WO2024166632A1 - 三次元光造形用硬化性組成物及びその製造方法、三次元光造形物の製造方法、並びに歯科用修復物の製造方法 - Google Patents

三次元光造形用硬化性組成物及びその製造方法、三次元光造形物の製造方法、並びに歯科用修復物の製造方法 Download PDF

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WO2024166632A1
WO2024166632A1 PCT/JP2024/001193 JP2024001193W WO2024166632A1 WO 2024166632 A1 WO2024166632 A1 WO 2024166632A1 JP 2024001193 W JP2024001193 W JP 2024001193W WO 2024166632 A1 WO2024166632 A1 WO 2024166632A1
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mass
light
inorganic filler
dimensional
particles
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French (fr)
Japanese (ja)
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英武 坂田
慶 中島
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Tokuyama Dental Corp
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Tokuyama Dental Corp
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Priority to CN202480011661.6A priority Critical patent/CN120659706A/zh
Priority to JP2024576198A priority patent/JPWO2024166632A1/ja
Priority to KR1020257026897A priority patent/KR20250148596A/ko
Priority to AU2024218051A priority patent/AU2024218051A1/en
Priority to EP24753078.5A priority patent/EP4663388A1/en
Publication of WO2024166632A1 publication Critical patent/WO2024166632A1/ja
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    • 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
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • 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
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/307—Handling of material to be used in additive manufacturing
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C19/00—Dental auxiliary appliances
    • A61C19/003—Apparatus for curing resins by radiation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C5/00—Filling or capping teeth
    • A—HUMAN NECESSITIES
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    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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    • A61K6/15—Compositions characterised by their physical properties
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    • A—HUMAN NECESSITIES
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    • 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
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    • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • 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
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    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
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    • B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
    • 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
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    • 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
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/379—Handling of additively manufactured objects, e.g. using robots
    • 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
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/20—Post-treatment, e.g. curing, coating or polishing
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • 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
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    • C08K3/36—Silica
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C—CHEMISTRY; METALLURGY
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    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond

Definitions

  • the present disclosure relates to a curable composition for three-dimensional photolithography and a method for producing the same, a method for producing a three-dimensional photolithography object, and a method for producing a dental restoration.
  • photolithography The technology of forming a three-dimensional object by irradiating a photocurable composition (also called a photocurable resin or photocurable resin composition) containing a polymerizable monomer and a photopolymerization initiator with light that activates the photopolymerization initiator (activating light) to harden the composition is known as photolithography.
  • photolithography There are several methods of photolithography, among which the liquid vat photopolymerization method is widely used because the equipment is relatively inexpensive and objects with smooth surfaces can be produced with high precision.
  • a three-dimensional object to be manufactured is generally obtained as follows. First, the height direction of the three-dimensional object is digitized and ranked from three-dimensional shape data showing the shape of the three-dimensional object, and two-dimensional shape data showing the cross-sectional shape of the three-dimensional object at each ranked height is generated.
  • activation light is irradiated to a predetermined position of the liquid photocurable composition held in the tank, which is determined in advance based on the two-dimensional shape data, to selectively cure the liquid photocurable composition present at that position to form a modeling layer having the above-mentioned cross-sectional shape, and modeling layers having the cross-sectional shape at each height are sequentially formed and stacked in the order of the ranking to obtain a laminate having a shape corresponding to the shape of the three-dimensional object.
  • the laminate is washed with an organic solvent if necessary, and then secondary curing is performed to obtain the target object.
  • dental restorations such as dentures and crown prostheses must be manufactured with high precision in unique shapes that correspond to the conditions inside the oral cavity of each individual patient. For this reason, the manufacture of dental restorations by photolithography using liquid vat photopolymerization based on CAD (Computer Aided Design) data designed using digital data obtained from intraoral scans, etc., is being considered.
  • CAD Computer Aided Design
  • Dental prostheses used in the oral cavity require not only high dimensional (shape) accuracy as described above, but also high mechanical strength sufficient to withstand the loads imposed during chewing.
  • an inorganic filler is blended into a photocurable composition
  • polymerization shrinkage which is one of the causes of reduced accuracy
  • the mechanical strength and surface hardness of the cured body can be improved.
  • a liquid vat photopolymerization method using a photocurable composition blended with an inorganic filler is considered to be suitable, and a curable composition for three-dimensional photofabrication blended with such an inorganic filler has also been proposed.
  • Patent Document 1 discloses a composition containing a polymerizable monomer (a), ultraviolet absorbing inorganic particles (b), and a photopolymerization initiator (c) as a composition for optical three-dimensional modeling that is excellent in molding accuracy, mechanical properties, and transparency, and is particularly suitable for dental materials.
  • Patent Document 2 discloses a composition containing a translucent resin and two or more types of translucent particles with different refractive indices and Abbe numbers as a resin composition capable of producing a cured body (three-dimensional model) with excellent design.
  • Patent Document 3 discloses a composition containing a urethane-modified (meth)acrylic compound (a), a (meth)acrylamide compound (b), a photopolymerization initiator (c), and spherical inorganic particles (d) with an average particle size of 0.75 to 10 ⁇ m as a resin composition for optical modeling that can obtain a three-dimensional model with high strength, high elasticity, and excellent abrasion resistance, and in which the content of the spherical inorganic particles (d) is 50 to 400 parts by mass per 100 parts by mass of the total amount of the polymerizable monomers.
  • Patent Documents 1 to 3 compositions in which inorganic fillers are added to polymerizable monomers are used, making it possible to obtain molded objects with good mechanical strength, elastic modulus, and abrasion resistance.
  • the optical three-dimensional modeling composition described in Patent Document 1 has low fluidity, which may limit the shape of the applicable molded object.
  • the resin composition described in Patent Document 2 may cause the translucent particles (glass filler, etc.) contained in the composition to settle when left to stand for a long period of time.
  • the optical modeling resin composition described in Patent Document 3 often causes fine cracks on the surface of the molded object that are difficult to distinguish by the naked eye (see Figure 4). If a molded object with such fine cracks is used as a dental prosthesis, it is problematic because it may become the starting point for the dental prosthesis to fracture in the oral cavity.
  • the objective of this disclosure is to provide a technology that enables the production of high-precision, high-strength three-dimensional objects without generating cracks on the surface when producing three-dimensional objects by photolithography using a liquid vat photopolymerization method using a curable composition for three-dimensional photolithography that contains a certain amount of inorganic filler to increase strength.
