WO2018212596A1 - Polymer resin composition, 3d printer filament comprising same, and method for manufacturing 3d printer filament - Google Patents

Abstract

The present invention relates to a polymer resin composition, a 3D printer filament comprising same, and a method for manufacturing the 3D printer filament, the polymer resin composition comprising: a polyester copolymer A, which comprises a residue of a dicarboxylic acid component including terephthalic acid and a residue of a diol component including a dianhydrohexitol; a polyester copolymer B, which comprises a residue of a dicarboxylic acid component including terephthalic acid and a residue of a diol component excluding the dianhydrohexitol; and an impact modifier.

Description

 【Specification】

 [Name of invention]

 Polymer resin composition, filament for 3D printer comprising the same, and method for producing filament for 3D printer

 Technical Field

 Cross Citation with Related Application (s)

 This application claims the benefit of priority based on Korean Patent Application No. 10—2017-0061798 dated May 18, 2017, and all content disclosed in the literature of such Korean patent applications is incorporated as part of this specification.

 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.

 [Technique to become background of invention]

 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) and SLA (Stereo 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. Among the three methods, 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. As the filament material used in the FDM method, polylactic acid (PLA), acrylonitrile butadiene styrene (ABS), polycarbonate (PC) and the like are used.

However, 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. Specifically, 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.

 On the other hand, 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. In addition, the ABS is known to release a large amount of carbon dioxide which is the main culprit of global warming.

Therefore, when 3D printing with the filament using the PC or ABS, there is a problem that harmful substances such as BPA and styrene and odors are generated. In addition, there is a problem that the shrinkage (deformation) of the molding when printing using ABS, the bed temperature is high, the bed temperature is higher than 100 ^° C high, there is a problem that requires a high processing temperature and bed temperature when printing using a PC and the chemical resistance is weak There is a problem. Furthermore, PLA is free of harmful substances and has a low processing temperature, but has a problem in that mechanical properties and heat resistance properties are poor.

 Therefore, 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.

 [Content of invention]

 Problem to be solved

 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.

[Measures of problem] The present invention provides a polyester copolymer A comprising a residue of a dicarboxylic acid component containing terephthalic acid and a residue of a diol component; Polyester copolymer B containing the residue of the dicarboxylic acid component containing terephthalic acid, and the residue of a dial component; And a layering reinforcing agent, wherein the residue of the diol component of the polyester copolymer A includes isosorbide, 1,4-cyclonucleic acid di, and ethylene glycol, and the residue of the diol component of the polyester copolymer B is cyclo It provides a polymer resin composition comprising a nucleic acid dimethanol.

 The present invention also provides a filament for a 3D printer comprising the polymer resin composition.

 Furthermore, 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.

 Hereinafter, a polymer resin composition according to a specific embodiment of the present invention, a 3D printer filament including the same, and a method for manufacturing a 3D printer filament will be described in more detail. According to one embodiment of the invention, 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; 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 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.

 In the process of preparing the polymer resin composition, conventional methods and apparatuses used to prepare blends or mixtures of polymer resins may be used without particular limitation. For example, 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. In the process of preparing the polymer resin composition, 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.

In addition, the content of 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. In the present specification, '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. For example, 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. It means a part or a part derived from the diol component. 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. .

 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. Examples of the aromatic dicarboxylic acid 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. ， Maleic acid ， Fumaric acid ， Adipic acid ， Although linear, branched, or cyclic aliphatic dicarboxylic acid components such as glutaric acid and azelaic acid are used, specific examples of the aliphatic dicarboxylic acid are not limited thereto.

 On the other hand, the diol component (diol component) used in the synthesis of the polyester copolymer A is 0.1 to 60 mol ¾>, 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.

In the above, ¾ 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.

[Formula 2]

In the above,,, R ₃ and are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms.

상기에서， n 은 1 내지 7의 정수이다.

In the above, 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.

 In addition, the polyester copolymer B contained in the said polymeric resin composition contains the residue of a diol component. In addition, the residue of the diol component may include cyclonucleic acid dimethanol. In addition, 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. Of the 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. For example, 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).

 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.

The glycol-modified polycyclonuclear styrenedimethylene terephthalate may include one or more diols except for the cyclohexane dimethyl methane. For example, 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.

In addition, 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.

 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. When 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.

 Compared to the polyester co-polymer A, the polyester copolymer

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.

