WO2019132472A1 - Composition photodurcissable et article moulé fabriqué à l'aide de celle-ci - Google Patents

Composition photodurcissable et article moulé fabriqué à l'aide de celle-ci Download PDF

Info

Publication number
WO2019132472A1
WO2019132472A1 PCT/KR2018/016576 KR2018016576W WO2019132472A1 WO 2019132472 A1 WO2019132472 A1 WO 2019132472A1 KR 2018016576 W KR2018016576 W KR 2018016576W WO 2019132472 A1 WO2019132472 A1 WO 2019132472A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
acrylate
photocurable composition
weight
bisphenol
Prior art date
Application number
PCT/KR2018/016576
Other languages
English (en)
Korean (ko)
Inventor
박성원
Original Assignee
박성원
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 박성원 filed Critical 박성원
Publication of WO2019132472A1 publication Critical patent/WO2019132472A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • 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
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C08F291/12—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to nitrogen-containing macromolecules
    • 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
    • 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
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C5/00—Filling or capping teeth
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • 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
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/147—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/148—Polysiloxanes

Definitions

  • the present invention relates to a photo-curing resin composition for dental use in which a 3D printer can be used, and a dental molding manufactured using the same.
  • tooth restorations usually made of metal, porcelain (ceramics), polymeric materials, etc. are used to repair damaged teeth in the oral cavity.
  • ceramic restorations are mainly used in consideration of esthetics.
  • Examples of the method of manufacturing the ceramic restoration include a method of laminating a ceramic material on a metal tube and firing the ceramic material, a method of laminating the ceramic material on the ceramic core and firing or pressing the ceramic material, a method of forming a ceramic block by CAD / CAM ) System to obtain a molded body and sinter it.
  • a method of processing and firing a ceramic block through a CAD / CAM system is superior in productivity, elaborate, superior in aesthetic and mechanical properties to zirconia Zirconia) can be used as the material, has received the spotlight recently.
  • the conventional technology has a problem that the loss rate of the ceramic block is high in the manufacturing process, the number of the restoration to be manufactured is less than the time required for manufacturing the restoration, and the amount of cutting tools used in the manufacturing process is large.
  • a method for manufacturing a dental restoration using a 3D printer has recently been spotlighted.
  • the data obtained by scanning a work model is designed and corrected using a CAD program, and then a process of printing and solidification of a polymer or a metal powder material is repeated to obtain a molded article.
  • a 3D printer is used, a large amount of various restorations can be manufactured in a short time.
  • conventional dental compositions have been difficult to use 3D printers because of the slow curing rate and high viscosity.
  • the present invention provides a photocurable composition
  • a photocurable composition comprising a (meth) acrylate modified siloxane resin, a urethane (meth) acrylate oligomer, a di (meth) acrylate based reactive monomer and a photopolymerization initiator.
  • the present invention provides a molded article produced by printing and curing the above-mentioned photocurable composition through a 3D printer.
  • the photocurable composition of the present invention can use a 3D printer due to its low viscosity and high curing speed, it is possible to produce a dental molding having excellent workability and productivity at the time of production of a molded product, and having excellent aesthetics and mechanical properties .
  • the photocurable composition according to the present invention is applicable to the manufacture of a dental molding.
  • the photocurable composition according to the present invention is a composition capable of producing a three-dimensional molded article usable for dental treatment through a 3D printer.
  • the photocurable composition includes a (meth) acrylate modified siloxane resin, a urethane (meth) acrylate oligomer, Acrylate-based reactive monomer and a photopolymerization initiator.
