KR101391293B1 - Composition for 3d printer filament - Google Patents

Composition for 3d printer filament Download PDF

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KR101391293B1
KR101391293B1 KR1020130133204A KR20130133204A KR101391293B1 KR 101391293 B1 KR101391293 B1 KR 101391293B1 KR 1020130133204 A KR1020130133204 A KR 1020130133204A KR 20130133204 A KR20130133204 A KR 20130133204A KR 101391293 B1 KR101391293 B1 KR 101391293B1
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thermoplastic polyester
polyester elastomer
polymer base
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filament
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KR1020130133204A
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Korean (ko)
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이성율
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화인케미칼 주식회사
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion 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
    • B29C48/05Filamentary, e.g. strands
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/266Means 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/285Feeding the extrusion material to the extruder
    • B29C48/288Feeding the extrusion material to the extruder in solid form, e.g. powder or granules
    • B29C48/2888Feeding the extrusion material to the extruder in solid form, e.g. powder or granules in band or in strip form, e.g. rubber strips
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive 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
    • B29C64/10Processes of additive manufacturing
    • B29C64/106Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118Processes 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]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y70/00Materials specially adapted for additive manufacturing

Abstract

(DSC) A polymer substrate containing a thermoplastic polyester elastomer (TPEE) having a melting point peak temperature of 130 to 180 DEG C upon thermal analysis, wherein the polymer base has a melt index (190 DEG C, 2.16 kg) A composition for a three-dimensional printer filament of 30 g / 10 min.

Description

Composition for 3D printer filament [0002]

TECHNICAL FIELD [0002] The present invention 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 speed and excellent sliding property when producing a solid article through three-dimensional printing.

3D (3-Dimension, 3-D) printer is a device that produces three-dimensional objects by stacking layers with fine thickness by sequentially injecting ink of a special material. 3D printing is spreading in various fields. In addition to the automotive sector, which is composed of many parts, many manufacturers use it for making various models such as medical human body models and household products such as toothbrushes and razors.

Currently, the most commonly used material for 3D printing is photopolymer, a photocurable polymer material that solidifies when exposed to light. This accounts for 56% of the total market. The next most popular material is solid, thermoplastic, which is free to melt and solidify. It occupies 40% of the market and metal powder is expected to grow gradually in the future. The shape of the double thermoplastics material may be in the form of filaments, particles or powder powders. Filament-type 3D printing is faster than other types in terms of speed, so productivity is high and diffusion speed is fast.

Polylactic acid (PLA), acrylonitrile butadiene styrene (ABS), HDPE (high density polyethylene), and polycarbonate (PC) are used as the existing filament materials. First, since the melting point is moderately high, the solidification speed is fast after printing, so that even if the printing speed is fast, it is not deformed and the dimensional and shape stability are good. Second, since the melting point is moderately low, the extrusion is easy and the production efficiency is high when the filament is manufactured. In addition, if the melting point is too high, it is necessary to dissolve the filament, which consumes a lot of electric power, and the parts in the printer must be made of a material capable of withstanding high temperatures.

There are four kinds of materials suitable for the above-mentioned various conditions. All of them are high hardness materials having a hardness of Shore D50 or more, and they can not satisfy the requirement as a 3D printing material requiring a soft feeling of low hardness. For example, models for infants, schools, and models for shoes and toys can be made more realistic in 3D printing with soft materials of low hardness. Therefore, the development of new materials is required.

According to one aspect of the present invention, there is provided a polymer base material comprising a polymer base material containing a thermoplastic polyester elastomer (TPEE) having a melting peak temperature of 130 to 180 DEG C in differential scanning calorimetry (DSC) thermal analysis, wherein the melt index Lt; 0 > C, 2.16 kg) is 1 to 30 g / 10 min.

According to another aspect of the present invention, there is provided a three-dimensional printer filament produced by extruding a composition comprising a polymer base material containing a thermoplastic polyester elastomer, wherein the polymer base has a hardness of Shore A 90 or less, a melt index 2.16 kg) of 1 to 30 g / 10 min and a melt index (150 캜, 10 kg) of 3.0 g / 10 min or less.

According to still another aspect of the present invention, there is provided a method of manufacturing a three-dimensional printer comprising the steps of: supplying a three-dimensional printer filament to a printhead; Discharging the melted material of the three-dimensional printer filament heated from the print head; Solidifying the melt to form a print layer; And a step of laminating a plurality of layers of the print layer to form a solid article.

