WO2023163241A1 - Composition de photodurcissement pour imprimante 3d et procédé de préparation associé - Google Patents

Composition de photodurcissement pour imprimante 3d et procédé de préparation associé Download PDF

Info

Publication number
WO2023163241A1
WO2023163241A1 PCT/KR2022/002635 KR2022002635W WO2023163241A1 WO 2023163241 A1 WO2023163241 A1 WO 2023163241A1 KR 2022002635 W KR2022002635 W KR 2022002635W WO 2023163241 A1 WO2023163241 A1 WO 2023163241A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
substituted
carbon atoms
unsubstituted
formula
Prior art date
Application number
PCT/KR2022/002635
Other languages
English (en)
Korean (ko)
Inventor
김훈
심운섭
Original Assignee
주식회사 그래피
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 주식회사 그래피 filed Critical 주식회사 그래피
Priority to PCT/KR2022/002635 priority Critical patent/WO2023163241A1/fr
Publication of WO2023163241A1 publication Critical patent/WO2023163241A1/fr

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C7/00—Orthodontics, i.e. obtaining or maintaining the desired position of teeth, e.g. by straightening, evening, regulating, separating, or by correcting malocclusions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B29C64/129—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 characterised by the energy source therefor, e.g. by global irradiation combined with a mask
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/08—Anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08K3/34—Silicon-containing compounds

