WO2017195927A1 - Novel 2,4,6-triaminotriazine-based urethane acrylate compound and preparation method therefor - Google Patents

Novel 2,4,6-triaminotriazine-based urethane acrylate compound and preparation method therefor Download PDF

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WO2017195927A1
WO2017195927A1 PCT/KR2016/005656 KR2016005656W WO2017195927A1 WO 2017195927 A1 WO2017195927 A1 WO 2017195927A1 KR 2016005656 W KR2016005656 W KR 2016005656W WO 2017195927 A1 WO2017195927 A1 WO 2017195927A1
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formula
triaminotriazine
urethane acrylate
novel
acrylate compound
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PCT/KR2016/005656
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French (fr)
Korean (ko)
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박형남
서순용
이종민
이환표
진귀숙
최원석
윤도우
최광식
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애경화학 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/54—Three nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C08G18/3831—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing urethane groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/343—Polycarboxylic acids having at least three carboxylic acid groups
    • C08G18/346—Polycarboxylic acids having at least three carboxylic acid groups having four carboxylic acid groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
    • C08G71/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/13—Morphological aspects

Definitions

  • the present invention relates to a novel 2,4,6-triaminotriazine-based urethane acrylate compound and a preparation method thereof, and more particularly to an isocyanate group (-NCO) in the mother nucleus of 2,4,6-triaminotriazine.
  • -NCO isocyanate group
  • the present invention relates to a novel 2,4,6-triaminotriazine-based urethane acrylate compound which is excellent in bending strength and can be used in photocuring compositions for high-resolution 3D printing.
  • photocuring resins are formed by applying a thin film to a surface of a material in various industries, including display substrates, ships, automobile exterior parts, construction materials, paper, wood, furniture, soundproof walls, optical materials, cosmetic containers, and the like. It is widely used as a coating agent to supplement the surface properties.
  • the photocurable resin is widely used as a 3D printer ink for forming a master model by printing three-dimensionally and photocuring with a 3D printer controlled based on three-dimensional CAD data, and research on this is actively conducted. It is becoming.
  • a photocurable resin which can print the master model by a 3D printer is a cured product of a composition comprising (i) 100 parts by weight of organopolysiloxane and ii) 0.01-5 parts by weight of a photoinitiator according to Korean Patent No. 10-0357785.
  • the organopolysiloxane (i) is (A) 30 to 100% by weight of the organopolysiloxane of the average composition formula (1); R a R 1 b SiO (4-ab) / 2 (1) wherein the same or different R is a substituted or unsubstituted monovalent hydrocarbon group without an aliphatic unsaturated bond or an alkoxy group; Same or different R1 is a photoreactor selected from (meth) acryloyl-containing groups, vinyloxyalkyl groups and epoxy-containing groups; Letters a and b are positive numbers satisfying 1.90 ⁇ a ⁇ 2.40, 0.0003 ⁇ b ⁇ 0.10 and 1.90 ⁇ a + b ⁇ 2.40, organopolysiloxane contains at least two photoreactive groups in the molecule and 100 to 1,000,000 at 25 ° C has a viscosity of cp and, and (B) R p R 1 q SiO 1/2 units (M), SiO 2 units (q
  • Korean Patent Laid-Open Publication No. 2003-0009435 which is a chemical composition for forming a three-dimensional object in a three-dimensional printer, wherein the component comprises a non-aqueous organic monomer compound, and the compound is an alcohol, an ester, an ether, a silane, a vinyl monomer, an acrylic monomer or a meta.
  • At least one of a acrylate monomer wherein the acrylic monomer comprises at least one of tri (propylene glycol) diacrylate, ethylene glycol phenyl ether acrylate or 1,6 hexanediol diacrylate, or wherein the methacryl monomer is At least one of 1,3 butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, butyl methacrylate, 1,6 hexanediol dimethacrylate or di (propylene glycol) allyl ether methacrylate BACKGROUND OF THE INVENTION Photocuring compositions for three-dimensional printers are known.
  • Korean Patent Laid-Open Publication No. 10-2012-0055242 discloses 50 to 80 parts by weight of an acrylic compound, 10 to 50 parts by weight of silsesquioxane, 0.5 to 5 parts by weight of a photocurable release agent, and an ultraviolet initiator based on 100 parts by weight of a photocurable resin composition. 1 to 5 parts by weight, wherein the acrylic compound is selected from the group consisting of monofunctional monomers, difunctional monomers, trifunctional monomers, polyfunctional monomers, and mixtures thereof, wherein the silsesquioxane is acrylate or methacrylate Photocurable resin compositions are known which are selected from the group consisting of silsesquioxanes having groups and mixtures thereof.
  • the photocurable resin compositions have excellent heat resistance due to siloxane network bonds, but the hardness and bending strength are weak, so that copolymerization of other acrylic monomers to siloxane groups should be used to supplement physical properties.
  • Korean Patent Laid-Open No. 10-2012-0137258 is a photocurable inkjet ink having excellent wettability with respect to substrates such as an acrylic resin substrate, and is a photocurable inkjet ink capable of forming a surface-repellent cured film having excellent adhesion to a substrate.
  • An organic solvent (A), a bifunctional or less (meth) acrylate (B) having a hydroxy group, a urethane (meth) acrylate (C), a surfactant (D) and a photopolymerization initiator (E) are contained, and the urethane Photocurable inkjet inks in which (meth) acrylate (C) is represented by the formula (2) are known.
  • R1, R2 and R3 are each independently a divalent organic group having 1 to 20 carbon atoms
  • R4 and R5 are each independently hydrogen or alkyl having 1 to 6 carbon atoms
  • m and n are each independently Is an integer of 1 to 3.
  • Korean Patent Publication No. 10-2016-0045095 discloses a photocurable resin composition capable of forming a hard coat layer having improved blocking resistance and excellent printability without deteriorating transparency, and a hydroxyl group thereof.
  • Is 10-350 mgKOH / g, (meth) acrylic equivalent is 100-800 g / eq, weight average molecular weight is 10,000-200,000, glass transition point is 50-110 degreeC, and it has a photopolymerizable group and a hydroxyl group in a side chain.
  • the photocurable resin composition which contains the photopolymerizable polyfunctional compound (D) which has the above photopolymerizable group is known.
  • the photocurable compositions of the Korean Patent Publication No. 10-2012-0137258 and the Korean Patent Publication No. 10-2016-0045095 also copolymerize a photopolymerizable polyfunctional compound or use inorganic particles, so that the adhesiveness is excellent but heat resistance and hardness are insufficient. There was a problem.
  • Korean Patent No. 10-1569344 forms a film having excellent hardness and transparency at the same time, such as a liquid crystal display screen and a plasma display for displaying an electronic image in addition to general use such as the surface of window glass and glasses.
  • the photocurable triazine monomer compound represented by the above [Formula 1a] or [Formula 1b] is slightly improved in hardness than the conventional photocurable resin, the hardness is still not satisfactory for use as the photocurable composition for 3D printing, and heat resistance. , Lack of bending strength and tensile strength.
  • the present inventors urethane-react a methacrylate having an isocyanate group (-NCO) to the mother nucleus of 2,4,6-triaminotriazine, thereby obtaining a 2,4,6-triaminotriazine-based urethane acrylate backbone (back bone).
  • a methacrylate having an isocyanate group (-NCO)
  • the present invention is excellent in hardness, heat resistance and bending strength than the existing 2,4,6-triaminotriazine methacrylate, and 2,4,6- for use in photocurable compositions and photocurable coating compositions for high-resolution 3D printing
  • New 2,4,6 having 2,4,6-triaminotriazine-based urethane acrylate backbone structure by urethane reaction of methacrylate having isocyanate group (-NCO) to the nucleus of triaminotriazine It is a technical problem to provide a triamino triazine urethane acrylate compound.
  • the present invention provides a novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the following [Formula 1] as a technical solution.
  • R1, R2, R3, R4, R5 and R6 are the same or different alkyl groups of the same or different C1 ⁇ C3 or methacrylate having an isocyanate group (-OCN) at the terminal, wherein, R1, R2, At least three or more of R3, R4, R5 and R6 are methacrylates having an isocyanate group (-OCN) at the terminal.
  • the methacrylate having an isocyanate group (-OCN) at the terminal is 2-isocyanatoethyl methacrylate represented by the following [Formula 2] as a technical solution.
  • the novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the above [Formula 1] is a novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the following [Formula 3] This is a technical solution.
  • the novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the above [Formula 1] is a novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the following [Formula 4] This is a technical solution.