  • (meth) acrylate means acrylate or methacrylate.
  • the (meth) acrylate modified siloxane resin prevents yellowing of the photocurable composition and contributes to enhancement of tensile strength.
  • the (meth) acrylate modified siloxane is a siloxane compound having a (meth) acrylate group, and a compound having a (meth) acrylate group bonded to one end or both ends of the siloxane can be used have.
  • the (meth) acrylate modified siloxane may be represented by the following formula (1) or (2).
  • R 1 to R 8 are the same or different groups and are an alkyl group or an alkenyl group having 1 to 10 carbon atoms,
  • n is an integer of 0 to 5
  • n is an integer from 0 to 100;
  • R 9 to R 16 are the same or different groups and are an alkyl group or an alkenyl group having 1 to 10 carbon atoms,
  • n and m ' are the same or different integers of 0 to 5
  • n is an integer from 0 to 100;
  • (Meth) acrylate modified polydimethylsiloxane such as mono- (meth) acryloxy-modified polydialkylsiloxane can be used as the (meth) acrylate modified siloxane, Alkyl-terminated polydimethylsiloxane or bis- (meth) acryloxyalkyl-terminated polydimethylsiloxane. These may be used alone or in combination of two or more.
  • the weight average molecular weight (Mw) of the (meth) acrylate modified siloxane may be 1,000 to 5,000 g / mol and the viscosity (25 ° C) may be 10 to 100 cps.
  • the content of (meth) acrylate in the (meth) acrylate modified siloxane may be from 0.25 to 0.85 mmol / g.
  • the content of the (meth) acrylate modified siloxane ranges from about 3 to 35% by weight based on the total weight of the photocurable composition. If the content of the (meth) acrylate modified siloxane is less than the above range, the flexural strength and flexural modulus of the final molded product may be lowered. If the content is larger than the above range, the shore D hardness of the final molded product may be lowered.
  • the urethane (meth) acrylate oligomer is a component that controls the physical properties (e.g., hardness, adhesion, flexibility, etc.) of the cured resin by forming a crosslinking structure with the (meth) acrylate based reactive monomer which is a photoreactive monomer , Molding workability, elasticity and adhesiveness can be improved in the production of a molded article by a 3D printer.
  • urethane (meth) acrylate oligomer a reaction product of an aliphatic or aromatic diisocyanate and a hydroxy (meth) acrylate monomer may be used.
  • the urethane (meth) acrylate resin may be, for example, a urethane di (meth) acrylate resin, a urethane tri (meth) acrylate resin, a urethane tetra (meth) acrylate resin or a urethane hexa .
  • Examples of the aliphatic or aromatic diisocyanate include 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate, cyclopentylene-1,3-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, iso Tolylene diisocyanate, 4,4'-methylenebis (phenylisocyanate), 2,2-diphenylpropane-diisocyanate, 2,4-tolylene diisocyanate, 4,4'-diisocyanate, p-phenylenediisocyanate, m-phenylenediisocyanate, xylene diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, Isocyanate, azobenzene-4,4'-diisocyanate, m- or p-tetramethyl xylene diisocyanate
  • the hydroxy (meth) acrylate monomer is not limited as long as it is well known in the art, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Hydroxybutyl (meth) acrylate, 2-hydroxyethyleneglycol (meth) acrylate, 2-hydroxypropyleneglycol (meth) (Meth) acrylate, and the like, but are not limited thereto. These may be used alone or in combination of two or more.
  • the weight average molecular weight of the urethane (meth) acrylate oligomer may range, for example, from about 300 to 1,000 g / mol, and in another example from about 400 to 600 g / mol.
  • the viscosity (25 ⁇ ) of the urethane (meth) acrylate oligomer may range, for example, from about 8,000 to 9,000 cps.
  • the content of the urethane (meth) acrylate oligomer ranges from about 25 to 45% by weight based on the total weight of the photocurable composition. If the content of the urethane (meth) acrylate oligomer is smaller than the above-mentioned range, the bending strength of the final molded product may be lowered. If the content is larger than the above-mentioned range, the bending elastic modulus of the final molded product may be lowered.
  • the di (meth) acrylate-based reactive monomer includes a mixture of a bisphenol A ethoxylate di (meth) acrylate monomer and an alkylene glycol di (meth) acrylate monomer.
