WO2018212596A1 - Composition de résine polymère, filament d'imprimante 3d la contenant, et procédé de fabrication de filaments d'imprimante 3d - Google Patents

Composition de résine polymère, filament d'imprimante 3d la contenant, et procédé de fabrication de filaments d'imprimante 3d Download PDF

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Publication number
WO2018212596A1
WO2018212596A1 PCT/KR2018/005626 KR2018005626W WO2018212596A1 WO 2018212596 A1 WO2018212596 A1 WO 2018212596A1 KR 2018005626 W KR2018005626 W KR 2018005626W WO 2018212596 A1 WO2018212596 A1 WO 2018212596A1
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Prior art keywords
resin composition
polymer resin
filament
copolymer
polyester copolymer
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PCT/KR2018/005626
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English (en)
Korean (ko)
Inventor
박민아
김태영
김도균
김민석
Original Assignee
에스케이케미칼 주식회사
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Publication of WO2018212596A1 publication Critical patent/WO2018212596A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings

Definitions

  • Polymer resin composition comprising the same, and method for producing filament for 3D printer
  • the present invention relates to a polymer resin composition, a filament for a 3D printer comprising the same, and a method for producing a filament for a 3D printer.
  • 3D printer is a equipment that manufactures products by processing and laminating materials such as liquid, powder-type resin, metal powder, solid, etc. based on design data.
  • 3D printer technology uses FDM (Fused Depos it ion Modeling) depending on the material.
  • SLS Selective Laser Sintering
  • SLA Stepo Lithography Apparatus
  • the FDM method dissolves a filament-like thermoplastic material in a nozzle and outputs it in the form of a thin film.
  • the SLS method outputs a product by selectively irradiating a laser or an adhesive to a powder, and the SLA method applies a laser beam to a photocurable material. It is a method of outputting the product by scanning.
  • the FOM method of manufacturing and using the thermoplastic plastic in the form of filament has the advantages of lower production cost, faster printing speed than other methods, and miniaturization.
  • the filament material used in the FDM method polylactic acid (PLA), acrylonitrile butadiene styrene (ABS), polycarbonate (PC) and the like are used.
  • FDM type 3D printer heats the filament to melt and print the material, so when printing using PC and ABS as filament material, harmful substances such as bisphenol A (BPA) and styrene (Styrene) There is a disadvantage that occurs.
  • PC is a harmful substance bisphenol A (BPA) It is included as a raw material, and when the PC is placed in a high temperature and high humidity environment, hydrolysis occurs gradually and the constituent BPA is separated.
  • Isolated BPA is an endocrine disruptor, and recent studies have shown that endocrine disruptors in synthetic resin products such as BPA not only disrupt human immune function but, in excess, increase free radicals that cause cancer and aging. It is reported that there is a possibility.
  • ABS is a toxic substance using styrene as a raw material, there is a problem that toxic gases and odors such as styrene is generated when printing using the filament material.
  • the ABS is known to release a large amount of carbon dioxide which is the main culprit of global warming.
  • the material of the filament used in the FDM type 3D printer does not generate harmful substances and odors such as BPA and styrene, which is environmentally friendly, has excellent mechanical and heat resistance properties, and requires materials capable of 3D printing at low temperatures. have.
  • the present invention is eco-friendly because it does not generate harmful substances such as BPA and styrene and does not generate odor, and is a polymer resin composition having excellent mechanical properties and heat resistance, and is capable of outputting even at low silver using the composition, and thus has excellent processability. It is to provide a filament for a 3D printer, and a method for manufacturing the filament for the 3D printer.
  • the present invention also provides a filament for a 3D printer comprising the polymer resin composition.
  • the present invention provides a method for producing a filament for a 3D printer comprising the step of performing a common extrusion of the polymer resin composition using an extruder, and manufacturing a filament by winding using an ER.
  • polyester co-polymer A comprising a residue of a dicarboxylic acid component and a diol component, including terephthalic acid
  • Polyester copolymer B containing the residue of the dicarboxylic acid component containing terephthalic acid, and the residue of the diol component
  • an impact modifier wherein the residues of the diol component of the polyester copolymer A include isosorbide, 1,4-cyclonucleic acid di, and ethylene glycol, and the residues of the diol component of the polyester copolymer B are cyclo
  • a polymer resin composition containing nucleic acid dimethane may be provided.
  • the present inventors conducted a study on a polymer resin composition having no toxic substances and odors such as bisphenol A and styrene during molding, and having excellent mechanical and heat resistance properties, and residues of dicarboxylic acid components including terephthalic acid; Polyester copolymer A comprising a residue of a diol component; Residues of the dicarboxylic acid component including terephthalic acid; Polyester copolymer B containing; And an impact modifier, wherein the residues of the diol component of the polyester copolymer A include isosorbide, 1,4-cyclonucleic acid di, and ethylene glycol, and the residues of the diol component of the polyester copolymer B are cyclo It was confirmed through experiments that the polymer resin composition including nucleic acid dimethanol does not generate the harmful substances and does not generate odor and is environmentally friendly, and has excellent mechanical and heat resistance properties through experiments.