  • a first aspect of the present disclosure is a three-dimensional optically modeled curable composition used as the liquid photocurable composition in a liquid tank photopolymerization method for producing a three-dimensional optically modeled object by irradiating a predetermined position of a liquid photocurable composition held in a tank with activating light (hereinafter also referred to as "specific activating light") containing light of a specific wavelength ⁇ (nm) in the ultraviolet light region or visible light region to selectively cure the liquid photocurable composition present at the predetermined position, comprising:
  • the composition comprises 100 parts by mass of a polymerizable monomer component (A), 40 to 400 parts by mass of an inorganic filler (B) composed of a single type or multiple types of inorganic powder or particles, and 0.01 to 5 parts by mass of a photopolymerization initiator (C) having a function of initiating photopolymerization upon irradiation with specific activating light,
  • a photopolymerization initiator having a function of initi
  • the particle diameter of each particle constituting the inorganic filler (B) is x (nm) and pi is ⁇
  • the inorganic powder particles constituting the inorganic filler (B) are, when an inorganic powder particle consisting of an aggregate of a single type of inorganic particles having a refractive index at 25° C. within the range of 1.500 to 1.550 is defined as a specific inorganic powder particle (b1), and an inorganic powder particle consisting of an aggregate of a single inorganic particle having a refractive index outside the above range is defined as a non-specific inorganic powder particle (b2), the inorganic filler (B) is (1) Consisting of a single type of specific inorganic powder or particle (b1), (2) It is composed of multiple types of specific inorganic powder particles (b1), and at least one of the multiple types of specific inorganic powder particles (b1) accounts for 10 mass% or more of the total mass of the inorganic filler (B); or (3) It is composed of a single type or multiple types of specific inorganic powder particles (b1): 90 mass% or more and less than 100 mass%
  • nF refractive index that has the largest difference from nM
  • refractive index that has the largest difference from nM
  • a second aspect of the present disclosure is a method for producing a curable composition for three-dimensional optical modeling, comprising the steps of:
  • the method includes a mixing step of mixing 100 parts by mass of a polymerizable monomer component (A), 40 to 400 parts by mass of an inorganic filler (B) composed of a single type or multiple types of inorganic powder or particles, 0.01 to 5 parts by mass of a photopolymerization initiator (C) having a function of initiating photopolymerization upon irradiation with specific activating light, and 0.01 to 2.5 parts by mass of an activating light absorber (D) having a function of absorbing the specific activating light but not having photopolymerization initiation ability,
  • the polymerizable monomer component (A) and the inorganic filler (B) are mixed under the following conditions 1 to 4:
  • Condition 1 When the particle diameter of each particle constituting the inorganic filler (B) is x (nm) and pi is ⁇ , in the particle size distribution of the in
  • a specific inorganic powder particle (b1) an inorganic powder particle consisting of an aggregate of a single type of inorganic particles having a refractive index outside the above range is defined as a non-specific inorganic powder particle (b2)
  • the inorganic filler (B) satisfies the following conditions: (1) Consisting of a single type of specific inorganic powder or particle (b1), (2) composed of multiple types of specific inorganic powders (b1), and at least one of the multiple types of specific inorganic powders (b1) accounts for 10 mass% or more of the total mass of the inorganic filler (B); or (3) composed of a single type or multiple types of specific inorganic powders (b1): 90 mass% or more and less than 100 mass% and a single type or multiple types of non-specific inorganic powders (b2): more than 0 mass% and less than 10 mass%, and at least one of the single type or multiple types of specific inorganic powders (b1)
  • Condition 4 When the refractive index having the largest difference from nM among the refractive indexes of at least one specific inorganic powder or particle (b1) accounting for 10 mass % or more of the inorganic filler (B) is nF , the absolute value of the difference between nF and nM :
  • the present invention relates to a method for producing a curable composition for three-dimensional optical molding, the method using the composition satisfying all of the above requirements.
  • a base composition is separately prepared using the polymerizable monomer component (A) and the inorganic filler (B) that satisfy the above conditions 1 to 4, the base composition being a composition consisting of only the polymerizable monomer component (A) and the inorganic filler (B) and having the same compositional ratio of these components as the curable composition for three-dimensional optical modeling that is the target of production;
  • a third aspect of the present disclosure is a method for producing a three-dimensional optically shaped object by irradiating a specific activating light to a predetermined position of a liquid photocurable composition held in a tank, thereby selectively curing the liquid photocurable composition present at the predetermined position, the method comprising: a molding process in which, from three-dimensional shape data representing the shape of a three-dimensional object, the height direction of the three-dimensional object is digitized and ranked, and two-dimensional shape data representing the cross-sectional shape of the three-dimensional object at each ranked height is generated, and specific activating light is applied to a liquid photocurable composition held in a tank at a predetermined position determined in advance based on the two-dimensional shape data to selectively primarily cure the liquid photocurable composition present at that position to form a modeling layer having the cross-sectional shape, and modeling layers having the cross-sectional shapes at each height are sequentially formed and stacked in accordance with the ranked order to obtain a laminate having a shape corresponding
  • a fourth aspect of the present disclosure is a method for manufacturing a dental restoration, which includes manufacturing a dental restoration by the method for manufacturing a three-dimensional optically shaped object of the present disclosure.
  • the disclosed curable composition for three-dimensional photopolymerization makes it possible to produce three-dimensional photopolymerized objects with excellent mechanical strength and good modeling accuracy while suppressing the decrease in fluidity and settling of inorganic fillers and preventing the occurrence of cracks on the surface of the cured object.
  • FIG. 13 is a diagram showing the surface of the three-dimensional optically molded object obtained in Example 7, as observed with an optical microscope (magnification: 50 times).
  • FIG. 13 is a diagram showing the surface of the three-dimensional optically molded object obtained in Example 11, observed with an optical microscope (magnification: 50 times).
  • FIG. 2 is a diagram showing the surface of the three-dimensional optically molded object obtained in Comparative Example 1, as observed with an optical microscope (magnification: 50 times).
  • FIG. 13 is a diagram showing the surface of the three-dimensional optically molded object obtained in Comparative Example 9, as observed with an optical microscope (magnification: 50 times).
  • 1 is a graph showing the wavelength distribution (relative spectral distribution) of measurement light used when measuring the light scattering index Sc in Examples and Comparative Examples.
  • photocurable compositions that contain a certain amount of inorganic filler to improve the mechanical strength and surface hardness of the cured product can suffer from problems such as reduced fluidity and particle settling during storage. Furthermore, when a model is produced by a liquid tank photopolymerization method using the stereolithography resin composition described in Patent Document 3, fine cracks that are difficult to distinguish by visual inspection often occur on the surface of the model (although this is not recognized in Patent Document 3).
  • photo-fabrication curable composition (hereinafter also simply referred to as "photo-fabrication curable composition") and its manufacturing method, the manufacturing method of a three-dimensional photo-fabricated object, and the manufacturing method of a dental restoration.
  • the notation "x to y" using the numerical values x and y means "x or more and y or less.” In such notations, when a unit is added only to the numerical value y, the unit is also applied to the numerical value x.
  • (meth)acrylic means both “acrylic” and “methacrylic.”
  • (meth)acrylate means both “acrylate” and “methacrylate”
  • (meth)acryloyl means both “acryloyl” and “methacryloyl.”
  • Curable Composition for Stereolithography is a composition used as a liquid photocurable composition when producing a three-dimensional stereolithography object using a liquid vat photopolymerization method, i.e., a curable composition for three-dimensional stereolithography using a liquid vat photopolymerization method.
  • the liquid vat photopolymerization method refers to a method of obtaining a three-dimensional photo-modeled object having a shape corresponding to the shape of the three-dimensional object by digitizing and ranking the height direction of the three-dimensional object from three-dimensional shape data showing the shape of the three-dimensional object and generating two-dimensional shape data showing the cross-sectional shape of the three-dimensional object at each ranked height, irradiating the liquid photocurable composition held in the vat with activation light at a predetermined position determined in advance based on the two-dimensional shape data, selectively (primarily) curing the liquid photocurable composition present at that position to form a modeling layer having the above-mentioned cross-sectional shape, and sequentially forming and stacking modeling layers having the cross-sectional shape at each height in the order of the ranking (hereinafter also referred to as the "molding step").
  • a cleaning process with an organic solvent hereinafter also referred to as the “cleaning step” or a secondary curing process (hereinafter also referred to as the “secondary curing step”) is performed to obtain a three-dimensional photo-modeled object having a shape corresponding to the shape of the three-dimensional object.
  • the photopolymerization curable composition disclosed herein contains 100 parts by mass of a polymerizable monomer component (A), 40 to 400 parts by mass of an inorganic filler (B) composed of a single type or multiple types of inorganic powder and particles, and 0.01 to 5 parts by mass of a photopolymerization initiator (C) having a function of initiating photopolymerization upon irradiation with specific activating light, and is characterized in that in the particle size distribution of the inorganic filler (B) measured by a microscopy method using a scanning microscope, 80% or more of all particles constituting the inorganic filler (B) have a particle diameter of 0.05 to 5.0 ⁇ m, and the transmittance to the specific activating light measured on a 0.5 mm thick sample composed of the photopolymerization curable composition is 1.00 to 50.00 (%).
  • the polymerizable monomer component (A) and the inorganic filler (B) in the above-mentioned ratio, it is possible to increase the strength and surface hardness of the cured body that will become the three-dimensional photo-modeled object, which is the target product of manufacture.
  • the particles that make up the inorganic filler (B) satisfy the above-mentioned particle size conditions, it is possible to suppress an increase in the viscosity of the composition and the risk of the particles settling during storage.
  • the fact that 80% or more of all primary particles constituting the inorganic filler (B) are particles with a particle diameter of 0.05 to 5.0 ⁇ m can be confirmed by the particle size distribution of the inorganic filler (B) measured by a microscopy method using a scanning microscope. That is, the inorganic filler (B) used to prepare the stereolithography curable composition of the present disclosure is photographed by a scanning electron microscope, and the number of all primary particles (50 or more) observed within a unit field of view of the photograph: n (pieces) is measured, and the primary particle diameter (maximum diameter): Xi (nm) of each particle is measured for all primary particles, thereby obtaining the particle size distribution.