Definitions

  • the present invention relates to a photocurable composition for a 3D printer and a method for producing the same, and more particularly, to a photocurable composition capable of producing an output product using a DLP-type 3D printer and a method for producing the same.
  • 3D printing is a process technology that outputs a three-dimensional shape by repeatedly stacking two-dimensional cross sections using digitally designed data. Design design or modification is very free, and the cost and time required for prototyping can be greatly reduced.
  • 3D printing technology since even products with complex shapes can be easily produced, the types of products that can be produced using 3D printing technology can be said to be virtually endless. As a result, 3D printing technology is expected to lead industrial innovation by changing the paradigm of technology in many fields such as manufacturing, medical, and IT fields.
  • 3D printer technology can be divided into photocuring lamination method, laser sintering lamination method, resin extrusion lamination method, inkjet lamination method, polyjet lamination method, and thin film lamination method according to the material.
  • the double photocuring lamination method is a method of manufacturing a molded product by curing a photo curing resin with a laser beam or strong ultraviolet (UV, Ultraviolet ray). , SLA) and digital light processing (DLP).
  • UV ultraviolet
  • SLA strong ultraviolet
  • DLP digital light processing
  • the photocurable lamination method has excellent surface roughness and can be used in the medical field where it is necessary to manufacture a molded product with a complex shape.
  • Patent Document 1 KR 10-2020-0120992
  • An object of the present invention is to provide a photocurable composition for a 3D printer and a method for producing the same.
  • Another object of the present invention is to further include nano-clay in the photocurable composition for 3D printers to enhance the mechanical properties of the output printed by 3D printing and to maintain a viscosity capable of 3D printing.
  • a photocurable composition for 3D printers is to provide
  • Another object of the present invention is to provide a manufacturing method capable of preparing a photocurable composition capable of 3D printing by uniformly distributing nano-clay in the photocurable composition.
  • Another object of the present invention is to apply 3D printing technology, can be output and manufactured in a form suitable for the patient's oral structure, can increase the corrective force due to excellent mechanical properties, and can change and restore the shape when heat is provided It can be provided as a transparent orthodontic appliance capable of exhibiting a high orthodontic effect.
  • a photocurable composition for a 3D printer includes a photocurable oligomer; reactive monomers; photoinitiators; and nano-clay, wherein the nano-clay may enhance mechanical properties of an output product output by 3D printing due to an interaction between a reactive monomer and electrical attraction.
  • the nano-clay is sepiolite, and the sepiolite is in the form of a single fiber, has an average length of 0.2 to 4 ⁇ m, a width of 10 to 30 nm, and an average thickness of 5 to 10 nm.
  • the photocurable oligomer is a compound represented by Formula 1 below:
  • n is an integer from 1 to 1,000;
  • A is a compound represented by Formula 2 or Formula 3,
  • R 1 to R 6 are the same as or different from each other, and each independently represents hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted cyclo group having 1 to 20 carbon atoms.
  • the silyl group and the substituted aryloxy group are hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxy group, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 30 carbon atoms, and 2 to 24 carbon atoms.
  • alkynyl group aralkyl group having 7 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms, heteroaryl group having 5 to 60 nuclear atoms, heteroarylalkyl group having 6 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, and 1 carbon atom to 30 alkylamino groups, C6-30 arylamino groups, C6-30 aralkylamino groups, C2-24 heteroarylamino groups, C1-30 alkylsilyl groups, C6-30 arylsilyl groups, and It is substituted with one or more substituents selected from the group consisting of aryloxy groups having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, they are the same as or different from each other.
  • the reactive monomer is an acrylate-based monomer.
  • a transparent orthodontic device includes the photocurable composition for the 3D printer.
  • a method for preparing a photocurable composition for a 3D printer includes: 1) mixing and stirring at least one reactive monomer; 2) preparing a first mixture by adding nanoclay to the reactive monomer, pulverizing and dispersing; 3) preparing a second mixture by adding a photocurable oligomer heated in an oven at 50 to 70° C. for 10 to 15 hours into the first mixture; and 4) adding a photoinitiator to the second mixture, mixing, and defoaming.
  • the present invention further comprises a nano-clay in the photocurable composition for a 3D printer, is uniformly distributed, enhances mechanical properties of the output printed by 3D printing, and maintains a viscosity capable of 3D printing.
  • a photocurable type for a 3D printer. Compositions and methods for their preparation.
  • the photocurable composition by 3D printing using the photocurable composition, it can be output and manufactured in a form suitable for the oral structure of the patient, and the mechanical properties are excellent to increase the corrective force, and when heat is provided, the change and restoration of the shape It is possible to provide a transparent orthodontic appliance capable of exhibiting a high orthodontic effect.