  • the present invention comprises the steps of homogeneously stirring the triazine-triethanol represented by the following [Formula 5] or triazine-hexaethanol represented by the [Formula 6] and the polymerization inhibitor and the reaction catalyst at room temperature; and the homogeneous 2-isocyanatoethyl methacrylate was added dropwise to the stirred mixture to increase the temperature and dropping at 50-70 ° C .; and checking the NCO with FT-IR and reacting when there was no -OH group.
  • a method for producing a novel 2,4,6-triaminotriazine-based urethane acrylate compound comprising the step of terminating;
  • novel 2,4,6-triaminotriazine-based urethane acrylate compound of the present invention is urethane-reacted with 2-isocyanatoethyl methacrylate to the mother nucleus of 2,4,6-triaminotriazine.
  • 6-triaminotriazine-based urethane acrylate backbone (back bone) structure higher hardness, heat resistance, bending strength, tensile strength than conventional 2,4,6-triaminotriazine methacrylate, high resolution 3D printing
  • Figure 4 is an optical microscope and SEM comparison picture showing the print resolution of the 2,4,6-triaminotriazine-based urethane acrylate of the present invention
  • the present invention is characterized by a novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the following [Formula 1].
  • R1, R2, R3, R4, R5 and R6 are the same or different alkyl groups of the same or different C1 ⁇ C3 or methacrylate having an isocyanate group (-OCN) at the terminal, wherein, R1, R2, At least three or more of R3, R4, R5 and R6 are methacrylates having an isocyanate group (-OCN) at the terminal.
  • the methacrylate which has an isocyanate group (-OCN) at the said terminal is characterized by the technical structure of 2-isocyanatoethyl methacrylate represented by following [Formula 2].
  • the novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the above [Formula 1] is a novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the following [Formula 3] It is characterized by the technical configuration.
  • the novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the above [Formula 1] is a novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the following [Formula 4] It is characterized by the technical configuration.
  • the present invention comprises the steps of homogeneously stirring the triazine-triethanol represented by the following [Formula 5] or triazine-hexaethanol represented by the [Formula 6] and the polymerization inhibitor and the reaction catalyst at room temperature; and the homogeneous 2-isocyanatoethyl methacrylate was added dropwise to the stirred mixture to increase the temperature and dropping at 50-70 ° C .; and checking the NCO with FT-IR and reacting when there was no -OH group. Terminating step; characterized in that the manufacturing method of the novel 2,4,6-triaminotriazine-based urethane acrylate compound comprising a technical configuration.
  • the novel 2,4,6-triaminotriazine-based urethane acrylate compound of the present invention is a urethane methacrylate having an isocyanate group (-OCN) at its terminal in the mother nucleus of 2,4,6-triaminotriazine.
  • the reaction is synthesized to have a 2,4,6-triaminotriazine-based urethane acrylate backbone structure.
  • methacrylic acid 2- (O- [1'-methylpropylideneamino] carboxyamino) ethyl, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate, etc. are mentioned. .
  • 2-isocyanatoethyl methacrylate represented by [Formula 2] is preferable.
  • the compound having a mother nucleus of 2,4,6-triaminotriazine which is urethane-reacted with 2-isocyanatoethyl methacrylate represented by the above [Formula 2] is a triazine represented by the following [Formula 5] -Triethanol or triazine-hexaethanol represented by [Formula 6].
  • the triazine-triethanol represented by the above [Formula 5] was added with cyanuric chloride, acetone and potassium carbonate under a nitrogen atmosphere, followed by stirring. Then, 2- (methylamino) ethanol was slowly added to the mixture and stirred for 48 hours at 60 ° C. After refluxing, cooling may be carried out at room temperature, filtration and distillation under reduced pressure, and solvent removal.
  • the synthesis process is as follows.
  • Korean Patent No. 10-1569344 has a pencil hardness of 5H ⁇ 6H by reacting triazine-triethanol represented by [Formula 5] or triazine-hexaethanol represented by [Formula 6] with methacrylic anhydride 2,4,6-triaminotriazine methacrylate used in the photocurable coating composition is prepared as follows, and the synthesis process thereof is shown in [Scheme 3] and [Scheme 4].
  • the 2,4,6-triaminotriazine methacrylate compound is a 3D print by introducing methacrylate by reacting methacrylate anhydride to -OH of triazine-triethanol or triazine-hexaethanol.
  • methacrylate anhydride to reacting methacrylate anhydride to -OH of triazine-triethanol or triazine-hexaethanol.
  • the present invention has been studied to improve the above-mentioned shortcomings, as a result of urethane reaction of -NCO of 2-isocyanatoethyl methacrylate to -OH of the triazine-triethanol or triazine-hexaethanol to heat resistance, hardness, bending
  • the novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by [Formula 3] or [Formula 4] having excellent strength and tensile strength was synthesized, and the synthesis process was described in [Scheme 5] and It is the same as [Scheme 6].
  • the novel 2,4,6-triaminotriazine-based urethane acrylate compound is prohibited from polymerization with triazine-triethanol represented by [Formula 5] or triazine-hexaethanol represented by [Formula 6] under a nitrogen atmosphere. And homogeneously stirring the agent and the reaction catalyst at room temperature; and dropping 2-isocyanatoethyl methacrylate dropwise to the homogeneously stirred mixture to drop the reaction at 50 to 70 ° C.
  • the mixture may be prepared by a manufacturing method including a; checking NCO with FT-IR and terminating the reaction when there is no -OH group.
  • hydroquinone monomethyl ether is used as the polymerization inhibitor, and as the reaction catalyst, for example, dibutyl tin dilaurate, dioctyl tin laurate, dioctyl tin dilaurate, and tri Phenylphosphine, bismuth type catalyst, etc. can be used, A dibutyl tin dilaurate (DIBUTYLTIN DILAURATE) is preferred.
  • the final structure of the synthesized 2,4,6-triaminotriazine-based urethane acrylate compound is 2,4,6-triamino via 13 C-NMR of [FIG. 1] and 1 H-NMR of [FIG. 2] It was confirmed that triazine-based trifunctional urethane acrylate group was formed.
  • the 2,4,6-triaminotriazine-based urethane acrylate compound (TU) of the present invention is a conventional 2,4,6-triaminotriazine trimethacrylate (TA) Compared with the hardness, the hardness, heat resistance and bending strength is significantly improved, it can be seen that excellent properties.
  • the resolution of the 2,4,6-triaminotriazine-based urethane acrylate compound (TU) of the present invention can be confirmed that the excellent 22 ⁇ m horizontal, zirconia surface
  • the organic-inorganic hybridization (20 Wt% content) and dispersion control (30 nm possible) can be applied to the light-curing 3D ink with improved light scattering and dispersibility.
  • the inorganic inorganic hybridization and dispersion control within 45 ⁇ m showed a stable improvement effect, and as a result of evaluation of the influence of the monomer functional group, in the case of the compound (TU) of the present invention, the print resolution is improved in the printing top portion The results could be confirmed.
  • the surface roughness of the 2,4,6-triaminotriazine-based urethane acrylate compound (TU) of the present invention is zirconia-MPTMS synthesis through the compound alone (TU)) and zirconia surface treatment as shown in FIG. All of the inks were improved in dispersibility and shelf life to confirm the surface roughness of 20 ⁇ m or less.
  • novel 2,4,6-triaminotriazine-based urethane acrylate compound of the present invention is urethane-reacted with 2-isocyanatoethyl methacrylate to the mother nucleus of 2,4,6-triaminotriazine.
  • 6-triaminotriazine-based urethane acrylate backbone (back bone) structure higher hardness, heat resistance, bending strength, tensile strength than conventional 2,4,6-triaminotriazine methacrylate, high resolution 3D printing Since there is an excellent effect that can be usefully used in a photocurable composition or a photocurable coating composition for the industrial application.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention relates to a novel 2,4,6-triaminotriazine-based urethane acrylate compound and a preparation method therefor and, more specifically, to a novel 2,4,6-triaminotriazine-based urethane acrylate compound having superior hardness, heat resistance and flexural strength over those of a conventional 2,4,6-triaminotriazine methacrylate, and usable in a radiation curable composition for high definition 3D printing by having a 2,4,6-triaminotriazine-based urethane acrylate backbone structure obtained from a urethane reaction of methacrylate, having an isocyanate group (-NCO), with a 2,4,6-triaminotriazine mother nucleus.