  • polyester co-polymer A containing the residue of the dicarboxylic acid component containing terephthalic acid, and the residue of the said diol component
  • Polyester copolymer B containing the residue of the dicarboxylic acid component containing terephthalic acid, and the residue of the said diol component
  • the polymer resin composition may be provided by adding an impact modifier to a conventional mixer, mixer, or timber, and mixing the same through an extruder, for example, a twin screw extruder.
  • each of the resins are preferably used in a completely dried state.
  • the polymer resin composition prepared in this way may be used in materials of electrical and electronic products and mobile phones, interior materials such as home refrigerators and washing machines, automobile parts and interior materials, food and industrial packaging materials, and particularly, such as bisphenol A and styrene. It is preferable to be used as a material for FDM type 3D printer filament because it can output at low temperature without generating harmful substances and odors.
  • the polymer resin composition may include 55 to 90% by weight of polyester copolymer A, 7 to 33% by weight of polyester copolymer B, and 0.7 to 13% by weight of the layer modifier.
  • each component in the polymer resin composition is, for example, 59 to 87% by weight of polyester copolymer A, 10 to 30% by weight of the polyester copolymer B, and 1 to 12% by weight of the layer modifier. It is preferable.
  • 'residual 1 ' means a certain part or unit included in the result of the chemical reaction and derived from the specific compound when the specific compound participates in the chemical reaction.
  • each of the 'residues' of the dicarboxylic acid component or one residue of the dial component is derived from the dicarboxylic acid component in polyester copolymers A and B which are formed by esterification reaction or condensation polymerization reaction.
  • the 'dicarboxylic acid component' is a dicarboxylic acid such as terephthalic acid, an alkyl ester thereof (lower alkyl ester having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester) and / or their It is used in the sense of containing an acid anhydride (ac id anhydride), and can react with the diol component to form a di carboxyl ic acidmoi ety such as terephthaloyl moi ety. .
  • polyester copolymers A and B As terephthalic acid is included in the dicarboxylic acid component used in the synthesis of the polyester copolymers A and B, physical properties such as mechanical properties and heat resistance properties of the polyester resin composition to be produced may be improved.
  • the dicarboxylic acid component contained in the polyester copolymers A and B may further include an aromatic dicarboxylic acid component, an aliphatic dicarboxylic acid component or a mixture thereof.
  • the aromatic dicarboxylic acid component may be an aromatic polycarboxylic acid having 8 to 20 carbon atoms, or 8 to 14 carbon atoms or a mixture thereof.
  • aromatic dicarboxylic acid examples include naphthalenedicarboxylic acid such as isophthalic acid and 2,6-naphthalenedicarboxylic acid, diphenyl dicarboxylic acid, 4,4'-steelbendicarboxylic acid, 2, 5-furandicarboxylic acid, 2, 5-thiophene dicarboxylic acid, but the specific examples of the aromatic dicarboxylic acid is not limited thereto.
  • the aliphatic dicarboxylic acid component may be an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms, or 4 to 12 carbon atoms or a mixture thereof.
  • Examples of the aliphatic dicarboxylic acids include tetrachlorodicarboxylic acid, phthalic acid, sebacic acid, succinic acid and isodecyl succinic acid such as 1,4-cyclonucleic acid dicarboxylic acid and 1,3-cyclonucleic acid dicarboxylic acid.
  • the diol component (diol component) used in the synthesis of the polyester copolymer A is 0.1 to 60 mol 3 ⁇ 4>, 1, 4-cyclonucleodiol diol 5 to 80 mol%, and 5 to ethylene glycol And 80 mole percent.
  • the content of the iso carbide may be 0.1 to 60, or 5 to 60 mol% with respect to the total content of the diol component. If the content of isosorbide in the diol component is less than 0.1 mol%, the heat resistance or mechanical properties of the prepared polyester copolymer A may be insufficient, and when the content of more than 60 mol% includes the polyester copolymer A prepared There is a fear that the resin composition to be yellowed (yel lowing).
  • the diol component in the polyester copolymer A may further include one or more selected from the group consisting of compounds represented by the following Chemical Formulas 1, 2, and 3.
  • 3 ⁇ 4 and 4 are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and n 2 are each independently an integer of 0 to 3.
  • R 3 and are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms.
  • n is an integer of 1 to 7.
  • the content of the polyester copolymer A in the polymer resin composition may be 55 to 90% by weight, or 59 to 87% by weight. When the content of the polyester copolymer A is less than 55% by weight, heat resistance may be lowered. When the content of the polyester copolymer A is greater than 90% by weight, it may be difficult to lower the extrusion processing temperature and the 3D printing nozzle temperature.
  • the polyester copolymer B contained in the said polymeric resin composition contains the residue of a diol component.
  • the residue of the diol component may include cyclonucleic acid dimethanol.
  • the residue of the diol component may further include at least one member selected from the group consisting of an aromatic diol component, an aliphatic diol component, and an alicyclic diol component, in addition to cyclohexane dimethane.