  • 1 is an evaluation result for storage stability of a photocurable composition according to an embodiment of the present invention.
  • 3 relates to the structure of sepiolite according to an embodiment of the present invention.
  • FIG. 4 is a schematic view of the content of sepiolite and its alignment according to an embodiment of the present invention.
  • the present invention relates to a photocurable composition for a 3D printer and a method for preparing the same, including a photocurable oligomer; reactive monomers; photoinitiators; and a nano-clay, wherein the nano-clay relates to a photocurable composition for a 3D printer capable of enhancing mechanical properties of an output product output by 3D printing due to an interaction between a reactive monomer and electrical attraction.
  • 3D printing of the present invention refers to a process of manufacturing a three-dimensional object by laminating materials using 3D digital data.
  • DLP Device Light Processing
  • SLA Stepo Lithography Apparatus
  • PolyJet method PolyJet method
  • the photocurable composition of the present invention is a material that is cured by light irradiation, and refers to a polymer that is crosslinked and polymerized into a polymer network structure.
  • the description is centered on UV light, but it is not limited to UV light and can be applied to other lights as well.
  • a photocurable composition for a 3D printer includes a photocurable oligomer; reactive monomers; photoinitiators; and nano-clay, wherein the nano-clay may enhance mechanical properties of an output product output by 3D printing due to an interaction between a reactive monomer and electrical attraction.
  • the nano-clay is characterized in that it is sepiolite, but the nano-clay is not limited to sepiolite, and any nano-clay that can be included in a photocurable composition for a 3D printer to enhance mechanical properties is not limited thereto. Available.
  • Polymer composite technology can be applied to overcome the limitations of mechanical strength of 3D printing materials.
  • 3D printing materials there are several problems in applying the composite material to 3D printing.
  • the most important issue is the size of additives used in composite materials. As the size of the additive increases, the size of the printing gap also increases, and as a result, a problem of lowering the printing resolution may occur.
  • nano-sized materials may be used as additives.
  • graphene, carbon nanotube (CNT), etc. which are conventionally known as nano-sized materials
  • price competitiveness may be a problem.
  • nanoclay has a reasonable price, making it more suitable for industrial applications.
  • sepiolite is a hydrated magnesium silicate with a half unit cell formula of Mg 8 Si 12 O 30 (OH) 4 .12H 2 O.
  • the sepiolite has a cross-sectional chemical structure as shown in FIG. 2 and a lettis crystal form as shown in FIG. 3. More specifically, it is a needle-like or fiber-like shape composed of several blocks and tunnels parallel to the fiber direction. Each structural block contains a central octahedral magnesium (MgOH 6 ) sheet sandwiched between two tetrahedral silica (SiO 4 ) sheets.
  • MgOH 6 octahedral magnesium
  • SiO 4 tetrahedral silica
  • the viscosity of the photocurable composition increases, and when the viscosity increases, the composition cannot be manufactured as an output product through a 3D printer.
  • the nano-clay is included in a certain amount or more, the mechanical strength of the output may increase.
  • the viscosity of the photocurable composition is preferably included within a certain range.
  • the photocurable composition may include 0.5 to 5 parts by weight of nanoclay and 1 part by weight of a photoinitiator based on 100 parts by weight of the UV resin.
  • the UV resin includes a photocurable oligomer and a reactive oligomer. When mixed and used within the above range, not only can it be manufactured as an output using a 3D printer, but also the manufactured output can exhibit excellent mechanical strength. More specifically, the 3D printer is a DLP type 3D printer.
  • the photocurable oligomer may be a compound represented by Formula 1 below:
  • n is an integer from 1 to 1,000;
  • A is a compound represented by Formula 2 or Formula 3,
  • R 1 to R 6 are the same as or different from each other, and each independently represents hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted cyclo group having 1 to 20 carbon atoms.
  • the silyl group and the substituted aryloxy group are hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxy group, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 30 carbon atoms, and 2 to 24 carbon atoms.
  • alkynyl group aralkyl group having 7 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms, heteroaryl group having 5 to 60 nuclear atoms, heteroarylalkyl group having 6 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, and 1 carbon atom to 30 alkylamino groups, C6-30 arylamino groups, C6-30 aralkylamino groups, C2-24 heteroarylamino groups, C1-30 alkylsilyl groups, C6-30 arylsilyl groups, and It is substituted with one or more substituents selected from the group consisting of aryloxy groups having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, they are the same as or different from each other.
  • R 1 to R 6 are the same as or different from each other, and may be each independently selected from the group consisting of hydrogen, heavy hydrogen, a hydroxyl group, and an alkyl group having 1 to 30 carbon atoms.