Description

신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물 및 그 제조방법 Novel 2,4,6-triaminotriazine-based urethane acrylate compound and preparation method thereof
본 발명은 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물 및 그 제조방법에 관한 것으로, 보다 상세하게는 2,4,6-트리아미노트리아진의 모핵에 이소시아네이트기(-NCO)를 가지는 메타크릴레이트를 우레탄 반응시켜 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 백본(back bone)구조를 가지므로 기존의 2,4,6-트리아미노트리아진 메타크릴레이트보다 경도, 내열성, 굽힘강도가 우수하고 고해상도 3D 프린트용 광경화 조성물에 사용될 수 있는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물에 관한 것이다.The present invention relates to a novel 2,4,6-triaminotriazine-based urethane acrylate compound and a preparation method thereof, and more particularly to an isocyanate group (-NCO) in the mother nucleus of 2,4,6-triaminotriazine. The urethane reaction of methacrylate having a 2,4,6-triaminotriazine-based urethane acrylate backbone (back bone) structure, so the hardness, heat resistance than conventional 2,4,6-triaminotriazine methacrylate The present invention relates to a novel 2,4,6-triaminotriazine-based urethane acrylate compound which is excellent in bending strength and can be used in photocuring compositions for high-resolution 3D printing.
일반적으로, 광경화수지는 디스플레이 기판, 선박, 자동차 외장부품, 건축자재, 종이, 목재, 가구용, 방음벽, 광학재료, 화장품 용기를 비롯하여 다양한 산업분야에서 재료의 표면에 도포하여 얇은 박막을 형성함으로써 재료의 표면 특성을 보완하기 위한 코팅제로 널리 사용되고 있다.In general, photocuring resins are formed by applying a thin film to a surface of a material in various industries, including display substrates, ships, automobile exterior parts, construction materials, paper, wood, furniture, soundproof walls, optical materials, cosmetic containers, and the like. It is widely used as a coating agent to supplement the surface properties.
뿐만 아니라, 상기 광경화수지는 3차원 CAD 데이터를 기준으로 제어되는 3D 프린터로 3차원 인쇄하고 광경화시켜 마스터모델 등을 성형하는 3D 프린터용 잉크로도 널리 사용되고 있으며, 현재에도 이에 대한 연구가 활발히 진행되고 있다.In addition, the photocurable resin is widely used as a 3D printer ink for forming a master model by printing three-dimensionally and photocuring with a 3D printer controlled based on three-dimensional CAD data, and research on this is actively conducted. It is becoming.
종래, 3D 프린터로 상기 마스터모델을 인쇄할 수 있는 광경화수지로는 한국등록특허 10-0357785에 (i) 100중량부의 오르가노폴리실록산과 ii) 0.01∼5중량부의 광개시제를 포함하는 조성물의 경화 생성물이고, 상기 오르가노폴리실록산(i)은 (A) 다음의 평균 조성식 (1)의 30∼100중량%의 오르가노폴리실록산; RaR1 bSiO(4-a-b)/2 (1) 여기서 같거나 다른 R은 지방족 불포화 결합 또는 알콕시기가 없는 치환 혹은 치환되지 않은 1가 탄화수소기이고; 같거나 다른 R1 은 (메트)아크릴로일-함유기, 비닐옥시알킬기 및 에폭시-함유기로부터 선택된 광반응기이며; 문자 a 와 b 는 1.90 ≤ a ＜ 2.40, 0.0003 ≤ b ≤ 0.10 및 1.90 ＜ a + b ≤ 2.40을 만족시키는 양수이고, 오르가노폴리실록산은 분자에 적어도 두 개의 광반응성기를 함유하고 25℃에서 100∼1,000,000 cp의 점도를 가지고 있으며, 및 (B) RpR1 qSiO1 /2 단위(M), SiO2 단위(Q) 및/또는 XSiO3 /2 단위(T)를 포함하는 0∼70중량%의 실리콘수지(여기서 R 과 R1 은 상기에 정의된 것과 같고 문자 p와 q는 각각 0, 1, 2 또는 3 이고 p+q=3을 만족시키며, X는 R 과 R 1 로부터 선택되고 몰비 M/(Q+T)은 0.6∼1.2이고 몰비 R1 /Si은 0.01∼0.10이며)로 구성되는 광경화 액체 실리콘 고무 조성물이 공지되어 있다.Conventionally, a photocurable resin which can print the master model by a 3D printer is a cured product of a composition comprising (i) 100 parts by weight of organopolysiloxane and ii) 0.01-5 parts by weight of a photoinitiator according to Korean Patent No. 10-0357785. In addition, the organopolysiloxane (i) is (A) 30 to 100% by weight of the organopolysiloxane of the average composition formula (1); R a R 1 b SiO (4-ab) / 2 (1) wherein the same or different R is a substituted or unsubstituted monovalent hydrocarbon group without an aliphatic unsaturated bond or an alkoxy group; Same or different R1 is a photoreactor selected from (meth) acryloyl-containing groups, vinyloxyalkyl groups and epoxy-containing groups; Letters a and b are positive numbers satisfying 1.90 ≤ a <2.40, 0.0003 ≤ b ≤ 0.10 and 1.90 <a + b ≤ 2.40, organopolysiloxane contains at least two photoreactive groups in the molecule and 100 to 1,000,000 at 25 ° C has a viscosity of cp and, and (B) R p R 1 q SiO 1/2 units (M), SiO 2 units (q), and / or XSiO 3/2 0~70% by weight, comprising units (T) Silicone resins, wherein R and R1 are as defined above and the letters p and q are 0, 1, 2 or 3 respectively and satisfy p + q = 3, X is selected from R and R 1 and the molar ratio M / Photocurable liquid silicone rubber compositions consisting of (Q + T) of 0.6 to 1.2 and molar ratio R 1 / Si of 0.01 to 0.10) are known.
또한, 한국공개특허 특2003-0009435에는 삼차원 프린터에서 입체물을 형성시키는 화학 조성물로서, 성분이 비수성 유기 단량체 화합물을 포함하며, 상기 화합물이 알코올, 에스테르, 에테르, 실란, 비닐 단량체, 아크릴 단량체 또는 메타크릴레이트 단량체 중 하나 이상을 포함하되, 상기 아크릴 단량체가 트리(프로필렌 글리콜) 디아크릴레이트, 에틸렌 글리콜 페닐 에테르 아크릴레이트 또는 1,6 헥산디올 디아크릴레이트중 하나 이상을 포함하거나, 상기 메타크릴 단량체가 1,3 부틸렌 글리콜 디메타크릴레이트, 네오펜틸 글리콜 디메타크릴레이트, 부틸메타크릴레이트, 1,6 헥산디올 디메타크릴레이트 또는 디(프로필렌 글리콜) 알릴 에테르 메타크릴레이트중 하나 이상을 포함함을 특징으로 하는 삼차원 프린터용 광경화 조성물이 공지되어 있다.In addition, Korean Patent Laid-Open Publication No. 2003-0009435, which is a chemical composition for forming a three-dimensional object in a three-dimensional printer, wherein the component comprises a non-aqueous organic monomer compound, and the compound is an alcohol, an ester, an ether, a silane, a vinyl monomer, an acrylic monomer or a meta. At least one of a acrylate monomer, wherein the acrylic monomer comprises at least one of tri (propylene glycol) diacrylate, ethylene glycol phenyl ether acrylate or 1,6 hexanediol diacrylate, or wherein the methacryl monomer is At least one of 1,3 butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, butyl methacrylate, 1,6 hexanediol dimethacrylate or di (propylene glycol) allyl ether methacrylate BACKGROUND OF THE INVENTION Photocuring compositions for three-dimensional printers are known.
또한, 한국공개특허 10-2012-0055242에는 광경화형 수지 조성물 100 중량부에 대하여, 아크릴계 화합물 50~80 중량부, 실세스퀴옥산 10~50 중량부, 광경화성 이형제 0.5~5 중량부 및 자외선 개시제 1~5 중량부를 포함하고, 상기 아크릴계 화합물은 단관능성 모노머, 이관능성 모노머, 삼관능성 모노머, 다관능성 모노머 및 이들의 혼합물로 구성된 군에서 선택되며, 상기 실세스퀴옥산은 아크릴레이트 또는 메타크릴레이트 기를 가지는 실세스퀴옥산 및 이들 의 혼합물로 구성된 군에서 선택되는 것을 특징으로 하는 광경화형 수지 조성물이 공지되어 있다.In addition, Korean Patent Laid-Open Publication No. 10-2012-0055242 discloses 50 to 80 parts by weight of an acrylic compound, 10 to 50 parts by weight of silsesquioxane, 0.5 to 5 parts by weight of a photocurable release agent, and an ultraviolet initiator based on 100 parts by weight of a photocurable resin composition. 1 to 5 parts by weight, wherein the acrylic compound is selected from the group consisting of monofunctional monomers, difunctional monomers, trifunctional monomers, polyfunctional monomers, and mixtures thereof, wherein the silsesquioxane is acrylate or methacrylate Photocurable resin compositions are known which are selected from the group consisting of silsesquioxanes having groups and mixtures thereof.
