WO2015064877A1 - Composition pour filament d'imprimante tridimensionnelle - Google Patents

Composition pour filament d'imprimante tridimensionnelle Download PDF

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Publication number
WO2015064877A1
WO2015064877A1 PCT/KR2014/004684 KR2014004684W WO2015064877A1 WO 2015064877 A1 WO2015064877 A1 WO 2015064877A1 KR 2014004684 W KR2014004684 W KR 2014004684W WO 2015064877 A1 WO2015064877 A1 WO 2015064877A1
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Prior art keywords
dimensional printer
filament
thermoplastic polyester
composition
polyester elastomer
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PCT/KR2014/004684
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English (en)
Korean (ko)
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이성율
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화인케미칼 주식회사
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    • 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
    • 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
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/06—Making preforms by moulding the material
    • B29B11/10—Extrusion moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • 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
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/266—Means for allowing relative movements between the apparatus parts, e.g. for twisting the extruded article or for moving the die along a surface to be coated
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/285—Feeding the extrusion material to the extruder
    • B29C48/288—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules
    • B29C48/2888—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules in band or in strip form, e.g. rubber strips
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]

Definitions

  • the technology disclosed herein relates to a composition for a three-dimensional printer filament, and more particularly to a composition for a three-dimensional printer filament having a high solidification rate and excellent sliding characteristics when producing a solid article through three-dimensional printing.
  • 3D (3-Dimension, 3D) printer is a equipment to produce three-dimensional shape by stacking layers with fine thickness by spraying ink of special material sequentially. 3D printing is spreading in various fields. In addition to the automotive field, which is made up of many parts, many manufacturers use them to make various models of medical human body models and household products such as toothbrushes and shavers.
  • the most widely used material for 3D printing is photopolymer, a photocurable polymer material that hardens when light is received. This accounts for 56% of the total market.
  • the next most popular material is a solid thermoplastic that is free to melt and harden, accounting for 40% of the market, and metal powder is expected to grow in the future.
  • the form of the dual thermoplastic material may have a filament, particle or powder form.
  • the filament type 3D printing is faster than other types in terms of speed, so the productivity is high and the diffusion speed is high.
  • Existing filament materials include polylactic acid (PLA), acrylonitrile butadiene styrene (ABS), high density polyethylene (HDPE), polycarbonate (PC), and the like.
  • PLA polylactic acid
  • ABS acrylonitrile butadiene styrene
  • HDPE high density polyethylene
  • PC polycarbonate
  • the melting point is moderately high, so the solidification speed after printing is high, so even if the printing speed is fast, the deformation and deformation are good, and the dimensional and shape stability is good.
  • the melting point is moderately low, easy extrusion and high production efficiency during filament production.
  • the melting point is too high, it can be an unnecessary cost increase, because it consumes a lot of power to melt the filament and the parts inside the printer must be made of a material that can withstand high heat.
  • the above four kinds of materials meet the above conditions, all of which are high hardness materials of hardness Shore D50 or more, and cannot satisfy the requirements of 3D printing materials requiring low hardness and soft texture.
  • high hardness materials of hardness Shore D50 or more are high hardness materials of hardness Shore D50 or more, and cannot satisfy the requirements of 3D printing materials requiring low hardness and soft texture.
  • models for infants, school models, shoes and toys can be made more realistic when 3D printed with soft, low-hard materials. Therefore, the development of new materials is required.
  • the differential scanning calorimetry (DSC) thermal analysis includes a polymer substrate containing a thermoplastic polyester elastomer (TPEE) having a melting point peak temperature of 130 to 180 °C, the melt index of the polymer substrate (190) C, 2.16 kg) is provided a composition for three-dimensional printer filament 1 to 30g / 10 minutes.
  • TPEE thermoplastic polyester elastomer
  • a three-dimensional printer filament produced by extruding a composition comprising a polymer substrate containing a thermoplastic polyester elastomer, the polymer substrate has a hardness of Shore A 90 or less, melt index (190 °C, 2.16 kg) is provided with a three-dimensional printer filament having 1 to 30 g / 10 minutes and a melt index (150 ° C., 10 kg) of 3.0 g / 10 minutes or less.