  • the photocurable oligomer is a compound represented by Formula 1, and includes both a compound in which A is selected from Formula 2 and a compound in which A is selected from Formula 3.
  • it is a polymer compound to which a photocurable functional group is bound for UV curing, and includes a double bond structure between carbons, and a photocurable action can be exhibited by the carbon-carbon double bond.
  • the photocurable oligomer includes a polyurethane structure as a main chain, a photocurable functional group is bonded to the polyurethane structure, and a soft functional group and a hard functional group are included in the compound.
  • a print may exhibit flexible properties due to the soft functional group included in the photocurable composition, and may exhibit heat resistance due to the hard functional group.
  • a flexible effect can be exhibited by using a carbon skeleton having a soft property at room temperature, and a hard property at room temperature.
  • the carbon skeleton having a carbon skeleton it is possible to exhibit a property that is resistant to heat.
  • the photocurable oligomer includes a carbon skeleton having a hard property, it is possible to manufacture a 3D printed output having excellent physical properties such as thermal properties, strength, modulus of elasticity and tensile elongation, and which can be restored to its original shape by heat. there is.
  • the photocurable oligomer since the photocurable oligomer includes a carbon skeleton having a soft property, the shape can be deformed by an external force after heat is applied.
  • a composition for a 3D printer includes only a carbon skeleton having a hard property in order to increase the physical properties of an output product, which can increase the physical properties of an output product, but on the contrary, when the shape is deformed by use, the shape Since it cannot be restored, there is a problem that it cannot be used multiple times.
  • composition for a 3D printer in the present invention includes a carbon skeleton having a hard property and a carbon skeleton having a soft property, not only excellent physical properties such as thermal properties, strength, elastic modulus and tensile elongation, but also a soft functional group
  • the flexible property of can be used together, so that if the shape is deformed by an external force in a state where heat is applied, the deformed shape can be fixed, and then when heat is provided again, it is possible to restore the original shape.
  • the photocurable composition for a 3D printer of the present invention can be used as a transparent orthodontic device, and the transparent orthodontic device is used to straighten teeth to a desired position while being fitted to a patient's teeth.
  • the transparent orthodontic device output by the 3D printer must exhibit physical characteristics that will not be damaged against the resistance at the current position of the patient's teeth, and must be able to provide force to move the teeth to the position to be corrected.
  • the correction effect and the correction principle of the transparent orthodontic appliance of the present invention will be described later.
  • the photocurable composition for 3D printers of the present invention contains both soft functional groups and hard functional groups in the photocurable oligomer, so that it has excellent physical properties and is capable of shape deformation in a state where heat is applied.
  • the photocurable composition additionally includes nano-clay, so that physical properties can be supplemented to exhibit high corrective power.
  • the reactive monomer is an acrylate-based monomer.
  • the acrylate-based monomer may be selected from the group consisting of a compound represented by Chemical Formula 4, a compound represented by Chemical Formula 5, and a mixture thereof:
  • the transparent orthodontic appliance according to another embodiment of the present invention may include the photocurable composition for the 3D printer.
  • the transparent orthodontic device of the present invention is output by 3D printing using a photocurable composition, and unlike conventional transparent orthodontic devices, it is possible to precisely reproduce the curved surface of teeth, and the orthodontic effect is excellent because of its high adhesion to the teeth. .
  • the transparent orthodontic device of the present invention is manufactured by obtaining data on the patient's tooth structure and outputting it, and can be manufactured with almost no difference with the tooth structure and deviation of 50 to 80 ⁇ m, whereas the conventional transparent orthodontic device The deviation from the patient's teeth appears to be 200 to 300 ⁇ m, so the orthodontic force is poor because it cannot be closely adhered to.
  • the transparent orthodontic device of the present invention is heated to 40 ° C. or higher, and then inserted into the patient's teeth and fixed in shape in close contact with the teeth, and the transparent orthodontic device in close contact with the teeth is restored to its original shape by body temperature to straighten teeth
  • the transparent orthodontic device of the present invention can be deformed in shape by putting it in and out of heated water. When heat is applied, flexibility appears for a certain period of time, and shape deformation is possible. Using this property, the transparent orthodontic appliance is immersed in water at 60 to 100 ° C. before being inserted into the patient's teeth, then taken out and inserted into the teeth. Then, if you simply press it with your hand, the shape is deformed into a form that closely adheres to the teeth.
