WO2020209505A1 - 3d 프린팅용 경화용 수지 조성물 및 이로부터 제조된 성형물 - Google Patents
3d 프린팅용 경화용 수지 조성물 및 이로부터 제조된 성형물 Download PDFInfo
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- WO2020209505A1 WO2020209505A1 PCT/KR2020/003198 KR2020003198W WO2020209505A1 WO 2020209505 A1 WO2020209505 A1 WO 2020209505A1 KR 2020003198 W KR2020003198 W KR 2020003198W WO 2020209505 A1 WO2020209505 A1 WO 2020209505A1
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- 239000011342 resin composition Substances 0.000 title claims abstract description 26
- 238000007639 printing Methods 0.000 title description 5
- 238000010146 3D printing Methods 0.000 claims abstract description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 31
- 239000003999 initiator Substances 0.000 claims abstract description 17
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920002635 polyurethane Polymers 0.000 claims abstract description 10
- 239000004814 polyurethane Substances 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 41
- 238000001723 curing Methods 0.000 claims description 26
- -1 hydroxypropyl Chemical group 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- 238000000016 photochemical curing Methods 0.000 claims description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 239000005548 dental material Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000003672 processing method Methods 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 4
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 claims description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims description 3
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 claims description 3
- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 claims description 3
- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-UHFFFAOYSA-N 0.000 claims description 3
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 claims description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 3
- 241000510672 Cuminum Species 0.000 claims description 3
- 235000007129 Cuminum cyminum Nutrition 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- NSGQRLUGQNBHLD-UHFFFAOYSA-N butan-2-yl butan-2-yloxycarbonyloxy carbonate Chemical compound CCC(C)OC(=O)OOC(=O)OC(C)CC NSGQRLUGQNBHLD-UHFFFAOYSA-N 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 3
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 claims description 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 3
- AGKBXKFWMQLFGZ-UHFFFAOYSA-N (4-methylbenzoyl) 4-methylbenzenecarboperoxoate Chemical compound C1=CC(C)=CC=C1C(=O)OOC(=O)C1=CC=C(C)C=C1 AGKBXKFWMQLFGZ-UHFFFAOYSA-N 0.000 claims description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 2
- 238000003475 lamination Methods 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 12
- 238000004659 sterilization and disinfection Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 230000001954 sterilising effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000007943 implant Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 238000000110 selective laser sintering Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- TZJQCUDHKUWEFU-UHFFFAOYSA-N 2,2-dimethylpentanenitrile Chemical compound CCCC(C)(C)C#N TZJQCUDHKUWEFU-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F290/067—Polyurethanes; Polyureas
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C8/00—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools
- A61C8/0089—Implanting tools or instruments
- A61C8/009—Implanting tools or instruments for selecting the right implanting element, e.g. templates
-
- 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
-
- 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
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
Definitions
- the present invention relates to a curing resin composition for 3D printing and a molded article manufactured therefrom, and more particularly, to a curing resin composition for 3D printing capable of composite curing and a molded article prepared therefrom.
- a 3D printer is an equipment that manufactures products by processing and laminating materials such as liquid, powdery resin, metal powder, and solid based on design data.Since it is possible to easily manufacture a sculpture of a desired shape, it is possible to manufacture a prototype or a complex form. It is used in the manufacture of sculptures.
- 3D printer technology can be divided into photo-curing lamination method, laser sinter lamination method, resin extrusion lamination method, inkjet lamination method, polyjet lamination method, and thin film lamination method.
- the photocurable lamination method is a method of manufacturing a molded article by curing a photocurable liquid resin (photo curing resin) with a laser beam or strong ultraviolet ray (UV, Ultraviolet ray).
- This photocurable lamination method includes a stereo lithography apparatus (Stereo Lithography Apparatus). SLA) and Digital Light Processing (DLP).
- the laser sintering lamination method is a method of manufacturing a three-dimensional object by sintering a powdery material from a laser beam at high pressure and high temperature, and such a laser sintering lamination method includes SLS (Selective Laser Sintering).