  • the cyclohexane dimethane may be, for example, 1, 2-cyclonucleodimethanol 1, 3-cyclonucleodimethanol or 1,4-cyclonucleodimethanol, and in particular, excellent heat resistance and For layer resistance, it may be 1,4-cyclonucleic acid dimethanol.
  • the aromatic diol component is a compound in which a benzene ring and two hydroxy groups are substituted in the benzene ring, and may be an aromatic diol having 8 to 20 carbon atoms, or an aromatic diol having 8 to 14 carbon atoms, or a mixture thereof.
  • aromatic diol examples include biphenol, hydroquinone, 1,2-dihydroxy naphthalene, 1,3-dihydroxy naphthalene, 1,4-dihydroxy naphthalene, and the like, but specific examples of the aromatic diol are not limited thereto.
  • the aliphatic diol component is a component in which two hydroxy groups are substituted in a compound having a carbon atom chain shape, and may be an aliphatic di-carbon component having 2 to 20 carbon atoms or a combination thereof.
  • Examples of the aliphatic diol component include ethylene glycol, propylene glycol, butylene glycol, and the like, but specific examples of the aromatic diul are not limited thereto.
  • the cycloaliphatic (cyc loal iphat i c) diol component is a component substituted with two hydroxy groups in a compound having a carbon ring structure, the carbon bonds forming the ring structure may be in a saturated state.
  • the cycloaliphatic diaryl component may be, in addition to the cyclonucleic acid dimethanol, an alicyclic diol having 8 to 20 carbon atoms, or an aliphatic diol having 8 to 14 carbon atoms, or a mixture thereof.
  • the polyester copolymer B included in the polymer resin composition may be at least one selected from the group consisting of polycyclonuclear styrenedimethylene terephthalate (PCT) and glycol-modified polycyclonuclear silane dimethylene terephthalate (PCTG).
  • PCT polycyclonuclear styrenedimethylene terephthalate
  • PCTG glycol-modified polycyclonuclear silane dimethylene terephthalate
  • the glycol-modified polycyclonuclear silane dimethylene terephthalate is a copolymer of dicarboxylic acid containing terephthalic acid and di-containing cyclohexanedimethanol, and the content of the cyclohexane dimethanol is 40 to 90 mol%, 45 to 85 mol. %, 50 to 80 mol%, or 50 to 75 mol). If the content of the cyclohexanethanol is less than 40 mol%, the crystalline region in the resin is reduced, so that the heat resistance characteristics such as glass transition (Tg) are lowered, and if it exceeds 90 mol%, pyrolysis occurs due to an increase in processing temperature. As a result, the transparency of the product may be lowered, and the color may be unexpectedly yellow. In addition, crystallization of the filament may occur during the printing process, thereby decreasing the interlayer adhesion and the transparency of the product.
  • Tg glass transition
  • the glycol-modified polycyclonuclear styrenedimethylene terephthalate may include one or more diols except for the cyclohexane dimethyl methane.
  • ethylene glycol, diethylene glycol, 1, 2-propanediol, 1,3-propanedi, 1,4-butanedi, 2,2-dimethyl-1,3—propanedi, 1,6 It may further comprise a dinucleic acid diol, 1, 2- cyclohexanediol, 1, 4- cyclonucleic acid diol or a combination thereof.
  • the amount of diol except for cyclohexane dimethane is added so that the sum of the total diol components with respect to dicarboxylic acid is 100 mol% in consideration of the content of cyclonucleodimethanol.
  • the polyester copolymer B may be a glycol-modified polycyclohexylenedimethylene terephthalate (PCTG) having an amorphous structure that has a glass transition temperature of 80 ° C or more and excellent heat resistance and does not crystallize at low temperature after melting. have.
  • PCTG polycyclohexylenedimethylene terephthalate
  • the content of the polyester copolymer B in the polymer resin composition may be 7 to 33% by weight, or 10 to 30% by weight.
  • the content of the polyester copolymer B is less than 7% by weight, it may be difficult to lower the processing temperature, and when it exceeds 33% by weight, heat resistance may be lowered.
  • the weight ratio of B may be 1: 0.07 to 0.55 or 1: 0.1 to 0.51. When the weight ratio is less than 1: 0.07, it may be difficult to lower the processing temperature, and when the weight ratio is greater than 1: 0.55, heat resistance may be lowered.
  • the layer stiffener may be a core-shell structured impact modifier, a linear structured impact modifier, or a combination thereof.
  • acrylic rubber examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, double ethyl nucleus (meth) acrylate, nuclear chamber (meta ) (Meth) acrylate monomers such as acrylate may be used, wherein ethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, 1, 3- butylene glycol di (meth) acrylate, 1, 4- butylene glycol di (meth) acrylate, allyl (meth) acrylate, triallyl cyanurate, etc. Can be used further.
  • the silicone rubber is prepared from cyclosiloxane, and specific examples thereof include nuxamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclonuxasiloxane, trimethyltriphenylcyclotrisiloxane, and tetramethyltetraphenyl. It may be prepared from one selected from the group consisting of cyclotetrosiloxane, octaphenylcyclotetrasiloxane, and combinations thereof. Unless otherwise specified herein, "(meth) acrylic acid 1 " includes “acrylic acid 1 " and “methacrylic acid 1 ", and "(meth) acrylate” refers to "acrylate” and "methacrylate 1". Contains'
  • the core-shell impact modifier may be an alkyl methacrylate-diene rubber-aromatic vinyl graft copolymer, an alkyl methacrylate-silicone / alkyl acrylate graft copolymer, or a mixture thereof. Can be.
  • the layered stiffener of the linear structure polyethylene-butyl acrylate ⁇ glycidyl methacrylate copolymer, polyethylene methacrylate- glycidyl methacrylate copolymer, ethylene-alpha olefin-based layer stiffener, silicone type It may be at least one selected from the group consisting of a stratification enhancer and a polyester elastomer impact modifier.
