopolymerizable component.
  • the photopolymerizable component include compounds containing an ethylenic double bond.
  • the compound containing an ethylenic double bond include (meth) acrylic monomer, styrene, styrene derivative, (meth) acrylonitrile, and the like.
  • the photopolymerizable component As the photopolymerizable component, the photopolymerizable component described in paragraphs 0030 to 0059 of International Publication No. 2019/189652 may be used.
  • the photopolymerizable component preferably contains at least one (meth) acrylic monomer.
  • the total ratio of the (meth) acrylic monomer to the total photopolymerizable component is preferably 80% by mass or more, more preferably 90% by mass or more, and preferably 95% by mass or more. More preferred.
  • the (meth) acrylic monomer may be any monomer containing one or more (meth) acryloyl groups in the molecule, and is not particularly limited.
  • a monofunctional (meth) acrylic monomer that is, a monomer having one (meth) acryloyl group in the molecule
  • a bifunctional (meth) acrylic monomer that is, 2 in the molecule
  • It may be a monomer having one (meth) acryloyl group) or a polyfunctional (meth) acrylic monomer (that is, a monomer having three or more (meth) acryloyl groups in the molecule).
  • the (meth) acrylic monomer preferably contains at least one of an aromatic structure (for example, a bisphenol A structure, etc.), an alicyclic structure, and a urethane bond in the molecule.
  • the (meth) acrylic monomer of such a preferred embodiment may further contain at least one of an ethyleneoxy group and a propyleneoxy group.
  • the molecular weight of the (meth) acrylic monomer is preferably 5000 or less, more preferably 3000 or less, further preferably 2000 or less, further preferably 1500 or less, and preferably 1000 or less. More preferably, it is more preferably 800 or less.
  • the lower limit of the molecular weight of the (meth) acrylic monomer is not particularly limited as long as the monomer contains one or more (meth) acryloyl groups in the molecule.
  • the lower limit of the molecular weight of the (meth) acrylic monomer is, for example, 86, preferably 100, more preferably 200, and even more preferably 300.
  • the (meth) acrylic monomers that can be contained in the photocurable composition according to the first embodiment are monofunctional (meth) acrylic monomers and bifunctional. It preferably contains at least one of the (meth) acrylic monomers.
  • bifunctional (meth) with respect to the total amount of the (meth) acrylic monomer that can be contained in the photocurable composition according to the first embodiment is preferably 60% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.
  • the monofunctional (meth) acrylic monomer examples include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and 4-tert-butylcyclohexyl (meth).
  • bifunctional (meth) acrylic monomer examples include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, glycerin di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and ethoxy.
  • the (meth) acrylic monomer that can be contained in the photocurable composition according to the first embodiment is bifunctional (meth). Meta) It is preferable to contain an acrylic monomer.
  • the total amount of the (meth) acrylic monomer that can be contained in the photocurable composition according to the first embodiment is relative to the total amount of the (meth) acrylic monomer that can be contained in the photocurable composition.
  • the total amount of the bifunctional (meth) acrylic monomer is preferably 60% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.
  • the (meth) acrylic monomer that can be contained in the photocurable composition according to the first embodiment is Monomer M1, which is a bifunctional (meth) acrylic monomer containing at least one of an aromatic ring structure (for example, a bisphenol A structure, etc.) and an alicyclic structure in the molecule, Monomer M2, which is a bifunctional (meth) acrylic monomer containing a urethane bond in the molecule, It is more preferable to include.
  • the total amount of the monomers M1 and M2 with respect to the total amount of the (meth) acrylic monomers that can be contained in the photocurable composition according to the first embodiment is preferably 60% by mass or more, preferably 80% by mass or more. Is more preferable, and 90% by mass or more is further preferable.
  • the (meth) acrylic monomer that can be contained in the photocurable composition according to the first embodiment contains the monomer M1 and the monomer M2, the content mass ratio of the monomer M1 to the total of the monomers M1 and the monomer M2 (that is, the content).
  • the mass ratio [monomer M1 / (monomer M1 + monomer M2)]) is preferably 0.50 or more and less than 1.00, more preferably 0.55 or more and 0.95 or less, and further preferably 0.60 or more and 0.80 or less. ..
  • the monomer M1 further preferably contains at least one of an ethyleneoxy group and a propyleneoxy group.