- the resin extrusion lamination method extrudes a wire-shaped material with an injection head to produce a three-dimensional object, and such a resin extrusion lamination method includes FDM (Fused Deposition Modeling).
- the inkjet lamination method is a method of manufacturing a three-dimensional object by spraying a liquid binder onto a material from a print head nozzle, and such an inkjet lamination method includes CJP (Color Jetting Printing).
- the polyjet lamination method is a method of manufacturing a three-dimensional object by spraying the material from the printer head and curing it with ultraviolet rays at the same time in the form of a mixture of the photocuring method and the inkjet method.
- MJP Multi Jet Printing
- Polyjet are used. have.
- the thin-film lamination method is a method of manufacturing a three-dimensional object by cutting a thin plate-shaped material with a precision cutter and then heating and bonding it with heat.
- Such thin-film lamination methods include LOM (Laminated Object Manufacturing) and PLT (Paper Lamination Technology).
- the photo-curing lamination method has excellent surface roughness and is suitable for manufacturing a molded article having a complex shape such as an implant. Implants are easy to propagate after surgery, so thorough sterilization and disinfection are essential. However, the existing 3D printing curing material is only cured by light, so the strength of the molded product decreases rapidly in a high-temperature sterilization environment, and due to this decrease in strength, the required level of physical properties is not satisfied, and the implant is damaged. There is a problem that causes physical and property damage.
- Patent Document 0001 Registered Patent Publication No. 10-1772999 (2017.08.31.)
- the present invention is to solve the problems of the prior art described above, an object of the present invention is to provide a curable resin composition for 3D printing capable of manufacturing a molded article maintaining a constant strength even in a high temperature sterilization environment.
- a photo-curable polyurethane copolymer 20 to 40 parts by weight; 50 to 80 parts by weight of bisphenol A ethoxylate di(meth)acrylate; 1 to 20 parts by weight of a (meth)acrylate-based monomer; 1 to 4 parts by weight of a photoinitiator; And 10 to 200 parts by weight of a thermal initiator based on 100 parts by weight of the photoinitiator. It provides a curing resin composition for 3D printing.
- the (meth) acrylate monomer is hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetraethylene glycol di (meth) It may be one selected from the group consisting of acrylate, hexanedioldi(meth)acrylate, and a mixture of two or more of them.
- the composition may be a liquid composition used for 3D printing using a stereolithography apparatus method or a digital light source processing method.
- the photoinitiator is an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, a thioxanthone compound, an oxime ester compound, an acylphosphine oxide compound, and 2 of them. It may be one selected from the group consisting of the above mixtures.
- the thermal initiator is benzoyl peroxide, di-t-butyl peroxide, cumin hydroperoxide, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxybenzoate, azobis Dimethylvaleronitrile, azobisisobutyronitrile, diisobutyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, disuccinate peroxide, di(4-methylbenzoyl) ) Peroxide, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, di(2-ethylhexyl)peroxydicarbonate and di( It may be one selected from the group consisting of 4-t-butylcyclohexyl)peroxydicarbonate.
- Another aspect of the present invention provides a molded article prepared by irradiating light with the aforementioned curing resin composition for 3D printing.
- the molding may have a flexural strength of 90 MPa or more.
- the molded product may have a flexural strength of 70 MPa or more after heat treatment at 120 to 135° C. for 1 to 30 minutes.
- the molded article may be manufactured by 3D printing using a stereolithography apparatus method or a digital light source processing method.
- the molded article may be a dental material.
- a curing resin composition for 3D printing used for manufacturing a molded article that maintains a certain strength even after high-temperature sterilization treatment.
- (meth)acrylic- means “methacryl-", “acrylic-”, or both.
- a resin composition for curing for 3D printing includes 20 to 40 parts by weight of a polyurethane copolymer capable of photocuring; 50 to 80 parts by weight of bisphenol A ethoxylate di(meth)acrylate; 1 to 20 parts by weight of a (meth)acrylate-based monomer; 1 to 4 parts by weight of a photoinitiator; And 10 to 200 parts by weight of a thermal initiator based on 100 parts by weight of the photoinitiator.