  • a method for manufacturing a three-dimensional printer filament comprising: supplying a three-dimensional printer filament to a print head; Ejecting a melt of the three-dimensional printer filament heated from the print head; Solidifying the melt to form a printed layer; And stacking the printed layers in multiple layers to form a solid article.
  • FIG. 1 shows a typical filament type three-dimensional printing system.
  • FIG. 1 shows a typical filament type three-dimensional printing system.
  • the three-dimensional printing system of Figure 1 is an example of a model called LulzBot TAZ by Aleph Objects.
  • the bottom plate 110 moves in the Y-axis
  • the print head 120 moves in the X-axis and Z-axis, and further builds a predetermined shape by discharging the filament 130. It is done in such a way.
  • the filament 130 is supplied from the reel 140 on the right side and is supplied through the induction pipe 150.
  • the supply amount is controlled by the force and speed of the traction device included in the print head 120, and a hot melt adhesive gun (gun)
  • the melted filaments are extruded in a manner similar to) to form a printed layer on the bottom plate 110 and continue stacking these printed layers to form the article 160.
  • the principle of the induction pipe 150 is to serve as a passage for smoothly supplying the filament 130 to the print head 120 moving left and right up and down, if there is no induction pipe 150, the filament 130 is bent in the middle It cannot be fed vertically (always in a constant direction) to the print head 120, so that constant speed metering will be difficult.
  • the filament 130 having a diameter of about 1.75 mm passes through the filament 130 without shaking, so that the inner diameter of the guide tube 150 is less than about 2.0 mm so that the play is not large.
  • the filament 130 passing through the induction pipe 150 will also generally be a hard and smooth material.
  • thermoplastic polyester elastomer TPEE
  • composition for a three-dimensional printer filament comprising a polymer substrate containing a thermoplastic polyester elastomer having a melting point peak temperature of 130 to 180 ° C. during thermal analysis by a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the MI (190 ° C., 2.16 kg) of the composition, in which various additional components are mixed, is 1 to 30 g / 10 minutes, and the hardness is Shore A 90 or less.
  • thermoplastic polyester elastomer is an elastomer in which crystalline hard segments formed from aromatic dicarboxylic acids and aliphatic diols and soft soft segments formed from polyalkylene oxides are randomly arranged.
  • the aromatic dicarboxylic acid constituting the polyester of the hard segment is widely used as the conventional aromatic dicarboxylic acid, and is not particularly limited, but the main aromatic dicarboxylic acid is terephthalic acid or naphthalenedica It is preferable that it is a leric acid.
  • alicyclic dicarboxylic acids such as aromatic dicarboxylic acid, such as diphenyl dicarboxylic acid, isophthalic acid, and 5-sodium sulfoisophthalic acid, cyclohexanedicarboxylic acid, and tetrahydrophthalic anhydride, are mentioned.
  • aliphatic dicarboxylic acids such as acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecane diacid, dimer acid, hydrogenated dimer acid, and the like. These are used in the range which does not significantly reduce melting
  • thermoplastic polyester elastomer of the present invention as the aliphatic or alicyclic diols constituting the polyester of the hard segment, general aliphatic or alicyclic diols are widely used, and are not particularly limited, but mainly alkylene having 2 to 8 carbon atoms It is preferable that they are glycols. Specifically, ethylene glycol, 1, 3-propylene glycol, 1, 4- butanediol, 1, 6- hexanediol, 1, 4- cyclohexane dimethanol, etc. are mentioned. Most preferred are 1,4-butanediol and 1,4-cyclohexanedimethanol.
  • butylene terephthalate units or butylene naphthalate units is preferable at the point of a physical property, moldability, and cost performance.