  • i in the above Xi is a natural number from 1 to n, and represents the number of each measured primary particle.
  • inorganic filler (B) may be included as aggregated particles formed by agglomeration of primary particles.
  • the particle size distribution of the primary particles is not particularly limited, but in order to suppress the settling of inorganic filler (B), it is preferable that the number of aggregated particles of inorganic filler (B) contained in the curable composition for stereolithography of the present disclosure is small.
  • the average particle size of inorganic filler (B) including aggregated particles of primary particles measured by laser diffraction/scattering method is usually 0.05 to 100 ⁇ m, preferably 0.05 to 50 ⁇ m, and more preferably 0.05 to 30 ⁇ m.
  • the disclosed curable composition for stereolithography has a transmittance of 1.00 to 50.00% for specific activating light measured on a 0.5 mm thick sample made of the curable composition for stereolithography, which makes it possible to reduce the risk of cracks occurring on the surface of the cured product.
  • the reason why cracks occur on the surface of a cured body is not clear, but the present inventors have confirmed that cracks occur when the uncured curable composition attached to the surface of a laminate obtained using a photopolymerization device is washed with an organic solvent after the laminate is obtained.
  • the inorganic filler contained in the photopolymerization curable composition contains many particles with a particle size that causes scattering (specifically, Mie scattering or Reyleigh scattering) when irradiated with activation light.
  • interlayer low crosslink density region a region with a relatively low crosslink density (hereinafter also referred to as "interlayer low crosslink density region”) is formed between the layers of the laminate.
  • This is also thought to be one of the causes of cracks. That is, when an organic solvent penetrates into the interlayer low crosslink density region during washing, the region swells, the molecules of the polymer chains that make up the molded body spread, and the strength temporarily decreases. At that time, it is thought that the internal stress remaining in the molded body during the molding process destroys the part with reduced strength, causing cracks to occur in the region.
  • the transmittance to the specific activation light is set within the above range, thereby reducing the effect of scattering and reducing the risk of cracking on the surface of the cured product.
  • the photopolymerization curable composition disclosed herein is preferably in the above-mentioned specific blending mode.
  • a polymerizable monomer component, an inorganic filler with a particle size that suppresses the risk of viscosity increase and sedimentation, a photopolymerization initiator, and an activation light absorber are contained in a predetermined amount ratio, and the combination of the polymerizable monomer component and the inorganic filler is characterized by adopting a combination in which the light scattering index Sc falls within a specific range.
  • the transmittance to the specific activation light is set within a specific range, thereby preventing cracking and, in some cases, further improving the modeling accuracy.
  • the specific blending embodiment is a homogeneous composition containing 100 parts by mass of polymerizable monomer component (A), 40 to 400 parts by mass of inorganic filler (B) composed of a single type or multiple types of inorganic powder particles, 0.01 to 5 parts by mass of photopolymerization initiator (C) that has the function of initiating photopolymerization upon irradiation with specific activating light, and 0.01 to 2.5 parts by mass of activating light absorber (D) that has the function of absorbing specific activating light but does not have photopolymerization initiation ability, and by satisfying the following conditions [I] and [II], it achieves the effects of high strength, prevention of cracking, and high precision.
  • a base composition is made of only a polymerizable monomer component (A) and an inorganic filler (B) and the composition ratio of these components is the same as that of a curable composition for stereolithography
  • I 0 , I 70 , I 75 , and I 80 respectively indicate the intensity of transmitted light in the directions of emission angles of 0°, 70°, 75°, and 80°.
  • a curable composition for photopolymerization with a specific formulation does not satisfy the above conditions regarding the components and their blending ratios, and does not satisfy the condition regarding the transmittance to the specific activating light, it becomes difficult to manufacture a high-strength three-dimensional object with high precision. If condition [I] is not satisfied, for example, if the transmittance is less than 1%, sufficient curing depth is not obtained, and many low crosslink density interlayer regions are formed, resulting in significant cracking. On the other hand, with a composition containing inorganic filler (B) and activating light absorber (D), it is extremely difficult to achieve a system with the transmittance exceeding 50% while maintaining high modeling precision.
  • condition [I] corresponds to the "transmittance to the specific activating light in the photopolymerization curable composition of the specific formulation before photocuring" and is an index of the cure depth when the photopolymerization curable composition of the present disclosure is irradiated with the specific activating light.
  • the Sc stipulated in condition [II] is an index of the "scattering state of light when the photopolymerization curable composition of the present disclosure is irradiated with the specific activating light", specifically the state of side scattered light, and further the extent of the interlayer low crosslink density region formed thereby.
  • These cure depths and side scattered light states are important in expressing the effects of the photopolymerization curable composition of the present disclosure, and are determined by the combination of each component used.
  • the physical properties of each component affecting the transmittance defined by condition [I] and the Sc defined by condition [II] are so diverse, it is practically impossible to directly define a specific combination of substances that satisfies these conditions.
  • components (A), (B), (C), and (D) are defined as satisfying these conditions [I] and [II] simultaneously, and in the case of a photopolymerization curable composition that does not contain component (D), components (A), (B), and (C) are defined as satisfying these conditions [I] and [II] simultaneously.
  • the photopolymerization curable composition disclosed herein includes those obtained by the method for producing a photopolymerization curable composition disclosed herein later.
  • the curable composition for stereolithography according to the present disclosure contains a photopolymerization initiator, regardless of whether it is a specific blending embodiment or not, and therefore there is concern that curing may progress due to light irradiation during measurement.
  • a transmittance measurement method using a color difference meter as described below, it is possible to measure the transmittance of the specific activation light before curing progresses.
  • the transmittance of the photopolymerization curable composition of the present disclosure to a specific activation light can be measured as follows. First, a resin mold (25 mm x 25 mm x 0.5 mm thick) is filled with the photopolymerization curable composition of the present disclosure, and then the top and bottom surfaces are pressed with glass slides to a thickness of 0.5 mm, and the glass slides are then removed to prepare a measurement sample with a thickness of 0.5 mm.
  • this measurement sample is placed in a color difference meter (e.g., Spectrophotometer SE7700, manufactured by Nippon Denshoku Industries Co., Ltd.), and the transmittance of the activation light (e.g., 405 nm wavelength light or 385 nm wavelength light) is measured by transmittance measurement using a halogen lamp (measurement wavelength: 380 to 780 nm).
  • a color difference meter e.g., Spectrophotometer SE7700, manufactured by Nippon Denshoku Industries Co., Ltd.
  • the transmittance measured in this manner is lower than the lower limit of 1.00%, sufficient curing depth cannot be obtained, making photolithography difficult, and even if photolithography is possible, cracks are likely to occur on the model.
  • the transmittance is preferably 2.00 to 30.00%, and more preferably 5.00 to 20.00%.
  • the transmittance tends to be higher the higher the light transmittance of the polymerizable monomer component and the inorganic filler themselves, and the smaller the difference in refractive index between the two.
  • the transmittance of the polymerizable monomer component is significantly higher than 5.00%, so as long as the blending amount of inorganic filler is within the specified range, it is possible to make the transmittance not only 1.00% or more, but also 5.00% or more by using an inorganic filler that has light transmittance and reducing the difference in refractive index between the two.
  • condition [II] It is generally known that when light hits fine particles having a particle size suitable for a photopolymerization curable composition, i.e., fine particles having a particle size of 0.05 to 5.0 ⁇ m, phenomena such as light blocking, diffraction, Mie scattering, and Rayleigh scattering occur. When Mie scattering and/or Rayleigh scattering occurs, the scattered light spreads not only forward but also to the side and rear. The scattered light spreads to the side (side scattered light) reduces the transmittance of the specific activation light in condition [I], which is thought to cause cracks, and further reduces the molding accuracy of the molded body.
  • the spread and intensity of the side scattered light is affected not only by the particle size of the particle, but also by the refractive index of the particle and the polymerizable monomer component present around the particle (as a dispersion medium).
