WO2023113483A1 - Novel organic compound and photocurable composition for 3d printer comprising same - Google Patents
Novel organic compound and photocurable composition for 3d printer comprising same Download PDFInfo
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- WO2023113483A1 WO2023113483A1 PCT/KR2022/020405 KR2022020405W WO2023113483A1 WO 2023113483 A1 WO2023113483 A1 WO 2023113483A1 KR 2022020405 W KR2022020405 W KR 2022020405W WO 2023113483 A1 WO2023113483 A1 WO 2023113483A1
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- formula
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- 239000000203 mixture Substances 0.000 title claims abstract description 65
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
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- 125000005843 halogen group Chemical group 0.000 claims description 23
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- 125000006588 heterocycloalkylene group Chemical group 0.000 claims description 5
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 4
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- 238000005481 NMR spectroscopy Methods 0.000 description 8
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
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- 235000001498 Salvia hispanica Nutrition 0.000 description 1
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
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- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- 125000004404 heteroalkyl group Chemical group 0.000 description 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
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- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
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- 125000005561 phenanthryl group Chemical group 0.000 description 1
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- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- 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
- 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
- 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
- C08F290/062—Polyethers
Definitions
- the present invention relates to a novel organic compound and a photocurable composition for a 3D printer containing the same, and more particularly, to a novel organic compound capable of enhancing mechanical properties of a 3D printed output and maintaining a viscosity capable of 3D printing. It relates to a compound and a photocurable composition containing the same.
- a 3D printer has a 3D printing mechanism configured to form a physical object in 3D.
- a material for 3D printing that enables such a 3D printer to form a physical object in 3D
- research related to a resin composition for 3D printing continues.
- 3D printing is that the production cost is relatively low even when only one product is produced, and products of any shape can be freely produced.
- the cost required to make a single product is very high because a mold is made and then a product is produced using the mold, but 3D printing technology produces a product by stacking raw materials layer by layer without a mold. It is very suitable for small quantity production of various kinds.
- 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 printers As types of 3D printers, there are 3D printers of a Fused Deposition Medeling (FDM) method, a Stereo Lithography Apparatus (SLA) method, a Selective Laser Sintering (SLS) method, and a Digital Light Processing (DLP) method.
- FDM Fused Deposition Medeling
- SLA Stereo Lithography Apparatus
- SLS Selective Laser Sintering
- DLP Digital Light Processing
- 3D printers that are currently being sold as a low-end type mainly use the FDM method.
- the goal of using the entry-level FDM-type 3D printer is to see the appearance and shape.
- the 3D printer of the FDM method has a high failure rate in the shape manufacturing process due to many mechanical movements, which is a problem.
- SLA or DLP-type 3D printers are devices that produce outputs by irradiating and curing liquid photocurable resin with light. It is expected to be widely used as a replacement for the FDM method in the future 3D printing method because the enemy movement (Z-axis) is minimal and the failure rate is low during shape production.
- the SLA or DLP type 3D printer is a device that produces a three-dimensional plastic sculpture by irradiating light (visible light) to a photopolymer resin containing at least one of acrylic, urethane, and epoxy. . That is, after dividing the three-dimensional shape modeled by the CAD system into a plurality of layers with a thickness of 0.05 to 0.1 mm, each of these layers is converted into slice data, and using this, while irradiating light on the photocurable resin Various types of plastic models are manufactured by a method of completing a sculpture by stacking while curing one after another.
- Patent Document 1 KR 10-2020-0120992 A
- An object of the present invention is to provide a photocurable composition for a 3D printer containing a novel organic compound and the same.
- Another object of the present invention is to provide a photocurable composition containing a novel compound capable of enhancing mechanical properties of an output product printed by 3D printing and maintaining a viscosity capable of 3D printing.
- Another object of the present invention is to apply 3D printing technology to be output and manufactured in a form suitable for the patient's oral structure, to increase corrective force due to excellent mechanical properties, and to change and restore the shape when heat is provided It is possible to provide a transparent orthodontic device capable of exhibiting a high orthodontic effect.
- a novel organic compound according to an embodiment of the present invention is a compound represented by Formula 1 below:
- X 1 and X 2 are the same as or different from each other, and are each independently selected from the group consisting of NR 6 , O and S;
- Ar is a compound represented by Formula 2 above,
- L 1 and L 2 are the same as or different from each other, and are each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted An alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms , substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms, substituted or
- 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.
- L 1 , L 2 and R 1 to R 6 are substituted, hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 2 to 20 carbon atoms
- a photocurable composition for a 3D printer includes a photocurable oligomer; reactive monomers; and a photoinitiator, and the reactive monomer may include the compound represented by Chemical Formula 1.
- the photocurable oligomer may be a compound represented by Formula 3 below:
- n is an integer from 1 to 1,000;
- A is a compound represented by Formula 4 or Formula 5,
- R 7 to R 12 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 alkyl group having 1 to 20 carbon atoms.
- Cycloalkyl group substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms , A substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, or a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms , substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, substituted
- R 7 to R 12 When R 7 to R 12 are substituted, hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and a carbon atom Alkynyl group of 2 to 24, aralkyl group of 7 to 30 carbon atoms, aryl group of 6 to 30 carbon atoms, heteroaryl group of 5 to 60 nuclear atoms, heteroarylalkyl group of 6 to 30 carbon atoms, alkoxy group of 1 to 30 carbon atoms , C1-30 alkylamino group, C6-30 arylamino group, C6-30 aralkylamino group, C2-24 heteroarylamino group, C1-30 alkylsilyl group, C6-30 aryl It is substituted with one or more substituents selected from the group
- hydrogen is hydrogen, light hydrogen, deuterium or tritium.
- halogen group is fluorine, chlorine, bromine or iodine.
- alkyl means a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like.
- alkenyl refers to a monovalent substituent derived from a straight-chain or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon double bond. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, and 2-butenyl.
- alkynyl refers to a monovalent substituent derived from a straight-chain or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond. Examples thereof include, but are not limited to, ethynyl and 2-propynyl.
- aryl means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms in a single ring or a combination of two or more rings.
- a form in which two or more rings are simply attached to each other (pendant) or condensed may be included.
- Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, fluoryl, dimethylfluorenyl, and the like.
- heteroaryl means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 6 to 30 carbon atoms. At this time, at least one carbon, preferably 1 to 3 carbons in the ring is substituted with a heteroatom such as N, O, S or Se.
- a form in which two or more rings are simply attached to each other or condensed may be included, and furthermore, a form condensed with an aryl group may be included.
- heteroaryl examples include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, indolyl ( polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, carbazolyl and 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl and the like, but are not limited thereto.
- 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, indolyl ( polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, carbazo
- aryloxy is a monovalent substituent represented by RO-, wherein R means an aryl having 6 to 60 carbon atoms.
- R means an aryl having 6 to 60 carbon atoms.
- Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.
- alkyloxy is a monovalent substituent represented by R'O-, wherein R' means alkyl having 1 to 40 carbon atoms, and has a linear, branched or cyclic structure.
- R' means alkyl having 1 to 40 carbon atoms, and has a linear, branched or cyclic structure.
- alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy, and the like.
- alkoxy may be straight chain, branched chain or cyclic chain.
- the number of carbon atoms in alkoxy is not particularly limited, but is preferably 1 to 20 carbon atoms.
- aralkyl refers to an aryl-alkyl group where aryl and alkyl are defined above. Preferred aralkyls include lower alkyl groups. Non-limiting examples of suitable aralkyl groups include benzyl, 2-phenethyl and naphthalenylmethyl. Attachment to the parent moiety is via an alkyl.
- arylamino group means an amine substituted with an aryl group having 6 to 30 carbon atoms.
- alkylamino group means an amine substituted with an alkyl group having 1 to 30 carbon atoms.
- aralkylamino group means an amine substituted with an aryl-alkyl group having 6 to 30 carbon atoms.
- cycloalkyl means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms.
- examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.
- heterocycloalkyl means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 carbon atoms, and one or more carbons in the ring, preferably 1 to 3 carbons, are N, O, S or Se is substituted with a heteroatom such as Examples of such heterocycloalkyl include, but are not limited to, morpholine, piperazine, and the like.
- alkylsilyl refers to silyl substituted with alkyl having 1 to 40 carbon atoms
- arylsilyl refers to silyl substituted with aryl having 6 to 60 carbon atoms.
- substitution means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the hydrogen atom is substituted, that is, a position where the substituent can be substituted, and when two or more are substituted , Two or more substituents may be the same as or different from each other.
- the substituent is hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a carboxy group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, A heteroalkyl group having 2 to 30 carbon atoms, an aralkyl group having 6 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heteroarylalkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, It may be substituted with one or more substituents selected from the group consisting of an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon
- novel organic compound of the present invention and the photocurable composition for a 3D printer containing the same, mechanical properties of an output product output by 3D printing can be enhanced and a viscosity capable of 3D printing can be maintained.
- the composition it can be output and manufactured in a form suitable for the patient's oral structure, has excellent mechanical properties to increase orthodontic power, and when heat is provided, shape change and restoration are possible, resulting in high orthodontic treatment. There is an advantage that can provide a transparent orthodontic device that can show the effect.
- the present invention may be a compound represented by Formula 1 below:
- X 1 and X 2 are the same as or different from each other, and are each independently selected from the group consisting of NR 6 , O and S;
- Ar is a compound represented by Formula 2 above,
- L 1 and L 2 are the same as or different from each other, and are each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted An alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms , substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms, substituted or
- 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.
- L 1 , L 2 and R 1 to R 6 are substituted, hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 2 to 20 carbon atoms
- an acrylate compound As an active ingredient included in a general photocurable composition for a 3D printer, an acrylate compound is included, and among them, a bisphenol-A (BPA)-based epoxy resin, which is an aromatic composition, is mainly used as an epoxy acrylate compound.
- BPA bisphenol-A
- the BPA-based epoxy acrylate follows the basic physical properties of the existing BPA epoxy resin as it is, so it has fast curing reaction speed, low cost, and excellent heat resistance. There is a feature that
- the reactive monomer is included as an active ingredient in a photocurable composition for a 3D printer and may serve as a diluent that increases the strength and curing speed of the composition while lowering the viscosity of the composition.
- CTFA Cyclic Trimethylolpropane Formal Acrylate
- CHIA Cyclohexane Dicarboxyimide Ethyl Acrylate
- NPGDA Neopentyl Glycol Diacrylate
- the novel compound is a compound represented by Formula 1 below:
- X 1 and X 2 are the same as or different from each other, and are each independently selected from the group consisting of NR 6 , O and S;
- Ar is a compound represented by Formula 2 above,
- L 1 and L 2 are the same as or different from each other, and are each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted An alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms , substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms, substituted or
- 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.
- L 1 , L 2 and R 1 to R 6 are substituted, hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 2 to 20 carbon atoms
- the X 1 and X 2 may be O.
- R 1 to R 4 are the same as or different from each other and are each independently hydrogen, a halogen group, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, and a substituted or It may be selected from the group consisting of an unsubstituted C2-C24 alkynyl group.
- R 5 may be selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
- L 1 and L 2 are the same as or different from each other, and are each independently a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, and a carbon number It may be selected from the group consisting of 2 to 20 alkynylene groups.
- 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; and a photoinitiator, and the reactive monomer may include the compound represented by Chemical Formula 1.
- the photocurable composition for a 3D printer further includes nanoclay, and the nanoclay may enhance mechanical properties of an output product output by 3D printing due to an interaction between the 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 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 is in the form of lettis crystals. 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 central octahedral magnesium
- SiO 4 tetrahedral silica
- the sepiolite When the sepiolite is included in the nano-clay, it is possible to maintain a viscosity capable of 3D printing in the photocurable composition and exhibit high mechanical strength for the printed product.
- 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 monomer. 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 3 below:
- n is an integer from 1 to 1,000;
- A is a compound represented by Formula 4 or Formula 5,
- R 7 to R 12 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 alkyl group having 1 to 20 carbon atoms.
- Cycloalkyl group substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms , A substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, or a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms , substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, substituted
- R 7 to R 12 When R 7 to R 12 are substituted, hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and a carbon atom Alkynyl group of 2 to 24, aralkyl group of 7 to 30 carbon atoms, aryl group of 6 to 30 carbon atoms, heteroaryl group of 5 to 60 nuclear atoms, heteroarylalkyl group of 6 to 30 carbon atoms, alkoxy group of 1 to 30 carbon atoms , C1-30 alkylamino group, C6-30 arylamino group, C6-30 aralkylamino group, C2-24 heteroarylamino group, C1-30 alkylsilyl group, C6-30 aryl It is substituted with one or more substituents selected from the group
- R 7 to R 12 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 3, and includes both a compound in which A is selected from Formula 4 and a compound in which A is selected from Formula 5.
- 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 may include a compound represented by Formula 1 below:
- X 1 and X 2 are the same as or different from each other, and are each independently selected from the group consisting of NR 6 , O and S;
- Ar is a compound represented by Formula 2 above,
- L 1 and L 2 are the same as or different from each other, and are each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted An alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms , substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms, substituted or
- 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.
- L 1 , L 2 and R 1 to R 6 are substituted, hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 2 to 20 carbon atoms
- the X 1 and X 2 may be O.
- R 1 to R 4 are the same as or different from each other and are each independently hydrogen, a halogen group, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, and a substituted or It may be selected from the group consisting of an unsubstituted C2-C24 alkynyl group.
- R 5 may be selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
- L 1 and L 2 are the same as or different from each other, and are each independently a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, and a carbon number It may be selected from the group consisting of 2 to 20 alkynylene groups.
- the reactive monomer may include the compound represented by Formula 1, and includes both a compound in which R 5 is hydrogen and a compound in which R 5 is selected from an unsubstituted alkyl group having 1 to 30 carbon atoms. .