  • the content of the impact modifier is less than 0.7% by weight, the effect of improving the impact characteristics may not be exhibited. If the content of the impact modifier is greater than 13% by weight, the flowability may be lowered due to the increase in viscosity, and the processing temperature may increase.
  • the polymer resin composition may be used for FDM-type 3D printer filament material electronics and mobile phone materials home steamer and washing machine interior materials, automobile parts and interior materials food and industrial packaging materials.
  • a filament for a 3D printer including the polymer resin composition may be provided.
  • the 3D printer is operated on the principle that the filament material is melted through the nozzle and output on the 3D printer bed.
  • the filament material can be printed under the condition that the nozzle temperature is below 270 ° C or below 260 ° C.
  • Preferred is a material capable of outputting at temperatures below 90 ° C or below 70 ° C.
  • PC polycarbonate
  • ABS acrylonitrile butadiene styrene
  • a nozzle temperature of 300 ° C or higher and a bed temperature of 140 ° C or higher are used.
  • ABS bisphenol A
  • the present inventors conducted a study on a filament material capable of 3D printing at low temperature without generating harmful substances and odors such as bisphenol A and styrene during 3D printing, and dicarboxylic acid including terephthalic acid.
  • Polyester co-polymer A comprising a residue of a component and a residue of a diol component including isosorbide, 1,4-cyclonucleic acid diol, and ethylene glycol
  • Polyester copolymer B containing the residue of the dicarboxylic acid component containing terephthalic acid, and the residue of the di component containing cyclohexane dimethyl methane
  • 3D printing filament using a polymer resin composition comprising a layer reinforcing agent it is eco-friendly because the harmful substances do not occur and no odor during printing, has excellent mechanical properties and heat resistance properties, nozzle temperature below 270 ° C and Experiments confirmed that 3D printing is possible at a bed temperature of 90 ° C or less, and completed the invention
  • the extruder is a type of pressure molding machine, which includes a reciprocating type for putting a material into a cylinder, and extrudes a material for an extrusion cylinder, and a continuous type for extruding by rotating a screw in the cylinder, both of which depend on the type of die installed at the outlet of the cylinder.
  • a single rod-shaped or thread shape can be extruded.
  • the screw extruder is a linear or tubular Molded articles are obtained continuously and can be used for extrusion spinning of plastics and synthetic fibers (filaments) and the like.
  • the 'kumyeon' refers to an operation to mix evenly by applying a mechanical shear force to disperse, in the present invention to set the appropriate blending sequence, kneading time, temperature in order to produce a polymer optimized for 3D printing It was.
  • the shake extrusion may be extruded at a screw rotational speed of 150 to 300rpm. If the screw rotational speed is less than 150rpni, the thickness of the filament is thickened to pass through the gear (Gear) is not fed to the nozzle (feeding), printing is impossible, or if the screw rotational speed exceeds 300rpm thickness of the filament produced May become thin and unevenly melted, resulting in a problem of degrading the quality of the output.
  • the method may further include cooling the shake-extruded polymer resin composition in a water bath.
  • the filaments may be manufactured by winding a polymer resin supernatant sensed in the water bath using a roller.
  • the filament prepared may have a diameter of 1.70 to 1.80 mm 3 or 2.95 to 3.05 mm.
  • the diameter of the filament does not satisfy this value In the case of 3D printer operation, filament passes between gears and is not fed to the nozzle, so printing cannot be performed, or the filament is melted sufficiently so that the quality of the printout may be degraded.
  • the present invention it is eco-friendly because no harmful substances such as BPA and styrene do not occur and no odor is generated, and a polymer resin composition having excellent mechanical properties and heat resistance properties, and the output is possible at low temperatures using the composition.
  • An excellent 3D printer filament, and the 3D printer filament manufacturing method can be provided.
  • Terephthalic acid-iso carbide-1, 4-cyclonucleic acid diol-ethylene glycol copolymer (EC0ZEN), a high-impact eco-friendly resin from SK Chemicals, Korea, in a twin screw kneading extruder ( ⁇ : 40mm, L / D 40) Glycol-modified polycyclonuclear silane dimethylene terephthalate resin (PCTG of SK Chemicals Co., Ltd.), and polyethylene-butylacrylate-glycidyl methacrylate copolymer (impregnator of Dupont), which is a linear impact modifier,
  • Other additives include acrylonitrile-styrene-glycidyl methacrylate copolymer (SAG-005 from SUNNY FC, Japan), phenol-based primary oxidation stabilizer (AO- 60 from ADEKA, Japan), and phosphorus secondary oxidation stabilizer. (I-168 from BASF) was added. In the following Table 1, each component was
  • Example 1 to 7 and the pellets prepared according to Comparative Examples 1 to 6 were injected in the same manner at 240 ° C. using an injection machine, and then the injected test pieces to the physical properties of the following Experimental Examples 1 to 3
  • the measurement results are shown in Table 2 below.
  • Experimental Example 1 Measurement of Heat Resistance In accordance with ASTM D648, the test specimen was made and measured for heat resistance using a heat deflection temperature tester (HDT Tester, Toyoseiki).
  • Experimental Example 2 Measurement of Tensile Properties