Figure 1 shows a typical filament-type three-dimensional printing system.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. Figure 1 shows a typical filament-type three-dimensional printing system. The 3D printing system of FIG. 1 is an example of a model called LulzBot TAZ by Aleph Objects. Referring to FIG. 1, in the three-dimensional printing, the bottom plate 110 moves in the Y-axis direction, and the print head 120 is moved in the X-axis and the Z-axis to discharge the filaments 130, . The filament 130 is released from the reel 140 on the right side and is supplied through the induction pipe 150. The supply amount of the filament 130 is controlled by the force and speed of the traction device provided in the print head 120, The melted filaments are extruded to form a printed layer on the bottom plate 110 and to continuously laminate the printed layers to form the article 160. [

 Here, the principle of the induction pipe 150 is that it serves as a passage for supplying the filament 130 smoothly to the print head 120 moving left and right. If the induction pipe 150 is not provided, the filament 130 is bent And can not be supplied vertically (always in a constant direction) to the print head 120, so that it is difficult to supply constant-speed constant amounts. In this case, in order for the filament 130 having a diameter of approximately 1.75 mm to pass therethrough and to enter the print head 120 without shaking, it is preferable that the inner diameter of the induction pipe 150 is within about 2.0 mm so that the clearance is not large. Also, it is generally preferable that the filament 130 passing through the induction pipe 150 is made of a hard and smooth material.

However, as described above in the background art, there is a problem that occurs when high-hardness polymers are used as a 3D printing material. In order to solve the above problems, various low-hardness polymers are not highly soluble, and polymers having a melting point suitable for the purpose have high hardness, which does not fit the purpose of the present patent. Accordingly, the present inventors propose a composition made of a thermoplastic polyester elastomer (TPEE) as an essential material.

According to one aspect of the present invention, there is provided a composition for a three-dimensional printer filament comprising a polymer base containing a thermoplastic polyester elastomer having a melting point peak temperature of 130 to 180 占 폚 during thermal analysis by a differential scanning calorimeter (DSC).

Further, MI (190 DEG C, 2.16 kg) of the above composition in which various additives are mixed is 1 to 30 g / 10 min and hardness is Shore A 90 or less.

The thermoplastic polyester elastomer is an elastomer in which crystalline soft segments formed from aromatic dicarboxylic acids and aliphatic diols and soft soft segments formed from polyalkylene oxides are randomly arranged.

In the thermoplastic polyester elastomer of the present invention, the aromatic dicarboxylic acid constituting the polyester of the hard segment is not particularly limited, and the aromatic dicarboxylic acid is widely used. As the main aromatic dicarboxylic acid, terephthalic acid or naphthalenedicarboxylic acid It is preferably a carboxylic acid. Examples of other acidic components include aromatic dicarboxylic acids such as diphenyldicarboxylic acid, isophthalic acid and 5-sodium sulfoisophthalic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and tetrahydrophthalic anhydride And aliphatic dicarboxylic acids such as acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecane diacid, dimeric acid and hydrogenated dimeric acid. They are used within a range that does not significantly lower the melting point of the resin, and the amount thereof is less than 30 mol%, preferably less than 20 mol%, of the total acid component.

In the thermoplastic polyester elastomer of the present invention, the aliphatic or alicyclic diol constituting the polyester of the hard segment is widely used, and is not particularly limited. However, an aliphatic or alicyclic diol having an alkylene group of 2 to 8 carbon atoms Glycols. Specific examples thereof include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol. 1,4-butanediol and 1,4-cyclohexanedimethanol are most preferred.

The component constituting the polyester of the hard segment is preferably a butylenes terephthalate unit or a butylene naphthalate unit from the viewpoints of physical properties, moldability and cost performance.

The aromatic polyester suitable as the polyester constituting the hard segment in the thermoplastic polyester elastomer of the present invention can be easily obtained in accordance with a usual polyester production method. It is preferable that such a polyester has a number average molecular weight of 10,000 to 400,000.