- the reactive monomer includes a compound represented by Formula 6 and a compound represented by Formula 7 below:
- 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 the steps of 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 the following formula (6) and a compound represented by the following formula (7):
- the reactive monomers are mixed and stirred in the same weight ratio. Thereafter, the nano-clay 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 dispersed by the above-mentioned dispersion 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 8 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;
- a reactive monomer more specifically, a compound in which A is selected from Formula 4 among compounds represented by Formula 3 below, a compound in which A is selected from Formula 5 among compounds represented by Formula 3 below, and a compound represented by Formula 6 below
- the compound and the compound represented by Formula 7 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 4 or Formula 5,
- R 7 to R 12 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 alkyl group having 1 to 20 carbon atoms.
- Cycloalkyl group substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms , A substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, or a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms , substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, substituted
- R 7 to R 12 When R 7 to R 12 are substituted, hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and a carbon atom Alkynyl group of 2 to 24, aralkyl group of 7 to 30 carbon atoms, aryl group of 6 to 30 carbon atoms, heteroaryl group of 5 to 60 nuclear atoms, heteroarylalkyl group of 6 to 30 carbon atoms, alkoxy group of 1 to 30 carbon atoms , C1-30 alkylamino group, C6-30 arylamino group, C6-30 aralkylamino group, C2-24 heteroarylamino group, C1-30 alkylsilyl group, C6-30 aryl It is substituted with one or more substituents selected from the group
- FIG. 1 shows the results of 1 H NMR and 13 C NMR analysis of the compound represented by Formula 6
- FIG. 2 shows the results of 1 H NMR and 13 C NMR analysis of the compound represented by Formula 7.
- the monomers represented by Chemical Formulas 6 and 7 were mixed in a weight ratio of 1:1, sepiolite was added, and then pulverized and dispersed for 1 minute at a power of 750 w 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 3 below, including both a compound in which A is selected from Formula 4 and a compound in which A is selected from Formula 5, and a compound selected from Formula 4 and a compound selected from Formula 5 in a weight ratio of 1:1.5.
- a photoinitiator represented by Formula 8 was mixed, and mixed and defoamed using a paste mixer.
- n is an integer from 1 to 1,000;
- R 7 to R 12 are methyl groups.
- the weight ratio of the photocurable composition is shown in Table 1 below.
- composition sample name sepiolite UV resin photoinitiator 100 One Example 1 0 Example 2 0.3 Example 3 0.5 Example 4 One Example 5 2 Example 6 3 Example 7 5 Example 8 7
- the UV resin includes photocurable oligomers and monomers
- a of Formula 3 is a compound selected from Formula 4, a compound selected from Formula 5, a monomer represented by Formula 6, and a monomer represented by Formula 7 in a ratio of 1:1.5 It is included in a weight ratio of 1:1.
- Example 2 Example 3
- Example 4 Example 5
- Example 6 Example 7
- Example 8 Floor separation X X X X X X X X
- Test Machine Universal Testing Machine
- the experiment was carried out by requesting the Korea Polymer Testing Laboratory, and the specimen was provided by outputting the photocurable compositions of Examples 1 to 8 in Table 1 as a specimen of ISO 20795-2 standard using the DLP method.
- Example 1 Example 2
- Example 3 Example 4
- Example 5 Example 6
- Example 7 Example 8
- Tensile strength (MPa) 46.15 52.55 58.23 57.12 59.32 58.17 57.54 53.21 Elongation (%) 36.25 38.12 43.59 44.14 44.56 45.56 43.11
- Modulus of elasticity (MPa) 1610 1700 1820 1880 1890 1886 1885 1710
- the shape After being immersed in water at 50 to 100 ° C for the first time, the shape is deformed by external force, the deformed shape is fixed, and after being immersed in water at 50 to 100 ° C, the shape is restored to its original shape at 20 to 30 ° C.
- Number of specimens 90 or more were marked as O, 50 or more and less than 90 were marked with ⁇ , and less than 50 were marked with X.
- Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 ⁇ ⁇ O O O O O O ⁇
- the present invention relates to a novel organic compound and a photocurable composition for a 3D printer containing the same, and more particularly, to a novel organic compound capable of enhancing mechanical properties of a 3D printed output and maintaining a viscosity capable of 3D printing. It relates to a compound and a photocurable composition containing the same.
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Abstract
The present invention relates to a novel organic compound and a photocurable composition for a 3D printer comprising same, in which, in the case of the composition, mechanical properties of an output product output by 3D printing can be enhanced and viscosity enabling 3D printing can be maintained. Furthermore, in the case of the composition, the output product may be manufactured by being output in a form suitable for the oral structure of a patient, and has excellent mechanical properties to enable increased orthodontic force. In addition, there is an advantage in that, when heat is provided, changes and restoration of shape are enabled to provide a transparent orthodontic device capable of exhibiting a high orthodontic effect.
Description
본 발명은 신규한 유기 화합물 및 이를 포함하는 3D 프린터용 광경화형 조성물에 관한 것으로, 보다 상세하게는 3D 프린팅으로 출력된 출력물의 기계적 물성을 강화하고, 3D 프린팅이 가능한 점도를 유지할 수 있는 신규한 유기 화합물 및 이를 포함하는 광경화형 조성물에 관한 것이다.The present invention relates to a novel organic compound and a photocurable composition for a 3D printer containing the same, and more particularly, to a novel organic compound capable of enhancing mechanical properties of a 3D printed output and maintaining a viscosity capable of 3D printing. It relates to a compound and a photocurable composition containing the same.
현재 세계 산업기술의 핵심 트렌드라고 꼽는다면 3D 프린터를 빼놓을 수 없다. 이에 3D 프린터는 향후 부가가치가 높은 산업으로의 발전이 예상됨에 따라 각국의 많은 업체들이 하드웨어(H/W)와 소프트웨어(S/W)를 자체개발 하고자 부단한 노력을 하고 있는 실정이다.3D printers cannot be left out of the current world industrial technology trend. Accordingly, as the 3D printer is expected to develop into an industry with high added value in the future, many companies in each country are making constant efforts to develop hardware (H/W) and software (S/W) on their own.
구체적으로, 3D 프린터는 물리적 객체를 3D로 형성하도록 구성되는 3D 프린팅 메커니즘을 갖는다. 이러한 3D 프린터로 하여금 물리적 객체를 3D으로 형성하도록 하는 3D 프린팅용 소재로서, 3D 프린팅용 수지 조성물과 관련된 연구가 계속되고 있다.Specifically, a 3D printer has a 3D printing mechanism configured to form a physical object in 3D. As a material for 3D printing that enables such a 3D printer to form a physical object in 3D, research related to a resin composition for 3D printing continues.
이러한, 3D 프린팅의 장점은 하나의 제품만을 생산하는 경우에도 생산 비용이 비교적 적게 들고, 어떤 모양의 제품이든 자유롭게 만들어낼 수 있다는데 있다. 기존의 모형 제조 기술에서는 틀을 만든 후, 틀을 이용하여 제품을 생산하기 때문에 하나의 제품을 만드는데 소요되는 비용이 매우 크지만, 3D 프린팅 기술은 틀 없이 원료를 한겹씩 적층하여 제품을 생산하기 때문에 다품종 소량생산에 매우 적합하다.The advantage of 3D printing is that the production cost is relatively low even when only one product is produced, and products of any shape can be freely produced. In the existing model manufacturing technology, the cost required to make a single product is very high because a mold is made and then a product is produced using the mold, but 3D printing technology produces a product by stacking raw materials layer by layer without a mold. It is very suitable for small quantity production of various kinds.
또한 3D 프린팅 기술에 의하면, 아무리 복잡한 모양의 제품이라도 간단하게 생산할 수 있기 때문에, 3D 프린팅 기술을 이용하여 생산할 수 있는 제품의 종류는 사실상 무궁무진하다고 할 수 있다. 그로 인해, 3D 프린팅 기술은 제조업, 의료, IT 분야 등 다방면에서 기술의 패러다임을 바꾸며, 산업 혁신을 이끌 것으로 기대되고 있다.In addition, according to 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.
이러한 3D 프린터의 종류로서, FDM(Fused Deposition Medeling), SLA(Stereo Lithography Apparatus), SLS(Selective Laser Sintering), DLP(Digital Light Processing) 방식의 3D 프린터가 존재한다.As types of 3D printers, there are 3D printers of a Fused Deposition Medeling (FDM) method, a Stereo Lithography Apparatus (SLA) method, a Selective Laser Sintering (SLS) method, and a Digital Light Processing (DLP) method.
상기 3D 프린터의 종류 중, 현재 보급형으로 판매되고 있는 3D 프린터는 상기 FDM 방식이 주를 이루고 있다. 상기 보급형 FDM 방식의 3D 프린터의 이용 목표는 외관 및 형상을 보는 것에 있다. 그러나, 상기 FDM 방식의 3D 프린터는 기계적인 움직임이 많기 때문에 형상 제작 과정에서 실패율이 높아 문제가 되고 있다.Among the types of 3D printers, 3D printers that are currently being sold as a low-end type mainly use the FDM method. The goal of using the entry-level FDM-type 3D printer is to see the appearance and shape. However, the 3D printer of the FDM method has a high failure rate in the shape manufacturing process due to many mechanical movements, which is a problem.
한편, 이러한 FDM 방식의 3D 프린터와는 달리 SLA 또는 DLP 방식의 3D 프린터는 액상의 광경화성 수지에 빛을 조사하여 경화시키는 것으로 출력물을 제작하는 기기로서, 자외선 빛을 이용한 경화방식을 이용하기 때문에 기구적 움 직임(Z축)이 최소이고 형상 제작 시, 실패율이 낮아 향후 3D 프린팅 방식에서 FDM 방식을 대체하여 많이 사용할 것으로 예상된다. On the other hand, unlike these FDM-type 3D printers, SLA or DLP-type 3D printers are devices that produce outputs by irradiating and curing liquid photocurable resin with light. It is expected to be widely used as a replacement for the FDM method in the future 3D printing method because the enemy movement (Z-axis) is minimal and the failure rate is low during shape production.
구체적으로, 상기 SLA 또는 DLP 방식의 3D 프린터는 아크릴, 우레탄, 에폭시 중 하나 이상을 포함하는 광경화성 고분자(photopolymer) 수지에 빛(가시광선)을 조사하여 3차원 형상의 플라스틱 조형물을 제작하는 기기이다. 즉, CAD 시스템으로 모델링한 3차원 형상을 0.05 내지 0.1mm 두께의 다수의 층으로 분할한 후, 이들 각 층을 슬라이스 데이터(slice data)로 변경하고, 이를 사용하여 광경화성 수지에 빛을 조사하면서 한층 또 한층 차례로 경화시키면서 적층함으로써 조형물을 완성하는 방식으로 각종 형태의 플라스틱 모델을 제조하고 있다.Specifically, the SLA or DLP type 3D printer is a device that produces a three-dimensional plastic sculpture by irradiating light (visible light) to a photopolymer resin containing at least one of acrylic, urethane, and epoxy. . That is, after dividing the three-dimensional shape modeled by the CAD system into a plurality of layers with a thickness of 0.05 to 0.1 mm, each of these layers is converted into slice data, and using this, while irradiating light on the photocurable resin Various types of plastic models are manufactured by a method of completing a sculpture by stacking while curing one after another.
그러나, 현재까지 이러한 광경화 방식 3D 프린터에 이용되는 원료는 매우 한정적이고, 다양한 3D 조형물을 제작하기 위한 원료 조성물에 한계가 있는 바, 최근 이에 대한 연구의 필요성이 대두되고 있다.However, until now, the raw materials used in these photocuring 3D printers are very limited, and there are limitations in raw material compositions for producing various 3D sculptures, and the need for research on them has recently emerged.
더 나아가, 특히 광경화형 적층 방식을 이용하는 3D 프린팅 기술은 표면 조도가 우수하여 복잡한 형상의 성형물로 제조될 필요성이 있는 의약 분야에 다수 적용하려는 시도가 계속되고 있다. 다만, 종래 3D 프린터용 소재를 이용하는 경우, 출력물에 대한 물리적 특성의 한계로 인해 의학 분야에 적용하기 어려운 문제가 있는 바, 다양한 의학 분야에 적용할 수 있는 광경화형 3D 프린터용 소재의 개발이 필요한 실정이다.Furthermore, in particular, 3D printing technology using a photocurable layering method has been attempted to apply a number of applications to the field of medicine, which needs to be manufactured into complex shaped moldings due to its excellent surface roughness. However, when using materials for conventional 3D printers, there is a problem in that it is difficult to apply to the medical field due to limitations in physical properties of the output, so it is necessary to develop materials for photocurable 3D printers that can be applied to various medical fields am.
[선행기술문헌][Prior art literature]
[특허문헌][Patent Literature]
(특허문헌1) KR 10-2020-0120992 A(Patent Document 1) KR 10-2020-0120992 A
본 발명의 목적은 신규한 유기 화합물 및 이를 포함하는 3D 프린터용 광경화형 조성물을 제공하는 것이다.An object of the present invention is to provide a photocurable composition for a 3D printer containing a novel organic compound and the same.
본 발명의 다른 목적은 3D 프린팅으로 출력된 출력물의 기계적 물성을 강화하고, 3D 프린팅이 가능한 점도를 유지할 수 있는 신규한 화합물을 포함하는 광경화형 조성물을 제공하는 것이다.Another object of the present invention is to provide a photocurable composition containing a novel compound capable of enhancing mechanical properties of an output product printed by 3D printing and maintaining a viscosity capable of 3D printing.
본 발명의 다른 목적은 3D 프린팅 기술을 적용하여 환자의 구강 구조에 맞는 형태로 출력되어 제조될 수 있고, 기계적 물성이 우수하여 교정력을 높일 수 있고, 열이 제공되는 경우, 형상의 변화 및 복원이 가능하여 높은 치아 교정 효과를 나타낼 수 있는 투명 치아 교정 장치를 제공하는 것이다.Another object of the present invention is to apply 3D printing technology to be output and manufactured in a form suitable for the patient's oral structure, to increase corrective force due to excellent mechanical properties, and to change and restore the shape when heat is provided It is possible to provide a transparent orthodontic device capable of exhibiting a high orthodontic effect.