  • a bifunctional (meth) acrylic monomer containing at least one of an ethyleneoxy group and a propyleneoxy group and a bisphenol A structure in the molecule is particularly preferable.
  • the monomer M2 further preferably contains at least one of an ethyleneoxy group and a propyleneoxy group, and an alkylene group.
  • a bifunctional (meth) acrylic monomer containing at least one of an ethyleneoxy group and a propyleneoxy group, a urethane bond and an alkylene group in the molecule is particularly preferable.
  • the amount of the photopolymerizable component contained in the photocurable composition according to the first embodiment is not particularly limited.
  • the content of the photopolymerizable component with respect to 100 parts by mass of the photocurable composition is preferably 60 parts by mass or more, and more preferably 80 parts by mass or more. It is preferably 90 parts by mass or more, and more preferably 90 parts by mass or more.
  • the photocurable composition according to the first embodiment contains at least one photopolymerization initiator.
  • the photopolymerization initiator include alkylphenone compounds, acylphosphine oxide compounds, titanosen compounds, oxime ester compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, thioxanthone compounds, ⁇ -acyloxime ester compounds, and phenylglycilate compounds.
  • examples thereof include benzyl compounds, azo compounds, diphenyl sulfide compounds, iron-phthalocyanine compounds, benzoine ether compounds, anthraquinone compounds and the like.
  • the photopolymerization initiator preferably contains at least one selected from the group consisting of alkylphenone compounds and acylphosphine oxide compounds.
  • the photopolymerization initiator is It preferably contains an acylphosphine oxide compound (eg, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, etc.). More preferably, it contains 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • the photopolymerization initiator contained in the photocurable composition according to the first embodiment preferably has a transmittance of 80% or more, preferably 82% or more, at a wavelength of 385 nm as measured under the condition of an optical path length of 1 cm. Is more preferable, and 84% or more is further preferable.
  • the transmittance of the photopolymerization initiator is 80% or more, the influence of the photopolymerization initiator on the light transmittance of the photocurable composition at the time of photopolymerization can be further reduced.
  • the photopolymerization initiator preferably has a peak light absorption wavelength of 340 nm or less in a wavelength region of 220 nm or more, in that the influence of the photocurable composition on the light transmittance during photopolymerization can be further reduced.
  • Examples of the photopolymerization initiator having a peak light absorption wavelength of 340 nm or less in the region having a wavelength of 220 nm or more include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine.
  • Oxide 1-Hydroxy-cyclohexylphenylketone, phenylglycolic acid methyl ester, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenyl-propane-1 -On, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one, 1,2-octanedione, 1- ⁇ 4 -(Phenylthio)-, 2- (O-benzoyloxime) ⁇ and the like can be mentioned.
  • the amount of the photopolymerization initiator contained in the photocurable composition according to the first embodiment is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the photopolymerizable component, and is 0.5. It is more preferably 1 part by mass to 10 parts by mass, and further preferably 1 part by mass to 5 parts by mass.
  • the photocurable composition according to the first embodiment may contain other components other than the above-mentioned components, if necessary.
  • other components include inorganic fillers, modifiers, stabilizers, antioxidants, solvents and the like.
  • the photocurable composition according to the first embodiment does not contain an inorganic filler (for example, silica, barium borosilicate glass, etc., the same applies hereinafter), or
  • an inorganic filler for example, silica, barium borosilicate glass, etc., the same applies hereinafter
  • the content of the inorganic filler with respect to the total amount of the photocurable composition is 10% by mass or less (more preferably 5% by mass or less, still more preferably 2% by mass or less, still more preferably 1% by mass). % Or less) is preferable.
  • the photocurable composition according to the second embodiment is a photocurable composition containing a photopolymerizable component and a photopolymerization initiator, and the above-mentioned photocurable composition has an ethanol content of ethanol.
  • the diluent (D1) diluted with ethanol so as to be 99% by mass is a photocurable composition that satisfies the following condition (2).
  • the transmittance at a wavelength of 385 nm, measured under the condition of an optical path length of 1 cm, is 1.0% or more and 70.0% or less.