  • a dispersion system in which particles are dispersed in a polymerizable monomer component as a powder with a particle size distribution, particularly in a dispersion system composed of multiple types of particles with different refractive indices, it is virtually impossible to grasp the scattering behavior of each particle, and it is necessary to grasp the scattering behavior of the entire system.
  • the photopolymerization curable composition disclosed herein when used for manufacturing dental prostheses, the greater the average "intensity of the activation light scattered in the side direction" of the entire system, the lower the modeling accuracy, and further the lower the transmittance of a specific activation light, raising concerns about the occurrence of cracks due to an increase in the low crosslink density region between layers.
  • the combination of the polymerizable monomer component and inorganic filler used in the photopolymerization curable composition of the present disclosure is indirectly specified using the light scattering index: Sc (%) defined by the above formula in the base composition (which is homogeneous and consists only of the polymerizable monomer component and the inorganic filler in a specified quantitative ratio) that serves as the base of the photopolymerization curable composition.
  • Measuring the refracted light that passes through a sample using a goniophotometer is used to evaluate the optical properties of materials that require light diffusion, such as lighting fixture covers and projector screens, and in the dental field, as described in Patent Document 4, it is also used as an index to evaluate the optical texture of tooth filling and restorative materials, specifically to determine the degree of diffusion D.
  • the measurement using a goniophotometer to determine the light scattering index Sc can be performed as follows. First, a portion of the base composition (for raw material) prepared in the preparation process of the curable composition for stereolithography of the present disclosure is sampled, or a base composition (for measurement) prepared by separately preparing is used to prepare a measurement sample having a thickness of 0.5 mm in the same manner as in the transmittance measurement.
  • the measurement sample is set in a three-dimensional goniophotometer (e.g., GP-200, manufactured by Murakami Color Research Laboratory Co., Ltd.), and "measurement light including light of a specific wavelength: ⁇ (nm), mainly composed of light within the range of ⁇ 50 (nm), and showing the maximum intensity within the range” is irradiated perpendicularly to the measurement sample, and the intensity of the transmitted light in each emission angle direction is measured.
  • a three-dimensional goniophotometer e.g., GP-200, manufactured by Murakami Color Research Laboratory Co., Ltd.
  • an interference filter e.g., for GP-200, manufactured by Murakami Color Research Laboratory Co., Ltd.
  • the main component being light within the range of ⁇ 50 (nm) means that in the spectrum showing the wavelength distribution (relative spectral distribution) of the measurement light, the integral value of the intensity of light with wavelengths of ⁇ 50 (nm) is 90% or more of the integral value of the intensity of the entire measurement light.
  • the light scattering index Sc of the base composition exceeds 10%, the formation of interlayer low crosslink density regions that cause cracks due to side scattered light is unavoidable.
  • the light scattering index Sc of the base composition is preferably 5.0% or less, and more preferably 3.0% or less. The lower the light scattering index Sc, the better, with the lower limit being 0.0%.
  • the light scattering index Sc of the base composition is affected by the blending ratio of the polymerizable monomer component and the inorganic filler, but when this ratio is constant, it can be controlled to some extent by adjusting the particle size distribution of the inorganic filler, the refractive index (or type) of the particles that make up the inorganic filler, and the refractive index of the entire polymerizable monomer component.
  • a particle size parameter ⁇ which is an index of light scattering and scattering intensity caused by particles.
  • Many dental inorganic fillers have particle sizes smaller than this value, so the above scattering occurs and cracks are likely to occur.
  • the inorganic filler (B) used satisfies the following condition 1.
  • Condition 1 When the particle diameter of each particle constituting the inorganic filler (B) is x (nm) and pi is ⁇ , in the particle size distribution of the inorganic filler (B) measured by a microscopy method using a scanning microscope, the total number of particles having a particle diameter x (nm) within the range of 0.7 ⁇ / ⁇ to 4 ⁇ / ⁇ (nm) is 40% or more, preferably 60% or more, and more preferably 80% or more of the total number of particles constituting the inorganic filler (B).
  • the proportion of particles having a particle diameter in which the particle diameter parameter ⁇ is in the range of 1.0 to 3.0 (129 to 386 nm when the wavelength of the activation light is 405 nm) in the inorganic filler (B) is preferably 50% or more, more preferably 60% or more, and the proportion of particles having a particle diameter in which the particle diameter parameter ⁇ is in the range of 1.8 to 2.8 (231 to 360 nm when the wavelength of the activation light is 405 nm) is preferably 45% or more, more preferably 50% or more.
  • the total number of particles having a particle diameter in the range of 85 to 535 nm is preferably 40% or more of the total number of particles constituting the inorganic filler (B), more preferably 60% or more, and even more preferably 80% or more.
  • a more preferable particle diameter range is 121 to 400 nm, and an even more preferable particle diameter range is 218 to 375 nm.
  • the total number of particles having a particle diameter in the range of 218 to 375 nm is 80% or more of the total number of particles constituting the inorganic filler (B).
  • the refractive index of the inorganic filler and the polymerizable monomer component used in dentistry it is preferable to adopt a combination of the inorganic filler and the polymerizable monomer component that satisfies the following conditions 2 to 4.
  • the inorganic filler (B) when an inorganic powder particle consisting of an aggregate of a single type of inorganic particles having a refractive index at 25° C. for the (sodium) D line in the range of 1.500 to 1.550 is defined as a specific inorganic powder particle (b1), and an inorganic powder particle consisting of an aggregate of a single inorganic particle having a refractive index outside the above range is defined as a non-specific inorganic powder particle (b2), the inorganic filler (B) satisfies the following conditions: (1) Consisting of a single type of specific inorganic powder or particle (b1), (2) It is composed of multiple types of specific inorganic powders (b1), and at least one of the multiple types of specific inorganic powders (b1) accounts for 10 mass% or more of the total mass of the inorganic filler (B), or (3) It is composed of a single type or multiple types of specific inorganic powders (
  • Condition 4 When the refractive index having the largest difference from nM among the refractive indexes of at least one specific inorganic powder or particle (b1) accounting for 10% by mass or more of the inorganic filler (B) is nF , the absolute value of the difference between nF and nM :
  • the refractive index of inorganic powders and particles made of a single material and the refractive index of polymerizable monomer components at 25°C for the D line can be measured as follows.
  • the refractive index of the polymerizable monomer component can be measured by using an Abbe refractometer (for example, Digital Abbe Refractometer DR-A1-PLUS, manufactured by Atago Co., Ltd.) to place the prepared monomer composition on a prism, looking into the sample through an eyepiece, and reading the value on the display when the boundary line and the intersection of the cross lines meet (this value becomes the refractive index).
  • Abbe refractometer for example, Digital Abbe Refractometer DR-A1-PLUS, manufactured by Atago Co., Ltd.
  • the refractive index of the inorganic powder or granule is determined by mixing toluene or ethanol with bromonaphthalene to prepare solutions with refractive indices that vary in increments of 0.001, mixing each inorganic powder or granule with each solution with a different refractive index, shaking, and determining the refractive index of the solution that is observed to be the most transparent as the refractive index of that inorganic powder or granule.
  • any radically polymerizable monomer (monomer) can be used without any particular limitation.
  • radically polymerizable monomers it is preferable to use a (meth)acrylate monomer because it has a fast curing rate and the strength of the resulting shaped object is excellent.
  • any of monofunctional (meth)acrylates, bifunctional (meth)acrylates, and trifunctional or higher polyfunctional (meth)acrylates may be used, but in order to produce stronger shaped objects, it is preferable that 50% by mass or more, and preferably 80% by mass or more, based on the total mass of all radically polymerizable monomers, be bifunctional or higher polyfunctional (meth)acrylates. It is more preferable that the proportion of bifunctional or higher polyfunctional (meth)acrylates is 95% by mass or more.