그러나, 상기 광경화형 수지 조성물들은 실록산 네트워크 결합으로 인해 내열성은 우수하지만 경도 및 굽힘강도가 약하여 실록산 그룹에 다른 아크릴 모노머를 공중합하여 물성을 보완하여야 하지만 이러한 물성 보완 역시 만족스럽지 못한 문제점이 있었다.However, the photocurable resin compositions have excellent heat resistance due to siloxane network bonds, but the hardness and bending strength are weak, so that copolymerization of other acrylic monomers to siloxane groups should be used to supplement physical properties.
한편, 한국공개특허 10-2012-0137258에는 아크릴수지 기판 등의 기판에 대한 습윤 전개성이 우수한 광경화성 잉크젯 잉크이며, 기판으로의 밀착성이 우수한 표면 발액성 경화막을 형성할 수 있는 광경화성 잉크젯 잉크로서, 유기용매(A), 히드록시기를 갖는 2관능 이하의 (메타)아크릴레이트(B), 우레탄(메타)아크릴레이트(C), 계면활성제(D) 및 광중합 개시제(E)를 함유하고, 상기 우레탄(메타)아크릴레이트(C)가 화학식(2)로 표시되는 광경화성 잉크젯 잉크가 공지되어 있다.On the other hand, Korean Patent Laid-Open No. 10-2012-0137258 is a photocurable inkjet ink having excellent wettability with respect to substrates such as an acrylic resin substrate, and is a photocurable inkjet ink capable of forming a surface-repellent cured film having excellent adhesion to a substrate. , An organic solvent (A), a bifunctional or less (meth) acrylate (B) having a hydroxy group, a urethane (meth) acrylate (C), a surfactant (D) and a photopolymerization initiator (E) are contained, and the urethane Photocurable inkjet inks in which (meth) acrylate (C) is represented by the formula (2) are known.
Figure PCTKR2016005656-appb-I000001
Figure PCTKR2016005656-appb-I000001
(화학식(2)에서, R1, R2 및 R3은 각각 독립적으로 탄소수 1 내지 20인 2가의 유기기이며, R4 및 R5는 각각 독립적으로 수소 또는 탄소수 1 내지 6의 알킬이며, m 및 n은 각각 독립적으로 1 내지 3의 정수이다.)(In formula (2), R1, R2 and R3 are each independently a divalent organic group having 1 to 20 carbon atoms, R4 and R5 are each independently hydrogen or alkyl having 1 to 6 carbon atoms, and m and n are each independently Is an integer of 1 to 3.)
또한, 한국공개특허 10-2016-0045095에는 투명성을 저하시키지 않고 내블로킹성이 향상되어 있고, 또한 뛰어난 인쇄성도 갖고 있는 하드 코트층을 형성하는 것이 가능한 광경화성 수지 조성물 및 그 경화막으로서, 수산기가가 10∼350㎎KOH/g이고, (메타)아크릴 당량이 100∼800g/eq이고, 중량 평균 분자량이 10,000∼200,000이고, 유리전이점이 50∼110℃이고, 또한 측쇄에 광중합성기 및 수산기를 갖고 있는 (메타)아크릴계폴리머(A)와, 평균 입자 지름이 10㎚∼500㎚인 무기 입자(B)와, 평균 입자 지름이 10㎚∼500㎚인 유기입자(C)와, 1분자 중에 2개 이상의 광중합성기를 갖고 있는 광중합성 다관능 화합물(D)을 포함하고 있는 것을 특징으로 하는 광경화성 수지 조성물이 공지되어 있다.In addition, Korean Patent Publication No. 10-2016-0045095 discloses a photocurable resin composition capable of forming a hard coat layer having improved blocking resistance and excellent printability without deteriorating transparency, and a hydroxyl group thereof. Is 10-350 mgKOH / g, (meth) acrylic equivalent is 100-800 g / eq, weight average molecular weight is 10,000-200,000, glass transition point is 50-110 degreeC, and it has a photopolymerizable group and a hydroxyl group in a side chain. (Meth) acrylic polymer (A) present, inorganic particles (B) having an average particle diameter of 10 nm to 500 nm, organic particles (C) having an average particle diameter of 10 nm to 500 nm, and two in one molecule The photocurable resin composition which contains the photopolymerizable polyfunctional compound (D) which has the above photopolymerizable group is known.
그러나, 상기 한국공개특허 10-2012-0137258 및 한국공개특허 10-2016-0045095의 광경화 조성물도 광중합성 다관능 화합물을 공중합 시키거나 무기입자를 사용함으로써, 밀착성 등은 우수하지만 내열성, 경도가 미흡한 문제점이 있었다.However, the photocurable compositions of the Korean Patent Publication No. 10-2012-0137258 and the Korean Patent Publication No. 10-2016-0045095 also copolymerize a photopolymerizable polyfunctional compound or use inorganic particles, so that the adhesiveness is excellent but heat resistance and hardness are insufficient. There was a problem.
이러한 문제점을 개선하기 위하여, 한국등록특허 10-1569344에 경도 및 투명성이 동시에 우수한 피막을 형성하므로 창유리, 안경 등의 표면과 같은 일용적 용도 외에, 전자화상을 표시하는 액정표시화면·플라즈마 디스플레이 등의 플랫 패널 디스플레이의 표면재료로 사용하는 것으로, 하기 [화학식 1a] 또는 [화학식 1b]로 표시되는 광경화성 트리아진계 단량체 화합물 49 내지 59 중량%; 아크릴레이트 화합물로 개질된 지르코니아 무기입자 1 내지 2 중량%; 및 디펜타에리쓰리톨 헥사아크릴레이트 40 내지 50 중량%를 포함하고, 40 내지 50 ㎛ 두께의 도막에서 7H~8H의 연필경도를 가지는 것을 특징으로 하는 광경화성 코팅조성물이 개발되었다.In order to improve this problem, Korean Patent No. 10-1569344 forms a film having excellent hardness and transparency at the same time, such as a liquid crystal display screen and a plasma display for displaying an electronic image in addition to general use such as the surface of window glass and glasses. 49 to 59% by weight of a photocurable triazine monomer compound represented by the following [Formula 1a] or [Formula 1b] to be used as a surface material of a flat panel display; 1-2 wt% of zirconia inorganic particles modified with acrylate compound; And dipentaerythritol hexaacrylate 40 to 50% by weight, and a photocurable coating composition was developed which has a pencil hardness of 7H to 8H in a 40-50 μm thick coating film.
[화학식 1a][Formula 1a]
Figure PCTKR2016005656-appb-I000002
Figure PCTKR2016005656-appb-I000002
[화학식 1b][Formula 1b]
Figure PCTKR2016005656-appb-I000003
Figure PCTKR2016005656-appb-I000003
그러나, 상기 [화학식 1a] 또는 [화학식 1b]로 표시되는 광경화성 트리아진계 단량체 화합물은 기존 광경화성 수지보다 경도는 다소 향상되었으나, 3D 프린트용 광경화 조성물로 사용하기에는 여전히 경도가 만족스럽지 못하고, 내열성, 굽힘강도, 인장강도가 미흡한 단점이 있었다.However, although the photocurable triazine monomer compound represented by the above [Formula 1a] or [Formula 1b] is slightly improved in hardness than the conventional photocurable resin, the hardness is still not satisfactory for use as the photocurable composition for 3D printing, and heat resistance. , Lack of bending strength and tensile strength.
이에 본 발명자들은, 2,4,6-트리아미노트리아진의 모핵에 이소시아네이트기(-NCO)를 가지는 메타크릴레이트를 우레탄 반응시켜 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 백본(back bone)구조를 가지므로 기존의 상기 [화학식 1a] 또는 [화학식 1b]로 표시되는 광경화성 트리아진계 단량체 화합물, 즉, 2,4,6-트리아미노트리아진 메타크릴레이트보다 굽힘강도, 인장강도가 우수하고 고해상도 3D 프린트용 광경화 조성물에 사용될 수 있는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물을 합성하고 본 발명을 완성하게 되었다.Accordingly, the present inventors urethane-react a methacrylate having an isocyanate group (-NCO) to the mother nucleus of 2,4,6-triaminotriazine, thereby obtaining a 2,4,6-triaminotriazine-based urethane acrylate backbone (back bone). ) Has a higher bending strength and tensile strength than conventional photocurable triazine monomer compounds represented by the above [Formula 1a] or [Formula 1b], that is, 2,4,6-triaminotriazine methacrylate And a novel 2,4,6-triaminotriazine-based urethane acrylate compound that can be used in the photocuring composition for high resolution 3D printing was completed and the present invention was completed.