On the other hand, the aliphatic polycarbonate constituting the soft segment in the thermoplastic polyester elastomer of the present invention is preferably composed mainly of an aliphatic diol residue having 2 to 12 carbon atoms and a carbonate bond. Examples of these aliphatic diol residues include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8- 1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,9-nonanediol, - octanediol, and the like. In particular, an aliphatic diol residue having 5 to 12 carbon atoms is preferred from the viewpoints of flexibility and low-temperature characteristics of the resulting thermoplastic polyester elastomer. These components may be used alone, or two or more of them may be used in combination if necessary.

The aliphatic polycarbonate diol having a good low-temperature characteristic constituting the soft segment of the thermoplastic polyester elastomer in the present invention preferably has a low melting point (for example, 70 ° C or lower) and a low glass transition temperature. In general, an aliphatic polycarbonate diol comprising a 1,6-hexanediol residue used for forming a soft segment of a thermoplastic polyester elastomer has a low glass transition temperature of about -60 캜 and a melting point of about 50 캜, It becomes good. In addition, the aliphatic polycarbonate diol obtained by copolymerizing an appropriate amount of 3-methyl-1,5-pentanediol, for example, in the aliphatic polycarbonate diol has a slightly higher glass transition point than the original aliphatic polycarbonate diol, Or amorphous, which corresponds to an aliphatic polycarbonate diol having good low-temperature characteristics. Also, for example, an aliphatic polycarbonate diol comprising 1,9-nonanediol and 2-methyl-1,8-octanediol has a melting point of about 30 DEG C and a glass transition temperature of about -70 DEG C, And corresponds to an aliphatic polycarbonate diol.

The aliphatic polycarbonate diol is not necessarily composed of only the polycarbonate component but may be a copolymer obtained by copolymerizing a small amount of another glycol, a dicarboxylic acid, an ester compound or an ether compound. Examples of the copolymerization component include dicarboxylic acids such as dimer diol, hydrogenated dimer diol and glycol such as modified ones thereof, dimer acid and hydrogenated dimer acid, aliphatic, aromatic or alicyclic dicarboxylic acid Polyesters or oligosters composed of glycols, polyesters or oligosters composed of? -Caprolactone, polyalkylene glycols such as polytetramethylene glycol, polyoxyethylene glycols and oligoalkylene glycols. The copolymerization component can be used to such an extent that the effect of the substantially aliphatic polycarbonate segment is not lost. Specifically, it is not more than 40 parts by weight, preferably not more than 30 parts by weight, more preferably not more than 20 parts by weight, based on 100 parts by weight of the aliphatic polycarbonate segment. When the copolymerization amount is too large, the resulting thermoplastic polyester elastomer tends to have poor heat aging resistance and water resistance.

The thermoplastic polyester elastomer of the present invention may contain, as a soft segment, a polyalkylene glycol such as polyethylene glycol and polyoxytetramethylene glycol, polycaprolactone, polybutylene adipate and the like as long as the effect of the invention is not lost Of a polyester or the like may be introduced. The content of the copolymerization component is usually 40 parts by weight or less, preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the soft segment.

In the thermoplastic polyester elastomer of the present invention, the ratio of the weight of the polyester constituting the hard segment to the weight of the aliphatic polycarbonate and the copolymer constituting the soft segment is generally in the range of hard segment: soft segment = 30: 70 to 95: 5 Preferably in the range of 40:60 to 90:10, more preferably in the range of 45:55 to 87:13, and most preferably in the range of 50:50 to 85:15.

In one embodiment, the thermoplastic polyester elastomer has a melt index (MI) as measured by ASTM D1238 (190 占 폚, 2.16 kg) of 0.01 to 30 g / 10 min, or 0.01 to 20 g / 10 min, 10 g / 10 min, or 0.1 to 5.0 g / 10 min, or 0.1 to 3.0 g / 10 min, or 0.1 to 1.0 g / 10 min, or 0.3 to 0.6 g / 10 min, or 1 to 30 g / have.

Examples of specific polyesters include thermoplastic polyester elastomers having poly (1,4-butylene terephthalate) blocks and poly (tetramethylene ether) glycol blocks (EI du Pont de Nemours &Amp; Co. Inc., Wilmington, Del., USA, 19898, available as HYTREL).