  • the photocurable composition according to the second embodiment when the diluent (D1) satisfies the condition (2), insufficient and excessive light transmittance at a wavelength of 385 nm with respect to the photocurable composition is suppressed. NS. As a result, the curing of the photocurable composition according to the second embodiment becomes insufficient (leading to the occurrence of molding defects), and the thickness of the cured region in the photocurable composition according to the second embodiment. It is suppressed that (that is, the thickness in the traveling direction of light) becomes too thick, and as a result, a cured layer having a desired thickness is obtained.
  • the transmittance of the diluent (D1) at a wavelength of 385 nm is 1.0% or more, it is possible to prevent the photocurable composition according to the second embodiment from being sufficiently cured. As a result, molding defects are suppressed.
  • the transmittance of the diluted solution (D1) at a wavelength of 385 nm is 70.0% or less, it is possible to prevent the thickness of the cured region in the photocurable composition according to the second embodiment from becoming too thick.
  • the transmittance at a wavelength of 385 nm is preferably 3.0% or more and 65.0% or less, and more preferably 5.0% or more and 65.0% or less.
  • the diluent (D1) of the photocurable composition can be adjusted so as to satisfy the condition (2).
  • the diluent (D1) satisfies the condition (2) by adjusting the content of the photopolymerization initiator. Can be adjusted as follows.
  • the photocurable composition according to the second embodiment preferably further contains a dye compound. This makes it easier to adjust the diluent (D1) so as to satisfy the condition (2).
  • the dye compound contained in the photocurable composition according to the second embodiment may be only one kind or two or more kinds.
  • the dye compound in the second embodiment preferably contains at least one of a dye and a pigment.
  • the dyes and pigments that can be contained in the photocurable composition according to the second embodiment are the same as the dyes and pigments that can be contained in the photocurable composition according to the first embodiment, respectively.
  • Specific examples of the dye compound that can be contained in the photocurable composition according to the second embodiment are the same as the dye compound that can be contained in the photocurable composition according to the first embodiment.
  • As the dye compound a dye compound satisfying the condition (2-1) described later is preferable.
  • the sum of the values (B) defined by the following formula (b) for each of the contained dye compounds is 0.01. It is preferably 3.00 or less. This makes it easier to adjust the diluent (D1) so as to satisfy the condition (2).
  • the total of the values (B) defined by the following formula (b) for each of the contained dye compounds is more preferably 0.04 or more and 3.00 or less.
  • Equation (b) (x 2 / y 2 ) x 100 ... Equation (b)
  • x 2 represents the mass part of the content of the dye compound with respect to 100 parts by mass of the photopolymerizable component contained in the photocurable composition.
  • y 2 is the transmittance (%) at a wavelength of 385 nm, which is measured under the condition of an optical path length of 0.5 cm for a diluted solution (D2) diluted with ethanol so that the content of the dye compound is 0.01% by mass. Represents.
  • D2 diluted solution
  • each dye compound contained in the photocurable composition satisfies the following condition (2-1). This makes it easier to adjust the diluent (D1) so as to satisfy the condition (2).
  • the transmittance of the diluent (D2) at a wavelength of 385 nm is preferably 0.3% or more and 80.0% or less.
  • the photocurable composition according to the second embodiment contains at least one photopolymerizable component.
  • the photopolymerizable component and its preferred embodiment in the second embodiment are the same as the photopolymerizable component and its preferred embodiment in the first embodiment described above. Therefore, for the photopolymerizable component in the second embodiment, the description in the section of "photopolymerizable component" in the first embodiment can be appropriately referred to.
  • the photocurable composition according to the second embodiment contains at least one photopolymerization initiator.
  • the photopolymerization initiator and its preferred embodiments in the second embodiment are the same as those in the photopolymerization initiator and its preferred embodiments in the first embodiment described above. Therefore, for the photopolymerization initiator in the second embodiment, the description in the section of "photopolymerization initiator" in the first embodiment can be appropriately referred to.
  • the photopolymerization initiator contained in the photocurable composition according to the second embodiment preferably has a transmittance of 80% or more at a wavelength of 405 nm, which is measured under the condition of an optical path length of 1 cm. It is more preferably 83% or more, and further preferably 85% or more.
  • the photocurable composition according to the second embodiment may contain other components other than the above-mentioned components, if necessary.
  • other components include inorganic fillers, modifiers, stabilizers, antioxidants, solvents and the like.