- the curing rate may be too slow, or defects may occur on the surface of the manufactured molded article.
- the content of the photoinitiator and the thermal initiator satisfies the above range, it is possible to prevent deterioration of mechanical properties due to high temperature heat treatment.
- the content ratio of the polyurethane copolymer, the photoinitiator, and the thermal initiator is out of the above range, photocuring does not sufficiently occur and thus the required level of strength is not satisfied, or a sharp decrease in mechanical properties due to heat treatment occurs. It may not achieve the object of the invention.
- the content of the thermal initiator is 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 based on 100 parts by weight of the photoinitiator.
- the photoinitiator may be parts by weight, 110 parts by weight, 120 parts by weight, 130 parts by weight, 140 parts by weight, 150 parts by weight, 160 parts by weight, 170 parts by weight, 180 parts by weight, 190 parts by weight, or 200 parts by weight, and the content of the thermal initiator If the photoinitiator is less than 10 parts by weight or more than 200 parts by weight based on 100 parts by weight of the photoinitiator, the molded article manufactured therefrom may not be able to maintain the required level of strength after sterilization treatment.
- the content of the thermal initiator is more than 200 parts by weight based on 100 parts by weight of the photoinitiator, an excessive amount of thermal initiator may interfere with photocuring, resulting in deterioration or defects in the physical properties of the molded product. After the heat treatment of, the effect of maintaining strength may decrease.
- the (meth)acrylate monomers are hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tetraethylene glycol di (meth)acrylate, hexanediol di It may be one selected from the group consisting of (meth)acrylate and a mixture of two or more of them, but is not limited thereto.
- the composition may be a liquid composition used for 3D printing using a stereolithography apparatus method or a digital light source processing method. Therefore, the 3D printing can be performed using a printer of a method using a liquid resin.
- a photocurable 3D printer is a type of printer that cures a material by irradiating light onto a desired area for printing, and has superior surface roughness compared to other printing methods and is advantageous for manufacturing complex structures.
- an ultraviolet laser is projected onto a water tank containing a photocurable resin composition to be cured, and a molded article can be manufactured by laminating the same.
- the wavelength of the irradiated laser may be changed according to the type of the composition, and the curing speed, the strength of the cured molding, and the surface roughness may vary.
- the digital light source processing method is a mask projection image curing method.
- a molded object having a desired shape can be manufactured.
- the modeling plate descends to produce a product.
- the plate moves up and can create a product in a downward direction.
- the light provided from the beam projector may be projected onto the curable resin composition for 3D printing to manufacture a molded article. That is, on the molding plate, curing is sequentially performed in units of slice cross-sectional layers, and a 3D molded article can be manufactured.
- the photoinitiator is from the group consisting of an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, a thioxanthone compound, an oxime ester compound, an acylphosphine oxide compound, and a mixture of two or more of them. It may be one selected, but is not limited thereto.
- the thermal initiators are benzoyl peroxide, di-t-butyl peroxide, cumin hydroperoxide, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxybenzoate, azobisdimethylvaleronitrile, azo Bisisobutyronitrile, diisobutyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, disuccinate peroxide, di(4-methylbenzoyl) peroxide, di- n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, di(2-ethylhexyl)peroxydicarbonate and di(4-t-butylcyclo It may be one selected from the group consisting of hexyl) peroxydicarbonate, but is not limited thereto.
- the curable resin composition for 3D printing is used for 3D printing and may be used for manufacturing various dental materials such as surgical guides.
- a curing resin composition for 3D printing that satisfies a specific composition, it is possible to meet the strength required for the surgical guide before and after sterilization. If the composition of the composition is out of the above range, a sufficient crosslinked structure is not formed only by photocuring, so that required physical properties may not be satisfied, or defects may occur on the surface of the final product, making it difficult to manufacture a molded article having a desired structure.
- a molded article according to another aspect of the present invention may be prepared by irradiating light with the aforementioned curing resin composition for 3D printing.
- the light irradiation may be performed using a known SLA or DLP method.