상기 목적을 달성하기 위하여, 본 발명의 일 실시예에 따른 신규한 유기 화합물은 하기 화학식 1로 표시되는 화합물이다:In order to achieve the above object, a novel organic compound according to an embodiment of the present invention is a compound represented by Formula 1 below:
[화학식 1][Formula 1]
[화학식 2][Formula 2]
여기서,here,
*는 결합되는 부분을 의미하며,* means the part to be combined,
X1 및 X2는 서로 동일하거나 상이하며, 각각 독립적으로 NR6, O 및 S로 이루어진 군으로부터 선택되고,X 1 and X 2 are the same as or different from each other, and are each independently selected from the group consisting of NR 6 , O and S;
Ar은 상기 화학식 2로 표시되는 화합물이며,Ar is a compound represented by Formula 2 above,
L1 및 L2는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합, 치환 또는 비치환된 탄소수 6 내지 30의 아릴렌기, 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴렌기, 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬렌기, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알케닐렌기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로시클로알킬렌기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로알케닐렌기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로시클로알케닐렌기 및 탄소수 2 내지 20의 알키닐렌기로 이루어진 군에서 선택되며,L 1 and L 2 are the same as or different from each other, and are each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted An alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms , substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms, substituted or unsubstituted It is selected from the group consisting of a heterocycloalkenylene group having 3 to 20 carbon atoms and an alkynylene group having 2 to 20 carbon atoms,
R1 내지 R6는 서로 동일하거나 상이하며 각각 독립적으로 수소, 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬기, 치환 또는 비치환의 탄소수 1 내지 20개의 시클로알킬기, 치환 또는 비치환의 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환의 탄소수 2 내지 24의 알키닐기, 치환 또는 비치환의 탄소수 7 내지 30의 아르알킬기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴기, 치환 또는 비치환의 탄소수 5 내지 60의 헤테로아릴기, 치환 또는 비치환의 탄소수 6 내지 30의 헤테로아릴알킬기, 치환 또는 비치환의 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬아미노기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴아미노기, 치환 또는 비치환의 탄소수 6 내지 30의 아르알킬아미노기, 치환 또는 비치환의 탄소수 2 내지 24의 헤테로 아릴아미노기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴실릴기 및 치환 또는 비치환의 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택되며,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. An alkyl group, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, A substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, A substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, or a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms , It is selected from the group consisting of a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms,
상기 L1, L2 및 R1 내지 R6이 치환되는 경우, 수소, 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 20개의 시클로알킬기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 24의 알키닐기, 탄소수 7 내지 30의 아르알킬기, 탄소수 6 내지 30의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, 탄소수 6 내지 30의 헤테로아릴알킬기, 탄소수 1 내지 30의 알콕시기, 탄소수 1 내지 30의 알킬아미노기, 탄소수 6 내지 30의 아릴아미노기, 탄소수 6 내지 30의 아르알킬아미노기, 탄소수 2 내지 24의 헤테로 아릴아미노기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 6 내지 30의 아릴실릴기 및 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택된 1종 이상의 치환기로 치환되며, 복수 개의 치환기로 치환되는 경우 이들은 서로 동일하거나 상이하다.When L 1 , L 2 and R 1 to R 6 are substituted, hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 2 to 20 carbon atoms Alkenyl group having 30 carbon atoms, alkynyl group having 2 to 24 carbon atoms, 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, carbon atoms An alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, a heteroarylamino group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, It is substituted with one or more substituents selected from the group consisting of an arylsilyl group having 6 to 30 carbon atoms and an aryloxy group having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, they are the same as or different from each other.
본 발명의 다른 일 실시예에 따른 3D 프린터용 광경화형 조성물은 광경화성 올리고머; 반응성 모노머; 및 광개시제를 포함하며, 상기 반응성 모노머는 상기 화학식 1로 표시되는 화합물을 포함할 수 있다.A photocurable composition for a 3D printer according to another embodiment of the present invention includes a photocurable oligomer; reactive monomers; and a photoinitiator, and the reactive monomer may include the compound represented by Chemical Formula 1.
상기 광경화성 올리고머는 하기 화학식 3으로 표시되는 화합물일 수 있다:The photocurable oligomer may be a compound represented by Formula 3 below:
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
여기서,here,
n은 1 내지 1,000의 정수이고,n is an integer from 1 to 1,000;
A는 상기 화학식 4 또는 화학식 5로 표시되는 화합물이며,A is a compound represented by Formula 4 or Formula 5,
*는 결합되는 부분을 의미하며,* means the part to be combined,
R7 내지 R12는 서로 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬기, 치환 또는 비치환의 탄소수 1 내지 20개의 시클로알킬기, 치환 또는 비치환의 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환의 탄소수 2 내지 24의 알키닐기, 치환 또는 비치환의 탄소수 7 내지 30의 아르알킬기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴기, 치환 또는 비치환의 탄소수 5 내지 60의 헤테로아릴기, 치환 또는 비치환의 탄소수 6 내지 30의 헤테로아릴알킬기, 치환 또는 비치환의 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬아미노기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴아미노기, 치환 또는 비치환의 탄소수 6 내지 30의 아르알킬아미노기, 치환 또는 비치환의 탄소수 2 내지 24의 헤테로 아릴아미노기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴실릴기 및 치환 또는 비치환의 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택되며,R 7 to R 12 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 alkyl group having 1 to 20 carbon atoms. Cycloalkyl group, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms , A substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, or a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms , substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, substituted or unsubstituted alkylsilyl having 1 to 30 carbon atoms It is selected from the group consisting of a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms,
상기 R7 내지 R12 가 치환되는 경우, 수소, 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 20개의 시클로알킬기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 24의 알키닐기, 탄소수 7 내지 30의 아르알킬기, 탄소수 6 내지 30의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, 탄소수 6 내지 30의 헤테로아릴알킬기, 탄소수 1 내지 30의 알콕시기, 탄소수 1 내지 30의 알킬아미노기, 탄소수 6 내지 30의 아릴아미노기, 탄소수 6 내지 30의 아르알킬아미노기, 탄소수 2 내지 24의 헤테로 아릴아미노기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 6 내지 30의 아릴실릴기 및 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택된 1종 이상의 치환기로 치환되며, 복수 개의 치환기로 치환되는 경우 이들은 서로 동일하거나 상이하다.When R 7 to R 12 are substituted, hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and a carbon atom Alkynyl group of 2 to 24, aralkyl group of 7 to 30 carbon atoms, aryl group of 6 to 30 carbon atoms, heteroaryl group of 5 to 60 nuclear atoms, heteroarylalkyl group of 6 to 30 carbon atoms, alkoxy group of 1 to 30 carbon atoms , C1-30 alkylamino group, C6-30 arylamino group, C6-30 aralkylamino group, C2-24 heteroarylamino group, C1-30 alkylsilyl group, C6-30 aryl It is substituted with one or more substituents selected from the group consisting of a silyl group and an aryloxy group having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, they are the same as or different from each other.
본 발명에서 “수소”는 수소, 경수소, 중수소 또는 삼중수소이다.In the present invention, "hydrogen" is hydrogen, light hydrogen, deuterium or tritium.
본 명세서에서 “할로겐기”는 불소, 염소, 브롬 또는 요오드이다.In this specification, "halogen group" is fluorine, chlorine, bromine or iodine.
본 발명에서 “알킬”은 탄소수 1 내지 40개의 직쇄 또는 측쇄의 포화 탄화수소에서 유래되는 1가의 치환기를 의미한다. 이의 예로는 메틸, 에틸, 프로필, 이소부틸, sec-부틸, 펜틸, iso-아밀, 헥실 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, “alkyl” means a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like.
본 발명에서 “알케닐(alkenyl)”은 탄소-탄소 이중 결합을 1개 이상 가진 탄소수 2 내지 40개의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기를 의미한다. 이의 예로는 비닐(vinyl), 알릴(allyl), 이소프로펜일(isopropenyl), 2-부텐일(2-butenyl) 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, “alkenyl” refers to a monovalent substituent derived from a straight-chain or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon double bond. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, and 2-butenyl.
본 발명에서 “알키닐(alkynyl)”은 탄소-탄소 삼중 결합을 1개 이상 가진 탄소수 2 내지 40개의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기를 의미한다. 이의 예로는 에티닐(ethynyl), 2-프로파닐(2-propynyl)등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, “alkynyl” refers to a monovalent substituent derived from a straight-chain or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond. Examples thereof include, but are not limited to, ethynyl and 2-propynyl.
본 발명에서 “아릴”은 단독 고리 또는 2이상의 고리가 조합된 탄소수 6 내지 60개의 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 또한, 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태도 포함될 수 있다. 이러한 아릴의 예로는 페닐, 나프틸, 페난트릴, 안트릴, 플루오닐, 다이메틸플루오레닐 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, "aryl" means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms in a single ring or a combination of two or more rings. In addition, a form in which two or more rings are simply attached to each other (pendant) or condensed may be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, fluoryl, dimethylfluorenyl, and the like.
본 발명에서 “헤테로아릴”은 탄소수 6 내지 30개의 모노헤테로사이클릭 또는 폴리헤테로사이클릭 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이때, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S 또는 Se와 같은 헤테로원자로 치환된다. 또한, 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태도 포함될 수 있고, 나아가 아릴기와의 축합된 형태도 포함될 수 있다. 이러한 헤테로아릴의 예로는 피리딜, 피라지닐, 피리미디닐, 피리다지닐, 트리아지닐과 같은 6-원 모노사이클릭 고리, 페녹사티에닐(phenoxathienyl), 인돌리지닐(indolizinyl), 인돌릴(indolyl), 퓨리닐(purinyl), 퀴놀릴(quinolyl), 벤조티아졸(benzothiazole), 카바졸릴(carbazolyl)과 같은 폴리사이클릭 고리 및 2-퓨라닐, N-이미다졸릴, 2-이속사졸릴, 2-피리디닐, 2-피리미디닐 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, “heteroaryl” means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 6 to 30 carbon atoms. At this time, at least one carbon, preferably 1 to 3 carbons in the ring is substituted with a heteroatom such as N, O, S or Se. In addition, a form in which two or more rings are simply attached to each other or condensed may be included, and furthermore, a form condensed with an aryl group may be included. Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, indolyl ( polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, carbazolyl and 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl and the like, but are not limited thereto.
본 발명에서 “아릴옥시”는 RO-로 표시되는 1가의 치환기로, 상기 R은 탄소수 6 내지 60개의 아릴을 의미한다. 이러한 아릴옥시의 예로는 페닐옥시, 나프틸옥시, 디페닐옥시 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, "aryloxy" is a monovalent substituent represented by RO-, wherein R means an aryl having 6 to 60 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.
본 발명에서 “알킬옥시”는 R’O-로 표시되는 1가의 치환기로, 상기 R’는 탄소수 1 내지 40개의 알킬을 의미하며, 직쇄(linear), 측쇄(branched) 또는 사이클릭(cyclic) 구조를 포함할 수 있다. 알킬옥시의 예로는 메톡시, 에톡시, n-프로폭시, 1-프로폭시, t-부톡시, n-부톡시, 펜톡시 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, "alkyloxy" is a monovalent substituent represented by R'O-, wherein R' means alkyl having 1 to 40 carbon atoms, and has a linear, branched or cyclic structure. can include Examples of alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy, and the like.
본 발명에서 “알콕시”는 직쇄, 분지쇄 또는 고리쇄일 수 있다. 알콕시의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 20인 것이 바람직하다. 구체적으로, 메톡시, 에톡시, n-프로폭시, 이소프로폭시, i-프로필옥시, n-부톡시, 이소부톡시, tert-부톡시, sec-부톡시, n-펜틸옥시, 네오펜틸옥시, 이소펜틸옥시, n-헥실옥시, 3,3-디메틸부틸옥시, 2-에틸부틸옥시, n-옥틸옥시, n-노닐옥시, n-데실옥시, 벤질옥시, p-메틸벤질옥시 등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present invention, “alkoxy” may be straight chain, branched chain or cyclic chain. The number of carbon atoms in alkoxy is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. It may be, but is not limited thereto.
본 발명에서 "아르알킬"은, 아릴 및 알킬이 상기한 바와 같은 아릴-알킬 그룹을 의미한다. 바람직한 아르알킬은 저급 알킬 그룹을 포함한다. 적합한 아르알킬 그룹의 비제한적인 예는 벤질, 2-펜에틸 및 나프탈레닐메틸을 포함한다. 모 잔기에 대한 결합은 알킬을 통해 이루어진다.As used herein, "aralkyl" refers to an aryl-alkyl group where aryl and alkyl are defined above. Preferred aralkyls include lower alkyl groups. Non-limiting examples of suitable aralkyl groups include benzyl, 2-phenethyl and naphthalenylmethyl. Attachment to the parent moiety is via an alkyl.
본 발명에서 “아릴아미노기”는 탄소수 6 내지 30의 아릴기로 치환된 아민을 의미한다.In the present invention, "arylamino group" means an amine substituted with an aryl group having 6 to 30 carbon atoms.
본 발명에서 “알킬아미노기”는 탄소수 1 내지 30의 알킬기로 치환된 아민을 의미한다.In the present invention, "alkylamino group" means an amine substituted with an alkyl group having 1 to 30 carbon atoms.
본 발명에서 “아르알킬아미노기”는 탄소수 6 내지 30의 아릴-알킬기로 치환된 아민을 의미한다.In the present invention, “aralkylamino group” means an amine substituted with an aryl-alkyl group having 6 to 30 carbon atoms.
본 발명에서 “시클로알킬”은 탄소수 3 내지 40개의 모노사이클릭 또는 폴리사이클릭 비-방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이러한 사이클로알킬의 예로는 사이클로프로필, 사이클로부틸, 사이클로펜틸, 사이클로헥실, 노르보닐(norbornyl), 아다만틴(adamantine) 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, “cycloalkyl” means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.