  • Suitable examples of polyfunctional (meth)acrylates having two or more functional groups include (meth)acrylates containing a bisphenol A skeleton, such as 2,2'-bis ⁇ 4-[3-(meth)acryloyloxy-2-hydroxypropoxy]phenyl ⁇ propane, 2,2'-bis[4-(meth)acryloyloxyphenyl]propane, and 2,2'-bis[4-(meth)acryloyloxypolyethoxyphenyl]propane; ethylene glycol-based (meth)acrylates, such as triethylene glycol dimethacrylate and ethylene glycol dimethacrylate;
  • suitable acrylates include aliphatic di(meth)acrylates such as 1,3-propanediol di(meth)acrylate and 1,9-nonanediol dimethacrylate; urethane group-containing (meth)acrylates such as 1,6-bis(methacryloyloxy-2-ethoxycarbonylamin
  • 2,2'-bis[4-(meth)acryloyloxyphenyl]propane, 2,2'-bis[4-(meth)acryloyloxypolyethoxyphenyl]propane, triethylene glycol dimethacrylate, tris(2-methacryloyloxyethyl)isocyanurate, etc. are preferred due to their low viscosity and high strength.
  • examples of monofunctional (meth)acrylates suitable for use in combination with difunctional or higher polyfunctional (meth)acrylates include hydroxyethyl methacrylate, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, hydroxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and glycidyl (meth)acrylate.
  • radical polymerizable monomers may be used alone or in combination of two or more.
  • the curable composition for stereolithography contains 40 to 400 parts by mass of an inorganic filler composed of a single type or multiple types of inorganic powder particles, relative to 100 parts by mass of the polymerizable monomer component. If the content of the inorganic filler is too high, the viscosity of the composition becomes too high. On the other hand, if the content of the inorganic filler is too low, the mechanical strength becomes insufficient. For this reason, the content of the inorganic filler is preferably 50 to 350 parts by mass, more preferably 60 to 300 parts by mass, relative to 100 parts by mass of the polymerizable monomer component.
  • the inorganic filler must contain 80% or more particles with a particle diameter in the range of 0.05 to 5.0 ⁇ m in the particle size distribution of the inorganic filler measured by a microscopic method using a scanning microscope, and the proportion of particles having a particle diameter in the above range is preferably 90% or more, and more preferably 95% or more.
  • the lower limit of the particle diameter of particles that make up 80% or more of the inorganic filler is preferably 0.08 ⁇ m, and more preferably 0.1 ⁇ m.
  • the upper limit of the particle diameter of particles that make up 80% or more of the inorganic filler is preferably 2.0 ⁇ m, and more preferably 1.0 ⁇ m.
  • inorganic powders and granules used as inorganic fillers in dental restorative materials can be used without any particular restrictions, provided that they satisfy the above condition [I] and also satisfy the above condition [II] in combination with the polymerizable monomer component.
  • Suitable inorganic powders and granules include powders and granules made of metals (simple substances); powders and granules made of metal oxides or metal composite oxides; powders and granules made of metal salts such as metal fluorides, carbonates, sulfates, silicates, hydroxides, chlorides, sulfites, and phosphates; mixtures of these powders and granules; and the like.
  • Particularly suitable constituent materials of the inorganic filler include metal oxides such as amorphous silica, quartz, alumina, zirconia, barium oxide, yttrium oxide, lanthanum oxide, and ytterbium oxide; silica-based composite oxides such as silica-zirconia, silica-titania, silica-titania-barium oxide, and silica-titania-zirconia; glass such as borosilicate glass, aluminosilicate glass, and fluoroaluminosilicate glass; metal fluorides such as barium fluoride, strontium fluoride, yttrium fluoride, lanthanum fluoride, and ytterbium fluoride; inorganic carbonates such as calcium carbonate, magnesium carbonate, strontium carbonate, and barium carbonate; metal sulfates such as magnesium sulfate and barium sulfate. These inorganic fillers may be used in
  • silica-zirconia it is preferable to use amorphous silica, silica-zirconia, silica-titania, silica-titania-barium oxide, silica-titania-zirconia, borosilicate glass, aluminosilicate glass, or fluoroaluminosilicate glass, because these materials are likely to satisfy the above condition [II]. Furthermore, it is more preferable to use silica-zirconia, from the viewpoint of the wear resistance of the hardened body.
  • inorganic fillers can also be compounded as so-called organic-inorganic composite fillers.
  • silane coupling agents include methyl trimoxysilane, methyl triethoxysilane, methyl trichlorosilane, dimethyl dichlorosilane, trimethyl chlorosilane, vinyl trichlorosilane, vinyl triethoxysilane, vinyl tris ( ⁇ -methoxyethoxy) silane, ⁇ -methacryloyloxypropyl trimethoxysilane, methacryloxyoctyl-8-trimethoxysilane, ⁇ -chloropropyl trimethoxysilane, ⁇ -glycidoxypropyl methoxysilane, and hexamethyl disilazane.
  • silica-zirconia When manufacturing dental restorations, it is preferable to use particles such as silica-zirconia, silica-titania, silica-titania-barium oxide, and silica-titania-zirconia because they have strong X-ray contrast properties. From the standpoint of wear resistance of the hardened body, it is most preferable to use silica-zirconia particles.
  • the photopolymerization initiator must have the function of generating radicals by specific activation light including light of a specific wavelength: ⁇ (nm) in the ultraviolet or visible light region irradiated from a light source mounted on the stereolithography device, and radically polymerizing the polymerizable monomer component.
  • the photopolymerization initiator must absorb light of a specific wavelength ⁇ (nm) to generate radicals.
  • the specific wavelength ⁇ may be appropriately determined according to the wavelength of the activation light used in the stereolithography device, as long as it is a wavelength in the ultraviolet or visible light region.
  • Examples of general-purpose stereolithography devices include SLA-type stereolithography devices that irradiate semiconductor laser light as the activation light, DLP-type stereolithography devices that irradiate projector light, and LCD-type stereolithography devices that irradiate liquid crystal panel light, and the like, and a light source with an activation light wavelength of about 405 nm or about 385 nm is often used.
  • the specific wavelength ⁇ is preferably 405 nm or 385 nm
  • the stereolithography device is preferably an SLA type, a DLP type, or an LCD type.
  • the content of the photopolymerization initiator should be 0.05 to 5.0 parts by mass per 100 parts by mass of the polymerizable monomer component. If the content of the photopolymerization initiator is too high, burrs will appear on the resulting molded object, resulting in poor precision. On the other hand, if the content of the photopolymerization initiator is too low, it will be impossible to mold the object in the molding process. Therefore, the content of the photopolymerization initiator is preferably 0.3 to 4.0 parts by mass, and more preferably 0.5 to 3.0 parts by mass, per 100 parts by mass of the polymerizable monomer component.
  • the photopolymerization initiator may be appropriately selected from known photopolymerization initiators that satisfy the above conditions. There are no particular limitations on the photopolymerization initiator to be selected, and examples include self-cleavage type photopolymerization initiators, bimolecular hydrogen abstraction type photopolymerization initiators, photoacid generators, and combinations of these. These photopolymerization initiators may be used in combination with photosensitizing dyes, electron donating compounds, etc.
  • Suitable examples of self-cleavage type photopolymerization initiators include acylphosphine oxide compounds such as diphenyl(2,4,6-trimethylbenzoyl)-phosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide; benzoketal compounds, benzyne compounds, ⁇ -aminoacetophenone compounds, ⁇ -hydroxyacetophenone compounds, titanocene compounds, and acyloxime compounds.
  • Photoacid generators include iodonium salt compounds such as p-isopropylphenyl-p-methylphenyliodonium tetrakispentafluorophenylborate salt; sulfonium salt compounds such as dimethylphenacylsulfonium hexafluoroantimonate salt; and halomethyl group-substituted triazine compounds such as 2,4,6-tris(trichloromethyl)-s-triazine.
  • iodonium salt compounds such as p-isopropylphenyl-p-methylphenyliodonium tetrakispentafluorophenylborate salt
  • sulfonium salt compounds such as dimethylphenacylsulfonium hexafluoroantimonate salt
  • halomethyl group-substituted triazine compounds such as 2,4,6-tris(trichloromethyl)-s-triazine.
  • photosensitizing dyes include ketone compounds, coumarin dyes, cyanine dyes, merocyanine dyes, thiazine dyes, azine dyes, acridine dyes, xanthene dyes, squarium dyes, pyrylium salt dyes, condensed polycyclic aromatic compounds (anthracene, perylene, etc.), thioxanthone compounds, etc.
  • electron donors include 4-dimethylaminobenzoic acid esters, 4-dimethylaminotoluene, p-dimethoxybenzene, 1,2,4-trimethoxybenzene, thiophene compounds, etc.