  • the photocurable composition according to the second embodiment does not contain an inorganic filler (for example, glass fiber or the like; the same applies hereinafter), or contains an inorganic filler.
  • the content of the inorganic filler with respect to the total amount of the photocurable composition is 10% by mass or less (more preferably 5% by mass or less, further preferably 2% by mass or less, still more preferably 1% by mass or less). Is preferable.
  • the photocurable compositions of the present disclosure (for example, each of the photocurable compositions according to the first embodiment and the second embodiment described above) have viscosities measured by an E-type viscometer under the conditions of 25 ° C. and 50 rpm. (Hereinafter, also simply referred to as “viscosity”) is preferably 5 mPa ⁇ s to 6000 mPa ⁇ s. Here, rpm means revolutions per minute. When the viscosity is 5 mPa ⁇ s to 6000 mPa ⁇ s, the handleability of the photocurable composition when producing a three-dimensional model by stereolithography is excellent.
  • the viscosity is more preferably 10 mPa ⁇ s to 5000 mPa ⁇ s, further preferably 20 mPa ⁇ s to 4000 mPa ⁇ s, further preferably 100 mPa ⁇ s to 3000 mPa ⁇ s, and 200 mPa ⁇ s to 2000 mPa ⁇ s.
  • -S is more preferably 400 mPa ⁇ s to 1500 mPa ⁇ s.
  • the three-dimensional model of the present disclosure is a cured product of the above-mentioned photocurable composition of the present disclosure. Therefore, the three-dimensional model of the present disclosure is excellent in modeling accuracy.
  • the three-dimensional model of the present disclosure is preferably a three-dimensional model having at least one of a recess and a space. The recesses and spaces are as described above.
  • the dental products of the present disclosure include the three-dimensional shaped objects of the present disclosure described above (preferably three-dimensional shaped objects having recesses or spaces). Therefore, the dental products of the present disclosure are excellent in molding accuracy. Specific examples of dental products are as described above.
  • ABE300 Ethoxylated bisphenol A diacrylate (Shin-Nakamura Chemical Industry Co., Ltd., structure shown below)
  • UDA Urethane diacrylate (Fuji Film Wako Pure Chemical Industries, Ltd., structure is as follows)
  • SR540 Ethoxylated bisphenol A dimethacrylate (Sartmer Co., Ltd., structure shown below)
  • UDMA Urethane dimethacrylate (Fujifilm Wako Pure Chemical Industries, Ltd., structure shown below)
  • TPO Acylphosphine oxide compound (specifically, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) (Omnirad TPO H, IGM Resins BV, the structure is shown below)
  • Acylphosphine oxide compound (specifically, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide) (Omnirad 819, IGM Resins BV, the structure is shown below)
  • Solvent Orange 2 (Tokyo Chemical Industry Co., Ltd., structure shown below)
  • Solvent Yellow 2 (Tokyo Chemical Industry Co., Ltd., structure shown below)
  • Solvent Yellow 11 (Tokyo Chemical Industry Co., Ltd., structure shown below)
  • Solvent Yellow 7 (Tokyo Chemical Industry Co., Ltd., structure shown below)
  • Phthalocyanine green (Tokyo Chemical Industry Co., Ltd., structure shown below)
  • Phthalocyanine blue (Tokyo Chemical Industry Co., Ltd., structure shown below)
  • the viscosities of the photocurable compositions in Examples 1 to 30 and 101 to 120, and Comparative Examples 1 to 4 and 101 to 107 were all in the range of 700 mPa ⁇ s to 1000 mPa ⁇ s.
  • ⁇ Measurement of transmittance (405 nm) of diluted solution (D1) of photocurable composition The following transmittance measurements were carried out on the prepared photocurable composition.
  • the prepared photocurable composition was diluted with ethanol so that the ethanol content was 99% by mass to prepare a diluted solution (D1).
  • the transmittance of the diluted solution (D1) in the wavelength range of 300 nm to 750 nm was measured using an ultraviolet-visible spectrophotometer (Evolution 220 manufactured by Thermo Scientific) under the condition of an optical path length of 1 cm. From the measurement results, the transmittance at 405 nm, which is the irradiation wavelength of the 3D printer, was read. The measurement results are shown in the “Diluted liquid (D1) transmittance (%) at 405 nm” column in Tables 1 to 3.