본 발명에서 “헤테로시클로알킬”은 탄소수 3 내지 40개의 비-방향족 탄화수소로부터 유래된 1가의 치환기를 의미하며, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S 또는 Se와 같은 헤테로 원자로 치환된다. 이러한 헤테로시클로알킬의 예로는 모르폴린, 피페라진 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, “heterocycloalkyl” means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 carbon atoms, and one or more carbons in the ring, preferably 1 to 3 carbons, are N, O, S or Se is substituted with a heteroatom such as Examples of such heterocycloalkyl include, but are not limited to, morpholine, piperazine, and the like.
본 발명에서 “알킬실릴”은 탄소수 1 내지 40개의 알킬로 치환된 실릴이고, “아릴실릴”은 탄소수 6 내지 60개의 아릴로 치환된 실릴을 의미한다.In the present invention, “alkylsilyl” refers to silyl substituted with alkyl having 1 to 40 carbon atoms, and “arylsilyl” refers to silyl substituted with aryl having 6 to 60 carbon atoms.
본 명세서에서 "치환"은 화합물의 탄소 원자에 결합된 수소 원자가 다른 치환기로 바뀌는 것을 의미하며, 치환되는 위치는 수소 원자가 치환되는 위치 즉, 치환기가 치환 가능한 위치라면 한정하지 않으며, 2 이상 치환되는 경우, 2 이상의 치환기는 서로 동일하거나 상이할 수 있다. 상기 치환기는 수소, 시아노기, 니트로기, 할로겐기, 히드록시기, 카복시기, 탄소수 1 내지 10의 알콕시기, 탄소수 1 내지 30의 알킬기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 24의 알키닐기, 탄소수 2 내지 30의 헤테로알킬기, 탄소수 6 내지 30의 아르알킬기, 탄소수 5 내지 30의 아릴기, 탄소수 2 내지 30의 헤테로아릴기, 탄소수 3 내지 30의 헤테로아릴알킬기, 탄소수 1 내지 30의 알콕시기, 탄소수 1 내지 30의 알킬아미노기, 탄소수 6 내지 30의 아릴아미노기, 탄소수 6 내지 30의 아르알킬아미노기 및 탄소수 2 내지 24의 헤테로 아릴아미노기로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환될 수 있고, 복수 개의 치환기로 치환되는 경우 이들은 서로 동일하거나 상이하며, 상기 예시에 국한되지 않는다.In this specification, "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the hydrogen atom is substituted, that is, a position where the substituent can be substituted, and when two or more are substituted , Two or more substituents may be the same as or different from each other. The substituent is hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a carboxy group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, A heteroalkyl group having 2 to 30 carbon atoms, an aralkyl group having 6 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heteroarylalkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, It may be substituted with one or more substituents selected from the group consisting of an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, and a hetero arylamino group having 2 to 24 carbon atoms, and a plurality of When substituted with a substituent, they are the same as or different from each other, and are not limited to the above examples.
본 발명의 신규한 유기 화합물 및 이를 포함하는 3D 프린터용 광경화형 조성물에 의하면, 3D 프린팅으로 출력된 출력물의 기계적 물성을 강화하고, 3D 프린팅이 가능한 점도를 유지할 수 있다. According to the novel organic compound of the present invention and the photocurable composition for a 3D printer containing the same, mechanical properties of an output product output by 3D printing can be enhanced and a viscosity capable of 3D printing can be maintained.
한편, 상기 조성물에 의하면, 환자의 구강 구조에 맞는 형태로 출력되어 제조될 수 있고, 기계적 물성이 우수하여 교정력을 높일 수 있고, 열이 제공되는 경우, 형상의 변화 및 복원이 가능하여 높은 치아 교정 효과를 나타낼 수 있는 투명 치아 교정 장치를 제공할 수 있는 장점이 있다.On the other hand, according to the composition, it can be output and manufactured in a form suitable for the patient's oral structure, has excellent mechanical properties to increase orthodontic power, and when heat is provided, shape change and restoration are possible, resulting in high orthodontic treatment. There is an advantage that can provide a transparent orthodontic device that can show the effect.
도 1은 본 발명의 일 실시예에 따른 반응성 모노머의 1H NMR 및 13C NMR 분석 결과를 나타낸 것이다.1 shows the results of 1 H NMR and 13 C NMR analysis of a reactive monomer according to an embodiment of the present invention.
도 2는 본 발명의 일 실시예에 따른 반응성 모노머의 1H NMR 및 13C NMR 분석 결과를 나타낸 것이다.2 shows the results of 1 H NMR and 13 C NMR analysis of a reactive monomer according to an embodiment of the present invention.
본 발명은 하기 화학식 1로 표시되는 화합물일 수 있다:The present invention may be a compound represented by Formula 1 below:
[화학식 1][Formula 1]
[화학식 2][Formula 2]
여기서,here,
*는 결합되는 부분을 의미하며,* means the part to be combined,
X1 및 X2는 서로 동일하거나 상이하며, 각각 독립적으로 NR6, O 및 S로 이루어진 군으로부터 선택되고,X 1 and X 2 are the same as or different from each other, and are each independently selected from the group consisting of NR 6 , O and S;
Ar은 상기 화학식 2로 표시되는 화합물이며,Ar is a compound represented by Formula 2 above,
L1 및 L2는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합, 치환 또는 비치환된 탄소수 6 내지 30의 아릴렌기, 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴렌기, 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬렌기, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알케닐렌기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로시클로알킬렌기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로알케닐렌기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로시클로알케닐렌기 및 탄소수 2 내지 20의 알키닐렌기로 이루어진 군에서 선택되며,L 1 and L 2 are the same as or different from each other, and are each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted An alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms , substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms, substituted or unsubstituted It is selected from the group consisting of a heterocycloalkenylene group having 3 to 20 carbon atoms and an alkynylene group having 2 to 20 carbon atoms,
R1 내지 R6는 서로 동일하거나 상이하며 각각 독립적으로 수소, 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬기, 치환 또는 비치환의 탄소수 1 내지 20개의 시클로알킬기, 치환 또는 비치환의 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환의 탄소수 2 내지 24의 알키닐기, 치환 또는 비치환의 탄소수 7 내지 30의 아르알킬기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴기, 치환 또는 비치환의 탄소수 5 내지 60의 헤테로아릴기, 치환 또는 비치환의 탄소수 6 내지 30의 헤테로아릴알킬기, 치환 또는 비치환의 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬아미노기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴아미노기, 치환 또는 비치환의 탄소수 6 내지 30의 아르알킬아미노기, 치환 또는 비치환의 탄소수 2 내지 24의 헤테로 아릴아미노기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴실릴기 및 치환 또는 비치환의 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택되며,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. An alkyl group, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, A substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, A substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, or a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms , It is selected from the group consisting of a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms,
상기 L1, L2 및 R1 내지 R6이 치환되는 경우, 수소, 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 20개의 시클로알킬기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 24의 알키닐기, 탄소수 7 내지 30의 아르알킬기, 탄소수 6 내지 30의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, 탄소수 6 내지 30의 헤테로아릴알킬기, 탄소수 1 내지 30의 알콕시기, 탄소수 1 내지 30의 알킬아미노기, 탄소수 6 내지 30의 아릴아미노기, 탄소수 6 내지 30의 아르알킬아미노기, 탄소수 2 내지 24의 헤테로 아릴아미노기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 6 내지 30의 아릴실릴기 및 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택된 1종 이상의 치환기로 치환되며, 복수 개의 치환기로 치환되는 경우 이들은 서로 동일하거나 상이하다.When L 1 , L 2 and R 1 to R 6 are substituted, hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 2 to 20 carbon atoms Alkenyl group having 30 carbon atoms, alkynyl group having 2 to 24 carbon atoms, 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, carbon atoms An alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, a heteroarylamino group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, It is substituted with one or more substituents selected from the group consisting of an arylsilyl group having 6 to 30 carbon atoms and an aryloxy group having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, they are the same as or different from each other.
이하, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예에 대하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다.Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.
일반적인 3D 프린터용 광경화형 조성물에 포함되는 유효성분으로는 아크릴레이트 화합물이 포함되어 있으며, 이 중 에폭시 아크릴레이트 화합물로는 방향족 조성물인 BPA(bisphenol-A) 계열 에폭시 수지가 주로 이용되고 있다. As an active ingredient included in a general photocurable composition for a 3D printer, an acrylate compound is included, and among them, a bisphenol-A (BPA)-based epoxy resin, which is an aromatic composition, is mainly used as an epoxy acrylate compound.
상기 BPA계 에폭시 아크릴레이트는 기존의 BPA 에폭시 수지의 기본 물성을 그대로 따르므로 경화반응의 속도가 빠르고, 저렴하며 내열성 등이 우수한 특징을 나타내는 한편, 높은 분자량과 점도로 인해 반응성 모노머를 희석제로 함께 사용해야 하는 특징이 있다. The BPA-based epoxy acrylate follows the basic physical properties of the existing BPA epoxy resin as it is, so it has fast curing reaction speed, low cost, and excellent heat resistance. There is a feature that
구체적으로, 상기 반응성 모노머는 3D 프린터용 광경화형 조성물에 유효성분으로 포함되어 상기 조성물의 강도 및 경화속도는 증가시키되, 조성물의 점도는 떨어뜨리는 희석제 역할을 할 수 있다.Specifically, the reactive monomer is included as an active ingredient in a photocurable composition for a 3D printer and may serve as a diluent that increases the strength and curing speed of the composition while lowering the viscosity of the composition.
종래, 3D 프린터용 광경화형 조성물에 포함될 수 있는 반응성 모노머로는 CTFA(Cyclic Trimethylolpropane Formal Acrylate), CHIA(Cyclohexane Dicarboxyimide Ethyl Acrylate) 및 NPGDA(Neopentyl Glycol Diacrylate) 등이 이용되어 왔다.Conventionally, as reactive monomers that may be included in photocurable compositions for 3D printers, CTFA (Cyclic Trimethylolpropane Formal Acrylate), CHIA (Cyclohexane Dicarboxyimide Ethyl Acrylate), NPGDA (Neopentyl Glycol Diacrylate), etc. have been used.
다만, 이들 화합물을 포함하더라도, 상기 조성물의 기계적 물성을 향상시키는 효과는 다소 미미한 점이 존재하였는 바, 본 출원인은 3D 프린터용 광경화형 조성물에 반응성 모노머로 포함됨으로써 상기 조성물의 기계적 물성 등을 향상시킬 수 있는 신규 화합물을 개발하였다.However, even if these compounds are included, the effect of improving the mechanical properties of the composition is somewhat insignificant, and the present applicant can improve the mechanical properties of the composition by being included as a reactive monomer in the photocurable composition for 3D printers. A new compound has been developed.
구체적으로, 상기 신규한 화합물은 하기 화학식 1로 표시되는 화합물이다:Specifically, the novel compound is a compound represented by Formula 1 below:
[화학식 1][Formula 1]
[화학식 2][Formula 2]
여기서,here,
*는 결합되는 부분을 의미하며,* means the part to be combined,
X1 및 X2는 서로 동일하거나 상이하며, 각각 독립적으로 NR6, O 및 S로 이루어진 군으로부터 선택되고,X 1 and X 2 are the same as or different from each other, and are each independently selected from the group consisting of NR 6 , O and S;
Ar은 상기 화학식 2로 표시되는 화합물이며,Ar is a compound represented by Formula 2 above,
L1 및 L2는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합, 치환 또는 비치환된 탄소수 6 내지 30의 아릴렌기, 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴렌기, 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬렌기, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알케닐렌기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로시클로알킬렌기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로알케닐렌기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로시클로알케닐렌기 및 탄소수 2 내지 20의 알키닐렌기로 이루어진 군에서 선택되며,L 1 and L 2 are the same as or different from each other, and are each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted An alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms , substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms, substituted or unsubstituted It is selected from the group consisting of a heterocycloalkenylene group having 3 to 20 carbon atoms and an alkynylene group having 2 to 20 carbon atoms,
R1 내지 R6는 서로 동일하거나 상이하며 각각 독립적으로 수소, 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬기, 치환 또는 비치환의 탄소수 1 내지 20개의 시클로알킬기, 치환 또는 비치환의 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환의 탄소수 2 내지 24의 알키닐기, 치환 또는 비치환의 탄소수 7 내지 30의 아르알킬기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴기, 치환 또는 비치환의 탄소수 5 내지 60의 헤테로아릴기, 치환 또는 비치환의 탄소수 6 내지 30의 헤테로아릴알킬기, 치환 또는 비치환의 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬아미노기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴아미노기, 치환 또는 비치환의 탄소수 6 내지 30의 아르알킬아미노기, 치환 또는 비치환의 탄소수 2 내지 24의 헤테로 아릴아미노기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴실릴기 및 치환 또는 비치환의 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택되며,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. An alkyl group, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, A substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, A substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, or a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms , It is selected from the group consisting of a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms,
상기 L1, L2 및 R1 내지 R6이 치환되는 경우, 수소, 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 20개의 시클로알킬기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 24의 알키닐기, 탄소수 7 내지 30의 아르알킬기, 탄소수 6 내지 30의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, 탄소수 6 내지 30의 헤테로아릴알킬기, 탄소수 1 내지 30의 알콕시기, 탄소수 1 내지 30의 알킬아미노기, 탄소수 6 내지 30의 아릴아미노기, 탄소수 6 내지 30의 아르알킬아미노기, 탄소수 2 내지 24의 헤테로 아릴아미노기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 6 내지 30의 아릴실릴기 및 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택된 1종 이상의 치환기로 치환되며, 복수 개의 치환기로 치환되는 경우 이들은 서로 동일하거나 상이하다.When L 1 , L 2 and R 1 to R 6 are substituted, hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 2 to 20 carbon atoms Alkenyl group having 30 carbon atoms, alkynyl group having 2 to 24 carbon atoms, 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, carbon atoms An alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, a heteroarylamino group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, It is substituted with one or more substituents selected from the group consisting of an arylsilyl group having 6 to 30 carbon atoms and an aryloxy group having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, they are the same as or different from each other.