  • Activated Light Absorber When using the curable composition for photopolymerization of the present disclosure to manufacture a molded body such as a dental prosthesis with high precision, in order to prevent excessive transmission of the activating light irradiated from a photopolymerization device, which would result in a decrease in the modeling precision of the molded body, it is preferable to contain 0.01 to 2.5 parts by mass of an activating light absorber that has the function of absorbing the activating light irradiated from the photopolymerization device and does not have photopolymerization initiation ability, per 100 parts by mass of the polymerizable monomer component.
  • the content of the activated light absorber is preferably 0.04 to 2.5 parts by mass, more preferably 0.08 to 2.0 parts by mass, and even more preferably 0.25 to 1.0 parts by mass, relative to 100 parts by mass of the polymerizable monomer component.
  • the activated light absorber is not particularly limited as long as it is a compound that absorbs light irradiated from a light source mounted in the stereolithography device, and examples of such compounds include triazole-based compounds such as 2-(hydroxy-5-methylphenyl)-2H-benzotriazole and 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole; benzophenone-based compounds such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone; and the like.
  • triazole-based compounds such as 2-(hydroxy-5-methylphenyl)-2H-benzotriazole and 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole
  • benzophenone-based compounds such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone; and the like.
  • a polymerization inhibitor is preferably blended in the range of 0.01 to 5.0 parts by mass relative to 100 parts by mass of the polymerizable monomer component. If the content of the polymerization inhibitor is too high, the composition tends to be insufficiently cured in the molding process, and if the content of the polymerization inhibitor is too low, the storage stability and molding accuracy of the composition tend to decrease.
  • the content of the polymerization inhibitor is preferably 0.01 to 5.0 parts by mass, more preferably 0.03 to 4.0 parts by mass, and even more preferably 0.05 to 2.5 parts by mass relative to 100 parts by mass of the polymerizable monomer component.
  • a compound that reacts with radicals generated in the photopolymerization curable composition to deactivate the radicals can be used, such as di-tert-butyl-p-cresol and 4-methoxyphenol.
  • a chain transfer agent may be blended in the stereolithography curable composition of the present disclosure in an amount of 0.00001 to 1.0 part by mass per 100 parts by mass of the polymerizable monomer component. If the content of the chain transfer agent is too high, the polymerization reaction of the stereolithography curable composition is suppressed more than necessary, whereas if the content of the chain transfer agent is too low, the effect of adding the chain transfer agent cannot be obtained.
  • chain transfer agents examples include thiol compounds such as butanethiol, thiophenol, mercaptoethanol, octylthiol, and lauryl mercaptan; ⁇ -alkylstyrene compounds such as 2,4-diphenyl-4-methyl-1-pentene ( ⁇ -methylstyrene dimer) and 2-phenyl-1-propene ( ⁇ -methylstyrene); and halogenated hydrocarbons substituted with at least one halogen atom such as carbon tetrachloride and ethylene bromide.
  • ⁇ -alkylstyrene compounds especially ⁇ -methylstyrene dimer, because of their high crack suppression effect.
  • thermal polymerization initiator may be blended into the stereolithography curable composition of the present disclosure as a polymerization initiator for secondary curing.
  • a thermal polymerization initiator having a 10-hour half-life temperature of 50 to 130° C., from the viewpoint that the initiator does not function during primary curing and remains effectively in the laminate.
  • thermal polymerization initiators include organic peroxides such as tert-butyl peroxylaurate and benzoyl peroxide; azo compounds such as azobutyronitrile and azobis(dimethylvaleronitrile); and the like.
  • the content of the thermal polymerization initiator is usually 0.001 to 1.0 parts by mass, preferably 0.005 to 0.3 parts by mass, and more preferably 0.01 to 0.1 parts by mass, per 100 parts by mass of the polymerizable monomer component.
  • the stereolithography curable composition of the present disclosure may contain a coloring substance within a range that satisfies the above condition [I].
  • a coloring substance may be a pigment or a dye.
  • the pigment examples include inorganic pigments such as titanium oxide, zinc oxide, zirconium oxide, zinc sulfide, aluminum silicate, calcium silicate, carbon black, iron oxide, copper chromite black, chromium oxide green, chrome green, violet, chrome yellow, lead chromate, lead molybdate, cadmium titanate, nickel titanium yellow, ultramarine blue, cobalt blue, bismuth vanadate, cadmium yellow, and cadmium yellow; and organic pigments such as monoazo pigments, diazo pigments, diazo condensation pigments, perylene pigments, and anthraquinone pigments.
  • inorganic pigments such as titanium oxide, zinc oxide, zirconium oxide, zinc sulfide, aluminum silicate, calcium silicate, carbon black, iron oxide, copper chromite black, chromium oxide green, chrome green, violet, chrome yellow, lead chromate, lead molybdate, cadmium titanate, nickel titanium yellow, ultramarine blue, cobalt blue, bis
  • the substances exemplified in Section 1-3 may be used, and each component may be mixed to obtain the above-mentioned predetermined composition to form a homogeneous liquid composition, but it is necessary to satisfy the above conditions [I] and [II].
  • the manufacturing method of the curable composition for stereolithography of the present disclosure is characterized by using a combination of a polymerizable monomer component and an inorganic filler that satisfies specific conditions, and by employing this manufacturing method, the curable composition for stereolithography of the present disclosure can be easily manufactured.
  • the manufacturing method of the curable composition for photopolymerization disclosed herein includes a mixing step of mixing 100 parts by mass of a polymerizable monomer component (A), 40 to 400 parts by mass of an inorganic filler (B) composed of a single type or multiple types of inorganic powder particles, 0.01 to 5 parts by mass of a photopolymerization initiator (C) having the function of initiating photopolymerization upon irradiation with specific activating light, and 0.01 to 2.5 parts by mass of an activating light absorber (D) having the function of absorbing the specific activating light and not having photopolymerization initiation ability, and in the mixing step, the polymerizable monomer component (A) and the inorganic filler (B) used satisfy all of the following conditions 1 to 4.
  • Condition 1 When the particle diameter of each particle constituting the inorganic filler (B) is x (nm) and pi is ⁇ , in the particle size distribution of the inorganic filler (B) measured by a microscopy method using a scanning microscope, the total number of particles having a particle diameter x (nm) within the range of 0.7 ⁇ / ⁇ to 4 ⁇ / ⁇ (nm) is 40% or more of the total number of particles constituting the inorganic filler (B).
  • the inorganic filler (B) is (1) Consisting of a single type of specific inorganic powder or particle (b1), (2) It is composed of multiple types of specific inorganic powders (b1), and at least one of the multiple types of specific inorganic powders (b1) accounts for 10 mass% or more of the total mass of the inorganic filler (B), or (3) It is composed of a single type or multiple types of specific inorganic powders (b1): 90 mass% or more and less than 100 mass% and a
  • Condition 4 When the refractive index having the largest difference from nM among the refractive indexes of at least one specific inorganic powder or particle (b1) accounting for 10% by mass or more of the inorganic filler (B) is nF , the absolute value of the difference between nF and nM :
  • a combination that meets the above criteria is selected from the polymerizable monomer components and inorganic fillers exemplified in Sections 1-3, a photopolymerization initiator that has the function of initiating photopolymerization by irradiating specific activating light as a photopolymerization initiator is selected, and an activating light absorber that absorbs the specific activating light is further selected, and these are weighed out so that the polymerizable monomer components are 100 parts by mass, the inorganic filler is 40 to 400 parts by mass, the photopolymerization initiator is 0.01 to 5 parts by mass, and the activating light absorber is 0.01 to 2.5 parts by mass, and mixed to obtain a uniform liquid composition.
  • the particle size range of particles that account for 40% or more of the inorganic filler should be 90 to 514 nm
  • a photopolymerization initiator that generates radicals when irradiated with light with a wavelength of 405 nm should be selected
  • an activated light absorber that absorbs light with a wavelength of 405 nm should be selected.
  • the particle size range of particles that make up 40% or more (preferably 60% or more, more preferably 80% or more) of the inorganic filler should be 85 to 535 nm (preferably 121 to 400 nm, more preferably 218 to 375 nm), a photopolymerization initiator that generates radicals when irradiated with light of a wavelength of 380 to 420 nm should be selected, and an activation light absorber that absorbs light of a wavelength of 380 to 420 nm should be selected.