  • the aromatic polyester suitable as polyester which comprises a hard segment in the thermoplastic polyester elastomer of this invention can be obtained easily according to a conventional polyester manufacturing method. Moreover, it is preferable that such polyester has the number average molecular weights 10000-40000.
  • the aliphatic polycarbonate which comprises the soft segment in the thermoplastic polyester elastomer of this invention mainly consists of a C2-C12 aliphatic diol residue and a carbonate bond.
  • these aliphatic diol residues for example, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2, 2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8 And residues such as -octanediol.
  • an aliphatic diol residue having 5 to 12 carbon atoms is preferable in view of flexibility and low temperature characteristics
  • the melting point is low (for example, 70 ° C. or lower) and the glass transition temperature is low.
  • aliphatic polycarbonate diols composed of 1,6-hexanediol moieties used to form soft segments of thermoplastic polyester elastomers have a low glass transition temperature of around -60 ° C and a melting point of about 50 ° C, which is why It becomes good thing.
  • the aliphatic polycarbonate diol obtained by copolymerizing an appropriate amount of the aliphatic polycarbonate diol, for example, 3-methyl-1,5-pentanediol has a slightly higher glass transition point compared to the original aliphatic polycarbonate diol, but a lower melting point. Or it becomes an amorphous and corresponds to the aliphatic polycarbonate diol which is favorable in low temperature characteristic.
  • aliphatic polycarbonate diols composed of 1,9-nonanediol and 2-methyl-1,8-octanediol have good low temperature characteristics because the melting point is about 30 ° C. and the glass transition temperature is sufficiently low around ⁇ 70 ° C. It corresponds to aliphatic polycarbonate diol.
  • the aliphatic polycarbonate diol is not necessarily composed of only the polycarbonate component but may be a copolymer of a small amount of other glycol, dicarboxylic acid, ester compound, ether compound, or the like.
  • a copolymerization component For example, dicarboxylic acid, such as glycol, dimer acid, hydrogenated dimer acid, such as dimerdiol, hydrogenated dimerdiol, and these modified bodies, aliphatic, aromatic, or alicyclic dicarboxylic acid, Polyalkylene glycol or oligoalkylene glycol, such as polyester or oligoester consisting of glycol, polyester or oligoester consisting of epsilon -caprolactone, polytetramethylene glycol, polyoxyethylene glycol, etc.
  • the copolymerization component can be used to such an extent that the effect of the aliphatic polycarbonate segment is not substantially lost. Specifically, it is 40 parts by weight or less, preferably 30 parts by weight or less, and more preferably 20 parts by weight or less based on 100 parts by weight of the aliphatic polycarbonate segment. When there is too much copolymerization quantity, it becomes inferior to the heat aging resistance and water resistance of the obtained thermoplastic polyester elastomer.
  • thermoplastic polyester elastomer of the present invention is a soft segment only to the extent that the effects of the invention are not lost.
  • polyalkylene glycols such as polyethylene glycol, polyoxytetramethylene glycol, polycaprolactone, polybutylene adipate, etc.
  • Copolymerization components such as polyester, may be introduce
  • the thermoplastic polyester elastomer has a melt index (MI) as measured by ASTM D1238 (190 ° C., 2.16 kg) of 0.01 to 30 g / 10 minutes, or 0.01 to 20 g / 10 minutes, or 0.1 to 10 g / 10 minutes, or 0.1 to 5.0 g / 10 minutes, or 0.1 to 3.0 g / 10 minutes, or 0.1 to 1.0 g / 10 minutes, or 0.3 to 0.6 g / 10 minutes, or 1 to 30 g / 10 minutes have.
  • MI melt index
  • thermoplastic polyester elastomers include thermoplastic polyester elastomers having a poly (1,4-butylene terephthalate) block and a poly (tetramethylene ether) glycol block. Pont de Nemours & Co. Inc., Wilmington, Delaware, USA, 19898, available as HYTREL).
  • the thermoplastic polyester elastomer may have a poly (ethylene terephthalate) block and a polyalkylene glycol block.