구체적으로, 상기 X1 및 X2는 O일 수 있다.Specifically, the X 1 and X 2 may be O.
구체적으로, 상기 R1 내지 R4는 서로 동일하거나 상이하며 각각 독립적으로 수소, 할로겐기, 히드록시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬기, 치환 또는 비치환의 탄소수 2 내지 30의 알케닐기 및 치환 또는 비치환의 탄소수 2 내지 24의 알키닐기로 이루어진 군으로부터 선택될 수 있다.Specifically, R 1 to R 4 are the same as or different from each other and are each independently hydrogen, a halogen group, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, and a substituted or It may be selected from the group consisting of an unsubstituted C2-C24 alkynyl group.
구체적으로, 상기 R5는 수소 및 치환 또는 비치환의 탄소수 1 내지 30의 알킬기로 이루어진 군으로부터 선택될 수 있다.Specifically, R 5 may be selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
구체적으로, 상기 L1 및 L2는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합, 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐렌기 및 탄소수 2 내지 20의 알키닐렌기로 이루어진 군에서 선택될 수 있다.Specifically, L 1 and L 2 are the same as or different from each other, and are each independently a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, and a carbon number It may be selected from the group consisting of 2 to 20 alkynylene groups.
한편, 본 발명의 3D 프린팅은 3D 디지털 데이터를 이용하여 소재를 적층해 3차원 물체를 제조하는 프로세스를 말한다. 본 명세서에는 3D 프린팅 기술로서 DLP(Disital Light Processing), SLA(Stereo Lithography Apparatus) 및 PolyJet 방식을 중심으로 기술하나, 다른 3D 프린팅 기술에도 적용가능한 것으로 이해될 수 있다.On the other hand, 3D printing of the present invention refers to a process of manufacturing a three-dimensional object by laminating materials using 3D digital data. In this specification, as 3D printing technologies, DLP (Disital Light Processing), SLA (Stereo Lithography Apparatus), and PolyJet method are mainly described, but it can be understood that they are applicable to other 3D printing technologies.
본 발명의 광경화형 조성물은 광 조사에 의해 경화되는 물질로서, 가교되고 중합체 망상구조로 중합되는 고분자를 말한다. 본 명세서에서는 UV 광을 중심으로 기술하나, UV 광에 한정되지 않고 다른 광에 대해서도 적용 가능하다.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. In this specification, the description is centered on UV light, but it is not limited to UV light and can be applied to other lights as well.
본 발명의 다른 일 실시예에 따른 3D 프린터용 광경화형 조성물은 광경화성 올리고머; 반응성 모노머; 및 광개시제를 포함하며, 상기 반응성 모노머는 상기 화학식 1로 표시되는 화합물을 포함할 수 있다.A photocurable composition for a 3D printer according to another embodiment of the present invention includes a photocurable oligomer; reactive monomers; and a photoinitiator, and the reactive monomer may include the compound represented by Chemical Formula 1.
바람직하게는, 상기 3D 프린터용 광경화형 조성물은 나노 클레이를 더 포함하며, 상기 나노 클레이는 상기 반응성 모노머와 전기적 인력의 상호 작용으로 인해, 3D 프린팅에 의해 출력된 출력물의 기계적 물성을 강화할 수 있다.Preferably, the photocurable composition for a 3D printer further includes nanoclay, and the nanoclay may enhance mechanical properties of an output product output by 3D printing due to an interaction between the reactive monomer and electrical attraction.
구체적으로, 상기 나노 클레이는 세피올라이트(Sepiolite)이며, 상기 세피올라이트는 단일 섬유 형태로, 평균 길이는 0.2 내지 4㎛이며, 폭은 10 내지 30nm이고, 평균 두께는 5 내지 10nm이다.Specifically, 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 μm, a width of 10 to 30 nm, and an average thickness of 5 to 10 nm.
상기 나노 클레이는 세피올라이트(Sepiolite)인 것을 특징으로 하나, 상기 나노 클레이는 세피올라이트에 국한되지 않고, 3D 프린터용 광경화형 조성물에 포함되어, 기계적 물성을 강화할 수 있는 나노 클레이는 제한 없이 모두 사용 가능하다.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.
3D 프린팅 재료가 가지는 기계적 강도의 한계를 극복하기 위해 고분자 복합 기술을 적용할 수 있다. 다만, 상기 복합 재료를 3D 프린팅에 적용하려면 몇 가지 문제가 있다. 가장 중요한 문제는 복합 재료에 사용되는 첨가제의 크기이다. 상기 첨가제의 크기가 커짐에 따라 프린팅 gap의 크기도 증가하여, 결과적으로 인쇄 해상도가 낮아지는 문제가 발생할 수 있다.Polymer composite technology can be applied to overcome the limitations of mechanical strength of 3D printing materials. However, 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.
상기 문제를 방지하기 위해, 나노 크기의 물질을 첨가제로 사용할 수 있다. 종래 나노 크기의 재료로 알려진 그래핀, 탄소나노튜브(CNT) 등의 경우, 가격 경쟁력이 문제될 수 있다. 반면, 나노 클레이는 합리적인 가격을 가지고 있어 산업 적용에 더 적합하다. 나노 클레이 중, 세피올라이트(Sepiolite)는 Mg8Si12O30(OH)4·12H2O의 반 단위 셀 공식을 가진 수화된 규산 마그네슘이다.In order to avoid the above problems, nano-sized materials may be used as additives. In the case of graphene, carbon nanotube (CNT), etc., which are conventionally known as nano-sized materials, price competitiveness may be a problem. On the other hand, nanoclay has a reasonable price, making it more suitable for industrial applications. Among nanoclays, sepiolite is a hydrated magnesium silicate with a half unit cell formula of Mg 8 Si 12 O 30 (OH) 4 .12H 2 O.
상기 세피올라이트는 레티스 결정의 형태를 이루고 있다. 보다 구체적으로 섬유 방향에 평행한 여러 블록과 터널로 구성된 바늘 모양 또는 섬유 모양의 형태이다. 각 구조 블록에는 두개의 사면체 실리카(SiO4) 시트가 끼인 중앙 팔면체 마그네슘(MgOH6) 시트가 포함되어 있다. 단일 세피올라이트 섬유는 길이가 0.2 내지 4㎛, 폭이 10 내지 30nm, 두께가 5 내지 10 nm이다.The sepiolite is in the form of lettis crystals. 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. A single sepiolite fiber is 0.2 to 4 μm long, 10 to 30 nm wide, and 5 to 10 nm thick.
상기 세피올라이트를 나노 클레이로 포함하게 되면, 광경화형 조성물 내에서 3D 프린팅이 가능한 점도를 유지하며, 출력된 출력물에 대한 높은 기계적 강도를 나타낼 수 있다.When the sepiolite is included in the nano-clay, it is possible to maintain a viscosity capable of 3D printing in the photocurable composition and exhibit high mechanical strength for the printed product.
즉, 나노 클레이를 다량 포함 시, 광경화형 조성물의 점도가 커지게 되고, 점도가 커지면 상기 조성물이 3D 프린터를 통해 출력물로 제조가 불가능한 문제가 있다. 나노 클레이를 일정량 이상으로 포함 시, 출력물의 기계적 강도가 증가할 수 있으나, 3D 프린팅을 위해선 높은 점도의 조성물은 이용이 불가능한 문제로 인해, 광경화형 조성물의 점도도 일정 범위 내로 포함되는 것이 바람직하다.That is, when a large amount of nano-clay is included, 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. When the nano-clay is included in a certain amount or more, the mechanical strength of the output may increase. However, since a high-viscosity composition cannot be used for 3D printing, the viscosity of the photocurable composition is preferably included within a certain range.
이에, 상기 광경화형 조성물은 UV 레진 100 중량부에 대해, 나노 클레이 0.5 내지 5 중량부 및 광개시제 1 중량부로 포함할 수 있다. 상기 UV 레진은 광경화성 올리고머 및 반응성 모노머를 포함하는 것이다. 상기 범위 내에서 혼합하여 사용 시, 3D 프린터를 이용하여 출력물로 제조가 가능할 뿐 아니라, 제조된 출력물이 우수한 기계적 강도를 나타낼 수 있다. 보다 구체적으로, 상기 3D 프린터는 DLP 방식의 3D 프린터이다.Accordingly, 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 monomer. 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.
상기 광경화성 올리고머는 하기 화학식 3으로 표시되는 화합물일 수 있다:The photocurable oligomer may be a compound represented by Formula 3 below:
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
여기서,here,
n은 1 내지 1,000의 정수이고,n is an integer from 1 to 1,000;
A는 상기 화학식 4 또는 화학식 5로 표시되는 화합물이며,A is a compound represented by Formula 4 or Formula 5,
*는 결합되는 부분을 의미하며,* means the part to be combined,
R7 내지 R12는 서로 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬기, 치환 또는 비치환의 탄소수 1 내지 20개의 시클로알킬기, 치환 또는 비치환의 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환의 탄소수 2 내지 24의 알키닐기, 치환 또는 비치환의 탄소수 7 내지 30의 아르알킬기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴기, 치환 또는 비치환의 탄소수 5 내지 60의 헤테로아릴기, 치환 또는 비치환의 탄소수 6 내지 30의 헤테로아릴알킬기, 치환 또는 비치환의 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬아미노기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴아미노기, 치환 또는 비치환의 탄소수 6 내지 30의 아르알킬아미노기, 치환 또는 비치환의 탄소수 2 내지 24의 헤테로 아릴아미노기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴실릴기 및 치환 또는 비치환의 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택되며,R 7 to R 12 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 alkyl group having 1 to 20 carbon atoms. Cycloalkyl group, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms , A substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, or a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms , substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, substituted or unsubstituted alkylsilyl having 1 to 30 carbon atoms It is selected from the group consisting of a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms,
상기 R7 내지 R12 가 치환되는 경우, 수소, 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 20개의 시클로알킬기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 24의 알키닐기, 탄소수 7 내지 30의 아르알킬기, 탄소수 6 내지 30의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, 탄소수 6 내지 30의 헤테로아릴알킬기, 탄소수 1 내지 30의 알콕시기, 탄소수 1 내지 30의 알킬아미노기, 탄소수 6 내지 30의 아릴아미노기, 탄소수 6 내지 30의 아르알킬아미노기, 탄소수 2 내지 24의 헤테로 아릴아미노기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 6 내지 30의 아릴실릴기 및 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택된 1종 이상의 치환기로 치환되며, 복수 개의 치환기로 치환되는 경우 이들은 서로 동일하거나 상이하다.When R 7 to R 12 are substituted, hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and a carbon atom Alkynyl group of 2 to 24, aralkyl group of 7 to 30 carbon atoms, aryl group of 6 to 30 carbon atoms, heteroaryl group of 5 to 60 nuclear atoms, heteroarylalkyl group of 6 to 30 carbon atoms, alkoxy group of 1 to 30 carbon atoms , C1-30 alkylamino group, C6-30 arylamino group, C6-30 aralkylamino group, C2-24 heteroarylamino group, C1-30 alkylsilyl group, C6-30 aryl It is substituted with one or more substituents selected from the group consisting of a silyl group and an aryloxy group having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, they are the same as or different from each other.
구체적으로, 상기 R7 내지 R12는 서로 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, 히드록시기 및 탄소수 1 내지 30의 알킬기로 이루어진 군으로부터 선택될 수 있다.Specifically, R 7 to R 12 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.
보다 구체적으로, 상기 광경화성 올리고머는 상기 화학식 3으로 표시되는 화합물이며, 상기 A가 화학식 4로 선택되는 화합물 및 상기 A가 화학식 5로 선택되는 화합물을 모두 포함한다.More specifically, the photocurable oligomer is a compound represented by Formula 3, and includes both a compound in which A is selected from Formula 4 and a compound in which A is selected from Formula 5.
보다 구체적으로, UV 경화를 위하여, 광경화 작용기가 결합된 고분자 화합물로, 탄소 간의 이중결합 구조를 포함하고 있고, 상기 탄소-탄소 이중 결합에 의해 광경화 작용을 나타낼 수 있다.More specifically, 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.
또한, 상기 광경화성 올리고머는 메인 체인으로 폴리 우레탄 구조를 포함하며, 상기 폴리 우레탄 구조에 광경화 작용기가 결합되고, 화합물 내 소프트 작용기 및 하드 작용기를 포함한 것을 특징으로 한다.In addition, 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.
상기 광경화성 조성물 내 포함된 소프트 작용기에 의해 출력물은 플렉서블한 성질을 나타내며, 또한, 하드 작용기에 의해, 열 저항성(Heat resistant)을 나타낼 수 있다.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.
즉, 광경화성 올리고머에 광경화 작용기를 결합시키고, 소프트 작용기 및 하드 작용기를 이용함에 따라, 상온에서 부드러운 성질을 갖는 탄소 골격을 이용하여, 플렉서블 효과를 나타낼 수 있을 뿐만 아니라, 상온에서 하드한 성질을 갖는 탄소 골격을 이용하여, 열에 강한 성질을 함께 나타낼 수 있다.That is, as the photocurable functional group is bonded to the photocurable oligomer and the soft functional group and the hard functional group are used, 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. By using the carbon skeleton having a carbon skeleton, it is possible to exhibit a property that is resistant to heat.
상기 광경화성 올리고머는 하드한 성질을 갖는 탄소 골격을 포함함에 따라, 열적 물성, 강도, 탄성율 및 인장신율과 같은 물리적 특성이 우수하고, 열에 의해 원래의 형상으로 복원이 가능한 3D 프린팅 출력물을 제조할 수 있다.As 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.
또한, 광경화성 올리고머는 소프트한 성질을 갖는 탄소 골격을 포함함에 따라, 열이 제공된 후 외력에 의해 형상의 변형이 가능하다.In addition, 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.