  • the bisphenol A ethoxylate di (meth) acrylate monomer affects the water resistance and adhesiveness of the molded product, and the alkylene glycol di (meth) acrylate monomer can control the viscosity of the composition and control the cross- . If the content of the bisphenol A ethoxylate di (meth) acrylate monomer is too small, the bending strength and flexural modulus may be lowered, and if the content is too high, the bending strength may be lowered. In addition, when the alkylene glycol di (meth) acrylate is used in too small amounts, Shore D strength and bending strength may be lowered.
  • the bisphenol A ethoxylate di (meth) acrylate monomer used in the present invention is a compound having an intramolecular ethylene oxide group and having a (meth) acrylate group at the terminal, and may be used without limitation as long as it is known in the art.
  • the bisphenol A ethoxylate di (meth) acrylate monomer may be represented by the following formula (3).
  • n are the same or different integers of 0 to 20,
  • the bisphenol A ethoxylate di (meth) acrylate monomer may be a mixture of two or more bisphenol A ethoxylate di (meth) acrylate monomers having different molar numbers.
  • the bisphenol A ethoxylate di (meth) acrylate monomer may be selected from the group consisting of a first bisphenol A ethoxylated di (meth) acrylate monomer having a number of moles of ethylene oxide (EO) (n + m) And a second bisphenol A ethoxylate di (meth) acrylate monomer having a number of moles (n + m) of ethylene oxide (EO) in the range of 7 to 20.
  • a copolymer comprising two or more first bisphenol A ethoxylate di (meth) acrylate monomers having a number of moles of ethylene oxide (EO) (n + m) in the range of 0 to 6 or a number of moles of ethylene oxide (EO) (meth) acrylate monomers having a number-average molecular weight (Mn) in the range of 7 to 20, and a second bisphenol A ethoxylate di (meth) acrylate monomer having an n + m range of 7 to 20.
  • EO ethylene oxide
  • Mn number-average molecular weight
  • the mixing ratio of the first bisphenol A ethoxylate di (meth) acrylate monomer to the second bisphenol A ethoxylate di (meth) acrylate monomer is, for example, 1: 1 to 2: 1: 1.1 to 1.5 weight ratio.
  • the weight average molecular weight of the bisphenol A ethoxylate di (meth) acrylate monomer may range, for example, from 300 to 800 g / mol, in other embodiments from about 400 to 600 g / mol.
  • the viscosity (25 ⁇ ) of the ethoxylated di (meth) acrylate monomer may range from about 1,300 to 2,500 cps.
  • alkylene glycol di (meth) acrylate monomer compounds known in the art having an intramolecular (meth) acrylate group and an alkylene structure can be used without limitation.
  • alkylene glycol di (meth) acrylates that can be used include polyethylene glycol diacrylate (PEGDA), glycerin diacrylate, triethylene glycol dimethacrylate (TEGDMA), hexanediol Diacrylate and the like. These may be used alone or in combination of two or more.
  • PEGDA polyethylene glycol diacrylate
  • glycerin diacrylate glycerin diacrylate
  • TEGDMA triethylene glycol dimethacrylate
  • hexanediol Diacrylate hexanediol Diacrylate
  • Such alkylene glycol di (meth) acrylate monomers may have a weight average molecular weight in the range of about 100 to 500 g / mol, and in another example about 200 to 400 g / mol.
  • the viscosity (25 ⁇ ) of the alkylene glycol di (meth) acrylate monomer may range from about 5 to 12 cps.
  • the di (meth) acrylate-based reactive monomer may further include a bisphenol A glycol di (meth) acrylate monomer.
  • the bisphenol A glycol di (meth) acrylate monomer affects the mechanical properties such as the hardness of the final molded article. If the bisphenol A glycol di (meth) acrylate monomer is used in an excessively small amount, the Shore D hardness, bending strength and flexural modulus may be lowered, and if too large, the flexural strength and flexural modulus may decrease. According to one example, from 10 to 40% by weight, based on the total weight of the photocurable composition, bisphenol A glycol di (meth) acrylate monomers can be mixed and used.
  • the bisphenol A glycol di (meth) acrylate monomer used in the present invention may have a weight average molecular weight ranging from about 400 to 600 g / mol, for example.
  • the viscosity (65 ⁇ ) of the bisphenol A glycol di (meth) acrylate monomer may range, for example, from about 1,400 to 2,000 cps.
  • the photopolymerization initiator is a component that is excited by ultraviolet (UV) or visible light to induce photopolymerization, and any photopolymerization initiator known in the art can be used without limitation.
  • UV ultraviolet