  • the three-dimensional model 10 shown in FIG. 1 described above was manufactured by DLP-type stereolithography.
  • the thickness (design value) of the bottom surface portion 12 is 1.500 mm.
  • the three-dimensional model 10 is formed in order from the upper side (opposite side to the gravity direction G) to the lower side (gravity direction G side) of the side surface portions 14 and 16 of the three-dimensional model 10.
  • the bottom surface portion 12 was formed. The detailed operation is as in the above-mentioned example.
  • Each cured layer was formed by irradiating the photocurable composition with visible light having a wavelength of 405 nm at an irradiation amount of 10 mJ / cm 2 .
  • the thickness of each cured layer was set to 50 ⁇ m.
  • the entire formed three-dimensional model 10 is irradiated with ultraviolet rays having a wavelength of 365 nm at an irradiation amount of 3 mJ / cm 2 .
  • the three-dimensional model 10 was finally cured.
  • the thickness of the bottom surface 12 of the three-dimensional model 10 after the main curing was measured with a caliper (manufactured by Mitutoyo, CD-P15S).
  • the measured thickness of the bottom surface is shown in Tables 1 to 3 (“Thickness of bottom surface at 405 nm” column). If the measured thickness of the bottom surface is within the range of 1.500 mm (design value) to 1.600 mm, it can be judged that the thickness accuracy is excellent.
  • the diluent (D1) satisfies the condition (1) (transmittance at a wavelength of 405 nm is 1.0% or more and 70.0% or less).
  • the thickness of the bottom surface of the modeled object was in the range of 1.500 mm (design value) to 1.600 mm, and the thickness accuracy was excellent.
  • Comparative Examples 1 and 2 in which the transmittance of the diluent (D1) at a wavelength of 405 nm is more than 70.0%, the thickness of the bottom surface of the three-dimensional model is more than 1.600 mm, which is inferior in thickness accuracy. It was (thickness was too thick).
  • Comparative Examples 3 and 4 in which the transmittance of the diluted solution (D1) at a wavelength of 405 nm was less than 1.0%, curing was insufficient and molding defects occurred.
  • ⁇ Measurement of transmittance (385 nm) of diluted solution (D1) of photocurable composition The following transmittance measurements were carried out on the prepared photocurable composition.
  • the prepared photocurable composition was diluted with ethanol so that the ethanol content was 99% by mass to prepare a diluted solution (D1).
  • the transmittance of the diluted solution (D1) in the wavelength range of 300 nm to 750 nm was measured using an ultraviolet-visible spectrophotometer (Evolution 220 manufactured by Thermo Scientific) under the condition of an optical path length of 1 cm. From the measurement results, the transmittance at 385 nm, which is the irradiation wavelength of the 3D printer, was read. The results are shown in the “Diluted liquid (D1) transmittance (%) at 385 nm” column in Tables 4 and 5.
  • the measured thickness of the bottom surface is shown in the “Bottom thickness at 385 nm” column in Tables 4 and 5.
  • the criteria for determining the thickness accuracy are the same as the criteria for determining the thickness accuracy in the "accuracy evaluation of the thickness of the bottom surface of the three-dimensional model (405 nm)".