일반적으로, 3D 프린터용 조성물은 출력물의 물리적인 특성을 높이기 위해, 하드한 성질을 갖는 탄소 골격만을 포함하고, 이는 출력물의 물리적 특성을 높일 수 있으나, 반대로, 사용에 의해 형상이 변형되는 경우, 형상 복원이 불가하여, 다 회 사용이 불가한 문제가 있다.In general, 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.
본 발명에서의 3D 프린터용 조성물은 하드한 성질을 갖는 탄소 골격 및 소프트한 성질을 갖는 탄소 골격을 포함함에 따라, 열적 물성, 강도, 탄성율 및 인장신율과 같은 물리적 특성이 우수할 뿐만 아니라, 소프트 작용기의 플렉서블한 성질을 함께 이용할 수 있어, 열이 제공된 상태에서 외력에 의해 형상을 변형시키면 변형된 형상으로 고정될 수 있고, 이후 다시 열이 제공되면 원래의 형상으로 복원을 가능하게 한다.As the 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.
후술하는 바와 같이, 본 발명의 3D 프린터용 광경화형 조성물은 투명 치아 교정 장치로 이용될 수 있으며, 상기 투명 치아 교정 장치는 환자의 치아에 끼워진 상태에서, 원하는 치아의 위치로 교정하기 위해 사용되는 것이다. 이에 3D 프린터로 출력된 투명 치아 교정 장치는 현재 환자의 치아 위치에서의 저항에 대해 파손되지 않을 물리적 특성을 나타내야 하며, 치아를 교정하고자 하는 위치로 이동할 수 있는 힘을 제공할 수 있어야 한다. 본 발명의 투명 치아 교정 장치의 교정 효과 및 교정 원리에 대해서는 후술하고자 한다. 다만, 상기 본 발명의 3D 프린터용 광경화형 조성물은, 광경화성 올리고머에 소프트한 작용기 및 하드한 작용기를 모두 포함하고 있어, 물리적인 특성이 우수할 뿐 아니라, 열이 가해진 상태에서의 형상 변형이 가능할 뿐 아니라, 열에 의해 원래의 형상으로의 복원도 가능한 특성으로 인해 우수한 교정력을 가지는 투명 치아 교정 장치로 제조가 가능하다.As will be described later, 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. . Accordingly, 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. However, 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. In addition, it is possible to manufacture a transparent orthodontic appliance having excellent orthodontic power due to the property that it can be restored to its original shape by heat.
또한, 앞서 설명한 바와 같이 상기 광경화형 조성물은 나노 클레이를 추가로 포함하고 있어, 물리적 특성이 보완되어 높은 교정력을 나타낼 수 있다.In addition, as described above, the photocurable composition additionally includes nano-clay, so that physical properties can be supplemented to exhibit high corrective power.
보다 구체적으로, 상기 반응성 모노머는 하기 화학식 1로 표시되는 화합물을 포함할 수 있다:More specifically, the reactive monomer may include a compound represented by Formula 1 below:
[화학식 1][Formula 1]
[화학식 2][Formula 2]
여기서,here,
*는 결합되는 부분을 의미하며,* means the part to be combined,
X1 및 X2는 서로 동일하거나 상이하며, 각각 독립적으로 NR6, O 및 S로 이루어진 군으로부터 선택되고,X 1 and X 2 are the same as or different from each other, and are each independently selected from the group consisting of NR 6 , O and S;
Ar은 상기 화학식 2로 표시되는 화합물이며,Ar is a compound represented by Formula 2 above,
L1 및 L2는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합, 치환 또는 비치환된 탄소수 6 내지 30의 아릴렌기, 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴렌기, 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬렌기, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알케닐렌기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로시클로알킬렌기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로알케닐렌기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로시클로알케닐렌기 및 탄소수 2 내지 20의 알키닐렌기로 이루어진 군에서 선택되며,L 1 and L 2 are the same as or different from each other, and are each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted An alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms , substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms, substituted or unsubstituted It is selected from the group consisting of a heterocycloalkenylene group having 3 to 20 carbon atoms and an alkynylene group having 2 to 20 carbon atoms,
R1 내지 R6는 서로 동일하거나 상이하며 각각 독립적으로 수소, 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬기, 치환 또는 비치환의 탄소수 1 내지 20개의 시클로알킬기, 치환 또는 비치환의 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환의 탄소수 2 내지 24의 알키닐기, 치환 또는 비치환의 탄소수 7 내지 30의 아르알킬기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴기, 치환 또는 비치환의 탄소수 5 내지 60의 헤테로아릴기, 치환 또는 비치환의 탄소수 6 내지 30의 헤테로아릴알킬기, 치환 또는 비치환의 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬아미노기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴아미노기, 치환 또는 비치환의 탄소수 6 내지 30의 아르알킬아미노기, 치환 또는 비치환의 탄소수 2 내지 24의 헤테로 아릴아미노기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴실릴기 및 치환 또는 비치환의 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택되며,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. An alkyl group, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, A substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, A substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, or a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms , It is selected from the group consisting of a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms,
상기 L1, L2 및 R1 내지 R6이 치환되는 경우, 수소, 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 20개의 시클로알킬기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 24의 알키닐기, 탄소수 7 내지 30의 아르알킬기, 탄소수 6 내지 30의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, 탄소수 6 내지 30의 헤테로아릴알킬기, 탄소수 1 내지 30의 알콕시기, 탄소수 1 내지 30의 알킬아미노기, 탄소수 6 내지 30의 아릴아미노기, 탄소수 6 내지 30의 아르알킬아미노기, 탄소수 2 내지 24의 헤테로 아릴아미노기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 6 내지 30의 아릴실릴기 및 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택된 1종 이상의 치환기로 치환되며, 복수 개의 치환기로 치환되는 경우 이들은 서로 동일하거나 상이하다.When L 1 , L 2 and R 1 to R 6 are substituted, hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 2 to 20 carbon atoms Alkenyl group having 30 carbon atoms, alkynyl group having 2 to 24 carbon atoms, 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, carbon atoms An alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, a heteroarylamino group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, It is substituted with one or more substituents selected from the group consisting of an arylsilyl group having 6 to 30 carbon atoms and an aryloxy group having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, they are the same as or different from each other.
구체적으로, 상기 X1 및 X2는 O일 수 있다.Specifically, the X 1 and X 2 may be O.
구체적으로, 상기 R1 내지 R4는 서로 동일하거나 상이하며 각각 독립적으로 수소, 할로겐기, 히드록시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬기, 치환 또는 비치환의 탄소수 2 내지 30의 알케닐기 및 치환 또는 비치환의 탄소수 2 내지 24의 알키닐기로 이루어진 군으로부터 선택될 수 있다.Specifically, R 1 to R 4 are the same as or different from each other and are each independently hydrogen, a halogen group, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, and a substituted or It may be selected from the group consisting of an unsubstituted C2-C24 alkynyl group.
구체적으로, 상기 R5는 수소 및 치환 또는 비치환의 탄소수 1 내지 30의 알킬기로 이루어진 군으로부터 선택될 수 있다.Specifically, R 5 may be selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
구체적으로, 상기 L1 및 L2는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합, 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐렌기 및 탄소수 2 내지 20의 알키닐렌기로 이루어진 군에서 선택될 수 있다.Specifically, L 1 and L 2 are the same as or different from each other, and are each independently a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, and a carbon number It may be selected from the group consisting of 2 to 20 alkynylene groups.
바람직하게는 상기 반응성 모노머는 상기 화학식 1로 표시되는 화합물을 포함할 수 있으며, 상기 R5가 수소로 선택되는 화합물 및 상기 R5가 비치환의 탄소수 1 내지 30의 알킬기로 선택되는 화합물을 모두 포함한다.Preferably, the reactive monomer may include the compound represented by Formula 1, and includes both a compound in which R 5 is hydrogen and a compound in which R 5 is selected from an unsubstituted alkyl group having 1 to 30 carbon atoms. .
보다 바람직하게는 상기 반응성 모노머는 하기 화학식 6으로 표시되는 화합물 및 하기 화학식 7로 표시되는 화합물을 포함하는 것이다:More preferably, the reactive monomer includes a compound represented by Formula 6 and a compound represented by Formula 7 below:
[화학식 6][Formula 6]
[화학식 7][Formula 7]
본 발명의 다른 일 실시예에 따른 투명 치아 교정 장치는 상기 3D 프린터용 광경화형 조성물을 포함할 수 있다.The transparent orthodontic appliance according to another embodiment of the present invention may include the photocurable composition for the 3D printer.
본 발명의 투명 교정 장치는 광경화형 조성물을 이용하여 3D 프린팅으로 출력된 것이며, 기존 투명 치아 교정 장치와 달리 치아의 굴곡면까지 정밀하게 재현이 가능하고, 치아와의 밀착력이 높아 교정 효과가 우수하다.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. .
본 발명의 투명 치아 교정 장치는 환자의 치아 구조에 대한 데이터를 획득하고 이를 출력하여 제조하는 것으로, 치아 구조와 편차가 50 내지 80㎛로 거의 차이가 없이 제조가 가능한 반면, 종래 투명 치아 교정 장치는 환자의 치아와 편차가 200 내지 300㎛로 나타나 밀착하지 못해 교정력이 떨어진다.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 μm, whereas the conventional transparent orthodontic device The deviation from the patient's teeth appears to be 200 to 300 μm, so the orthodontic force is poor because it cannot be closely adhered to.
본 발명의 투명 치아 교정 장치는 40℃ 이상으로 가열 후, 환자의 치아에 끼워 치아와 밀착된 형태로 형상이 고정되며, 상기 치아에 밀착된 투명 치아 교정 장치는 체온에 의해 원래의 형상으로 복원되어 치아를 교정하는 것이다.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
상기 본 발명의 투명 치아 교정 장치는 가열된 물 속에 넣었다 빼면, 형상의 변형이 가능하다. 열을 가하게 되면 일정 시간 유연성이 나타나게 되어, 형상의 변형이 가능하게 되는데, 이러한 성질을 이용하여, 투명 치아 교정 장치를 환자의 치아에 끼우기 전에 60 내지 100℃의 물에 담근 후, 꺼내서 치아에 끼운 후 손으로 간단히 눌러주면, 치아에 밀착하는 형태로 형상이 변형된다.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.
이후, 구강 내 체온에 의해 투명 치아 교정 장치에 열이 제공되게 되면 본래 출력된 형태로의 복원이 일어나게 된다.Thereafter, when heat is provided to the transparent orthodontic device by body temperature in the oral cavity, restoration to the original output form occurs.
즉, 60 내지 100℃의 물에 담근 후, 치아에 끼우고, 형태를 치아와 동일한 형태로 변형시키고 나면, 본 발명의 투명 치아 교정 장치는 현재 환자의 치아 구조에 맞춰 형상이 변형되게 되고, 이후 체온에 의해 열이 제공되면 원래 출력된 형태로 서서히 복원되게 되고, 이때 투명 치아 교정 장치가 원래의 형상으로 복원하고자 하는 힘에 의해, 치아를 교정하고자 하는 위치로 이동시키게 된다.That is, after immersing it in water at 60 to 100 ° C., inserting it into the teeth, and transforming the shape into the same shape as 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.
즉, 종래 치아 교정 장치는 환자의 치아 구조로부터 획득된 정보에서 단계적으로 교정하고자 하는 치아의 위치에 맞춰 투명 치아 교정 장치로 제조한 후, 치아에 끼워, 경질 소재의 성질에 의해 치아를 이동시키게 된다. 앞서 설명한 바와 같이 종래 투명 치아 교정 장치는 소재의 성질에 의해 치아를 이동시키는 것으로, 치아 내 균일한 힘이 제공되지 못하여, 치아 교정 효과가 떨어진다.That is, 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. . As described above, 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.
반면, 본 발명의 투명 치아 교정 장치는 앞서 설명한 바와 같이, 투명 치아 교정 장치가 최초 사용 시, 치아의 구조와 동일한 상태로 변형된 상태이나, 체온에 의해 열이 제공되면, 투명 치아 교정 장치가 원래의 형상으로 복원되어, 치아에 힘이 전달되는 것으로, 치아에 전달되는 힘이 교정 장치의 소재에 의한 힘이 아니며, 형상의 복원에 의한 힘의 발생 및 전달인 점에서 치아 전체에 균일한 힘이 제공되고, 치아가 전체로 이동할 수 있게 된다.On the other hand, as described above, 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.
본 발명의 다른 일 실시예에 따른 3D 프린터용 광경화형 조성물의 제조 방법은 1) 1종 이상의 반응성 모노머를 혼합하고 교반하는 단계; 2) 상기 반응성 모노머에 나노 클레이를 첨가하고, 분쇄 및 분산하여 제1 혼합물을 제조하는 단계; 3) 50 내지 70℃ 오븐에서 10 내지 15시간 동안 가열한 광경화성 올리고머를 상기 제1 혼합물에 넣고 제2 혼합물을 제조하는 단계; 및 4) 상기 제2 혼합물에 광개시제를 추가하고 혼합 및 탈포하는 단계를 포함할 수 있다.A method for preparing a photocurable composition for a 3D printer according to another embodiment of the present invention includes the steps of 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.
상기 1) 단계는, 반응성 모노머를 혼합하고 교반하는 단계로, 하기 화학식 6으로 표시되는 화합물 및 하기 화학식 7로 표시되는 화합물을 혼합하고 교반하는 것이다:Step 1) is a step of mixing and stirring a reactive monomer, mixing and stirring a compound represented by the following formula (6) and a compound represented by the following formula (7):
[화학식 6][Formula 6]
[화학식 7][Formula 7]
상기 반응성 모노머는 동일한 중량 비율로 혼합하고 교반하는 단계이다. 이후, 반응성 모노머가 혼합된 혼합물에 나노 클레이를 첨가하고, 분쇄 및 분산하여 제1 혼합물을 제조한다.The reactive monomers are mixed and stirred in the same weight ratio. Thereafter, the nano-clay is added to the mixture in which the reactive monomer is mixed, and pulverized and dispersed to prepare a first mixture.