  • the thermoplastic polyester elastomer may have a poly (1,4-butylene terephthalate) block and a polyalkylene glycol block.
  • the TPEE used in the present invention has a high melting point of at least 130 ° C. or higher and a high solidification speed after printing, and excellent dimensional and shape stability.
  • the TPEE used in the present invention has a melting point of 180 ° C. or less, so that the melting point is not very high, so that the extrusion is easy and the productivity is high during filament production.
  • the hardness of the used TPEE may be many grades over Shore A 95, but in these cases, the plasticizer, etc. must be formulated in order to make the hardness low, so there is a fear of migration and the slipperiness of the surface of the product becomes poor. A 95 or less is recommended.
  • TPEE When TPEE is used as the main material of filament material, it is softer than existing high hardness filament materials such as PLA, ABS, HDPE, and PC, and it is also soft and has good heat resistance and oil resistance. In addition, it is possible to secure an additional advantage, such as making a variety of products, such as shoe soles, parts and prefabricated toys can be easily adhered by an adhesive.
  • thermoplastic polyester elastomer may include various additional components to improve physical properties.
  • the additional component may be at least one selected from the group consisting of wax, plasticizer, thermoplastic elastomer (TPE), ethylene copolymer, and olefin random copolymer (ORC).
  • the additional component may include 1 to 25 parts by weight based on 100 parts by weight of the thermoplastic polyester elastomer.
  • the wax may include paraffin wax, microcrystalline wax, polyethylene wax, and the like, and the surface filament of the filament may be improved to allow the filament to easily pass through the guide tube of the printer.
  • the wax may be included in an amount of 1 to 5 parts by weight based on 100 parts by weight of the thermoplastic polyester elastomer. When the amount of the wax exceeds 5 parts by weight, the hardness of the filament is increased, and the flexibility of the filament may be lowered and broken.
  • the plasticizer comprises a propylene glycol polymer (PPG) or polyethylene glycol polymer (PEG) having a number average molecular weight of 200 to 20,000, preferably 200 to 3,500, more preferably 200 to 1,500.
  • PPG propylene glycol polymer
  • PEG polyethylene glycol polymer
  • the addition of the plasticizer has the effect of lowering the hardness of the entire polymer substrate.
  • the plasticizer may be included in an amount of 1 to 5 parts by weight based on 100 parts by weight of the thermoplastic polyester elastomer. If the amount of the plasticizer exceeds 5 parts by weight, the sliding property of the filament surface may be lowered by migration.
  • the thermoplastic elastomer is styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-isoprene-styrene (SIS), 1,2-polybutadiene, ethylene-propylene-diene (EPDM), and the like. These may be used alone or in combination of two or more.
  • the addition of the thermoplastic elastomer has an effect of reinforcing elasticity than when TPEE alone.
  • the thermoplastic elastomer may be included in an amount of 1 to 20 parts by weight based on 100 parts by weight of the thermoplastic polyester elastomer. When the amount of the thermoplastic elastomer exceeds 20 parts by weight, the slipperiness of the surface of the filament may be degraded.
  • Ethylene copolymers or olefin random copolymers may be mixed to control the price of the entire filament composition.
  • the ethylene copolymer comprises i) ethylene, and ii) C3-C10 alpha monoolefins, C1-C12 alkyl esters of C3-C20 monocarboxylic acids, unsaturated C3-C20 mono or dicarboxylic acids, anhydrides and unsaturated C4-C8 dicarboxylic acids. It may be a copolymer of one or more ethylenically unsaturated monomers selected from the group consisting of vinyl esters of C2-C18 carboxylic acids.
  • ethylene copolymers include ethylene vinyl acetate, (Ethylene Vinylacetate, EVA), ethylene butyl acrylate (Ethylene Butylacrylate, EBA), ethylene methyl acrylate (Ethylene Methylacrylate, EMA), ethylene ethyl acrylate (Ethylene Ethylacrylate, EEA), ethylene methyl methacrylate (Ethylene Methylmethacrylate, EMMA), ethylene butene copolymer (Ethylene Butene Copolymer, EB-Co), ethylene octene copolymer (Ethylene Octene Coplymer, EO-Co), and the like.