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025100441A1 (ja) * 2023-11-07 2025-05-15 クラレノリタケデンタル株式会社 光造形用樹脂組成物

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4624537A1 (de) * 2024-03-25 2025-10-01 LANXESS Deutschland GmbH 3d druckerzeugnisse

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08300492A (ja) * 1995-05-12 1996-11-19 Nippon Kayaku Co Ltd 光造形方法
JP2005331695A (ja) * 2004-05-19 2005-12-02 Fuji Photo Film Co Ltd 感光性転写シート、感光性積層体、画像パターン形成方法、及び配線パターン形成方法
JP2006348214A (ja) * 2005-06-17 2006-12-28 Jsr Corp 光造形用光硬化性液状組成物、立体造形物及びその製造方法
JP4160311B2 (ja) 2001-03-12 2008-10-01 イボクラール ビバデント アクチェンゲゼルシャフト 合成材料部品の製造方法
JP2010188610A (ja) * 2009-02-18 2010-09-02 Asahi Kasei E-Materials Corp レーザー彫刻印刷原版の製造方法
JP2016505525A (ja) * 2012-11-14 2016-02-25 デンツプライ インターナショナル インコーポレーテッド 歯科製品を製造するための三次元加工材料系
JP2016077887A (ja) * 2014-10-20 2016-05-16 株式会社 和光製作所 歯列矯正具の製造方法
WO2018234898A1 (en) * 2017-06-20 2018-12-27 3M Innovative Properties Company Radiation curable composition for additive manufacturing processes
JP2019026594A (ja) * 2017-07-31 2019-02-21 クラレノリタケデンタル株式会社 ジルコニア成形体の製造方法
WO2019189652A1 (ja) 2018-03-30 2019-10-03 三井化学株式会社 光造形用硬化性組成物、消失模型及び立体造形物の製造方法
JP2019528197A (ja) * 2016-08-25 2019-10-10 スリーエム イノベイティブ プロパティズ カンパニー 付加製造プロセスのための着色硬化性組成物、３次元複合材物品及びその使用
JP2020008136A (ja) 2018-07-11 2020-01-16 ジヤトコ株式会社 レンジ切替装置

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7189344B2 (en) 2001-03-12 2007-03-13 Ivoclar Vivadent Ag Method for producing a synthetic material part
JP4692092B2 (ja) 2005-06-17 2011-06-01 Ｊｓｒ株式会社 光造形用光硬化性液状組成物、立体造形物及びその製造方法
JP5507256B2 (ja) 2006-12-13 2014-05-28 スリーエム イノベイティブ プロパティズ カンパニー 酸性成分及び光退色性染料を有する歯科用組成物の使用方法
JP5250371B2 (ja) * 2008-10-01 2013-07-31 株式会社松風 混合可能で色調再現が自在にできる歯科用着色材組成物とそのセットおよび方法
EP3335687B1 (de) * 2016-12-15 2020-02-12 Ivoclar Vivadent AG Ausbrennbares dentales modelliermaterial
TWI750321B (zh) * 2017-02-21 2021-12-21 日商住友化學股份有限公司 樹脂組成物及硬化膜
CN108714109A (zh) * 2018-05-17 2018-10-30 河源然生新材料有限公司 一种用于dlp快速成型3d打印设备的uv光固化牙科铸造材料

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08300492A (ja) * 1995-05-12 1996-11-19 Nippon Kayaku Co Ltd 光造形方法
JP4160311B2 (ja) 2001-03-12 2008-10-01 イボクラール ビバデント アクチェンゲゼルシャフト 合成材料部品の製造方法
JP2005331695A (ja) * 2004-05-19 2005-12-02 Fuji Photo Film Co Ltd 感光性転写シート、感光性積層体、画像パターン形成方法、及び配線パターン形成方法
JP2006348214A (ja) * 2005-06-17 2006-12-28 Jsr Corp 光造形用光硬化性液状組成物、立体造形物及びその製造方法
JP2010188610A (ja) * 2009-02-18 2010-09-02 Asahi Kasei E-Materials Corp レーザー彫刻印刷原版の製造方法
JP2016505525A (ja) * 2012-11-14 2016-02-25 デンツプライ インターナショナル インコーポレーテッド 歯科製品を製造するための三次元加工材料系
JP2016077887A (ja) * 2014-10-20 2016-05-16 株式会社 和光製作所 歯列矯正具の製造方法
JP2019528197A (ja) * 2016-08-25 2019-10-10 スリーエム イノベイティブ プロパティズ カンパニー 付加製造プロセスのための着色硬化性組成物、３次元複合材物品及びその使用
WO2018234898A1 (en) * 2017-06-20 2018-12-27 3M Innovative Properties Company Radiation curable composition for additive manufacturing processes
JP2019026594A (ja) * 2017-07-31 2019-02-21 クラレノリタケデンタル株式会社 ジルコニア成形体の製造方法
WO2019189652A1 (ja) 2018-03-30 2019-10-03 三井化学株式会社 光造形用硬化性組成物、消失模型及び立体造形物の製造方法
JP2020008136A (ja) 2018-07-11 2020-01-16 ジヤトコ株式会社 レンジ切替装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4079768A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025100441A1 (ja) * 2023-11-07 2025-05-15 クラレノリタケデンタル株式会社 光造形用樹脂組成物

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