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  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine polymère, un filament d'imprimante 3D la contenant et un procédé de fabrication du filament d'imprimante 3D, où la composition de résine polymère comprend : un copolymère de polyester A, qui comprend un fragment de type composant acide dicarboxylique contenant de l'acide téréphtalique et un fragment de type composant diol contenant un dianhydrohexitol ; un copolymère de polyester B, qui comprend un fragment de type composant acide dicarboxylique contenant de l'acide téréphtalique et un fragment de type composant diol exempt de dianhydrohexitol ; et un modificateur de résistance au choc.
PCT/KR2018/005626 2017-05-18 2018-05-16 Composition de résine polymère, filament d'imprimante 3d la contenant, et procédé de fabrication de filaments d'imprimante 3d WO2018212596A1 (fr)

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KR10-2017-0061798 2017-05-18
KR20170061798 2017-05-18

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022008097A1 (fr) 2020-07-10 2022-01-13 Roquette Freres Polyester thermoplastique pour la fabrication d'objet d'impression 3d
WO2022008096A1 (fr) 2020-07-10 2022-01-13 Roquette Freres Polyesier thermoplastique pour la fabrication d'objet d'impression 3d

Citations (5)

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WO2022008097A1 (fr) 2020-07-10 2022-01-13 Roquette Freres Polyester thermoplastique pour la fabrication d'objet d'impression 3d
WO2022008096A1 (fr) 2020-07-10 2022-01-13 Roquette Freres Polyesier thermoplastique pour la fabrication d'objet d'impression 3d
FR3112305A1 (fr) 2020-07-10 2022-01-14 Roquette Freres Polyester thermoplastique pour la fabrication d’objet d’impression 3D
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