  • the transparent orthodontic device of the present invention is transformed in shape according to the current patient's tooth structure, and then When heat is provided by body temperature, the original output form is gradually restored, and at this time, the transparent orthodontic appliance moves the teeth to the position to be corrected by the force to restore the original shape.
  • the conventional orthodontic device is manufactured as a transparent orthodontic device according to the position of the tooth to be corrected step by step from information obtained from the patient's tooth structure, and then inserted into the tooth to move the tooth by the nature of the hard material. .
  • the conventional transparent orthodontic device moves the teeth due to the nature of the material, and does not provide a uniform force within the teeth, so the orthodontic effect is reduced.
  • the transparent orthodontic device of the present invention is in a state in which the transparent orthodontic device is deformed to the same structure as the teeth when first used, but when heat is provided by body temperature, the transparent orthodontic device is originally It is restored to the shape of the tooth, and the force transmitted to the tooth is not the force of the material of the orthodontic device, but the force generated and transmitted by the restoration of the shape. provided, and the tooth becomes movable as a whole.
  • a method for preparing a photocurable composition for a 3D printer includes: 1) mixing and stirring at least one reactive monomer; 2) preparing a first mixture by adding nanoclay to the reactive monomer, pulverizing and dispersing; 3) preparing a second mixture by adding a photocurable oligomer heated in an oven at 50 to 70° C. for 10 to 15 hours into the first mixture; and 4) adding a photoinitiator to the second mixture, mixing, and defoaming.
  • Step 1) is a step of mixing and stirring a reactive monomer, mixing and stirring a compound represented by Formula 4 and a compound represented by Formula 5 below:
  • the reactive monomers are mixed in the same weight ratio and stirred. Thereafter, the nanoclay is added to the mixture in which the reactive monomer is mixed, and pulverized and dispersed to prepare a first mixture.
  • the first mixture is a form in which nanoclay is uniformly dispersed, and more specifically, a grinding and dispersing process is performed for 30 seconds to 90 seconds at an output of 700 to 800 w using a tip sonicator.
  • a grinding and dispersing process is performed for 30 seconds to 90 seconds at an output of 700 to 800 w using a tip sonicator.
  • the nanoclay is not uniformly dispersed and the dispersion stability is deteriorated, so that the first mixture is layer-separated over time. That is, when dispersing by the above dispersing method, it is not only uniformly dispersed, but also exhibits excellent stability.
  • a photocurable oligomer heated in an oven at 50 to 70° C. for 10 to 15 hours is added to the first mixture to prepare a second mixture. Since the photocurable oligomer has a high viscosity and is difficult to mix at room temperature, it is mixed by heating in an oven.
  • a photoinitiator is added and mixed and defoamed using a paste mixer to prepare a photocurable composition.
  • the photoinitiator is a compound represented by Formula 6 below:
  • the photocurable composition may include a photocurable oligomer; reactive monomers; photoinitiators; And in addition to the nano-clay, additives may be included, for example, a leveling agent, a slip agent, or a stabilizer to improve thermal and oxidative stability, storage stability, surface properties, flow properties, and process properties. Conventional additives may be included.
  • the photocurable composition according to an embodiment of the present invention may include 0.5 to 5 parts by weight of nanoclay and 1 part by weight of a photoinitiator based on 100 parts by weight of the UV resin.
  • the UV resin is a photocurable oligomer of the present invention; and a reactive monomer, more specifically, a compound in which A is selected from Formula 2 among compounds represented by Formula 1 below, a compound in which A is selected from Formula 3 among compounds represented by Formula 1 below, and a compound represented by Formula 4 below
  • the compound and the compound represented by Formula 5 may be included in a weight ratio of 1:1:1:1 to 1:2:1:1:
  • n is an integer from 1 to 1,000;
  • A is a compound represented by Formula 2 or Formula 3,
  • R 1 to R 6 are the same as or different from each other, and each independently represents hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted cyclo group having 1 to 20 carbon atoms.
  • the silyl group and the substituted aryloxy group are hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxy group, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 30 carbon atoms, and 2 to 24 carbon atoms.
  • alkynyl group aralkyl group having 7 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms, heteroaryl group having 5 to 60 nuclear atoms, heteroarylalkyl group having 6 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, and 1 carbon atom to 30 alkylamino groups, C6-30 arylamino groups, C6-30 aralkylamino groups, C2-24 heteroarylamino groups, C1-30 alkylsilyl groups, C6-30 arylsilyl groups, and It is substituted with one or more substituents selected from the group consisting of aryloxy groups having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, they are the same as or different from each other.
  • the monomers represented by Chemical Formulas 4 and 5 were mixed in a weight ratio of 1:1, sepiolite was added, and then pulverized and dispersed for 1 minute at 750w output using a tip sonicator. Thereafter, the photocurable oligomer having fluidity was mixed by heating in an oven at 60° C. for 12 hours.