  • visible light any photopolymerization initiator known in the art can be used without limitation.
  • the photopolymerization initiator examples include a carbonyl compound photopolymerization initiator of? -Diketone type such as camphor quinone and an acylphosphine oxide photopolymerization initiator.
  • a photopolymerization initiator usually uses a hydrogen donor as a cocatalyst, and a tertiary amine-based catalyst can work together.
  • Non-limiting examples of usable photopolymerization initiators include tertiary amine initiators, diphenyl iodonium chloride, diphenyl iodonium hexafluorophosphate, diphenyl iodonium tetrafluoroborate, tolyl cumyl iodonium tetra Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-dihydroxybenzoate, Trimethylpentyl) phosphine oxide, ethyl-2,4,6-trimethylbenzyl phenylphosphinate, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2-hydroxy- Phenylpropan-1-one and the like. These may be used alone or in combination of two or more.
  • the content of such a photopolymerization initiator is not particularly limited and may be, for example, in the range of 1 to 5 wt% based on the total weight of the photocurable composition, and in another example, in the range of about 1 to 3 wt%. If the content of the photopolymerization initiator is less than the above range, it may lead to deterioration of appearance and deterioration of physical properties due to lowering of curability and uncuredness. If the content is larger than the above range, contamination due to unreacted photopolymerization initiator, , Causing cracks.
  • the weight average molecular weight of the photopolymerization initiator may range, for example, from about 200 to 600 g / mol, in other embodiments from about 300 to 450 g / mol.
  • the photocurable composition of the present invention may further contain additives commonly known in the art, in addition to the above-mentioned components, so long as the effects of the present invention are not impaired.
  • additives include polymerization inhibitors, pigments, coupling agents, reinforcing agents, and acrylic resins. These may be used alone or in combination of two or more.
  • the polymerization inhibitor is used to improve the storage stability of the composition while controlling the polymerization of the composition.
  • the polymerization inhibitor is not particularly limited as long as it is commonly used in the art and includes, for example, butylated hydroxytoluene, hydroquinone (HQ), methylhydroquinone (MQ), hydroquinone Hydroquinone monomethyl ether, 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol), phenothiazine, 4-methoxyphenol, pyrogallol, Di-t-butyl-4-methylphenol, 2-naphthol, p-benzoquinone, 2,5-diphenyl-p-benzoquinone and the like.
  • the content of the polymerization inhibitor may range, for example, from about 0.01 to 0.5% by weight, and in another example, from about 0.05 to 0.3% by weight, based on the total weight of the photocurable composition.
  • Pigments are used to express various tooth colors (e.g., white, colored, etc.) of the final dental molding.
  • the pigment that can be used in the present invention is not particularly limited as long as it is a pigment conventionally used in a dental restoration material. Examples thereof include iron oxide pigments of yellow, navy blue and red, and inorganic pigments such as titanium dioxide, but are not limited thereto. These may be used alone or in combination of two or more.
  • the content of such a pigment is not particularly limited and may be, for example, in the range of 0.005 to 0.5% by weight, and in another example, in the range of about 0.01 to 0.5% by weight based on the total weight of the photocurable composition.
  • the coupling agent is used to improve the compatibility between the hydrophobic di (meth) acrylate and a hydrophilic substance (e.g., an inorganic filler such as silica) while improving the elasticity and strength of the final molded product.
  • a hydrophilic substance e.g., an inorganic filler such as silica
  • the coupling agent usable in the present invention is not particularly limited as long as it is known in the art, and examples thereof include silane coupling agents, titanate coupling agents, zirconate coupling agents and the like, Or a mixture of two or more of them may be used.
  • silane coupling agent examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -aminopropylmethyldimethoxysilane, N-2- (aminoethyl) Trimethoxysilane, and the like, but are not limited thereto.