- the molding may have a flexural strength of 90 MPa or more, 90 to 110 MPa, 95 to 105 MPa, or 96 to 104 MPa, but is not limited thereto.
- the molded product may have a flexural strength of 70 MPa or more, 70 to 90 Mpa, 70 to 80 MPa, 70 to 75 MPa, or 72 to 74 MPa after heat treatment at 120 to 135°C for 1 to 30 minutes, but is not limited thereto. .
- a molded article manufactured using a conventional photocurable material has a problem in that the strength decreases rapidly after heat treatment such as sterilization treatment, or the flexural strength is less than 70 MPa, so that the desired physical properties cannot be realized.
- the molding according to an embodiment of the present invention has a flexural strength of 90 MPa or more, and may maintain a flexural strength of 70 MPa or more even after heat treatment.
- the molded article may be manufactured by 3D printing using a stereolithography apparatus method or a digital light source processing method. Accordingly, the molded product may have a smoother surface and a more complex structure than a molded product such as a fusion modeling method prepared by dissolving a filament.
- the molded article may be a dental material.
- a molded article is manufactured by irradiating the curable resin composition for 3D printing with light, the mechanical strength required for the dental material can be sufficiently realized, and at the same time, the mechanical strength after heat treatment is improved, so that the mechanical strength is reduced due to the sterilization treatment. It is possible to solve the problem of difficult conventional dental materials.
- An example of such a dental material may be a surgical guide, but is not limited thereto.
- the molded product made of the curing resin composition for 3D printing accelerates the reaction of the thermal initiator to cure the molded product. It can prevent deterioration of mechanical properties such as flexural strength.
- polyurethane 28 parts by weight of polyurethane, 60 parts by weight of bisphenol a ethoxylate di(meth)acrylate, 10 parts by weight of tetrahydrofurfuryl methacrylate, 2 parts by weight of phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide Parts and 2 parts by weight of benzoyl peroxide were mixed.
- polyurethane 28 parts by weight of polyurethane, 60 parts by weight of bisphenol a ethoxylate di(meth)acrylate, 10 parts by weight of tetrahydrofurfuryl methacrylate, 2 parts by weight of phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide Parts and 4 parts by weight of benzoyl peroxide were mixed.
- polyurethane 28 parts by weight of polyurethane, 60 parts by weight of bisphenol a ethoxylate di(meth)acrylate, 10 parts by weight of tetrahydrofurfuryl methacrylate, 2 parts by weight of phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide Parts and 8 parts by weight of benzoyl peroxide were mixed.
- compositions of the above examples and comparative examples were prepared using a 3D printer disclosed in Korean Patent No. 1,772,999 to prepare a specimen of a plate-shaped structure having a size of 64 mm ⁇ 10 mm ⁇ 3.3 mm, and the flexural strength was determined according to ISO 20795-1. Tested.
- the specimen of Comparative Example 1 that did not contain a thermal initiator before sterilization had a flexural strength of only 81.50 MPa, but the specimens of Examples 1 to 3 and Comparative Example 2 had flexural strength.
- Examples 1 to 3 in which the content of the thermal initiator is 10 to 200 parts by weight relative to 100 parts by weight of the photoinitiator, have excellent flexural strength of 70 MPa or more even after sterilization, whereas Comparative Example 1 or photoinitiator not containing a thermal initiator It can be seen that the flexural strength of the specimen of Comparative Example 2 including an excessive amount compared to each other was rapidly decreased to 48.19 MPa and 52.94 MPa, respectively.
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Orthopedic Medicine & Surgery (AREA)
- Dentistry (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
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- Veterinary Medicine (AREA)
Abstract
Description
Claims (10)
- 3D 프린팅용 경화용 수지 조성물에 있어서,광경화가 가능한 폴리우레탄 공중합체 20~40중량부;비스페놀 에이 에톡시레이트 디(메타)아크릴레이트 50~80중량부;(메타)아크릴레이트계 단량체 1~20중량부;광개시제 1~4중량부; 및상기 광개시제 100중량부를 기준으로 열개시제 10~200중량부;를 포함하는, 3D 프린팅용 경화용 수지 조성물.