The TPEE used in the present invention has a melting point of at least 130 캜 and a high melting point, so that it has a high solidification speed after printing, and is excellent in dimensional and shape stability. Also, the TPEE used in the present invention has a melting point of 180 ° C or less, so that the melting point is not so high, so that the TPEE can be easily extruded at the time of filament production and high in productivity. Also, the hardness of the TPEE used may be higher than the Shore A 95, but in these cases, since a lot of plasticizers and the like must be compounded in order to make the hardness lower, there is a fear of migration and the slipperiness of the product surface becomes worse. A 95 or less is recommended.

When TPEE is used as the main material of filament material, it is soft and has more heat resistance and oil resistance than PLA, ABS, HDPE and PC which are conventional hardness filament materials, so it can be used for seal and automobile parts of machine. And adhesion with an adhesive is easy, so that it is possible to secure various additional advantages such as the ability to make a variety of products such as a sole, a shoe, a component, and a toys.

Further, the thermoplastic polyester elastomer may contain various additional components for improving the physical properties. The additional component may be at least one member selected from the group consisting of wax, a plasticizer, a thermoplastic elastomer (TPE), an ethylene copolymer, and an olefin random copolymer (ORC). The additional component may be included in an amount of 1 to 25 parts by weight based on 100 parts by weight of the thermoplastic polyester elastomer.

The wax may be paraffin wax, microcrystalline wax, polyethylene wax or the like and may improve the surface slip property of the filament so that the filament easily passes 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. If the amount of the wax is more than 5 parts by weight, the hardness of the filament is increased, and the flexibility of the filament is lowered and broken.

The plasticizer includes a propylene glycol polymer (PPG) or a 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. For example, glycerin, such as CARBOWAX 600 from Union Carbide or Grade 916 USP from Emory. The addition of the plasticizer has the effect of lowering the hardness of the entire polymer base material. 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 due to migration.

The thermoplastic elastomer may be selected from the group consisting of styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-isoprene-styrene (SIS), 1,2-polybutadiene, ethylene- May be used alone or in combination of two or more. The addition of the thermoplastic elastomer has an effect of reinforcing the elasticity more 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. If the amount of the thermoplastic elastomer is more than 20 parts by weight, the sliding property of the filament surface may be lowered.

On the other hand, the ethylene copolymer or the olefin random copolymer (ORC) may be mixed to control the price of the entire filament composition. Wherein said ethylene copolymer is selected from the group consisting of i) ethylene, and ii) a C3-C10 alpha monoolefin, a C1-C12 alkyl ester of a C3-C20 monocarboxylic acid, an unsaturated C3-C20 mono- or dicarboxylic acid, an anhydride of an unsaturated C4-C8 dicarboxylic acid, And a vinyl ester of a C2-C18 carboxylic acid. Specific examples of the ethylene copolymer include ethylene vinyl acetate (EVA), ethylene butylacrylate (EBA), ethylene methylacrylate (EMA), ethylene ethyl acrylate, EEA), ethylene methyl methacrylate (EMMA), ethylene butene copolymer (EB-Co), ethylene octene copolymer (EO-Co) The olefin random copolymer may be a random polymer of ethylene or propylene and at least one copolymerizable? -Olefin comonomer. For example, the olefin random copolymer may be a copolymer of ethylene or propylene with octene.

The ethylene copolymer and the olefin random copolymer may be contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the thermoplastic polyester elastomer. If the amount of the ethylene copolymer or the olefin random copolymer exceeds 20 parts by weight, the solidification of the filament after extrusion may be delayed.

The composition may further contain an antioxidant or pigment. Examples of the antioxidant include sonnoc, butylated hydroxytoluene (BHT), and octadecyl 3,5-di- tert- butyl-4-hydroxyhydrocinnamate (Songnox 1076) It is also possible to use various pigments.

The antioxidant or the dye 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 antioxidant or the dye exceeds 5 parts by weight, the quality of the filament may be deteriorated due to a phenomenon such as blooming.

The MI of the final composition (190 占 폚, 2.16 kg) may be 1 to 30 g / 10 min, preferably 1 to 20 g / 10 min, more preferably 1 to 10 g / 10 min. If the MI (190 DEG C, 2.16 kg) is less than 1.0 g / 10 min, the melting speed of the filament is slow and the printing can not be smoothly performed or the printing speed should be slowed down. On the other hand, if the MI (190 ° C, 2.16 kg) is more than 30 g / 10 min, the filament melts too quickly, and it is difficult to maintain a constant discharge rate at a constant speed.