  • titanate-based coupling agent examples include cyclodioctyl pyrophosphate dioctyl pyrophosphate dioctyl titanate, dicyanodioctyl pyrophosphate dioctyl titanate ( dicyclo (dioctyl) pyrophosphate dioctyl titanate, neopentyl (diallyl) oxy trineodecanoyl titanate, neopentyldialyloxy-tridodecylbenzenesulfonyltitanate (neopentyl (dodecyl) benzene-sulfonyl titanate, neopentyl (diallyl) oxy tri (dioctyl) phosphato titanate, neopentyldialyloxy-tridioctyl pyrophosphate Neopentyl (diallyl) oxy tri (diooc
  • zirconate-based coupling agent examples include neopentyldiallyl oxy-trineodecanoyl zirconate, neopentyldiallyloxy-tridodecylbenzenesulfonyl (Diallyl) oxy tri (dodecyl) benzene-sulfonyl zirconate, neopentyl (diallyl) oxy tri (dioctyl) phosphato zirconate, neopentyl (Diallyl) oxy tri (dioctyl) pyro-phosphato zirconate, neopentyldiallyloxy-tri (n-ethylenediamino) ethyl zirconate neopentyl (diallyl) oxy tri (N-ethylenediamino) ethyl zirconate, neopentyldiallyloxy tri (N-ethylenediamino
  • the content of such a coupling agent is not particularly limited and may be, for example, in the range of about 0.01 to 5 wt% based on the total weight of the photocurable composition, and in another example, in the range of about 0.1 to 3 wt%.
  • the reinforcing agent is used to improve the strength and abrasion resistance of the molded article.
  • the reinforcing agent usable in the present invention is not particularly limited as long as it is known in the art, and examples thereof include inorganic particles such as alumina, silica, zirconia, titanium dioxide, and carbon, or resins in which the inorganic particles are dispersed.
  • the size of the inorganic particles may be in the range of, for example, about 10 to 100 nm, and in another example, in the range of about 10 to 50 nm.
  • a thermoplastic acrylic resin can be used as the resin for dispersing the inorganic particles.
  • the content of the reinforcing agent in the present invention is not particularly limited and may be, for example, in the range of about 0.01 to 20% by weight, in another example about 5 to 10% by weight, based on the total weight of the photocurable composition.
  • the acrylic resin is used to improve the elasticity of the molded article.
  • the acrylic resin is a polymer obtained by polymerizing a (meth) acrylic ester monomer containing a C 1 -C 14 alkyl group and containing at least one acrylic repeating unit.
  • Examples of the (meth) acrylate monomer containing the C 1 -C 14 alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (Meth) acrylate, hexyl (meth) acrylate, allyl (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, ethylene glycerol di Propane diol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like.
  • the content of the acrylic resin in the present invention is not particularly limited and can be, for example, in the range of about 0.01 to 10% by weight, and in another example about 3 to 7% by weight based on the total weight of the photocurable composition.
  • medicines or other therapeutic materials may be optionally added to the photo-curable composition.
  • the content of the additive may be suitably controlled within the range known in the art, and may be 0.001 to 5 wt%, for example, based on the total weight of the photocurable composition.
  • the photo-curable composition according to the present invention is a photo-curable composition comprising a (meth) acrylate modified siloxane resin, a urethane (meth) acrylate oligomer, a di (meth) acrylate- based reactive monomer, a photopolymerization initiator and, , A reinforcing agent, an acrylic resin, and other additives according to a conventional method known in the art.
  • a high-speed stirrer is used in combination with (meth) acrylate modified siloxane resin, urethane (meth) acrylate oligomer, di (meth) acrylate based reactive monomer, photopolymerization initiator, polymerization inhibitor, coupling agent, The mixture is stirred for 0.5 to 60 minutes, then the pigment is added thereto, and the mixture is stirred at a rate of 1,000 to 3,000 rpm for 0.5 to 60 minutes to prepare a photocurable composition.
  • the photocurable composition of the present invention which is constituted as described above, can maintain a low viscosity even without containing a diluent or a solvent, so that a 3D printer can be used in the production of a molded article, The problem can be solved.
  • the composition of the present invention produces a molded article using a 3D printer, it is superior in workability and productivity as compared with the production of a conventional ceramic restoration using a ceramic block.
  • the composition of the present invention can exhibit excellent aesthetics and mechanical properties (e.g., bending strength, flexural modulus, shore strength, etc.).