  • the components are preferably mixed using a stirrer in the dark, for example under red light, at room temperature until homogenous, in the dark to activate the photopolymerization initiator. After mixing, it is preferable to perform a degassing process.
  • the liquid composition thus obtained usually satisfies the above conditions [I] and [II], but for reasons of higher reliability, it is preferable to select the polymerizable monomer component (A) and inorganic filler (B) to be used in the mixing step as follows: That is, using the polymerizable monomer component (A) and inorganic filler (B) that satisfy the above conditions 1 to 4, a base composition consisting of only the polymerizable monomer component (A) and inorganic filler (B) and having the same compositional ratio of these components as the curable composition for stereolithography that is the target of production is separately prepared; A measurement was performed using a goniophotometer that vertically irradiated a sample of the base composition having a thickness of 0.5 mm with measurement light that contained light of the specific wavelength: ⁇ (nm), had light in the range of ⁇ 50 (nm) as the main component, and exhibited maximum intensity within the range, and based on the intensity of the transmitted light in the specific emission angle direction obtained by the
  • the manufacturing method of a three-dimensional optically shaped object and the manufacturing method of a dental restoration according to the present disclosure is a method for manufacturing a three-dimensional object by a liquid vat photopolymerization method including the above-mentioned molding step, washing step, and secondary curing step, characterized in that the optically shaped curable composition according to the present disclosure is used as the liquid photocurable composition supplied into the vat of the liquid vat photopolymerization device. Since the manufacturing method of a three-dimensional optically shaped object according to the present disclosure uses the optically shaped curable composition according to the present disclosure, it is possible to manufacture a three-dimensional optically shaped object having high mechanical strength and no cracks on the actual surface.
  • the molding step includes: A first step of forming a modeling layer having a shape corresponding to the two-dimensional shape data based on the two-dimensional shape data at the height of the initial ranking order by irradiating a predetermined position of the liquid photocurable composition held in a tank with activating light and curing the composition, thereby forming the "modeling layer" into a bonded layer; a second step of moving the bonded layer up or down to supply a liquid photocurable composition directly above or directly below the bonded layer in the tank; A third step of applying activation light to a predetermined position of the liquid photocurable composition supplied just above or just below the bonded layer based on the two-dimensional shape data at the next highest level in the ranking order in the previous step, thereby hardening the composition, thereby forming a new modeling layer having a shape corresponding to the two-dimensional shape data and bonding the new modeling layer to the bonded layer, thereby obtaining a laminate
  • the new bonded layer is used as the bonded layer in the third step, and a cycle consisting of the third step and the fourth step is repeated, and in the final third step, a new modeling layer is formed based on the two-dimensional shape data at the height of the final ranking order, thereby obtaining a laminate.
  • This type of liquid vat photopolymerization method which includes a molding process, can be suitably carried out using a commercially available liquid vat photopolymerization device known as a 3D printer.
  • the obtained laminate is washed with an organic solvent (a washing step is performed), and then it is subjected to additional irradiation with activating light, heat treatment, or both for secondary curing (a secondary curing step is performed).
  • the organic solvents used in the cleaning process include alcohol-based solvents such as ethanol, methanol, isopropyl alcohol, etc.; ketone-based solvents such as acetone, methyl ethyl ketone, etc.; ether-based solvents such as diethyl ether, diisopropyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, etc.; amide-based solvents such as N-methylpyrrolidone, dimethylacetamide, etc.; halogen-based solvents such as methylene chloride, chloroform, etc.
  • alcohol-based solvents and ether-based solvents are preferred because of their high cleaning effect, and alcohol-based solvents are more preferred because of their low environmental impact.
  • the wavelength of irradiation when additional activation light irradiation is performed in the secondary curing step is not particularly limited as long as it is a wavelength that the photopolymerization initiator remaining in the laminate absorbs and generates radicals.
  • the irradiation intensity of the additional activation light irradiation is preferably 5 mW/cm 2 or more, more preferably 10 mW/cm 2 or more, and even more preferably 30 mW/cm 2 or more, so that the photopolymerization initiator remaining in the laminate generates a sufficient amount of radicals.
  • the irradiation time is not particularly limited, and is preferably 1 minute or more, more preferably 3 minutes or more, and even more preferably 5 minutes or more.
  • the irradiation intensity during the additional activation light irradiation is too strong, the model may be excessively heated, which may cause cracks in the model. Therefore, the irradiation intensity is preferably 10,000 mW/cm 2 or less.
  • the curable composition for stereolithography disclosed herein contains a thermal polymerization initiator, this can be used to carry out secondary curing by heating.
  • the heating temperature at this time is preferably 45 to 120°C, more preferably 50 to 90°C, and even more preferably 55 to 80°C.
  • the method for manufacturing a dental restoration disclosed herein is characterized in that it manufactures dental restorations such as inlays, onlays, crowns, and dentures using the method for manufacturing a three-dimensional photo-fabricated object disclosed herein.
  • dental restorations such as inlays, onlays, crowns, and dentures
  • the three-dimensional shape data showing the shape of the dental restoration (three-dimensional object) used in the molding process CAD data designed based on digital data obtained by scanning the intraoral shape of an individual patient or an intraoral model created for each individual patient may be used. According to the method for manufacturing a dental restoration disclosed herein, it is possible to manufacture a dental restoration that has high mechanical strength and is free of cracks on the actual surface.
  • Monomer compositions A1 to A6 were used, which were prepared by mixing the following monomer compounds as shown below.
  • ACMO acryloylmorpholine (monomer composition)
  • the refractive index nM of each monomer composition is the refractive index for the D line at 25° C.
  • This refractive index nM was measured using a digital Abbe refractometer (DR-A1-PLUS, manufactured by Atago Co., Ltd.) by placing each prepared monomer composition on a prism, looking into the sample through an eyepiece, and reading the value on the display when the boundary line and the intersection of the cross lines were aligned.
  • DR-A1-PLUS digital Abbe refractometer
  • Inorganic filler (B) The inorganic powders and particles shown below were used as they were or in combination with each other to obtain the compositions shown in Table 1 as inorganic fillers B1 to B8.
  • SZ-1 spherical silica-zirconia (surface treated with ⁇ -methacryloyloxypropyltrimethoxysilane, average primary particle size: 280 nm, refractive index n F : 1.522)
  • SZ-2 spherical silica-zirconia (surface treated with ⁇ -methacryloyloxypropyltrimethoxysilane, average primary particle size: 150 nm, refractive index n F : 1.522)
  • SZ-3 Spherical silica-zirconia (surface treated with ⁇ -methacryloyloxypropyltrimethoxysilane, average primary particle size: 450 nm, refractive index n F : 1.540)
  • SZ-4 Spherical si
  • the average primary particle size and refractive index nF of each inorganic filler were measured by the method described in Section 1-2.
  • the content of particles having a particle diameter of 0.05 to 5.0 ⁇ m in the total primary particles constituting each inorganic filler was measured from the particle size distribution obtained by a microscopy method using a scanning microscope (represented as "specific particle content” in Table 1). Furthermore, for the inorganic fillers used in each Example and Comparative Example, the content of particles having a (primary) particle diameter in which the particle diameter parameter ⁇ falls within a specific range (represented as " ⁇ -sufficient particle content” in Table 1) was obtained from the particle size distribution obtained by a microscopy method using a scanning microscope.
  • the content of particles having a particle diameter parameter ⁇ in the range of 0.7 to 4: R1 (%), the content of particles having a particle diameter parameter ⁇ in the range of 1.0 to 3.0: R2 (%), and the content of particles having a particle diameter parameter ⁇ in the range of 1.8 to 2.8: R3 (%) were obtained.
  • the results are also shown in Table 1.
  • the particle size distribution was determined by measuring the number of all primary particles (50 or more) observed within a unit field of view in a scanning electron microscope photograph of each inorganic filler: n (number of particles), and the particle diameter (maximum diameter): Xi (nm) of all primary particles.