- 제1항에 있어서,상기 (메타)아크릴레이트계 단량체는 하이드록시프로필(메타)아크릴레이트, 하이드록시에틸(메타)아크릴레이트, 테트라하이드로퍼퓨릴(메타)아크릴레이트, 테트라에틸렌글리콜디(메타)아크릴레이트, 헥산디올디(메타)아크릴레이트 및 이들 중 2 이상의 혼합물로 이루어진 군에서 선택된 하나인, 3D 프린팅용 경화용 수지 조성물.
- 제1항에 있어서,상기 조성물은 스테레오리소그래피장치 방식 또는 디지털광원처리 방식의 3D 프린팅에 사용되는 액상 조성물인, 3D 프린팅용 경화용 수지 조성물.
- 제1항에 있어서,상기 광개시제는 아세토페논계 화합물, 벤조페논계 화합물, 트리아진계 화합물, 비이미다졸계 화합물, 티오크산톤계 화합물, 옥심에스테르계 화합물, 아실포스핀옥시드계 화합물 및 이들 중 2 이상의 혼합물로 이루어진 군에서 선택된 하나인, 3D 프린팅용 경화용 수지 조성물.
- 제1항에 있어서,상기 열개시제는 벤조일퍼옥사이드, 디-t-부틸퍼옥사이드, 큐민하이드로퍼옥사이드, t-부틸퍼옥시-2-에틸헥사노에이트, t-부틸퍼옥시벤조에이트, 아조비스디메틸발레로니트릴, 아조비스이소부티로니트릴, 디이소부틸퍼옥사이드, 디(3,5,5-트리메틸헥사노일)퍼옥사이드, 디라우로일퍼옥사이드, 디숙신산퍼옥사이드, 디(4-메틸벤조일)퍼옥사이드, 디-n-프로필퍼옥시디카르보네이트, 디이소프로필퍼옥시디카르보네이트, 디-sec-부틸퍼옥시디카르보네이트, 디(2-에틸헥실)퍼옥시디카르보네이트 및 디(4-t-부틸시클로헥실)퍼옥시디카르보네이트로 이루어진 군에서 선택된 하나인, 3D 프린팅용 경화용 수지 조성물.
- 제1항 내지 제5항 중 어느 한 항에 따른 3D 프린팅용 경화용 수지 조성물을 광조사하여 제조한, 성형물.
- 제6항에 있어서,상기 성형물은 굴곡강도가 90 MPa 이상인, 성형물.
- 제6항에 있어서,상기 성형물은 120~135℃에서 1~30분간 열처리한 후 굴곡강도가 70 MPa 이상인, 성형물.
- 제6항에 있어서,상기 성형물은 스테레오리소그래피장치 방식 또는 디지털광원처리 방식의 3D 프린팅으로 제조된, 성형물.
- 제6항에 있어서,상기 성형물은 치과용 재료인, 성형물.