  • the photocurable oligomer is a compound represented by Formula 1 below, including both a compound in which A is selected from Formula 2 and a compound in which A is selected from Formula 3, and a compound selected from Formula 2 and a compound selected from Formula 3 in a weight ratio of 1:1.5.
  • a photoinitiator represented by Formula 6 was mixed, and mixed and defoamed using a paste mixer.
  • n is an integer from 1 to 1,000;
  • R 1 to R 6 are methyl groups.
  • the weight ratio with respect to the photocurable composition is as follows.
  • composition sample name sepiolite UV resin photoinitiator 100 One DLP Sep-0 0 DLP Sep-0.5 0.5 DLP Sep-1 One DLP Sep-2 2 DLP Sep-3 3 DLP Sep-5 5
  • the UV resin includes a photocurable oligomer and a monomer, wherein A in Formula 1 is a compound selected from Formula 2, a compound selected from Formula 3, a monomer represented by Formula 4, and a compound represented by Formula 5 Monomers are included in a weight ratio of 1:1.5:1:1.
  • DLP Sep-0.5, DLP Sep-1, DLP Sep-2, DLP Sep-3, and DLP Sep-5 do not cause layer separation even after 3 days and remain stable.
  • Sepiolite is a type of clay, and it is not easy to disperse with monomers, and there is a problem of poor storage stability even after dispersion.
  • the pulverization and dispersion process is performed using the tips sonic equipment, it is not only uniformly dispersed, but also exhibits excellent stability even during long-term storage.
  • the tensile strength of the composite samples was measured using UTM (AllroundLine Z010, Zwick, Germany) to confirm the change in material properties and 3D printing effect as the SEP content and printing method increased. A crosshead speed of 5 mm/min was used during the measurement and the mechanical properties were analyzed at room temperature (RT, ⁇ 20 °C). Seven samples of each configuration were measured to calculate the margin of error.
  • a rheometer (MCR 302, Anton Paar Ltd., Austria) was used to measure the rheological properties of the photocurable composition.
  • the disposable parallel plate had a diameter of 25 mm, an experimental temperature of 25 °C, a plate interval of 100 ⁇ m, and a shear rate of 0.1 to 100 rad/s.
  • the rheological behavior before curing as the content of sepiolite increases is shown in FIG. 5 .
  • the viscosity of the composition increased, but shear thinning behavior began as the deformation increased.
  • sepiolite when it is included in 0.5 and 1 part by weight, no interference occurs even when both ends of the sepiolite rotate in any direction.
  • the sepiolite particles when included in an amount of 1 part by weight or more, a nanostructure was formed at a moment above a critical value for rheological permeation and aligned under shear force.
  • the photocurable composition comprising 5 parts by weight of sepiolite showed a critical point for entanglement and started to exhibit a clear shear thinning behavior.
  • the yield characteristics play an important role in maintaining the shape of the output.
  • the photocurable composition for 3D printing of the DLP method must flow in a liquid state. Otherwise, it cannot be printed in the DLP printing environment. Therefore, since the viscosity increases as the content of sepiolite increases, it is necessary to check the yield characteristics.
  • the shear modulus and viscosity of the photocurable composition according to an embodiment of the present invention vary not only by the content of sepiolite but also by shear stress and time, which can be confirmed through FIG. 7 .
  • the correlation between sepiolite content, stress and time is fluid as shown in FIG. 7 .
  • the storage modulus decreases during a shear force of 300 Pa, but recovers at a shear force of 0.5 pa. However, during the test process, the loss coefficient of the sample maintained a higher value than the storage coefficient.
  • An MCR 302 rheometer (Anton Paar Ltd., Austria) was used to measure the change in rheological properties during the curing behavior of the photocurable composition.
  • the diameter of the disposable parallel plates is 12 mm
  • the experimental temperature is 25 °C
  • the plate spacing is 100 ⁇ m
  • the shear rate is 0.01%
  • the radian is 10 rad/s.
  • An LED with a wavelength of 365 nm was used at an intensity of 15 mW/cm 2 .
  • the plate was vibrated for 30 seconds, then irradiated for 300 seconds, and at the same time, a force of 0.1 N was applied to measure the degree of shrinkage of the material while moving the plate.
  • the rheological behavior of the material was observed while irradiating with 385 nm UV. 8 is a result of monitoring the storage modulus change of the photocurable composition during the curing process. After stabilizing the composition for 30 seconds, UV irradiation was performed.
  • a photocurable composition to which nanomaterials are added tends to cure slowly because the nanomaterials absorb UV rays. If the photocuring behavior is delayed by sepiolite, a problem of applying different printing conditions for each sample may occur.
  • composition of the present invention increased the storage modulus of all samples 5 seconds after UV irradiation started.
  • the photocurable composition of the present invention can have improved mechanical properties and can change the mechanical properties depending on the purpose and use.
  • the present invention relates to a photocurable composition for a 3D printer and a method for producing the same, and more particularly, to a photocurable composition capable of producing an output product using a DLP-type 3D printer and a method for producing the same.