  • Photopolymerization initiator BAPO: phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (generates radicals when exposed to activating light of 405 nm)
  • TPO 2,4,6-trimethylbenzoyl-diphenylphosphine oxide
  • Activated light absorber SS3 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole
  • Coloring material Titanium oxide (average primary particle size: 200 ⁇ m)
  • Example 1 (1) Preparation of base composition for Sc evaluation and curable composition for stereolithography 150 parts by mass of SZ-1 was added as an inorganic filler to 100 parts by mass of polymerizable monomer component consisting of monomer composition A1 (UDMA: 50 parts by mass, 3G: 20 parts by mass, D-2.6E: 30 parts by mass), and the mixture was stirred and mixed until homogenous, and then degassed to prepare a base composition for Sc evaluation.
  • monomer composition A1 UDMA: 50 parts by mass, 3G: 20 parts by mass, D-2.6E: 30 parts by mass
  • a base composition for raw materials was prepared in the same manner, to which 1.4 parts by mass of BAPO as a photopolymerization initiator, 0.7 parts by mass of SS3 as an activated light absorber, 0.1 parts by mass of HQME as a polymerization inhibitor, and 0.1 parts by mass of BHT (all amounts are based on 100 parts by mass of polymerizable monomer component) were added, and the mixture was stirred under red light until homogenous, after which it was degassed to prepare a liquid curable composition for stereolithography.
  • optical modeling curable composition obtained in (1) above was supplied to the resin tray (tank) of a 3D printer (DWS, DW029D; wavelength: 405 nm, irradiation intensity: 83 mW), and a molding process was performed using stereolithography data (hereinafter abbreviated as "stl data") having a rectangular parallelepiped shape of 10 mm x 10 mm x 25 mm, and a molded body (laminate) having a laminated structure (composed of a cured body of the optical modeling curable composition) was produced.
  • stl data stereolithography data
  • the obtained molded body was immersed in a plastic container filled with ethanol for 15 minutes and gently shaken to perform a washing process, and then dried, and further additional light irradiation (secondary curing) was performed for 30 minutes using UV CURING UNIT UVIS-2 (DWS) to produce a three-dimensional optical modeling object.
  • DWS UV CURING UNIT UVIS-2
  • A2 The number of cracks observed on the surface of the cured body was 10 or less, and the width of each crack was 10 ⁇ m or less, which is within the acceptable range.
  • A3 The number of cracks observed on the surface of the cured body was 20 or less, and the width of each crack was 10 ⁇ m or less, which is within the acceptable range.
  • B The number of cracks observed on the surface of the cured body was 20 or less, and the crack width was 10 to 40 ⁇ m.
  • C 20 or more cracks with widths of 10 to 40 ⁇ m are observed on the surface of the cured body.
  • D A large number of cracks with a width of more than 40 ⁇ m are observed on the surface of the cured body.
  • Examples 2 to 14 and Comparative Examples 1 to 8> The Sc evaluation base composition and the stereolithography curable composition were prepared in the same manner as in Example 1, except that the components and amounts used in preparing the Sc evaluation base composition and the stereolithography curable composition in Example 1 were changed as shown in Tables 2 and 3. Thereafter, the evaluation of each composition obtained was performed in the same manner as in Example 1, and the production and evaluation of a three-dimensional stereolithography object using the obtained stereolithography curable composition was performed in the same manner as in Example 1. The evaluation results are shown in Tables 4 and 5.
  • a photo-curable composition was prepared according to the method described in Example 1 of Patent Document 3. Specifically, the polymerizable monomer component (A) and inorganic filler (B) shown in Table 3 were used in the blending ratio shown in Table 3, and 3.0 parts by mass of TPO as a polymerization initiator and 0.05 parts by mass of BHT as a polymerization inhibitor (the blending amounts are all relative to 100 parts by mass of the polymerizable monomer component) were added to prepare a photo-curable composition. Then, the production and evaluation of a three-dimensional photo-modeled object using the obtained photo-curable composition was performed in the same manner as in Example 1.
  • Example 1 a base composition for Sc evaluation was prepared in the same manner as in Example 1, and the evaluation of each composition was performed in the same manner as in Example 1. The evaluation results are shown in Table 5.
  • an optical microscope image (magnification 50 times) taken during observation at the time of crack evaluation of Comparative Example 9 (Evaluation C) is shown in FIG. 4.
  • the photopolymerization curable compositions of Examples 1 to 14 had a small light scattering index Sc and a high activation light transmittance, and therefore had high modeling precision and suppressed the occurrence of cracks.
  • the photopolymerization curable compositions of Comparative Examples 1 to 3 had a large light scattering index Sc and a small activation light transmittance, and therefore had low modeling precision and generated cracks.
  • the photopolymerization curable compositions of Comparative Examples 4 to 7 had a small light scattering index Sc but a small activation light transmittance, and therefore generated cracks.
  • the photopolymerization curable composition of Comparative Example 8 had a large light scattering index Sc, and therefore had low modeling precision and generated cracks.
  • the photopolymerization curable composition of Comparative Example 9 was prepared according to the method described in Patent Document 3, and had a small activation light transmittance, and therefore generated cracks.

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025164130A1 (ja) * 2024-01-31 2025-08-07 株式会社トクヤマデンタル 三次元光造形用硬化性組成物及びその製造方法、三次元光造形物の製造方法、並びに歯科用修復物の製造方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3917204B2 (ja) 1995-12-21 2007-05-23 株式会社クラレ 歯科用複合修復材料の選択方法
WO2016076180A1 (ja) * 2014-11-12 2016-05-19 日本電気硝子株式会社 立体造形用樹脂組成物、立体造形物の製造方法及び無機充填材粒子
WO2016084572A1 (ja) * 2014-11-25 2016-06-02 日本電気硝子株式会社 立体造形用樹脂組成物
JP2020044835A (ja) * 2018-09-12 2020-03-26 キヤノン株式会社 立体造形用の硬化性樹脂組成物
JP2020073333A (ja) * 2020-01-21 2020-05-14 日本電気硝子株式会社 立体造形用樹脂組成物
JP2020180171A (ja) 2019-04-23 2020-11-05 日本電気硝子株式会社 樹脂組成物、樹脂硬化体及び立体造形物の製造方法
JP2021165375A (ja) * 2020-04-07 2021-10-14 キヤノン株式会社 立体造形用の光硬化性樹脂組成物
JP2022041276A (ja) 2020-08-31 2022-03-11 クラレノリタケデンタル株式会社 光造形用樹脂組成物

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2017345913B2 (en) 2016-10-21 2022-07-21 Kuraray Noritake Dental Inc. Composition for optical three-dimensional modeling
KR102490483B1 (ko) 2020-09-24 2023-01-20 한국자동차연구원 온라인 전기차량의 충전 제어 시스템 및 방법

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3917204B2 (ja) 1995-12-21 2007-05-23 株式会社クラレ 歯科用複合修復材料の選択方法
WO2016076180A1 (ja) * 2014-11-12 2016-05-19 日本電気硝子株式会社 立体造形用樹脂組成物、立体造形物の製造方法及び無機充填材粒子
JP2020192810A (ja) * 2014-11-12 2020-12-03 日本電気硝子株式会社 立体造形用樹脂組成物、立体造形物の製造方法及び無機充填材粒子
WO2016084572A1 (ja) * 2014-11-25 2016-06-02 日本電気硝子株式会社 立体造形用樹脂組成物
JP2020044835A (ja) * 2018-09-12 2020-03-26 キヤノン株式会社 立体造形用の硬化性樹脂組成物
JP2020180171A (ja) 2019-04-23 2020-11-05 日本電気硝子株式会社 樹脂組成物、樹脂硬化体及び立体造形物の製造方法
JP2020073333A (ja) * 2020-01-21 2020-05-14 日本電気硝子株式会社 立体造形用樹脂組成物
JP2021165375A (ja) * 2020-04-07 2021-10-14 キヤノン株式会社 立体造形用の光硬化性樹脂組成物
JP2022041276A (ja) 2020-08-31 2022-03-11 クラレノリタケデンタル株式会社 光造形用樹脂組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4663388A1

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025164130A1 (ja) * 2024-01-31 2025-08-07 株式会社トクヤマデンタル 三次元光造形用硬化性組成物及びその製造方法、三次元光造形物の製造方法、並びに歯科用修復物の製造方法

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