The core-shell structured stiffener may have a form in which a shell component is graft-polymerized on a core (rubber core) to form a shell, and the rubber may be a diene rubber having 4 to 6 carbon atoms, an acrylic rubber, a silicone rubber, and It is preferable to use a polymerized rubber monomer selected from the group consisting of these combinations. Examples of the acrylic rubber 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 unsaturated monomers grafted to the rubber may be selected from the group consisting of alkyl (meth) acrylates, (meth) acrylates, acid anhydrides, alkyl or phenyl-substituted maleimides, and combinations thereof. In this case, the alkyl means alkyl having 1 to 8 carbon atoms. Specific examples of the alkyl (meth) acrylate include methyl methacrylate, ethyl methacrylate, propyl methacrylate and the like. Examples of the acid anhydride include carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride.

 For example, 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.

On the other hand, the layered stiffener of the linear structure polyethylene-butyl acrylate ᅳ 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 layer stiffener in the polymer resin composition according to the embodiment is

0.7-13 weight ¾>, or 1-12 wt%. If 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. According to another embodiment of the present invention, 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.In general, 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. Conventionally, polycarbonate (PC) and acrylonitrile butadiene styrene (ABS) are used as materials for 3D printer filaments.However, when outputting using the PC material, a nozzle temperature of 300 ^° C or higher and a bed temperature of 140 ^° C or higher are used. Necessary, because even if the output using ABS material requires a bed temperature of 100 ^° C or more, there is a problem that the 3D printing output conditions are difficult to be generalized. In addition, the PC is bisphenol A (BPA) is generated, ABS has a problem that odors and harmful substances such as styrene occurs. Therefore, it is required to develop a material capable of outputting at a nozzle temperature of 270 ^° C or below and a bed temperature of 90 ^° C or below and generating no harmful substances and odors.

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; And 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 filaments may generally have a diameter of 1.70 to 1.80 mm 3 or 2.95 to 3.05 mm. If the diameter of the filament does not satisfy this value, printing is impossible because the filament is not fed to the nozzle through the gear during operation of the 3D printer, or the filament melts unevenly and the quality of the printout is improved. Degradation problems may occur. According to another embodiment of the present invention, there may be provided a filament manufacturing method for a 3D printer comprising the step of ^* extruding the polymer resin composition using an extruder, and producing a filament by winding using an lor.

In the method for manufacturing a filament for a 3D printer of the present invention according to the embodiment, the polymer resin composition may be extruded by using an extruder, for example, the polymer resin composition may be extruder (Twin screw extruder, 40 Φ, L / D = 2) can be melt shaken extruded onto the strand. 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. In particular, 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.

 In the above embodiment, 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.

Extrusion of the stem extrusion step may be made at 240 to 320 ^° C, or 260 to 30 CTC. When the extrusion temperature is less than 240 ^° C it may be difficult to blend the polymer properly due to the inability to melt the polymer, when the temperature exceeds 320 ^° C may result in denaturation of the polymer.

 After the shake extrusion step, the method may further include cooling the shake-extruded polymer resin composition in a water bath. In addition, the filaments may be manufactured by winding a polymer resin supernatant sensed in the water bath using a roller.

 Winding the polymer resin composition using a lor can produce a filament having a certain thickness. At this time, the speed of the motor for rotating the roller when the winding may be 10 to 500ni / min. If the speed of the motor is less than 10m / min, the diameter of the filament is thicker than the base diameter, the productivity may be deteriorated, if exceeding 500m / min, the diameter of the filament is thinner than the base diameter, the filament is broken work Problems with poor sex can occur.

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.

 【Effects of the Invention】

 According to 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.

 [Specific contents to carry out invention]

 The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples. [Example 1 to 7: Preparation of polymer resin composition]

 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 (Φ: 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 uniformly subjected to a homogeneous extrusion, and pellets were prepared.

[Comparative Examples 1 to 6: Preparation of Polymer Resin Composition] After the components were added to the biaxial kneading extruder (Φ: 40 kPa, L / D = 40), respectively, in the composition shown in Table 1 below, uniform extrusion was performed and pellets were prepared.

 Table 1

Experimental Example: Measurement of Physical Properties of Test Piece and Filament Prepared from Polymer Resin Composition

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. In addition, the filaments produced by using an extruder (Twin screw extruder, 40 Φ, L / D = 2) was confirmed by the method of Experimental Example 4, each of the printing characteristics, and 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

 In accordance with ASTM D638, test specimens were made and tensile strength and elongation were measured using a universal testing machine (Zwick Roe 11 Z010). Experimental Example 3: Measurement of Lamellar Strength

 One piece (thickness of specimens: 1/8 "and 1/4") was measured according to ASTM D 256 and the impact strength value was measured using an Izoc Impact Tester (Impact Tester Yasuda). The measurement conditions were measured in an Izod notched type at a temperature of 25Γ. Experimental Example 4 Measurement of 3D Printing Characteristics