상기 제1 혼합물은 나노 클레이가 균일하게 분산된 형태이며, 보다 구체적으로 팁 초음파 처리기를 이용하여, 700 내지 800w의 출력으로 30초 내지 90초 동안 분쇄 및 분산 공정을 진행한다. 상기와 같은 분쇄 및 분산 공정이 아닌 다른 분산 공정으로 진행 시, 나노 클레이가 균일하게 분산되지 않고, 분산 안정성이 떨어져 시간의 경과 시, 제1 혼합물이 층 분리가 일어나게 된다. 즉 상기와 같은 분산 방법에 의해 분산 시 균일하게 분산될 뿐 아니라, 우수한 안정성을 나타낼 수 있다.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. When proceeding with a dispersion process other than the above grinding and dispersion process, 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 dispersed by the above-mentioned dispersion method, it is not only uniformly dispersed, but also exhibits excellent stability.
이후, 50 내지 70℃ 오븐에서 10 내지 15시간 동안 가열한 광경화성 올리고머를 상기 제1 혼합물에 넣고 제2 혼합물을 제조한다. 상기 광경화성 올리고머는 점도가 높아 상온에서 혼합이 어려워, 오븐에서 가열하여 혼합한다.Thereafter, 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.
마지막으로 광개시제를 추가하고 페이스트 믹서를 사용하여 혼합 및 탈포하여 광경화형 조성물을 제조한다.Finally, a photoinitiator is added and mixed and defoamed using a paste mixer to prepare a photocurable composition.
구체적으로, 상기 광개시제는 하기 화학식 8로 표시되는 화합물이다:Specifically, the photoinitiator is a compound represented by Formula 8 below:
[화학식 8][Formula 8]
상기 광경화형 조성물은 광경화성 올리고머; 반응성 모노머; 광개시제; 및 나노 클레이 이외에 추가로 첨가제를 포함할 수 있으며, 상기 첨가제는 열적 및 산화 안정성, 저장안정성, 표면특성, 유동 특성 및 공정 특성 등을 향상시키기 위하여 예를 들어 레벨링제, 슬립제 또는 안정화제 등의 통상의 첨가제를 포함할 수 있다.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.
본 발명의 일 실시예에 따른 광경화형 조성물은 UV 레진 100 중량부에 대해, 나노 클레이 0.5 내지 5 중량부 및 광개시제 1 중량부로 포함할 수 있다. 상기 UV 레진은 본 발명의 광경화성 올리고머; 및 반응성 모노머를 포함하는 것으로, 보다 구체적으로 하기 화학식 3로 표시되는 화합물 중 A가 화학식 4로 선택되는 화합물, 하기 화학식 3으로 표시되는 화합물 중 A가 화학식 5로 선택되는 화합물, 하기 화학식 6으로 표시되는 화합물 및 하기 화학식 7로 표시되는 화합물을 1:1:1:1 내지 1:2:1:1의 중량 비율로 포함할 수 있다: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 4 among compounds represented by Formula 3 below, a compound in which A is selected from Formula 5 among compounds represented by Formula 3 below, and a compound represented by Formula 6 below The compound and the compound represented by Formula 7 may be included in a weight ratio of 1:1:1:1 to 1:2:1:1:
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
[화학식 6][Formula 6]
[화학식 7][Formula 7]
여기서,here,
n은 1 내지 1,000의 정수이고,n is an integer from 1 to 1,000;
A는 상기 화학식 4 또는 화학식 5로 표시되는 화합물이며,A is a compound represented by Formula 4 or Formula 5,
*는 결합되는 부분을 의미하며,* means the part to be combined,
R7 내지 R12는 서로 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬기, 치환 또는 비치환의 탄소수 1 내지 20개의 시클로알킬기, 치환 또는 비치환의 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환의 탄소수 2 내지 24의 알키닐기, 치환 또는 비치환의 탄소수 7 내지 30의 아르알킬기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴기, 치환 또는 비치환의 탄소수 5 내지 60의 헤테로아릴기, 치환 또는 비치환의 탄소수 6 내지 30의 헤테로아릴알킬기, 치환 또는 비치환의 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬아미노기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴아미노기, 치환 또는 비치환의 탄소수 6 내지 30의 아르알킬아미노기, 치환 또는 비치환의 탄소수 2 내지 24의 헤테로 아릴아미노기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴실릴기 및 치환 또는 비치환의 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택되며,R 7 to R 12 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 alkyl group having 1 to 20 carbon atoms. Cycloalkyl group, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms , A substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, or a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms , substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, substituted or unsubstituted alkylsilyl having 1 to 30 carbon atoms It is selected from the group consisting of a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms,
상기 R7 내지 R12 가 치환되는 경우, 수소, 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 20개의 시클로알킬기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 24의 알키닐기, 탄소수 7 내지 30의 아르알킬기, 탄소수 6 내지 30의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, 탄소수 6 내지 30의 헤테로아릴알킬기, 탄소수 1 내지 30의 알콕시기, 탄소수 1 내지 30의 알킬아미노기, 탄소수 6 내지 30의 아릴아미노기, 탄소수 6 내지 30의 아르알킬아미노기, 탄소수 2 내지 24의 헤테로 아릴아미노기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 6 내지 30의 아릴실릴기 및 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택된 1종 이상의 치환기로 치환되며, 복수 개의 치환기로 치환되는 경우 이들은 서로 동일하거나 상이하다.When R 7 to R 12 are substituted, hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and a carbon atom Alkynyl group of 2 to 24, aralkyl group of 7 to 30 carbon atoms, aryl group of 6 to 30 carbon atoms, heteroaryl group of 5 to 60 nuclear atoms, heteroarylalkyl group of 6 to 30 carbon atoms, alkoxy group of 1 to 30 carbon atoms , C1-30 alkylamino group, C6-30 arylamino group, C6-30 aralkylamino group, C2-24 heteroarylamino group, C1-30 alkylsilyl group, C6-30 aryl It is substituted with one or more substituents selected from the group consisting of a silyl group and an aryloxy group having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, they are the same as or different from each other.
제조예manufacturing example
반응성 모노머의 제조Preparation of reactive monomers
triethylamine 촉매 조건에서 아이소소바이드(isosorbide)에 acryloyl chloride를 첨가하고, nucleophilic acyl substitution 반응을 진행시켜 하얀 가루 성상 파우더 형태의 상기 화학식 6으로 표시되는 화합물을 수득하였다.Acryloyl chloride was added to isosorbide under triethylamine catalyst conditions, and a nucleophilic acyl substitution reaction was performed to obtain a compound represented by Formula 6 in the form of a white powdery powder.
이와 유사하게, triethylamine 촉매 조건에서 아이소소바이드(isosorbide)에 methacryloyl chloride를 첨가하고, nucleophilic acyl substitution 반응을 진행시켜 노란색 액체 성상의 상기 화학식 7로 표시되는 화합물을 수득하였다.Similarly, methacryloyl chloride was added to isosorbide under triethylamine catalyst conditions, and a nucleophilic acyl substitution reaction was performed to obtain a compound represented by Formula 7 in the form of a yellow liquid.
한편, 도 1 은 상기 화학식 6으로 표시되는 화합물의 1H NMR 및 13C NMR 분석 결과를 나타낸 것이며, 도 2는 상기 화학식 7로 표시되는 화합물의 1H NMR 및 13C NMR 분석 결과를 나타낸 것이다.Meanwhile, FIG. 1 shows the results of 1 H NMR and 13 C NMR analysis of the compound represented by Formula 6, and FIG. 2 shows the results of 1 H NMR and 13 C NMR analysis of the compound represented by Formula 7.
광경화형 조성물의 제조Preparation of photocurable composition
하기 화학식 6 및 화학식 7로 표시되는 모노머를 1:1의 중량 비율로 혼합하고, 세피올라이트를 첨가한 후, 팁 초음파 처리기를 이용하여, 750w 출력으로 1 분간 분쇄 및 분산하였다. 이후, 60℃ 오븐에서 12 시간 동안 가열하여 유동성이 확보된 광경화성 올리고머를 혼합하였다. 상기 광경화성 올리고머는 하기 화학식 3으로 표시되는 화합물이며, A가 화학식 4로 선택되는 화합물 및 A가 화학식 5로 선택되는 화합물을 모두 포함하고, 화학식 4로 선택되는 화합물 및 화학식 5로 선택되는 화합물을 1:1.5의 중량 비율로 포함한다. 이후 하기 화학식 8로 표시되는 광개시제를 혼합하고, 페이스트 믹서를 사용하여 혼합 및 탈포하였다.The monomers represented by Chemical Formulas 6 and 7 were mixed in a weight ratio of 1:1, sepiolite was added, and then pulverized and dispersed for 1 minute at a power of 750 w 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 3 below, including both a compound in which A is selected from Formula 4 and a compound in which A is selected from Formula 5, and a compound selected from Formula 4 and a compound selected from Formula 5 in a weight ratio of 1:1.5. Then, a photoinitiator represented by Formula 8 was mixed, and mixed and defoamed using a paste mixer.
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
[화학식 6][Formula 6]
[화학식 7][Formula 7]
[화학식 8][Formula 8]
여기서,here,
n은 1 내지 1,000의 정수이며,n is an integer from 1 to 1,000;
*은 결합되는 부분을 의미하며,* means the part to be combined,
R7 내지 R12는 메틸기이다.R 7 to R 12 are methyl groups.
상기 광경화형 조성물에 대한 중량 비율은 하기 표 1과 같다.The weight ratio of the photocurable composition is shown in Table 1 below.
구성composition | 샘플명sample name | 세피올라이트sepiolite | |
UV 레진UV resin | 광개시제photoinitiator | ||
100100 | 1One | 실시예 1Example 1 | 00 |
실시예 2Example 2 | 0.30.3 | ||
실시예 3Example 3 | 0.50.5 | ||
실시예 4Example 4 | 1One | ||
실시예 5Example 5 | 22 | ||
실시예 6Example 6 | 33 | ||
실시예 7Example 7 | 55 | ||
실시예 8Example 8 | 77 |
(단위 중량부)(unit weight parts)
여기서 UV 레진은 광경화성 올리고머 및 모노머를 포함하는 것으로, 화학식 3의 A가 화학식 4로 선택되는 화합물, 화학식 5로 선택되는 화합물, 화학식 6으로 표시되는 모노머 및 화학식 7로 표시되는 모노머를 1:1.5:1:1의 중량비율로 포함하는 것이다.Here, the UV resin includes photocurable oligomers and monomers, and A of Formula 3 is a compound selected from Formula 4, a compound selected from Formula 5, a monomer represented by Formula 6, and a monomer represented by Formula 7 in a ratio of 1:1.5 It is included in a weight ratio of 1:1.
보관 안정성 평가Storage stability evaluation
반응성 모노머 및 세피올라이트의 분산에 의한 보관 안정성을 평가하기 위해, 세피올라이트 및 반응성 모노머가 혼합된 용액을 3일 동안 보관하여 층 분리 발생 여부를 확인하였으며, 그 결과는 하기 표 1과 같다.In order to evaluate the storage stability due to the dispersion of the reactive monomer and sepiolite, the mixed solution of sepiolite and the reactive monomer was stored for 3 days to check whether layer separation occurred, and the results are shown in Table 1 below.
3일 보관 후, 층 분리가 발생한 경우 "O" 로, 층 분리가 발생하지 않은 경우 "Ⅹ"로 나타내었다.After storage for 3 days, the case where layer separation occurred was indicated by "O", and the case where layer separation did not occur was indicated by "X".
실시예 2Example 2 | 실시예 3Example 3 | 실시예 4Example 4 | 실시예 5Example 5 | 실시예 6Example 6 | 실시예 7Example 7 | 실시예 8Example 8 | |
층분리 여부Floor separation | ⅩX | ⅩX | ⅩX | ⅩX | ⅩX | ⅩX | ⅩX |
상기 결과를 볼 때, 3일 경과 후, 모두 층 분리가 일어나지 않고, 안정하게 유지되는 것을 확인할 수 있다. 세피올라이트는 클레이의 일 종류로, 모노머와 분산이 용이하지 않고, 분산 후에도 보관 안성성이 떨어지는 문제가 있다. 다만, 본 발명에서와 같이 팁소닉 장비를 이용하여 분쇄 및 분산 공정을 진행하게 되면, 균일하게 분산될 뿐 아니라, 장기간 보관 시에도 우수한 안정성을 나타냄을 확인하였다.Looking at the above results, it can be confirmed that after 3 days, all layers do not separate 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. However, it was confirmed that, as in the present invention, when 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.
물성 평가 실험Physical property evaluation experiment
인장 시험 조건Tensile test conditions
시험 방법: ASTM D638Test method: ASTM D638
시험 기기: Universal Testing MachineTest Machine: Universal Testing Machine
시험 속도: 50mm/minTest speed: 50mm/min
그립 간 거리: 115mmDistance between grips: 115 mm
로드셀: 3000NLoad cell: 3000N
탄성구간: (0.05 ~ 0.25)%Elastic range: (0.05 ~ 0.25)%
항복점: 0.2% offsetYield point: 0.2% offset
시험환경: (23±2)℃, (50±5)% R.H.Test environment: (23±2)℃, (50±5)% R.H.
상기 실험은 한국고분자시험연구소에 의뢰하여 실험을 진행하였으며, 시편은 상기 표 1의 실시예 1 내지 8의 광경화성 조성물을 DLP 방식을 이용하여, ISO 20795-2 기준의 시편으로 출력하여 제공하였다. The experiment was carried out by requesting the Korea Polymer Testing Laboratory, and the specimen was provided by outputting the photocurable compositions of Examples 1 to 8 in Table 1 as a specimen of ISO 20795-2 standard using the DLP method.
실시예 1 내지 8에 대해, 인장시험 및 굴곡시험을 진행하였으며, 그 결과는 하기 표 2와 같다. For Examples 1 to 8, a tensile test and a bending test were performed, and the results are shown in Table 2 below.