본 발명은 기존의 2,4,6-트리아미노트리아진 메타크릴레이트보다 경도, 내열성, 굽힘강도가 우수하고 고해상도 3D 프린트용 광경화 조성물 및 광경화 코팅조성물에 사용하기 위하여 2,4,6-트리아미노트리아진의 모핵에 이소시아네이트기(-NCO)를 가지는 메타크릴레이트를 우레탄 반응시켜 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 백본(back bone)구조를 가지는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물을 제공하는 것을 기술적 과제로 한다.The present invention is excellent in hardness, heat resistance and bending strength than the existing 2,4,6-triaminotriazine methacrylate, and 2,4,6- for use in photocurable compositions and photocurable coating compositions for high-resolution 3D printing New 2,4,6 having 2,4,6-triaminotriazine-based urethane acrylate backbone structure by urethane reaction of methacrylate having isocyanate group (-NCO) to the nucleus of triaminotriazine It is a technical problem to provide a triamino triazine urethane acrylate compound.
본 발명은 상기 과제를 해결하기 위하여, 다음 [화학식 1]로 표시되는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물을 제공하는 것을 기술적 해결방법으로 한다.In order to solve the above problems, the present invention provides a novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the following [Formula 1] as a technical solution.
[화학식 1][Formula 1]
Figure PCTKR2016005656-appb-I000004
Figure PCTKR2016005656-appb-I000004
(상기 화학식 1에서, R1, R2, R3, R4, R5 및 R6은 각각 서로 같거나 다른 C1~C3의 알킬기 또는 말단에 이소시아네이트기(-OCN)를 갖는 메타크릴레이트이며, 이때, R1, R2, R3, R4, R5 및 R6 중 적어도 3개 이상은 말단에 이소시아네이트기(-OCN)를 갖는 메타크릴레이트이다.)(In Formula 1, R1, R2, R3, R4, R5 and R6 are the same or different alkyl groups of the same or different C1 ~ C3 or methacrylate having an isocyanate group (-OCN) at the terminal, wherein, R1, R2, At least three or more of R3, R4, R5 and R6 are methacrylates having an isocyanate group (-OCN) at the terminal.)
상기 말단에 이소시아네이트기(-OCN)를 갖는 메타크릴레이트는 하기 [화학식 2]로 표시되는 2-이소시아네이토에틸메타크릴레이트인 것을 기술적 해결방법으로 한다.The methacrylate having an isocyanate group (-OCN) at the terminal is 2-isocyanatoethyl methacrylate represented by the following [Formula 2] as a technical solution.
[화학식 2][Formula 2]
Figure PCTKR2016005656-appb-I000005
Figure PCTKR2016005656-appb-I000005
상기 [화학식 1]로 표시되는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물은 하기 [화학식 3]으로 표시되는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물인 것을 기술적 해결방법으로 한다.The novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the above [Formula 1] is a novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the following [Formula 3] This is a technical solution.
[화학식 3][Formula 3]
Figure PCTKR2016005656-appb-I000006
Figure PCTKR2016005656-appb-I000006
상기 [화학식 1]로 표시되는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물은 하기 [화학식 4]로 표시되는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물인 것을 기술적 해결방법으로 한다.The novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the above [Formula 1] is a novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the following [Formula 4] This is a technical solution.
[화학식 4][Formula 4]
Figure PCTKR2016005656-appb-I000007
Figure PCTKR2016005656-appb-I000007
또한, 본 발명은 하기 [화학식 5]로 표시되는 트리아진-트리에탄올 또는 [화학식 6]으로 표시되는 트리아진-헥사에탄올과 중합금지제 및 반응촉매를 상온에서 균질하게 교반하는 단계;와 상기 균질하게 교반된 혼합물에 2-이소시아네이토에틸메타크릴레이트를 적하하면서 승온하여 50~70℃에서 드로핑반응시키는 단계;와 상기 반응혼합물을 FT-IR로 NCO를 체크하고 -OH기가 없을 때 반응을 종료하는 단계;를 포함하는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물의 제조방법을 기술적 해결방법으로 한다.In addition, the present invention comprises the steps of homogeneously stirring the triazine-triethanol represented by the following [Formula 5] or triazine-hexaethanol represented by the [Formula 6] and the polymerization inhibitor and the reaction catalyst at room temperature; and the homogeneous 2-isocyanatoethyl methacrylate was added dropwise to the stirred mixture to increase the temperature and dropping at 50-70 ° C .; and checking the NCO with FT-IR and reacting when there was no -OH group. A method for producing a novel 2,4,6-triaminotriazine-based urethane acrylate compound comprising the step of terminating;
[화학식 5][Formula 5]
Figure PCTKR2016005656-appb-I000008
Figure PCTKR2016005656-appb-I000008
[화학식 6][Formula 6]
Figure PCTKR2016005656-appb-I000009
Figure PCTKR2016005656-appb-I000009
본 발명의 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물은 2,4,6-트리아미노트리아진의 모핵에 2-이소시아네이토에틸메타크릴레이트를 우레탄 반응시켜 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 백본(back bone)구조를 가지므로 기존의 2,4,6-트리아미노트리아진 메타크릴레이트보다 경도, 내열성, 굽힘강도, 인장강도가 우수하여 고해상도 3D 프린트용 광경화 조성물 또는 광경화 코팅조성물에 유용하게 사용될 수 있는 우수한 효과가 있다.The novel 2,4,6-triaminotriazine-based urethane acrylate compound of the present invention is urethane-reacted with 2-isocyanatoethyl methacrylate to the mother nucleus of 2,4,6-triaminotriazine. , 6-triaminotriazine-based urethane acrylate backbone (back bone) structure, higher hardness, heat resistance, bending strength, tensile strength than conventional 2,4,6-triaminotriazine methacrylate, high resolution 3D printing There is an excellent effect that can be usefully used in a photocurable composition or a photocurable coating composition.
도 1은 본 발명의 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 13C-NMR1 is 2,4,6-triaminotriazine-based urethane acrylate 13 C-NMR of the present invention
도 2는 본 발명의 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 1H-NMR2 is a 2,4,6-triaminotriazine-based urethane acrylate 1 H-NMR of the present invention
도 3은 본 발명의 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 GPC3 is a 2,4,6-triaminotriazine-based urethane acrylate GPC of the present invention
도 4는 본 발명의 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 인쇄해상도를 나타내는 광학현미경 및 SEM 비교사진Figure 4 is an optical microscope and SEM comparison picture showing the print resolution of the 2,4,6-triaminotriazine-based urethane acrylate of the present invention
도 5는 본 발명의 2,4,6-트리아미노트리아진계 우레탄아크릴레이트의 표면거칠기 비교사진5 is a surface roughness comparison of 2,4,6-triaminotriazine-based urethane acrylate of the present invention
본 발명은, 다음 [화학식 1]로 표시되는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물을 기술구성의 특징으로 한다.The present invention is characterized by a novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the following [Formula 1].
[화학식 1][Formula 1]
Figure PCTKR2016005656-appb-I000010
Figure PCTKR2016005656-appb-I000010
(상기 화학식 1에서, R1, R2, R3, R4, R5 및 R6은 각각 서로 같거나 다른 C1~C3의 알킬기 또는 말단에 이소시아네이트기(-OCN)를 갖는 메타크릴레이트이며, 이때, R1, R2, R3, R4, R5 및 R6 중 적어도 3개 이상은 말단에 이소시아네이트기(-OCN)를 갖는 메타크릴레이트이다.)(In Formula 1, R1, R2, R3, R4, R5 and R6 are the same or different alkyl groups of the same or different C1 ~ C3 or methacrylate having an isocyanate group (-OCN) at the terminal, wherein, R1, R2, At least three or more of R3, R4, R5 and R6 are methacrylates having an isocyanate group (-OCN) at the terminal.)
상기 말단에 이소시아네이트기(-OCN)를 갖는 메타크릴레이트는 하기 [화학식 2]로 표시되는 2-이소시아네이토에틸메타크릴레이트를 기술구성의 특징으로 한다.The methacrylate which has an isocyanate group (-OCN) at the said terminal is characterized by the technical structure of 2-isocyanatoethyl methacrylate represented by following [Formula 2].
[화학식 2][Formula 2]
Figure PCTKR2016005656-appb-I000011
Figure PCTKR2016005656-appb-I000011
상기 [화학식 1]로 표시되는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물은 하기 [화학식 3]으로 표시되는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물을 기술구성의 특징으로 한다.The novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the above [Formula 1] is a novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the following [Formula 3] It is characterized by the technical configuration.