According to another aspect of the present invention, there is provided a three-dimensional printer filament produced by extruding the composition described above. The filament comprises a polymeric substrate containing a thermoplastic polyester elastomer. The hardness of the polymer base is Shore A 90 or less. The melt index (190 占 폚, 2.16 kg) is 1 to 30 g / 10 min and the melt index (150 占 폚, 10 kg) is 3.0 g / 10 min or less. The melt index (150 DEG C, 10 kg) is preferably 0.01 to 2.0 g / 10 min, more preferably 0.01 to 1.0 g / 10 min or less. Thus, the filament has a high rate of solidification and excellent slipperiness I have. The thermoplastic polyester elastomer may have a melting point peak temperature of 130 to 180 ° C when subjected to DSC thermal analysis. Dissolving the filament in the melting point range is not only consuming less power but also facilitating extrusion.

The three-dimensional printer filament may have a diameter of 1.0 to 2.0 mm, preferably 1.5 to 1.8 mm. If the diameter of the filament is less than 1 mm, it is difficult to produce a printing head for pushing the filament, and the printing speed may be too slow. If the filament is more than 2 mm, the solidification speed is slow and the printing line becomes thick. The hardness of the filament is less than Shore A 90. When the hardness exceeds Shore A 90, the filament does not feel soft texture like rubber and thus does not fit the purpose of the present patent.

According to still another aspect of the present invention, there is provided a method of forming an article through three-dimensional printing using the above-described three-dimensional printer filament. The article forming method may proceed to the following process. First, the above-mentioned three-dimensional printer filament is supplied to the print head. The filament may be fed to the printhead through a guide tube. Next, the melted material of the heated three-dimensional printer filament is discharged from the print head. The lower plate of the printer moves in the Y-axis, the print head moves in the X-axis, and one layer is stacked. Then, one layer is raised in the Z-axis again and then moved in the X- and Y-axes as described above. Is printed in a three-dimensional manner. Next, the melt is solidified to form a print layer. The printed layer is then laminated to form a solid article.

Hereinafter, the present invention will be described in more detail with reference to various embodiments, but the technical idea of the present invention is not limited by the following embodiments.

(Example)

Various compositions were prepared by combining the following components, extruded with a single screw extruder having a screw diameter of 30 mm and a screw length of 105 mm, cooled with a cooling water bath having a length of 1.5 m, and wound into a filament having a diameter of 1.75 mm.

The melting points of the polymers were measured using DSC and the temperature was raised to 10 ° C per minute according to ASTM D-3418 to measure Tm.

TPEE-1: Thermoplastic Polyster elastomer KEYFLEX BT 1030D (LG Chem), DSC Melting point 165 캜, Hardness Shore A 80

TPEE-2: Thermoplastic Polyster elastomer KEYFLEX BT 1035D (LG Chem), DSC Melting point 165 캜, Hardness Shore A 88

TPEE-3: Thermoplastic Polyster elastomer KEYFLEX BT 1045D (LG Chem), DSC melting point 178 캜, hardness Shore A 94, Shore D 45

TPEE-4: Thermoplastic Polyster elastomer KEYFLEX BT 1047D (LG Chem), DSC melting point 190 캜, hardness Shore A 98, Shore D 47

TPEE-5: Thermoplastic Polyster elastomer Hytrel 5526 (Dupont), DSC melting point 203 占 폚, 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 ℃ (Shore A 88)

SEBS-1: Styrene Ethylene Butylene Styrene (DSC) Melting point: 140 캜, Hardness: Shore A 86

Test Methods

1. Solidification speed

The melt index (MI) of the final composition was measured by ASTM D-1238. A, 1.1-2.0, B, 2.1-3.0, C, 3.1-5.0, D and 5.1, respectively, of the final mixture were indicated as A, A and B, respectively. That is, the higher the MI (150 캜, 10 kg), the slower the solidification at 150 캜.

2. Melt speed

10 g / 10 min or more of B, 5 g / 10 min or more of C, 1 g / 10 min or more of D, 1 g / 10 min or less of E Respectively. The lower the MI (180 占 폚 10 kg), the slower the melting and the slower or impossible the printing speed.