  • the curable composition may have a viscosity at 25 DEG C of about 500 cps or less.
  • the curable composition constituted as described above is applicable to various applications applicable in the field of dentistry.
  • it can be used for dental restorative materials or fillers, and more specifically dental adhesives, orthodontic adhesives, composites, temporary restorative materials, indirect restorative materials, dental cements, orthodontic cements, sealants, coatings, impression materials, Materials or combinations thereof.
  • the present invention provides a molded article (e.g., a dental molded article such as a restorative material such as an artificial tooth, a denture, etc.) formed by printing the above-described photo-curable resin composition in a three-dimensional shape using a 3D printer.
  • a molded article is excellent in aesthetic and mechanical properties (for example, bending strength (bending strength), etc.) by using a photocurable composition in which the mixing ratio between the (meth) acrylate modified siloxane resin, the urethane (meth) acrylate oligomer and the di , Flexural modulus, shore D hardness, etc.).
  • the dental molding has a Shore D hardness D 80 to 90 according to the ISO 868: 2003 test method, a bending strength according to the ISO 10477: 2003 test method of 85 MPa or more, and the ISO 10477: 2033 test method
  • the flexural modulus of elasticity is 2.1 MPa or more.
  • the dental molding has a toughness of 5 or more according to the ASTM D638 test method, and does not cause yellowing.
  • Such a molded article can be produced by a 3D printer method.
  • a 3D printer method For example, after patient teeth are scanned, they are designed and corrected using a dental CAD / CAM program, and then the photocurable dental resin composition is printed (laminated) through a 3D printer based on the design, And the curing process is repeatedly carried out to produce an artificial tooth having a three-dimensional shape.
  • the 3D printer is generally operated according to a digital light process method or a stereolithography method.
  • the work model After the work model is scanned, it is designed and corrected using a CAD / CAM program. Then, the process of printing the photocurable composition prepared in the above 1-1 with a 3D printer and then hardening (solidifying) .
  • a photo-curable composition and a molded article were prepared in the same manner as in Example 1, except that the compositions shown in Table 2 were used.
  • each component content unit of the composition is% by weight based on the total weight of the composition.
  • UDMA urethane dimethacrylate - Viscosity (25 ° C): 8,200 cps, MW: 470
  • TEGDMA triethylene glycol dimethacrylate - Viscosity (25 ° C): 10 cps, MW: 286
  • Photopolymerization initiator Bis (2,4,6-trimethylbenzoyl) -phenylphosphineoxide - MW: 418
  • Coupling agent 1 neopentyl (diallyl) oxytri (dioctyl) pyro-phosphato titanate (neopentyl
  • Coupling agent 2 Neopentyldialyloxy-tri (n-ethylenediamino) ethyl zirconate (neopentyl (diallyl) oxy tri (N-ethylenediamino) ethyl zirconate)
  • the molded article of Example 1-12 had a Shore D hardness of 85-93, a flexural strength of 88-96 MPs, a flexural modulus of 2.5-3.2 MPa, a tensile strength of 6-9 MPs, E) was measured as 2.1-2.4. That is, the molded article produced from the photo-curing composition according to the present invention has a desired physical property (Shore D hardness: 80-95, bending strength: 85 MPa or more, flexural modulus: 2.1 MPa or more, tensile strength: 5 MPs or more , And yellowing ( ⁇ E): 2.5 or less). On the other hand, the molded articles of Comparative Examples 1-5 all suffered yellowing, and did not satisfy the target properties required in the art in at least one of Shore D hardness, bending strength and tensile strength.
  • the present invention provides a photocurable composition having a low viscosity and a high curing speed and exhibiting excellent aesthetics and mechanical properties.
  • the photocurable composition of the present invention is capable of producing a molded article having excellent workability and productivity at the time of production of a molded article, and having excellent aesthetics and mechanical properties.
  • the photocurable composition according to the present invention is applicable to the manufacture of a dental molding.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Animal Behavior & Ethology (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Dentistry (AREA)
  • Materials Engineering (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Dental Preparations (AREA)