[화학식 3][Formula 3]
Figure PCTKR2016005656-appb-I000012
Figure PCTKR2016005656-appb-I000012
상기 [화학식 1]로 표시되는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물은 하기 [화학식 4]로 표시되는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물을 기술구성의 특징으로 한다.The novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the above [Formula 1] is a novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the following [Formula 4] It is characterized by the technical configuration.
[화학식 4][Formula 4]
Figure PCTKR2016005656-appb-I000013
Figure PCTKR2016005656-appb-I000013
또한, 본 발명은 하기 [화학식 5]로 표시되는 트리아진-트리에탄올 또는 [화학식 6]으로 표시되는 트리아진-헥사에탄올과 중합금지제 및 반응촉매를 상온에서 균질하게 교반하는 단계;와 상기 균질하게 교반된 혼합물에 2-이소시아네이토에틸메타크릴레이트를 적하하면서 승온하여 50~70℃에서 드로핑반응시키는 단계;와 상기 반응혼합물을 FT-IR로 NCO를 체크하고 -OH기가 없을 때 반응을 종료하는 단계;를 포함하는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물의 제조방법을 기술구성의 특징으로 한다.In addition, the present invention comprises the steps of homogeneously stirring the triazine-triethanol represented by the following [Formula 5] or triazine-hexaethanol represented by the [Formula 6] and the polymerization inhibitor and the reaction catalyst at room temperature; and the homogeneous 2-isocyanatoethyl methacrylate was added dropwise to the stirred mixture to increase the temperature and dropping at 50-70 ° C .; and checking the NCO with FT-IR and reacting when there was no -OH group. Terminating step; characterized in that the manufacturing method of the novel 2,4,6-triaminotriazine-based urethane acrylate compound comprising a technical configuration.
[화학식 5][Formula 5]
Figure PCTKR2016005656-appb-I000014
Figure PCTKR2016005656-appb-I000014
[화학식 6][Formula 6]
Figure PCTKR2016005656-appb-I000015
Figure PCTKR2016005656-appb-I000015
이하에서는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 바람직한 실시예 및 도면을 통하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며, 여기에서 설명하는 실시예에 한정되지 않는다.Hereinafter will be described in detail with reference to the preferred embodiments and drawings of the present invention to be easily carried out by those skilled in the art. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.
우선, 본 발명의 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물은 2,4,6-트리아미노트리아진의 모핵에 말단에 이소시아네이트기(-OCN)를 갖는 메타크릴레이트를 우레탄 반응시켜 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 백본(back bone)구조를 가지도록 합성된다. First, the novel 2,4,6-triaminotriazine-based urethane acrylate compound of the present invention is a urethane methacrylate having an isocyanate group (-OCN) at its terminal in the mother nucleus of 2,4,6-triaminotriazine. The reaction is synthesized to have a 2,4,6-triaminotriazine-based urethane acrylate backbone structure.
이때 말단에 이소시아네이트기(-OCN)를 갖는 메타크릴레이트 화합물로는, (메타)아크릴로일기가 탄소수 2∼6의 알킬렌기를 통해서 이소시아네이트기와 결합한 (메타)아크릴로일이소시아네이트 및 이것들의 유도체 등을 들 수 있다. (메타)아크릴로일이소시아네이트로서는, 예를 들면 2-메타크릴로일옥시에틸이소시아네이트 등을 들 수 있다. 유도체로서는, 예를 들면 블록제로 마스킹한 이소시아네이트기를 갖는 (메타)아크릴레이트 등을 들 수 있다. 구체예로서는, 메타크릴산 2-(O-[1'-메틸프로필리덴아미노]카르복시아미노)에틸, 2-[(3,5-디메틸피라졸릴)카르보닐아미노]에틸메타크릴레이트 등을 들 수 있다. 이중에서도 [화학식 2]로 표시되는 2-이소시아나토에틸메타크릴레이트가 바람직하다.At this time, as a methacrylate compound which has an isocyanate group (-OCN) at the terminal, the (meth) acryloyl isocyanate which these (meth) acryloyl group couple | bonded with the isocyanate group through the alkylene group of C2-C6, these derivatives, etc. Can be mentioned. As (meth) acryloyl isocyanate, 2-methacryloyl oxyethyl isocyanate etc. are mentioned, for example. As a derivative, the (meth) acrylate etc. which have an isocyanate group masked with blocking agent are mentioned, for example. As a specific example, methacrylic acid 2- (O- [1'-methylpropylideneamino] carboxyamino) ethyl, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate, etc. are mentioned. . Among these, 2-isocyanatoethyl methacrylate represented by [Formula 2] is preferable.
여기서, 상기 [화학식 2]로 표시되는 2-이소시아네이토에틸메타크릴레이트와 우레탄 반응되는 2,4,6-트리아미노트리아진의 모핵을 가지는 화합물은 하기 [화학식 5]로 표시되는 트리아진-트리에탄올 또는 [화학식 6]으로 표시되는 트리아진-헥사에탄올이다.Here, the compound having a mother nucleus of 2,4,6-triaminotriazine which is urethane-reacted with 2-isocyanatoethyl methacrylate represented by the above [Formula 2] is a triazine represented by the following [Formula 5] -Triethanol or triazine-hexaethanol represented by [Formula 6].
[화학식 5][Formula 5]
Figure PCTKR2016005656-appb-I000016
Figure PCTKR2016005656-appb-I000016
[화학식 6][Formula 6]
Figure PCTKR2016005656-appb-I000017
Figure PCTKR2016005656-appb-I000017
상기 [화학식 5]로 표시되는 트리아진-트리에탄올은 질소분위기 하에서 시아누릭 클로라이드와 아세톤 및 탄산칼륨을 넣고 교반한 후, 2-(메틸아미노)에탄올을 천천히 가하여 교반 반응시키고, 60℃에서 48시간 동안 환류시킨 다음, 상온 냉각, 여과 및 감압 증류, 용매 제거를 통하여 제조될 수 있으며, 그 합성과정은 다음 [반응식 1]과 같다.The triazine-triethanol represented by the above [Formula 5] was added with cyanuric chloride, acetone and potassium carbonate under a nitrogen atmosphere, followed by stirring. Then, 2- (methylamino) ethanol was slowly added to the mixture and stirred for 48 hours at 60 ° C. After refluxing, cooling may be carried out at room temperature, filtration and distillation under reduced pressure, and solvent removal. The synthesis process is as follows.
[반응식 1] Scheme 1
Figure PCTKR2016005656-appb-I000018
Figure PCTKR2016005656-appb-I000018
또한, 상기 [화학식 6]으로 표시되는 트리아진-헥사에탄올은 질소분위기 하에서 시아누릭 클로라이드와 테트라하이드라퓨란 및 탄산칼륨을 넣고 교반한 후, 디에탄올아민을 천천히 가하여 교반 반응시키고, 70℃에서 48시간 동안 환류시킨 다음, 상온 냉각, 여과 및 감압 증류, 용매 제거를 통하여 제조될 수 있으며, 그 합성과정은 다음 [반응식 2]와 같다.In addition, triazine-hexaethanol represented by the above [Formula 6] was added with cyanuric chloride, tetrahydrofuran and potassium carbonate under a nitrogen atmosphere, followed by stirring. Then, by slowly adding diethanolamine, the reaction was stirred at 48C at 70 ° C. After refluxing for time, it can be prepared by cooling at room temperature, filtration and distillation under reduced pressure, solvent removal, the synthesis process is as shown in [Scheme 2].
[반응식 2] Scheme 2
Figure PCTKR2016005656-appb-I000019
Figure PCTKR2016005656-appb-I000019
한편, 한국등록특허 10-1569344에서는 [화학식 5]로 표시되는 트리아진-트리에탄올 또는 [화학식 6]으로 표시되는 트리아진-헥사에탄올을 메타크릴릭 안하이드라이드와 반응시켜 연필경도가 5H~6H인 광경화코팅 조성물에 사용되는 2,4,6-트리아미노트리아진 메타크릴레이트를 다음과 같이 제조하고 있으며, 그 합성과정은 다음 [반응식 3] 및 [반응식 4]와 같다.On the other hand, Korean Patent No. 10-1569344 has a pencil hardness of 5H ~ 6H by reacting triazine-triethanol represented by [Formula 5] or triazine-hexaethanol represented by [Formula 6] with methacrylic anhydride 2,4,6-triaminotriazine methacrylate used in the photocurable coating composition is prepared as follows, and the synthesis process thereof is shown in [Scheme 3] and [Scheme 4].