3. Slippery

The final composition was extruded to obtain a filament with a diameter of 1.75 mm. A, B, C, D, and E are used in order of decreasing resistance when hand is pulled at a speed of 1 cm / sec through a barrel made of polypropylene having an inner diameter of 2.5 mm, an outer diameter of 4.5 mm and a length of 40 cm, . In other words, A with the lowest resistance and E with the highest resistance are shown.

The test results are shown in Table 1 below.

<Table 1>

Figure 112013100439959-pat00001

From the results of Table 1, it can be seen that the compositions of Examples 1 to 6 are faster in melting and solidifying speed than the other compositions of Comparative Examples 1 to 9 and have superior slip characteristics and are suitable for use as filaments of a 3D printer and have low hardness Thus, it is possible to manufacture various shapes requiring a soft touch during 3D printing.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention. You will understand.

Claims (11)

  1. (DSC) A polymer substrate comprising a thermoplastic polyester elastomer (TPEE) having a melting point peak temperature of 130 to 180 DEG C upon thermal analysis,
    The thermoplastic polyester elastomer has a poly (1,4-butylene terephthalate) block and a poly (tetramethylene ether) glycol block,
    Wherein the polymer base has a melt index (190 占 폚, 2.16 kg) of 1 to 30 g / 10 minutes.
  2. The method according to claim 1,
    Wherein the polymer base further comprises at least one additional component selected from the group consisting of wax, plasticizer, thermoplastic elastomer (TPE), ethylene copolymer, and olefin random copolymer (ORC).
  3. 3. The method of claim 2,
    Wherein the additional component is contained in an amount of 1 to 25 parts by weight based on 100 parts by weight of the thermoplastic polyester elastomer.
  4. delete
  5. The method according to claim 1,
    Wherein the polymer base has a hardness of Shore A of 90 or less.
  6. A three-dimensional printer filament produced by extruding a composition comprising a polymer base material containing a thermoplastic polyester elastomer,
    The thermoplastic polyester elastomer has a poly (1,4-butylene terephthalate) block and a poly (tetramethylene ether) glycol block,
    Wherein the polymer base material has a hardness of Shore A 90 or less, a melt index (190 占 폚, 2.16 kg) of 1 to 30 g / 10 min and a melt index (150 占 폚, 10 kg) of 3.0 g / 10 min or less.
  7. The method according to claim 6,
    Wherein the thermoplastic polyester elastomer has a melting point peak temperature of 130 to 180 DEG C upon differential scanning calorimetry (DSC) thermal analysis.
  8. The method according to claim 6,
    A three-dimensional printer filament having a diameter of 1.0 to 2.0 mm.
  9. 9. A method of manufacturing a three-dimensional printer, comprising: supplying a three-dimensional printer filament according to any one of claims 6 to 8 to a print head;
    Discharging the melted material of the three-dimensional printer filament heated from the print head;
    Solidifying the melt to form a print layer; And
    And laminating a plurality of layers of the print layer to form a solid-phase article.
  10. A three-dimensional printer filament produced by extruding a composition comprising a polymer base material containing a thermoplastic polyester elastomer,
    The thermoplastic polyester elastomer has a poly (ethylene terephthalate) block and a polyalkylene glycol block,
    Wherein the polymer base material has a hardness of Shore A 90 or less, a melt index (190 占 폚, 2.16 kg) of 1 to 30 g / 10 min and a melt index (150 占 폚, 10 kg) of 3.0 g / 10 min or less.
  11. A three-dimensional printer filament produced by extruding a composition comprising a polymer base material containing a thermoplastic polyester elastomer,
    The thermoplastic polyester elastomer has a poly (1,4-butylene terephthalate) block and a polyalkylene glycol block,
    Wherein the polymer base material has a hardness of Shore A 90 or less, a melt index (190 占 폚, 2.16 kg) of 1 to 30 g / 10 min and a melt index (150 占 폚, 10 kg) of 3.0 g / 10 min or less.