Abstract

La présente invention concerne une composition photodurcissable et un article moulé fabriqué à l'aide de celle-ci. La composition photodurcissable comprend une résine de siloxane (méth) acrylate modifiée, un oligomère d'uréthane (méth) acrylate, un monomère réactif à base de di (méth) acrylate et un initiateur de photopolymérisation.
PCT/KR2018/016576 2017-12-29 2018-12-24 Composition photodurcissable et article moulé fabriqué à l'aide de celle-ci WO2019132472A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020170184739A KR102020131B1 (ko) 2017-12-29 2017-12-29 광경화성 조성물 및 이를 이용하여 제조된 성형품
KR10-2017-0184739 2017-12-29

Publications (1)

Publication Number Publication Date
WO2019132472A1 true WO2019132472A1 (fr) 2019-07-04

Family

ID=67067872

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/016576 WO2019132472A1 (fr) 2017-12-29 2018-12-24 Composition photodurcissable et article moulé fabriqué à l'aide de celle-ci

Country Status (2)

Country Link
KR (1) KR102020131B1 (fr)
WO (1) WO2019132472A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110294817A (zh) * 2019-07-23 2019-10-01 杭州天地数码科技股份有限公司 有机硅改性丙烯酸酯乳液及其制备方法、热转印背涂液、热转印碳带背涂层及碳带
CN115835851A (zh) * 2020-08-26 2023-03-21 Ods株式会社 人工牙成型组合物、人工牙的制作方法及根据该方法制作的人工牙
WO2023179286A1 (fr) * 2022-03-22 2023-09-28 广州黑格智造信息科技有限公司 Matériau d'impression 3d photodurcissable utilisé pour un modèle dentaire, et son procédé de préparation
US11932697B2 (en) 2016-11-28 2024-03-19 Chugai Seiyaku Kabushiki Kaisha Antigen-binding domain, and polypeptide including conveying section
US12030955B2 (en) 2017-11-28 2024-07-09 Chugai Seiyaku Kabushiki Kaisha Polypeptide including antigen-binding domain and carrying section
US12060654B2 (en) 2016-11-28 2024-08-13 Chugai Seiyaku Kabushiki Kaisha Ligand-binding molecule having adjustable ligand binding activity
JP7564627B2 (ja) 2020-02-14 2024-10-09 エア・ウォーター株式会社 歯科用光硬化性組成物

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102539486B1 (ko) * 2020-06-29 2023-06-05 에이온 주식회사 3d 프린팅 시스템에서 소성 공정을 고려한 3d 모델 데이터를 결정하기 방법 및 장치

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030236342A1 (en) * 2000-06-13 2003-12-25 Dentsply Research & Development Corp. Low shrinking polymerizable dental material
JP2015086363A (ja) * 2013-09-27 2015-05-07 株式会社リコー 活性エネルギー線硬化型組成物、その硬化物、該組成物を収容した容器、および該容器を備えるインクジェット吐出装置
KR20150065659A (ko) * 2012-07-06 2015-06-15 메르츠 덴탈 게엠베하 중합성 혼합 조성물, 이 혼합 조성물의 사용, 및 치과 보철물
KR20160087151A (ko) * 2015-01-13 2016-07-21 한국전자통신연구원 치과 임플란트 시술용 가이드의 3차원 조형을 위한 조성물
JP2016525150A (ja) * 2014-01-13 2016-08-22 デンカ インク 光硬化性樹脂組成物ならびに人工歯および義歯床を製造するための３次元印刷におけるその使用方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY148595A (en) * 2009-06-12 2013-05-15 Univ Malaya Polyurethane oligomers for use in restorative dentistry
CN104853693B (zh) * 2012-11-14 2018-06-26 邓特斯普里国际公司 用于生产牙科产品的三维制作材料体系
KR101579055B1 (ko) * 2013-12-17 2015-12-21 주식회사 바이오세텍 치과용 세라믹-레진 하이브리드 블록의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030236342A1 (en) * 2000-06-13 2003-12-25 Dentsply Research & Development Corp. Low shrinking polymerizable dental material
KR20150065659A (ko) * 2012-07-06 2015-06-15 메르츠 덴탈 게엠베하 중합성 혼합 조성물, 이 혼합 조성물의 사용, 및 치과 보철물
JP2015086363A (ja) * 2013-09-27 2015-05-07 株式会社リコー 活性エネルギー線硬化型組成物、その硬化物、該組成物を収容した容器、および該容器を備えるインクジェット吐出装置
JP2016525150A (ja) * 2014-01-13 2016-08-22 デンカ インク 光硬化性樹脂組成物ならびに人工歯および義歯床を製造するための３次元印刷におけるその使用方法
KR20160087151A (ko) * 2015-01-13 2016-07-21 한국전자통신연구원 치과 임플란트 시술용 가이드의 3차원 조형을 위한 조성물