[반응식 3] Scheme 3
Figure PCTKR2016005656-appb-I000020
Figure PCTKR2016005656-appb-I000020
[반응식 4]Scheme 4
Figure PCTKR2016005656-appb-I000021
Figure PCTKR2016005656-appb-I000021
그러나, 상기 2,4,6-트리아미노트리아진 메타크릴레이트 화합물은 트리아진-트리에탄올 또는 트리아진-헥사에탄올의 -OH에 메타크릴릭 안하이드라이드를 반응시켜 메타크릴레이트를 도입한 것으로 3D 프린트용 광경화 조성물 또는 광경화 코팅용으로 사용하기에는 경도, 굽힘강도, 인장강도가 미흡한 단점이 있었다.However, the 2,4,6-triaminotriazine methacrylate compound is a 3D print by introducing methacrylate by reacting methacrylate anhydride to -OH of triazine-triethanol or triazine-hexaethanol. In order to use for the photocurable composition or the photocurable coating for the hardness, bending strength, tensile strength was insufficient.
본 발명은 상기한 단점들을 개선하기 위하여 연구한 결과 상기 트리아진-트리에탄올 또는 트리아진-헥사에탄올의 -OH에 2-이소시아네이토에틸메타크릴레이트의 -NCO를 우레탄 반응시켜 내열성, 경도, 굽힘강도, 인장강도가 우수한 [화학식 3] 또는 [화학식 4]로 표시되는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물을 합성할 수 있었으며, 그 합성과정은 다음 [반응식 5] 및 [반응식 6]과 같다.The present invention has been studied to improve the above-mentioned shortcomings, as a result of urethane reaction of -NCO of 2-isocyanatoethyl methacrylate to -OH of the triazine-triethanol or triazine-hexaethanol to heat resistance, hardness, bending The novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by [Formula 3] or [Formula 4] having excellent strength and tensile strength was synthesized, and the synthesis process was described in [Scheme 5] and It is the same as [Scheme 6].
[반응식 5] Scheme 5
Figure PCTKR2016005656-appb-I000022
Figure PCTKR2016005656-appb-I000022
[반응식 6] Scheme 6
Figure PCTKR2016005656-appb-I000023
Figure PCTKR2016005656-appb-I000023
즉, 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물은 질소분위기 하에서 상기 [화학식 5]로 표시되는 트리아진-트리에탄올 또는 [화학식 6]으로 표시되는 트리아진-헥사에탄올과 중합금지제 및 반응촉매를 상온에서 균질하게 교반하는 단계;와 상기 균질하게 교반된 혼합물에 2-이소시아네이토에틸메타크릴레이트를 적하하면서 승온하여 50~70℃에서 드로핑반응시키는 단계;와 상기 반응혼합물을 FT-IR로 NCO를 체크하고 -OH기가 없을 때 반응을 종료하는 단계;를 포함하는 제조방법으로 제조될 수 있다.That is, the novel 2,4,6-triaminotriazine-based urethane acrylate compound is prohibited from polymerization with triazine-triethanol represented by [Formula 5] or triazine-hexaethanol represented by [Formula 6] under a nitrogen atmosphere. And homogeneously stirring the agent and the reaction catalyst at room temperature; and dropping 2-isocyanatoethyl methacrylate dropwise to the homogeneously stirred mixture to drop the reaction at 50 to 70 ° C. The mixture may be prepared by a manufacturing method including a; checking NCO with FT-IR and terminating the reaction when there is no -OH group.
이때 중합금지제로는 하이드로퀴논 모노메틸에테르(HQMME)을 사용하고, 반응촉매로는 예를 들면, 디부틸주석디라우레이트(DIBUTYLTIN DILAURATE), 디옥틸주석라우레이트, 디옥틸주석디라우레이트, 트리페닐포스핀, 비스무트계 촉매 등을 사용할 수 있으며, 디부틸주석디라우레이트(DIBUTYLTIN DILAURATE)가 바림직하다.In this case, hydroquinone monomethyl ether (HQMME) is used as the polymerization inhibitor, and as the reaction catalyst, for example, dibutyl tin dilaurate, dioctyl tin laurate, dioctyl tin dilaurate, and tri Phenylphosphine, bismuth type catalyst, etc. can be used, A dibutyl tin dilaurate (DIBUTYLTIN DILAURATE) is preferred.
[실시예 1]Example 1
[화학식 3 : 2,4,6-트리아미노트리아진계 우레탄아크릴레이트의 합성][Synthesis of 2,4,6-triaminotriazine urethane acrylate]
질소분위기 하에서 상기 [화학식 5]로 표시되는 트리아진-트리에탄올 118.305과 중합금지제(하이드로퀴논 모노메틸에테르;HQMME) 0.05g 및 반응촉매(디부틸주석디라우레이트;DIBUTYLTIN DILAURATE) 0.05을 혼합하여 상온에서 균질하게 교반한 다음, 상기 균질하게 교반된 혼합물에 26℃에서부터 2-이소시아네이토에틸메타크릴레이트를 서서히 1시간동안 50~70℃로 승온하면서 적하하여 24시간 드로핑반응시킨 후, 상기 반응혼합물을 FT-IR로 NCO를 체크하고 -OH기가 없을 때 반응을 종료하여 목적화합물인 [화학식 3]으로 표시되는 2,4,6-트리아미노트리아진계 우레탄아크릴레이트를 합성하였다.In a nitrogen atmosphere, room temperature by mixing 118.305 of triazine-triethanol represented by the above [Formula 5], 0.05 g of a polymerization inhibitor (hydroquinone monomethyl ether; HQMME) and 0.05 reaction catalyst (dibutyltin dilaurate; DIBUTYLTIN DILAURATE) After stirring homogeneously at, the 2-isocyanatoethyl methacrylate was slowly added dropwise to the homogeneously stirred mixture at 26 ° C. at a temperature of 50 ° C. to 70 ° C. for 1 hour, followed by a dropping reaction for 24 hours. The reaction mixture was checked for NCO by FT-IR and the reaction was terminated when there was no -OH group to synthesize 2,4,6-triaminotriazine-based urethane acrylate represented by the target compound [Formula 3].
상기 합성된 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물의 최종 구조는 [도 1]의 13C-NMR 및 [도 2]의 1H-NMR을 통해 2,4,6-트리아미노트리아진계 3관능 우레탄아크릴레이트 group이 형성됨을 확인하였다.The final structure of the synthesized 2,4,6-triaminotriazine-based urethane acrylate compound is 2,4,6-triamino via 13 C-NMR of [FIG. 1] and 1 H-NMR of [FIG. 2] It was confirmed that triazine-based trifunctional urethane acrylate group was formed.
또한, 상기 합성된 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물의 분자량 측정은 GPC로 확인하였으며, [도 3]의 GPC 그래프에 나타난 바와 같이, Mw : 772~559, Mn : 765~556, DPI.036 분포를 확인하였다.In addition, the molecular weight measurement of the synthesized 2,4,6-triaminotriazine-based urethane acrylate compound was confirmed by GPC, as shown in the GPC graph of [Fig. 3], Mw: 772 ~ 559, Mn: 765 ~ 556, DPI.036 distribution confirmed.
[실시예 2]Example 2
[잉크물성 비교 시험][Ink physical property comparison test]
[실시예 1]에서 합성된 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물(TU)과 기존의 2,4,6-트리아미노트리아진 트리메타크릴레이트(TA)의 잉크물성 비교시험결과를 다음 [표 1]에 나타내었다.Comparative ink properties of 2,4,6-triaminotriazine-based urethane acrylate compound (TU) synthesized in Example 1 and existing 2,4,6-triaminotriazine trimethacrylate (TA) The results are shown in the following [Table 1].
[표 1]TABLE 1
Figure PCTKR2016005656-appb-I000024
Figure PCTKR2016005656-appb-I000024
상기 [표 1]에 나타난 바와 같이, 본 발명의 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물(TU)은 기존의 2,4,6-트리아미노트리아진 트리메타크릴레이트(TA)와 비교하여 경도가 유사하며, 내열성 및 굽힘강도가 대폭 향상되어 우수한 물성을 나타냄을 확인할 수 있다.As shown in Table 1, the 2,4,6-triaminotriazine-based urethane acrylate compound (TU) of the present invention is a conventional 2,4,6-triaminotriazine trimethacrylate (TA) Compared with the hardness, the hardness, heat resistance and bending strength is significantly improved, it can be seen that excellent properties.