  • the olefin random copolymer may be in the form of random polymerization of ethylene or propylene with one or more copolymerizable ⁇ -olefin comonomers, for example, the olefin random copolymer may be a copolymer of ethylene or propylene and octene.
  • the ethylene copolymer or the olefin random copolymer may be included in an amount of 1 to 20 parts by weight based on 100 parts by weight of the thermoplastic polyester elastomer.
  • the amount of the ethylene copolymer or the olefin random copolymer exceeds 20 parts by weight, solidification of the filament may be delayed after extrusion.
  • the composition may further include an antioxidant or a pigment.
  • the antioxidant may be used, such as sunnoc, butylated hydroxytoluene (BHT), Songnox 1076 (songnox 1076, octadecyl 3,5-di- tert- butyl-4-hydroxyhydrocinnamate), etc., considering the color It is also possible to use a variety of pigments.
  • the antioxidant or the dye may be included 1 to 5 parts by weight based on 100 parts by weight of the thermoplastic polyester elastomer. When the antioxidant or the dye exceeds 5 parts by weight, the filament may be degraded due to a phenomenon such as blooming.
  • the MI (190 ° C., 2.16 kg) of the final composition may be 1 to 30 g / 10 minutes, preferably 1 to 20 g / 10 minutes, more preferably 1 to 10 g / 10 minutes. If the MI (190 °C, 2.16kg) is less than 1.0g / 10 minutes, the filament melting rate is not slow to smooth printing or slow down the printing speed. On the other hand, if the MI (190 °C, 2.16kg) is more than 30g / 10 minutes, the filament melts too fast, it is difficult to maintain a constant discharge amount at a constant speed, the error in printing thickness increases.
  • a three-dimensional printer filament produced by extruding the above-described composition.
  • the filament comprises a polymeric substrate containing a thermoplastic polyester elastomer.
  • the hardness of the polymer substrate is less than Shore A 90.
  • the melt index (190 ° C., 2.16 kg) is 1 to 30 g / 10 minutes
  • the melt index (150 ° C. and 10 kg) is 3.0 g / 10 minutes or less.
  • the melt index (150 ° C., 10 kg) is preferably 0.01 to 2.0 g / 10 minutes, more preferably 0.01 to 1.0 g / 10 minutes or less.
  • the filament has a high solidification rate and excellent sliding properties.
  • Have The thermoplastic polyester elastomer may have a melting point peak temperature of 130 to 180 ° C. in DSC thermal analysis. The melting of the filament in the melting point range is less power consumption and easy extrusion.
  • the three-dimensional printer filament may have a diameter of 1.0 to 2.0mm, preferably 1.5 to 1.8mm. If the diameter of the filament is less than 1mm, it is difficult to produce a print head that pushes out the filament, and the printing speed may be too slow. If the diameter of the filament exceeds 2mm, the solidification speed is slow and the printing line is thick, resulting in poor product accuracy. Since the hardness of the filament is less than Shore A 90, the hardness of Shore A 90 or more can not feel the soft texture, such as rubber does not fit the purpose of the present patent.
  • a method of forming an article through three-dimensional printing using the three-dimensional printer filament described above is provided.
  • the article forming method may proceed to the following process.
  • First, the above-mentioned three-dimensional printer filament is supplied to a print head.
  • the filament may be supplied to the print head through a guide tube.
  • Next, the melt of the three-dimensional printer filament heated from the print head is discharged.
  • the bottom of the printer moves on the Y-axis
  • the print head moves on the X-axis, stacks one layer and then raises one layer on the Z-axis, then moves on the X-axis and Y-axis as above, stacks the next layer, and back on the Z-axis.
  • This printing is going up three-dimensional printing.
  • the melt is then solidified to form a printed layer.
  • the printed layer is then laminated in layers to form a solid article.