실시예 1Example 1 | 실시예 2Example 2 | 실시예 3Example 3 | 실시예 4Example 4 | 실시예 5Example 5 | 실시예 6Example 6 | 실시예 7Example 7 | 실시예 8Example 8 | |
인장 강도(MPa)Tensile strength (MPa) | 46.1546.15 | 52.5552.55 | 58.2358.23 | 57.1257.12 | 59.3259.32 | 58.1758.17 | 57.5457.54 | 53.2153.21 |
연신율(%)Elongation (%) | 36.2536.25 | 38.1238.12 | 43.5943.59 | 44.1444.14 | 44.5644.56 | 45.5645.56 | 43.1143.11 | 37.2237.22 |
탄성 계수(MPa)Modulus of elasticity (MPa) | 16101610 | 17001700 | 18201820 | 18801880 | 18901890 | 18861886 | 18851885 | 17101710 |
상기 실험 결과에 의하면, 본 발명의 광경화성 조성물을 이용한 시편은 대체로 인장 강도가 우수하고, 높은 수준의 연신율 및 탄성력을 나타내는 것을 알 수 있다. 한편, 실시예 3 내지 7에서 그 효과가 가장 우수함을 확인하였다.According to the above experimental results, it can be seen that the specimens using the photocurable composition of the present invention generally have excellent tensile strength and exhibit high levels of elongation and elasticity. On the other hand, it was confirmed that the effect was the most excellent in Examples 3 to 7.
열에 의한 형상 변형 및 형상 복원 여부Shape deformation and shape restoration due to heat
상기와 마찬가지로 한국고분자시험연구소에 의뢰하여 실험을 진행하였으며, 시편은 상기 표 1의 실시예 1 내지 8의 광경화성 조성물을 DLP 방식을 이용하여, ISO 20795-2 기준의 시편으로 출력하여 제공하였다.As above, the experiment was conducted by requesting the Korea Polymer Testing Laboratory, and the specimen was provided by outputting the photocurable compositions of Examples 1 to 8 in Table 1 as a specimen of ISO 20795-2 standard using the DLP method.
구체적으로, 각 시편의 열에 의한 변형 및 형상 복원 여부에 대해 실험을 진행하였으며, 실험방법은 실시예 1 내지 8의 조성물을 이용하여 제조된 각 100개의 시편을 50 내지 100℃의 물에 담근 후, 외력을 가하여 형태를 변형시키고, 변형된 형태가 고정되는지 여부 및 변형된 형태에서 다시 50 내지 100℃ 사이의 물에 담근 후, 20 내지 30℃의 조건 하에서 원래의 형태로 복원되지는 여부를 확인하였다.Specifically, an experiment was conducted on whether each specimen was deformed by heat and whether the shape was restored, and the experimental method was to immerse each of 100 specimens prepared using the compositions of Examples 1 to 8 in water at 50 to 100 ° C., It was confirmed whether the shape was deformed by applying an external force, whether the deformed shape was fixed, and whether the deformed shape was restored to its original shape after being immersed in water between 50 and 100 ° C. and then restored to its original shape under conditions of 20 to 30 ° C. .
최초 50 내지 100℃의 물에 담근 후, 외력에 의해 형상이 변형되어 변형된 형상이 고정되고, 다시 50 내지 100℃의 물에 담근 후, 20 내지 30℃에서 형상이 원래대로 복원되는 시편의 갯수가 90개 이상인 경우를 O로 표시하고, 50개 이상 90개 미만인 경우 △로 표시하였으며, 50개 미만인 경우를 X로 표시하였다.After being immersed in water at 50 to 100 ° C for the first time, the shape is deformed by external force, the deformed shape is fixed, and after being immersed in water at 50 to 100 ° C, the shape is restored to its original shape at 20 to 30 ° C. Number of specimens 90 or more were marked as O, 50 or more and less than 90 were marked with △, and less than 50 were marked with X.
그 결과는 하기 표 4와 같다.The results are shown in Table 4 below.
실시예 1Example 1 | 실시예 2Example 2 | 실시예 3Example 3 | 실시예 4Example 4 | 실시예 5Example 5 | 실시예 6Example 6 | 실시예 7Example 7 | 실시예 8Example 8 | |
△△ | △△ | OO | OO | OO | OO | OO | △△ |
상기 표 4에 따르면, 본 발명의 조성물에 의할 경우, 대체로 쉽게 접근이 가능한 정수기의 온수 정도(50 내지 70℃)에 넣은 후, 형태의 변형이 가능하고 변형된 형태로의 고정이 가능하였으며, 다시 온수 온도의 물에 넣고 외력을 가하지 않으면 원래의 형태로 복원됨을 확인하였다.한편, 실시예 3 내지 7에서 상기 효과가 가장 우수함을 확인하였다.According to Table 4, in the case of the composition of the present invention, after putting it in the hot water level (50 to 70 ° C.) of a water purifier that is generally easily accessible, the shape can be modified and fixed in a deformed form, It was confirmed that the original shape was restored if no external force was applied after putting it in hot water temperature again.
이상에서 본 발명의 바람직한 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고 다음의 청구범위에서 정의하고 있는 본 발명의 기본 개념을 이용한 당업자의 여러 변형 및 개량 형태 또한 본 발명의 권리범위에 속하는 것이다.Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concept of the present invention defined in the following claims are also made according to the present invention. falls within the scope of the rights of
본 발명은 신규한 유기 화합물 및 이를 포함하는 3D 프린터용 광경화형 조성물에 관한 것으로, 보다 상세하게는 3D 프린팅으로 출력된 출력물의 기계적 물성을 강화하고, 3D 프린팅이 가능한 점도를 유지할 수 있는 신규한 유기 화합물 및 이를 포함하는 광경화형 조성물에 관한 것이다.The present invention relates to a novel organic compound and a photocurable composition for a 3D printer containing the same, and more particularly, to a novel organic compound capable of enhancing mechanical properties of a 3D printed output and maintaining a viscosity capable of 3D printing. It relates to a compound and a photocurable composition containing the same.
Claims (7)
- 하기 화학식 1로 표시되는 화합물:A compound represented by Formula 1 below:[화학식 1][Formula 1][화학식 2][Formula 2]여기서,here,*는 결합되는 부분을 의미하며,* means the part to be combined,X1 및 X2는 서로 동일하거나 상이하며, 각각 독립적으로 NR6, O 및 S로 이루어진 군으로부터 선택되고,X 1 and X 2 are the same as or different from each other, and are each independently selected from the group consisting of NR 6 , O and S;Ar은 상기 화학식 2로 표시되는 화합물이며,Ar is a compound represented by Formula 2 above,L1 및 L2는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합, 치환 또는 비치환된 탄소수 6 내지 30의 아릴렌기, 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴렌기, 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬렌기, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐렌기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알케닐렌기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로알킬렌기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로시클로알킬렌기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로알케닐렌기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로시클로알케닐렌기 및 탄소수 2 내지 20의 알키닐렌기로 이루어진 군에서 선택되며,L 1 and L 2 are the same as or different from each other, and are each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted An alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms , substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms, substituted or unsubstituted It is selected from the group consisting of a heterocycloalkenylene group having 3 to 20 carbon atoms and an alkynylene group having 2 to 20 carbon atoms,R1 내지 R6는 서로 동일하거나 상이하며 각각 독립적으로 수소, 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬기, 치환 또는 비치환의 탄소수 1 내지 20개의 시클로알킬기, 치환 또는 비치환의 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환의 탄소수 2 내지 24의 알키닐기, 치환 또는 비치환의 탄소수 7 내지 30의 아르알킬기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴기, 치환 또는 비치환의 탄소수 5 내지 60의 헤테로아릴기, 치환 또는 비치환의 탄소수 6 내지 30의 헤테로아릴알킬기, 치환 또는 비치환의 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬아미노기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴아미노기, 치환 또는 비치환의 탄소수 6 내지 30의 아르알킬아미노기, 치환 또는 비치환의 탄소수 2 내지 24의 헤테로 아릴아미노기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴실릴기 및 치환 또는 비치환의 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택되며,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. An alkyl group, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, A substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, A substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, or a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms , It is selected from the group consisting of a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms,상기 L1, L2 및 R1 내지 R6이 치환되는 경우, 수소, 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 20개의 시클로알킬기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 24의 알키닐기, 탄소수 7 내지 30의 아르알킬기, 탄소수 6 내지 30의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, 탄소수 6 내지 30의 헤테로아릴알킬기, 탄소수 1 내지 30의 알콕시기, 탄소수 1 내지 30의 알킬아미노기, 탄소수 6 내지 30의 아릴아미노기, 탄소수 6 내지 30의 아르알킬아미노기, 탄소수 2 내지 24의 헤테로 아릴아미노기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 6 내지 30의 아릴실릴기 및 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택된 1종 이상의 치환기로 치환되며, 복수 개의 치환기로 치환되는 경우 이들은 서로 동일하거나 상이하다.When L 1 , L 2 and R 1 to R 6 are substituted, hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 2 to 20 carbon atoms Alkenyl group having 30 carbon atoms, alkynyl group having 2 to 24 carbon atoms, 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, carbon atoms An alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, a heteroarylamino group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, It is substituted with one or more substituents selected from the group consisting of an arylsilyl group having 6 to 30 carbon atoms and an aryloxy group having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, they are the same as or different from each other.
- 제1항에 있어서,According to claim 1,상기 X1 및 X2는 O인 화합물.Wherein X 1 and X 2 are O.
- 제1항에 있어서,According to claim 1,상기 R1 내지 R4는 서로 동일하거나 상이하며 각각 독립적으로 수소, 할로겐기, 히드록시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬기, 치환 또는 비치환의 탄소수 2 내지 30의 알케닐기 및 치환 또는 비치환의 탄소수 2 내지 24의 알키닐기로 이루어진 군으로부터 선택되는 화합물.R 1 to R 4 are the same as or different from each other and are each independently hydrogen, a halogen group, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, and a substituted or unsubstituted carbon number A compound selected from the group consisting of 2 to 24 alkynyl groups.
- 제1항에 있어서,According to claim 1,상기 R5는 수소 및 치환 또는 비치환의 탄소수 1 내지 30의 알킬기로 이루어진 군에서 선택되는 화합물.Wherein R 5 is a compound selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
- 제1항에 있어서,According to claim 1,상기 L1 및 L2는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합, 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐렌기 및 탄소수 2 내지 20의 알키닐렌기로 이루어진 군에서 선택되는 화합물.L 1 and L 2 are the same as or different from each other, and each independently represents a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, and a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms. A compound selected from the group consisting of an alkynylene group of.
- 상기 화학식 1에 따른 반응성 모노머;a reactive monomer according to Chemical Formula 1;광경화성 올리고머; 및photocurable oligomers; and광개시제를 포함하는containing a photoinitiator3D 프린터용 광경화형 조성물.A photocurable composition for 3D printers.
- 제6항에 있어서,According to claim 6,상기 광경화성 올리고머는 하기 화학식 3으로 표시되는 화합물인The photocurable oligomer is a compound represented by the following formula (3)3D 프린터용 광경화형 조성물:Photocurable composition for 3D printers:[화학식 3][Formula 3][화학식 4][Formula 4][화학식 5][Formula 5]여기서,here,n은 1 내지 1,000의 정수이고,n is an integer from 1 to 1,000;A는 상기 화학식 4 또는 화학식 5로 표시되는 화합물이며,A is a compound represented by Formula 4 or Formula 5,*는 결합되는 부분을 의미하며,* means the part to be combined,R7 내지 R12는 서로 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬기, 치환 또는 비치환의 탄소수 1 내지 20개의 시클로알킬기, 치환 또는 비치환의 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환의 탄소수 2 내지 24의 알키닐기, 치환 또는 비치환의 탄소수 7 내지 30의 아르알킬기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴기, 치환 또는 비치환의 탄소수 5 내지 60의 헤테로아릴기, 치환 또는 비치환의 탄소수 6 내지 30의 헤테로아릴알킬기, 치환 또는 비치환의 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬아미노기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴아미노기, 치환 또는 비치환의 탄소수 6 내지 30의 아르알킬아미노기, 치환 또는 비치환의 탄소수 2 내지 24의 헤테로 아릴아미노기, 치환 또는 비치환의 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환의 탄소수 6 내지 30의 아릴실릴기 및 치환 또는 비치환의 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택되며,R 7 to R 12 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 alkyl group having 1 to 20 carbon atoms. Cycloalkyl group, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms , A substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, or a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms , substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, substituted or unsubstituted alkylsilyl having 1 to 30 carbon atoms It is selected from the group consisting of a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms,상기 R7 내지 R12 가 치환되는 경우, 수소, 중수소, 시아노기, 니트로기, 할로겐기, 히드록시기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 20개의 시클로알킬기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 24의 알키닐기, 탄소수 7 내지 30의 아르알킬기, 탄소수 6 내지 30의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, 탄소수 6 내지 30의 헤테로아릴알킬기, 탄소수 1 내지 30의 알콕시기, 탄소수 1 내지 30의 알킬아미노기, 탄소수 6 내지 30의 아릴아미노기, 탄소수 6 내지 30의 아르알킬아미노기, 탄소수 2 내지 24의 헤테로 아릴아미노기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 6 내지 30의 아릴실릴기 및 탄소수 6 내지 30의 아릴옥시기로 이루어진 군으로부터 선택된 1종 이상의 치환기로 치환되며, 복수 개의 치환기로 치환되는 경우 이들은 서로 동일하거나 상이하다.When R 7 to R 12 are substituted, hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and a carbon atom Alkynyl group of 2 to 24, aralkyl group of 7 to 30 carbon atoms, aryl group of 6 to 30 carbon atoms, heteroaryl group of 5 to 60 nuclear atoms, heteroarylalkyl group of 6 to 30 carbon atoms, alkoxy group of 1 to 30 carbon atoms , C1-30 alkylamino group, C6-30 arylamino group, C6-30 aralkylamino group, C2-24 heteroarylamino group, C1-30 alkylsilyl group, C6-30 aryl It is substituted with one or more substituents selected from the group consisting of a silyl group and an aryloxy group having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, they are the same as or different from each other.
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