 Using a 3D printer (LAZZ TAZ6), 100x100x4 plate specimens were output. At this time, the nozzle temperature (or processing temperature) and the bed temperature were checked. Table 2

충격강도 ( 1

Impact Strength (1

 J / m 428 428 230 428 253 428 428 428 428 90 428 428 428

/4" )

 Zuo t

 250 240 250 250 240 240 250 270 240 250 260 270 280

70 ~ 70- 70- 70- 70- 70 ~ 70- 70- 70- 70— 70- 70- Bed temperature

 80 80 80 80 80 80 80 80 80 80 80 80 80 As can be seen from the above measurement results, it can be seen that in the case of the examples, heat resistance, impact resistance, tensile properties, and 3D printing characteristics are superior to those of the comparative examples. Specifically, Comparative Examples 1, 5 and 6 have a nozzle temperature is significantly higher than the Example, Comparative Example 2 is significantly lower heat resistance than the Example, Comparative Example 3 is significantly lower than the impact strength, Comparative Example 4 confirmed that the tensile strength is significantly lower than the Example.

Claims

[Patent Claims]  [Claim 1]  Residues of dicarboxylic acid components, including terephthalic acid; Isosorbide ， Polyester copolymer A comprising residues of diol components including 1,4-cyclonucleodiol diol and ethylene glycol;  Residues of dicarboxylic acid components, including terephthalic acid; Polyester copolymer B comprising a residue of a dial component including cyclonucleic acid dimethanol; And  Polymer resin composition comprising a layer reinforcing agent. [Claim 2]  The residue of the diol component according to claim 1, wherein the polyester copolymer A is 0.1 to 60 mol% of isosorbide, 5 to 80 mol of 1,4-cyclonucleodiol and 5 to 80 mol% of ethylene glycol Polymer resin composition comprising a. [Claim 3]  The polymer resin composition of claim 1, wherein the polymer resin composition is for a filament of a 3D printer. [Claim 4]  The polymer resin of claim 1, wherein the polymer resin composition comprises 55 to 90 wt% of the polyester copolymer A, 7 to 33 wt% of the polyester copolymer B, and 0.7 to 13 wt ¾ of the impact modifier. Composition. [Claim 5] The method of claim 1, wherein the polymer resin composition is the polyester copolymer A 59 to 87 weight ¾>, the polyester copolymer B 10 to 30% by weight, and 1 to 12% by weight of the impact modifier. [Claim 6] The polymer resin composition according to claim 1, wherein a weight ratio of the polyester i ^' copolymer B to the polyester copolymer ^' A is 1: 0.07 to 0.55. [Claim 7]  The polymer resin composition of claim 1, wherein the polyester copolymer B is a polycyclonuclear silane dimethylene terephthalate (PCT), a glycol-modified polycyclonuclear silane dimethylene terephthalate resin (PCTG), or a mixture thereof. [Claim 8]  The polymer resin composition of claim 1, wherein the impact modifier is a core-shell structured stratifier, a linear impact modifier, or a mixture thereof. [Claim 9]  9. The core-shell structured impact modifier of claim 8 is an alkyl methacrylate-diene rubber-aromatic vinyl graft copolymer, an alkyl methacrylate-silicone / alkylacrylate graft copolymer, or a combination thereof. A polymer resin composition that is water. [Claim 10] 10. The method of claim 8, wherein the linear stiffener is a polyethylene- butyl acrylate- glycidyl methacrylate copolymer, polyethylene- methacrylate- glycidyl methacrylate copolymer ethylene- alpha olefin type At least one polymer resin composition selected from the group consisting of an impact modifier, a silicone-based laminar modifier, and a polyester elastomer impact modifier. [Claim 111]  The filament for 3D printers containing the polymeric resin composition of any one of Claims 1-10. [Claim 12]  The method of claim 1, wherein the step of the extrusion of the polymer resin composition of any one of claims 1 to 10 using an extruder; And  A method of manufacturing a filament for a 3D printer, comprising the steps of winding the extruded polymer resin composition with a roller to produce a filament. [Claim 13]  The method of claim 12, wherein the kneading extrusion screw rotation speed of 150 to Method for manufacturing filament for 3D printer at 300rpm. [Claim 14] The method of claim 12, wherein the spinal extrusion is a filament manufacturing method for a 3D printer made at a temperature of 240 to 320 ^° C. [Claim 15]  13. The method of claim 12, wherein the roller is rotated by a motor, and the speed of the motor is 10 to 500 m / min. [Claim 16]  The method according to claim 12, further comprising cooling the spin-extruded polymer resin composition in a water bath after the spin-extrusion step.