  • compositions were prepared by combining the following components, extruded by a single screw extruder having a screw diameter of 30 mm and a screw length of 105 mm, and cooled and wound with a 1.5 m length cooling water tank to make a filament having a diameter of 1.75 mm.
  • Melting points of the polymers were measured using DSC, and Tm was measured by raising the temperature to 10 ° C. per minute according to ASTM D-3418.
  • TPEE-1 Thermoplastic Polyseter elastomer KEYFLEX BT 1030D (LG Chemistry), DSC Melting Point 165 °C, Hardness Shore A 80
  • TPEE-2 Thermoplastic Polyseter elastomer KEYFLEX BT 1035D (LG Chemistry), DSC Melting Point 165 °C, Hardness Shore A 88
  • TPEE-3 Thermoplastic Polyseter elastomer KEYFLEX BT 1045D (LG Chemistry), DSC Melting Point 178 ° C, Hardness Shore A 94, Shore D 45
  • TPEE-4 Thermoplastic Polyseter elastomer KEYFLEX BT 1047D (LG Chemistry), DSC Melting Point 190 °C, Hardness Shore A 98, Shore D 47
  • TPEE-5 Thermoplastic Polyseter elastomer Hytrel 5526 (Dupont), DSC Melting Point 203 ° C, Hardness Shore A 99, Shore D 55
  • ORC-1 Ethylene Octene Random Copolymer, DSC Melting Point 90 ° C, Hardness Shore A 87
  • EVA-1 Ethylene Vinylacetate Copolymer DSC melting point 80 °C (Hardness Shore A 88)
  • SEBS-1 Styrene Ethylene Butylene Styrene, DSC Melting Point 140 °C, Hardness Shore A 86
  • the melt index (MI) of the final composition was measured by ASTM D-1238.
  • the MI (150 ° C., 10 kg) of the final mixture was expressed as A, 1.1-2.0 for B, 2.1-3.0 for C, 3.1-5.0 for D, and 5.1 for E for 1.0 g / 10 min or less. That is, the higher the MI (150 ° C, 10kg), the later the solidification at 150 ° C.
  • MI (180kg 10kg) of final mixture is 20g / 10min or more A, 10g / 10min or more B, 5g / 10min or more C, 1g / 10min or more D, less than 1g / 10min E Marked as.
  • the final composition was extruded to obtain a filament with a diameter of 1.75 mm. It passes through the inside of polypropylene made of polypropylene with an inner diameter of 2.5mm, an outer diameter of 4.5mm and a length of 40cm, and it feels the resistance when it is pulled at a speed of 1cm / sec by hand, in order of decreasing resistance. Graded. In other words, the least resistance is indicated by A, the strongest one by E.
  • compositions of Examples 1 to 6 have a faster melting rate and solidification rate than other compositions of Comparative Examples 1 to 9, and have excellent sliding characteristics, and are suitable for use as a filament of a 3D printer and have low hardness. Therefore, it is possible to produce a variety of shapes that require a soft feel in 3D printing.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une composition pour un filament d'une imprimante tridimensionnelle, comportant un substrat polymère contenant un élastomère thermoplastique polyester (TPEE) ayant une température de fusion maximale entre 130 et 180°C lors d'une analyse thermique par calorimétrie différentielle de balayage (DSC), l'indice de fusion du substrat polymère (190°C, 2,16kg) étant entre 1 et 30g/10 minutes.