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11932697B2 (en) 2016-11-28 2024-03-19 Chugai Seiyaku Kabushiki Kaisha Antigen-binding domain, and polypeptide including conveying section
US12060654B2 (en) 2016-11-28 2024-08-13 Chugai Seiyaku Kabushiki Kaisha Ligand-binding molecule having adjustable ligand binding activity
US12030955B2 (en) 2017-11-28 2024-07-09 Chugai Seiyaku Kabushiki Kaisha Polypeptide including antigen-binding domain and carrying section
CN110294817A (zh) * 2019-07-23 2019-10-01 杭州天地数码科技股份有限公司 有机硅改性丙烯酸酯乳液及其制备方法、热转印背涂液、热转印碳带背涂层及碳带
JP7564627B2 (ja) 2020-02-14 2024-10-09 エア・ウォーター株式会社 歯科用光硬化性組成物
CN115835851A (zh) * 2020-08-26 2023-03-21 Ods株式会社 人工牙成型组合物、人工牙的制作方法及根据该方法制作的人工牙
WO2023179286A1 (fr) * 2022-03-22 2023-09-28 广州黑格智造信息科技有限公司 Matériau d'impression 3d photodurcissable utilisé pour un modèle dentaire, et son procédé de préparation

Also Published As

Publication number Publication date
KR20190088097A (ko) 2019-07-26
KR102020131B1 (ko) 2019-09-09

Similar Documents

Publication Publication Date Title
WO2019132472A1 (fr) Composition photodurcissable et article moulé fabriqué à l'aide de celle-ci
WO2019132473A1 (fr) Composition photodurcissable et article moulé fabriqué en faisant appel à celle-ci
WO2020080643A1 (fr) Composition photodurcissable pour imprimante 3d pour produire un dispositif orthodontique transparent
US10973742B2 (en) Photocurable composition, denture base, and plate denture
TWI685519B (zh) 光硬化性組成物、假牙床及有床假牙
WO2022124509A1 (fr) Appareil orthodontique transparent ayant une meilleure aptitude à la correction
WO1992016183A1 (fr) Utilisation de compositions a base de polycondenses d'acide silicique organiquement modifies pour le revetement de dents et de protheses dentaires
JPH02178205A (ja) 可視光硬化性歯科用組成物
JPH07258018A (ja) 歯科用材料として用いられる熱硬化可能な組成物
JP2003507499A (ja) 可視光を用いて架橋する組成物およびその使用
WO2020040414A1 (fr) Composition de polymère durcissable par rayonnement pour imprimante 3d
JPH1045521A (ja) 歯科用材料
WO2018181832A1 (fr) Composition photodurcissable, base pour prothèse dentaire, et dentier
WO2020166869A1 (fr) Composite dentaire comprenant du verre cristallisé
KR101517628B1 (ko) 개선된 치과용 복합재를 유도하는 재료 및 그로부터 제조된 치과용 복합재
CA2099221C (fr) Materiau dentaire
CN114344171B (zh) 一种义齿修复用双组份缩合型室温快速固化硅橡胶
EP4188971A1 (fr) Composition de fabrication additive pour objet imprimé en 3d
WO2016171303A1 (fr) Composition de matériau d'empreinte dentaire présentant de bonnes performances de balayage et des propriétés mécaniques, et matériau d'empreinte dentaire comprenant la composition
WO2023190071A1 (fr) Composition de photodurcissable, article de forme tridimensionnelle, moule, procédé de fabrication de produit durci, et procédé de fabrication de prothèse dentaire à plaque
WO2023204416A1 (fr) Procédé de fabrication d'un plateau de blanchiment transparent
WO2020262814A1 (fr) Ébauche de composite dentaire et procédé de fabrication associé
WO2018169309A2 (fr) Émulsion, son procédé de production et procédé de formation d'une couche de revêtement l'utilisant
KR20190001794A (ko) 광경화성 조성물 및 이를 이용하여 제조된 성형품
KR20190001784A (ko) 광경화성 조성물 및 이를 이용하여 제조된 성형품

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18897341

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18897341

Country of ref document: EP

Kind code of ref document: A1