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KR1020190041952A KR102254001B1 (ko) | 2019-04-10 | 2019-04-10 | 3d 프린팅용 경화용 수지 조성물 및 이로부터 제조된 성형물 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113045708A (zh) * | 2021-03-17 | 2021-06-29 | 中国科学院化学研究所 | 一种光固化3d打印水凝胶用光敏树脂及其制备方法和应用 |
CN113717330A (zh) * | 2021-08-26 | 2021-11-30 | 爱迪特(秦皇岛)科技股份有限公司 | 一种光热固化的树脂组合物及其制备方法和应用 |
CN116568715A (zh) * | 2020-12-17 | 2023-08-08 | 奥齿泰种植体有限责任公司 | 光固化树脂组合物及由其制造的成型物 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102607733B1 (ko) | 2021-02-04 | 2023-11-29 | 주식회사 그래피 | 3d 프린터용 광경화형 조성물 및 이의 제조 방법 |
KR102658757B1 (ko) | 2021-12-16 | 2024-04-18 | 주식회사 그래피 | 신규한 유기 화합물 및 이를 포함하는 3d 프린터용 광경화형 조성물 |
KR20240013042A (ko) | 2022-07-21 | 2024-01-30 | 주식회사 그래피 | 3d 프린팅용 광경화형 올리고머 및 이를 포함하는 3d 프린팅용 형상기억 고분자 조성물 |
KR102507085B1 (ko) | 2022-09-13 | 2023-03-07 | 한밭대학교 산학협력단 | 나노 셀룰로오스 섬유를 유효성분으로 포함하는 친환경 3d 프린터용 광경화성 조성물 |
KR20240071217A (ko) | 2022-11-15 | 2024-05-22 | 국립한밭대학교 산학협력단 | 3d 프린팅용 광경화성 조성물 및 이의 제조 방법 |
KR20240086841A (ko) | 2022-12-09 | 2024-06-19 | 주식회사 그래피 | 3d 프린터용 광경화형 조성물 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20160087151A (ko) * | 2015-01-13 | 2016-07-21 | 한국전자통신연구원 | 치과 임플란트 시술용 가이드의 3차원 조형을 위한 조성물 |
JP2017506245A (ja) * | 2014-02-18 | 2017-03-02 | スリーエム イノベイティブ プロパティズ カンパニー | 歯科用組成物及びその使用 |
WO2018106531A1 (en) * | 2016-12-05 | 2018-06-14 | Arkema Inc. | Initiator blends and photocurable compositions containing such initiator blends useful for 3d printing |
KR101931454B1 (ko) * | 2017-12-29 | 2018-12-20 | 박성원 | 광경화성 조성물 및 이를 이용하여 제조된 성형품 |
KR20190022777A (ko) * | 2016-06-30 | 2019-03-06 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 고점성 성분을 포함하는 인쇄가능 조성물 및 그로부터 3d 물품을 생성하는 방법 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102185745B1 (ko) * | 2014-04-02 | 2020-12-02 | 성균관대학교산학협력단 | 입체 리소그래피용 틱소트로피성 올리고머 조성물 및 이로부터 얻어지는 입체 조형물 |
KR101772999B1 (ko) | 2016-07-14 | 2017-08-31 | 오스템임플란트 주식회사 | 3d 프린팅 장치 |
-
2019
- 2019-04-10 KR KR1020190041952A patent/KR102254001B1/ko active IP Right Grant
-
2020
- 2020-03-06 WO PCT/KR2020/003198 patent/WO2020209505A1/ko active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017506245A (ja) * | 2014-02-18 | 2017-03-02 | スリーエム イノベイティブ プロパティズ カンパニー | 歯科用組成物及びその使用 |
KR20160087151A (ko) * | 2015-01-13 | 2016-07-21 | 한국전자통신연구원 | 치과 임플란트 시술용 가이드의 3차원 조형을 위한 조성물 |
KR20190022777A (ko) * | 2016-06-30 | 2019-03-06 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 고점성 성분을 포함하는 인쇄가능 조성물 및 그로부터 3d 물품을 생성하는 방법 |
WO2018106531A1 (en) * | 2016-12-05 | 2018-06-14 | Arkema Inc. | Initiator blends and photocurable compositions containing such initiator blends useful for 3d printing |
KR101931454B1 (ko) * | 2017-12-29 | 2018-12-20 | 박성원 | 광경화성 조성물 및 이를 이용하여 제조된 성형품 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116568715A (zh) * | 2020-12-17 | 2023-08-08 | 奥齿泰种植体有限责任公司 | 光固化树脂组合物及由其制造的成型物 |
CN113045708A (zh) * | 2021-03-17 | 2021-06-29 | 中国科学院化学研究所 | 一种光固化3d打印水凝胶用光敏树脂及其制备方法和应用 |
CN113717330A (zh) * | 2021-08-26 | 2021-11-30 | 爱迪特(秦皇岛)科技股份有限公司 | 一种光热固化的树脂组合物及其制备方法和应用 |
WO2023024724A1 (zh) * | 2021-08-26 | 2023-03-02 | 爱迪特(秦皇岛)科技股份有限公司 | 一种光热固化的树脂组合物及其制备方法和应用 |
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