Landscapes

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

Abstract

La présente invention concerne une composition de photodurcissement pour imprimante 3D et un procédé de préparation associé, la composition de photodurcissement pour imprimante 3D comprenant en outre une nanoargile, uniformément répartie de façon à renforcer les propriétés mécaniques d'une sortie imprimée par impression 3D et permettant de maintenir une viscosité imprimable par 3D. En outre, la composition de photodurcissement est utilisée pour impression 3D de façon à être délivrée et fabriquée sous une forme convenant à la structure buccale d'un patient, présente des propriétés mécaniques considérables de telle sorte que la force orthodontique peut être augmentée et, pendant la fourniture de chaleur, permet un changement et une restauration des formes de façon à offrir un dispositif orthodontique transparent susceptible de produire un effet orthodontique amélioré.
PCT/KR2022/002635 2022-02-23 2022-02-23 Composition de photodurcissement pour imprimante 3d et procédé de préparation associé WO2023163241A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/KR2022/002635 WO2023163241A1 (fr) 2022-02-23 2022-02-23 Composition de photodurcissement pour imprimante 3d et procédé de préparation associé

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/KR2022/002635 WO2023163241A1 (fr) 2022-02-23 2022-02-23 Composition de photodurcissement pour imprimante 3d et procédé de préparation associé

Publications (1)

Publication Number Publication Date
WO2023163241A1 true WO2023163241A1 (fr) 2023-08-31

Family

ID=87766294

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2022/002635 WO2023163241A1 (fr) 2022-02-23 2022-02-23 Composition de photodurcissement pour imprimante 3d et procédé de préparation associé

Country Status (1)

Country Link
WO (1) WO2023163241A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100761426B1 (ko) * 2006-05-29 2007-10-04 주식회사 대하맨텍 광경화형 하드코팅 조성물 및 그 제조방법, 광경화형하드코팅 조성물이 코팅된 이동통신 단말기 윈도우,평판디스플레이용 전면판 및 필름
KR20190107737A (ko) * 2017-02-02 2019-09-20 이머리스 탈크 아메리카, 인코포레이티드 3d 프린팅으로 제작된 플라스틱 부품의 인터-로드 접착 및 융합의 개선
KR20200046153A (ko) * 2018-10-16 2020-05-07 주식회사 그래피 투명교정장치의 제조를 위한 3d 프린터용 광경화형 조성물
KR20220112393A (ko) * 2021-02-04 2022-08-11 주식회사 그래피 3d 프린터용 광경화형 조성물 및 이의 제조 방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100761426B1 (ko) * 2006-05-29 2007-10-04 주식회사 대하맨텍 광경화형 하드코팅 조성물 및 그 제조방법, 광경화형하드코팅 조성물이 코팅된 이동통신 단말기 윈도우,평판디스플레이용 전면판 및 필름
KR20190107737A (ko) * 2017-02-02 2019-09-20 이머리스 탈크 아메리카, 인코포레이티드 3d 프린팅으로 제작된 플라스틱 부품의 인터-로드 접착 및 융합의 개선
KR20200046153A (ko) * 2018-10-16 2020-05-07 주식회사 그래피 투명교정장치의 제조를 위한 3d 프린터용 광경화형 조성물
KR20220112393A (ko) * 2021-02-04 2022-08-11 주식회사 그래피 3d 프린터용 광경화형 조성물 및 이의 제조 방법