[실시예 3]Example 3
[인쇄해상도 비교시험][Print Resolution Comparison Test]
[도 4]의 광학현미경과 SEM사진에 나타난 바와 같이, 본 발명의 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물(TU)의 해상도는 가로 22㎛로서 우수함을 확인할 수 있으며, 지르코니아 표면처리를 통해서 유무기 하이브리드화(20Wt%함량) 및 분산제어(30nm가능)하여 광산란 및 분산성이 개선된 광경화 3D 잉크에 응용가능함을 확인하였다. As shown in the optical microscope and SEM photograph of Figure 4, the resolution of the 2,4,6-triaminotriazine-based urethane acrylate compound (TU) of the present invention can be confirmed that the excellent 22㎛ horizontal, zirconia surface Through the treatment, it was confirmed that the organic-inorganic hybridization (20 Wt% content) and dispersion control (30 nm possible) can be applied to the light-curing 3D ink with improved light scattering and dispersibility.
또한, 유무기 하이브리드화 및 분산제어를 통한 45㎛ 이내의 해상도를 보여 안정적인 개선효과를 보였으며, 모노머 관능기에 따른 영향도 평가결과, 본 발명의 화합물(TU)의 경우 인쇄 Top부에서 인쇄해상도 개선결과를 확인할 수 있었다.In addition, the inorganic inorganic hybridization and dispersion control within 45㎛ showed a stable improvement effect, and as a result of evaluation of the influence of the monomer functional group, in the case of the compound (TU) of the present invention, the print resolution is improved in the printing top portion The results could be confirmed.
[실시예 4]Example 4
[[ 표면거칠기Surface roughness 비교 시험] Comparison test]
본 발명의 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물(TU)의 인쇄표면 거칠기는 [도 5]에 나타난 바와 같이, 화합물 단독(TU)) 및 지르코니아 표면처리를 통한 지르코니아-MPTMS합성 잉크 모두 분산성 및 저장성이 개선되어 20㎛이하의 표면거칠기를 확인할 수 있었다.The surface roughness of the 2,4,6-triaminotriazine-based urethane acrylate compound (TU) of the present invention is zirconia-MPTMS synthesis through the compound alone (TU)) and zirconia surface treatment as shown in FIG. All of the inks were improved in dispersibility and shelf life to confirm the surface roughness of 20㎛ or less.
이상의 설명은 본 발명의 기술사상을 예시적으로 설명한 것에 불과한 것으로서, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 수정 및 변형이 가능할 것이다. 따라서, 본 발명에 개시된 실시예 및 도면은 본 발명의 기술 사상을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예 및 도면에 의하여 본 발명의 기술 사상의 범위가 한정되는 것은 아니다. 본 발명의 보호 범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술 사상은 본 발명의 권리범위에 포함되는 것으로 해석되어야 할 것이다.The above description is merely illustrative of the technical idea of the present invention, and those skilled in the art to which the present invention pertains may make various modifications and changes without departing from the essential characteristics of the present invention. Therefore, the embodiments and the drawings disclosed in the present invention are not intended to limit the technical idea of the present invention but to explain, and the scope of the technical idea of the present invention is not limited by the embodiments and the drawings. The protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of the present invention.
본 발명의 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물은 2,4,6-트리아미노트리아진의 모핵에 2-이소시아네이토에틸메타크릴레이트를 우레탄 반응시켜 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 백본(back bone)구조를 가지므로 기존의 2,4,6-트리아미노트리아진 메타크릴레이트보다 경도, 내열성, 굽힘강도, 인장강도가 우수하여 고해상도 3D 프린트용 광경화 조성물 또는 광경화 코팅조성물에 유용하게 사용될 수 있는 우수한 효과가 있으므로 산업상 이용가능성이 있다.The novel 2,4,6-triaminotriazine-based urethane acrylate compound of the present invention is urethane-reacted with 2-isocyanatoethyl methacrylate to the mother nucleus of 2,4,6-triaminotriazine. , 6-triaminotriazine-based urethane acrylate backbone (back bone) structure, higher hardness, heat resistance, bending strength, tensile strength than conventional 2,4,6-triaminotriazine methacrylate, high resolution 3D printing Since there is an excellent effect that can be usefully used in a photocurable composition or a photocurable coating composition for the industrial application.

Claims (5)

  1. 다음 [화학식 1]로 표시되는 화합물인 것을 특징으로 하는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물A novel 2,4,6-triaminotriazine-based urethane acrylate compound, which is a compound represented by the following [Formula 1]
    [화학식 1][Formula 1]
    Figure PCTKR2016005656-appb-I000025
    Figure PCTKR2016005656-appb-I000025
    (상기 화학식 1에서, R1, R2, R3, R4, R5 및 R6은 각각 서로 같거나 다른 C1~C3의 알킬기 또는 말단에 이소시아네이트기(-OCN)를 갖는 메타크릴레이트이며, 이때, R1, R2, R3, R4, R5 및 R6 중 적어도 3개 이상은 말단에 이소시아네이트기(-OCN)를 갖는 메타크릴레이트이다.)(In Formula 1, R1, R2, R3, R4, R5 and R6 are the same or different alkyl groups of the same or different C1 ~ C3 or methacrylate having an isocyanate group (-OCN) at the terminal, wherein, R1, R2, At least three or more of R3, R4, R5 and R6 are methacrylates having an isocyanate group (-OCN) at the terminal.)
  2. 제1항에 있어서,The method of claim 1,
    상기 말단에 이소시아네이트기(-OCN)를 갖는 메타크릴레이트는 하기 [화학식 2]로 표시되는 2-이소시아네이토에틸메타크릴레이트인 것을 특징으로 하는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물Methacrylate having an isocyanate group (-OCN) at the terminal is a novel 2,4,6-triaminotriazine system, characterized in that 2-isocyanatoethyl methacrylate represented by the following [Formula 2] Urethane Acrylate Compound
    [화학식 2][Formula 2]
    Figure PCTKR2016005656-appb-I000026
    Figure PCTKR2016005656-appb-I000026
  3. 제1항에 있어서,The method of claim 1,
    상기 [화학식 1]로 표시되는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물은 하기 [화학식 3]으로 표시되는 화합물인 것을 특징으로 하는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물The novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the above [Formula 1] is a novel 2,4,6-triaminotria characterized in that the compound represented by the following [Formula 3]. True urethane acrylate compound
    [화학식 3][Formula 3]
    Figure PCTKR2016005656-appb-I000027
    Figure PCTKR2016005656-appb-I000027
  4. 제1항에 있어서,The method of claim 1,
    상기 [화학식 1]로 표시되는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물은 하기 [화학식 4]로 표시되는 화합물인 것을 특징으로 하는 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물The novel 2,4,6-triaminotriazine-based urethane acrylate compound represented by the above [Formula 1] is a novel 2,4,6-triaminotria characterized in that the compound represented by the following [Formula 4]. True urethane acrylate compound
    [화학식 4][Formula 4]
    Figure PCTKR2016005656-appb-I000028
    Figure PCTKR2016005656-appb-I000028
  5. 하기 [화학식 5]로 표시되는 트리아진-트리에탄올 또는 [화학식 6]으로 표시되는 트리아진-헥사에탄올과 중합금지제 및 반응촉매를 상온에서 균질하게 교반하는 단계;와 상기 균질하게 교반된 혼합물에 2-이소시아네이토에틸메타크릴레이트를 승온하면서 적하하여 50~70℃에서 드로핑반응시키는 단계;와 상기 반응혼합물을 FT-IR로 NCO를 체크하고 -OH기가 없을 때 반응을 종료하는 단계;를 포함하는 것을 특징으로 하는 제1항 내지 제4항중 어느 한 항에 따른 신규한 2,4,6-트리아미노트리아진계 우레탄아크릴레이트 화합물의 제조방법Homogeneously stirring the triazine-triethanol represented by the following [Formula 5] or the triazine-hexaethanol represented by the [Formula 6], the polymerization inhibitor and the reaction catalyst at room temperature; and the homogeneously stirred mixture 2 -Dropping isocyanate ethyl methacrylate while raising the temperature and dropping the reaction at 50-70 ° C; and checking the NCO with FT-IR and terminating the reaction when there is no -OH group. Method for producing a novel 2,4,6-triaminotriazine-based urethane acrylate compound according to any one of claims 1 to 4, characterized in that it comprises
    [화학식 5][Formula 5]
    Figure PCTKR2016005656-appb-I000029
    Figure PCTKR2016005656-appb-I000029
    [화학식 6][Formula 6]
    Figure PCTKR2016005656-appb-I000030
    Figure PCTKR2016005656-appb-I000030
PCT/KR2016/005656 2016-05-13 2016-05-27 Novel 2,4,6-triaminotriazine-based urethane acrylate compound and preparation method therefor WO2017195927A1 (en)

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