PCT/KR2014/004684 2013-11-04 2014-05-26 Composition pour filament d'imprimante tridimensionnelle WO2015064877A1 (fr)

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KR10-2013-0133204 2013-11-04
KR1020130133204A KR101391293B1 (ko) 2013-11-04 2013-11-04 3차원 프린터 필라멘트용 조성물

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KR20190069172A (ko) * 2017-12-11 2019-06-19 아주대학교산학협력단 지방족 폴리카보네이트를 포함하는 바이오 프린팅용 생체 재료 및 이를 이용한 생체 구조체의 제조방법
US10899070B2 (en) 2015-05-13 2021-01-26 Mitsubishi Chemical Corporation Filament for material extrusion-type three-dimensional printers, wound body composed of said filament, cartridge containing said filament, and method for producing resin molded article using said filament
WO2021089898A1 (fr) * 2019-11-05 2021-05-14 Onate Molina Enrique Filament antibactérien, insecticide, aromatisé et ayant une capacité virucide pour imprimantes 3d

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EP3189959B1 (fr) 2014-09-05 2019-05-01 MCPP Innovation LLC Filament pour impression 3d et procédé de production d'article moulé en résine cristalline souple
KR101685760B1 (ko) * 2014-09-05 2016-12-12 롯데케미칼 주식회사 도색성 및 충격강도가 향상된 3차원 프린터 필라멘트용 생분해성 수지 조성물
KR101780475B1 (ko) * 2014-10-14 2017-09-21 주식회사 셀루메드 필라멘트 형성에 이어 연속적으로 형상화가 가능한 3차원 프린팅 방법
KR101689304B1 (ko) 2014-11-19 2016-12-23 퓨처사이버 주식회사 3d 프린터용 필라멘트 조성물
CN104611808B (zh) * 2014-11-28 2017-10-13 珠海天威飞马打印耗材有限公司 成型丝及其制备方法
KR102291563B1 (ko) * 2014-12-30 2021-08-19 코오롱플라스틱 주식회사 3d 프린팅용 조성물 및 이를 이용한 3d 프린터용 필라멘트
CN104629161B (zh) * 2015-03-04 2017-06-06 中国科学院福建物质结构研究所 一种低熔点3d打印材料及其制备方法
EP3377305B1 (fr) 2015-11-17 2023-01-25 Zephyros Inc. Systèmes pour des matériaux de fabrication additive
KR20180127216A (ko) * 2017-05-18 2018-11-28 에스케이케미칼 주식회사 고분자 수지 조성물, 이를 포함하는 3d 프린터용 필라멘트, 및 3d 프린터용 필라멘트 제조방법
KR101912919B1 (ko) * 2017-07-25 2018-10-31 코오롱글로텍주식회사 3d 프린팅 필라멘트사용 조성물 및 3d 프린팅용 필라멘트사
KR102291562B1 (ko) * 2017-09-28 2021-08-18 코오롱플라스틱 주식회사 3d 프린팅용 조성물 및 이를 이용한 3d 프린터용 필라멘트
KR102008584B1 (ko) * 2017-12-18 2019-08-07 롯데첨단소재(주) 폴리카보네이트 공중합체, 이를 포함하는 열가소성 수지 조성물 및 이로부터 제조된 성형품
KR20190114125A (ko) 2018-03-29 2019-10-10 (주)퓨레코 고기능성 친환경 3d 필라멘트 제조를 위한 원스탑 공정 및 그를 이용한 3d 필라멘트
KR102099039B1 (ko) * 2019-05-10 2020-04-08 박성호 고속 삼차원 구조체 출력 장치

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US10899070B2 (en) 2015-05-13 2021-01-26 Mitsubishi Chemical Corporation Filament for material extrusion-type three-dimensional printers, wound body composed of said filament, cartridge containing said filament, and method for producing resin molded article using said filament
KR20190069172A (ko) * 2017-12-11 2019-06-19 아주대학교산학협력단 지방족 폴리카보네이트를 포함하는 바이오 프린팅용 생체 재료 및 이를 이용한 생체 구조체의 제조방법
KR102181642B1 (ko) * 2017-12-11 2020-11-23 아주대학교산학협력단 지방족 폴리카보네이트를 포함하는 바이오 프린팅용 생체 재료 및 이를 이용한 생체 구조체의 제조방법
WO2021089898A1 (fr) * 2019-11-05 2021-05-14 Onate Molina Enrique Filament antibactérien, insecticide, aromatisé et ayant une capacité virucide pour imprimantes 3d

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