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DAPAWAN KUNWONG, NATTHAWADEE SUMANOCHITRAPORN, SUPRANEE KAEWPIROM: "Curing behavior of a UV-curable coating based on urethane acrylate oligomer: the influence of reactive monomers", SONGKLANAKARIN JOURNAL OF SCIENCE AND TECHNOLOGY., RESEARCH AND DEVELOPMENT OFFICE (RDO), THAILAND, vol. 33, no. 2, 1 April 2011 (2011-04-01), Thailand, pages 201 - 207, XP055331359, ISSN: 0125-3395 *
KIM HOON, RYU KWANG-HYUN, BAEK DOOYOUNG, KHAN TANVEER AHMED, KIM HYUN-JOONG, SHIN SUNGCHUL, HYUN JINHO, AHN JIN SOO, AHN SUG-JOON,: "3D Printing of Polyethylene Terephthalate Glycol–Sepiolite Composites with Nanoscale Orientation", APPLIED MATERIALS & INTERFACES, AMERICAN CHEMICAL SOCIETY, US, vol. 12, no. 20, 20 May 2020 (2020-05-20), US , pages 23453 - 23463, XP093086884, ISSN: 1944-8244, DOI: 10.1021/acsami.0c03830 *

Similar Documents

Publication Publication Date Title
WO2022225097A1 (fr) Procédé de post-durcissement d'impression 3d, et appareil orthodontique transparent fabriqué par celui-ci
KR102607733B1 (ko) 3d 프린터용 광경화형 조성물 및 이의 제조 방법
WO2020040414A1 (fr) Composition de polymère durcissable par rayonnement pour imprimante 3d
WO2017073921A1 (fr) Film de polyimide et procédé pour le produire
WO2020080643A1 (fr) Composition photodurcissable pour imprimante 3d pour produire un dispositif orthodontique transparent
WO2016190722A1 (fr) Graphène fonctionnalisé comprenant deux types d'amines ou plus, et son procédé de préparation
WO2022124509A1 (fr) Appareil orthodontique transparent ayant une meilleure aptitude à la correction
WO2018021674A1 (fr) Composition de résine durcissable par rayonnement et utilisation associée
WO2020159282A1 (fr) Matériau composite de polycarbonate-nanocellulose et son procédé de fabrication
WO2022196878A1 (fr) Composition à base de silicone et produit durci associé
WO2014133287A1 (fr) Composition de résine pour l'encapsulation d'un élément optique
WO2023163241A1 (fr) Composition de photodurcissement pour imprimante 3d et procédé de préparation associé
WO2021107366A1 (fr) Procédé de post-durcissement pour produit imprimé en 3d et dispositif associé
WO2019112227A1 (fr) Composite de silicone et leur procédé de production
WO2019132472A1 (fr) Composition photodurcissable et article moulé fabriqué à l'aide de celle-ci
WO2022045785A1 (fr) Composition de revêtement à base de silicone et pellicule anti-adhésive à base de silicone la comprenant
WO2020105968A1 (fr) Nanotubes de nitrure de bore liés à une molécule unique, et méthode de préparation d'une solution colloïdale à l'aide de ceux-ci
WO2021107365A1 (fr) Imprimante 3d à mode de fabrication descendante et procédé de production de produit la mettant en œuvre
WO2023113483A1 (fr) Nouveau composé organique et composition photodurcissable pour imprimante 3d comprenant celui-ci
WO2024122692A1 (fr) Composition photodurcissable pour imprimante 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
WO2022080759A1 (fr) Prothèse dentaire personnalisée à l'aide d'une imprimante 3d
WO2022080997A1 (fr) Prothèse dentaire partielle personnalisée pour un patient à l'aide d'une imprimante 3d
WO2010140804A2 (fr) Résines de norbornène pour encapsuler un dispositif optique
WO2023128535A1 (fr) Stabilisateur dentaire et son procédé de fabrication

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: 22928994

Country of ref document: EP

Kind code of ref document: A1