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CN104611808A (en) * 2014-11-28 2015-05-13 珠海天威飞马打印耗材有限公司 Forming wire and preparation method thereof
CN104629161A (en) * 2015-03-04 2015-05-20 中国科学院福建物质结构研究所 Low-melting-point 3D printing material and preparation method thereof
KR20160010202A (en) 2014-07-18 2016-01-27 정해영 3d printer with reinforcing material input means
KR20160029309A (en) * 2014-09-05 2016-03-15 롯데케미칼 주식회사 Biodegradable resin composition having improved paint-abillity and impact streangth for three dimensional printer filament
WO2016060469A1 (en) * 2014-10-14 2016-04-21 주식회사 셀루메드 Three-dimensional printing method for enabling continuous shaping in succession to filament shaping
KR20160059724A (en) 2014-11-19 2016-05-27 퓨처사이버 주식회사 Filament composition for 3d printer
WO2017087663A1 (en) * 2015-11-17 2017-05-26 Zephyros, Inc. Additive manufacturing materials system
EP3189959A4 (en) * 2014-09-05 2017-09-20 MCPP Innovation LLC Filament for 3d printing and method for producing crystalline soft resin molded article
KR101912919B1 (en) * 2017-07-25 2018-10-31 코오롱글로텍주식회사 Composition of 3D printing filament and filament for 3D manfacturing method thereof
WO2018212596A1 (en) * 2017-05-18 2018-11-22 에스케이케미칼 주식회사 Polymer resin composition, 3d printer filament comprising same, and method for manufacturing 3d printer filament
KR20190060958A (en) * 2019-05-10 2019-06-04 박성호 Three dimensional printing apparatus with high output speed
WO2019124787A1 (en) * 2017-12-18 2019-06-27 롯데첨단소재(주) Polycarbonate copolymer, thermoplastic resin composition comprising same, and molded product manufactured therefrom
KR20190114125A (en) 2018-03-29 2019-10-10 (주)퓨레코 One-stop process for manufacturing highly functional environment-friendly 3D filament and 3D filament using it

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KR20160010202A (en) 2014-07-18 2016-01-27 정해영 3d printer with reinforcing material input means
US10480098B2 (en) 2014-09-05 2019-11-19 Mcpp Innovation Llc Filament for 3D printing and method for producing crystalline soft resin molded article
KR20160029309A (en) * 2014-09-05 2016-03-15 롯데케미칼 주식회사 Biodegradable resin composition having improved paint-abillity and impact streangth for three dimensional printer filament
KR101685760B1 (en) 2014-09-05 2016-12-12 롯데케미칼 주식회사 Biodegradable resin composition having improved paint-abillity and impact streangth for three dimensional printer filament
EP3189959A4 (en) * 2014-09-05 2017-09-20 MCPP Innovation LLC Filament for 3d printing and method for producing crystalline soft resin molded article
WO2016060469A1 (en) * 2014-10-14 2016-04-21 주식회사 셀루메드 Three-dimensional printing method for enabling continuous shaping in succession to filament shaping
KR101689304B1 (en) 2014-11-19 2016-12-23 퓨처사이버 주식회사 Filament composition for 3d printer
KR20160059724A (en) 2014-11-19 2016-05-27 퓨처사이버 주식회사 Filament composition for 3d printer
CN104611808A (en) * 2014-11-28 2015-05-13 珠海天威飞马打印耗材有限公司 Forming wire and preparation method thereof
CN104629161A (en) * 2015-03-04 2015-05-20 中国科学院福建物质结构研究所 Low-melting-point 3D printing material and preparation method thereof
WO2017087663A1 (en) * 2015-11-17 2017-05-26 Zephyros, Inc. Additive manufacturing materials system
WO2018212596A1 (en) * 2017-05-18 2018-11-22 에스케이케미칼 주식회사 Polymer resin composition, 3d printer filament comprising same, and method for manufacturing 3d printer filament
KR101912919B1 (en) * 2017-07-25 2018-10-31 코오롱글로텍주식회사 Composition of 3D printing filament and filament for 3D manfacturing method thereof
WO2019124787A1 (en) * 2017-12-18 2019-06-27 롯데첨단소재(주) Polycarbonate copolymer, thermoplastic resin composition comprising same, and molded product manufactured therefrom
KR20190114125A (en) 2018-03-29 2019-10-10 (주)퓨레코 One-stop process for manufacturing highly functional environment-friendly 3D filament and 3D filament using it
KR20190060958A (en) * 2019-05-10 2019-06-04 박성호 Three dimensional printing apparatus with high output speed
KR102099039B1 (en) 2019-05-10 2020-04-08 박성호 Three dimensional printing apparatus with high output speed

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