Crystalline resin composition for three-dimensional modeling and three-dimensional modeled object

Abstract

To provide a crystalline resin composition for three-dimensional modeling and a three-dimensional modeled object, which suppress thermal collapse and warping.SOLUTION: There is provided a crystalline resin composition for three-dimensional modeling, comprising a crystalline polyethylene terephthalate resin having an intrinsic viscosity of 0.81 dl / g or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a crystalline resin composition for three-dimensional modeling and a method for producing a three-dimensional object. [Background technology]

[0002] In recent years, three-dimensional modeling devices (so-called 3D printers) have been developed and are being used in various fields. Various methods have been proposed for obtaining three-dimensional objects using 3D printers. For example, there is Fused Deposition Modeling (FDM), in which molten thermoplastic resin is extruded from a melting head to form layered models, Powder Bed Fusion (PBF), in which an energy source is irradiated onto a resin composition material for three-dimensional modeling to melt and bond it to form layered models, and Inkjet Powder Layering, in which an adhesive resin is sprayed from a nozzle onto a powder material to bond and solidify it to form layered models.

[0003] Among the above, fused deposition modeling 3D printers are relatively inexpensive and are used in a variety of fields. In fused deposition modeling, the filament method is generally used, in which resin molded into a filament shape is fed, but in recent years, the adoption of the pellet method, in which resin molded into a pellet shape is fed, is also being considered. In the pellet method, the type and amount of color, filler, additives, etc. can be changed, making prototyping easier, and the nozzle diameter can be made larger than in the filament method. Therefore, it has the advantage that even large objects used in industry can be manufactured in a short time. In fused deposition modeling (FDM), ABS resin, polycarbonate resin, polyester resin, etc. are mainly used as thermoplastic resins. For example, Prior Art Documents 1 to 4 disclose materials for three-dimensional modeling that employ an amorphous polyester resin as a thermoplastic resin. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2016 / 181995 [Patent Document 2] International Publication No. 2018 / 012539 [Patent Document 3] JP 2016-204642 A [Patent Document 4] JP 2023-53430 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, when a 3D model is created using a material for 3D modeling in the fused deposition modeling method, the viscosity of the material is low in the molten state immediately after it is discharged from the nozzle, and the material tends to collapse during modeling (hereinafter referred to as "thermal collapse"). This phenomenon is particularly noticeable when amorphous resin is used in the fused deposition modeling method, which creates 3D models by sequentially stacking 2D layers, and the structure of the 3D model is prone to collapse due to the heat of the discharged resin at inclined shapes and acute angles and corners. On the other hand, increasing the crystallinity to suppress thermal collapse can cause warping and poor adhesion between the layers of the model. In particular, with crystalline polymers with high melting points, the nozzle temperature is high, making it difficult to achieve both thermal collapse and warping.

[0006] The present disclosure has been made in view of the above, and aims to provide a crystalline resin composition for three-dimensional modeling and a three-dimensional model that suppresses thermal collapse and warping. [Means for solving the problem]

[0007] Means for solving the above problems include the following embodiments. <1> A crystalline resin composition for three-dimensional modeling, comprising a crystalline polyethylene terephthalate resin having an intrinsic viscosity of 0.81 dl / g or more. <2> The crystalline polyethylene terephthalate resin has the following composition relative to all constituent units constituting the crystalline polyethylene terephthalate resin: The content of structural units derived from terephthalic acid is 47 mol % or more and 50 mol % or less, The constituent units derived from the diacid monomer other than terephthalic acid are 0 mol % or less than 3 mol %; The content of structural units derived from ethylene glycol is 47 mol % or more and 50 mol % or less, A copolymer in which <1> The crystalline resin composition for three-dimensional modeling according to claim 1. <3> The intrinsic viscosity is 0.82 dl / g or more and 1.20 dl / g or less. <1> or <2> The crystalline resin composition for three-dimensional modeling according to claim 1. <4> The crystalline polyethylene terephthalate resin has a half-crystallization time range of 230 seconds or more and 800 seconds or less at 180°C. <1> ~ <3> 10. The crystalline resin composition for three-dimensional modeling according to claim 9, <5> The crystalline polyethylene terephthalate resin has a ratio of the half-crystallization time at 200°C to the half-crystallization time at 180°C (200°C / 180°C) of 1.6 or less. <1> ~ <4> 10. The crystalline resin composition for three-dimensional modeling according to claim 9, <6> The crystalline polyethylene terephthalate resin has a melting point of 240° C. or higher and 260° C. or lower. <1> ~ <5> 10. The crystalline resin composition for three-dimensional modeling according to claim 9, <7> <1> ~ <6> 2. A three-dimensional object formed using the crystalline resin composition for three-dimensional modeling according to claim 1. Effect of the Invention

[0008] According to the present disclosure, it is possible to provide a crystalline resin composition for three-dimensional modeling and a three-dimensional model that are suppressed from collapsing due to heat and warping. [Brief description of the drawings]

[0009] [Figure 1] This is a model for evaluating thermal collapse. [Diagram 2] This is a warpage evaluation model. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] In the present disclosure, a numerical range indicated using "~" indicates a range that includes the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in the present disclosure. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples. In the present disclosure, when a crystalline resin composition for three-dimensional modeling, etc. contains multiple substances corresponding to each component, the amount of each component means the total amount of the multiple substances contained in the crystalline resin composition for three-dimensional modeling, etc., unless otherwise specified. In the present disclosure, combinations of two or more preferred embodiments are more preferred embodiments. In this disclosure, the physical properties described in the description of the embodiment of the invention can be measured by the methods described in the examples section.

[0011] In the present disclosure, the "crystalline resin composition for three-dimensional modeling" is also simply referred to as the "crystalline resin composition."

[0012] <Crystalline resin composition for three-dimensional modeling> The crystalline resin composition for three-dimensional modeling according to the present disclosure is a crystalline resin composition containing a crystalline polyethylene terephthalate resin having an intrinsic viscosity of 0.81 dl / g or more. In the crystalline resin composition for three-dimensional modeling of the present disclosure, the polyethylene terephthalate resin has an intrinsic viscosity in the above range, so that the viscosity in the molten state is sufficiently guaranteed. And, since the polyethylene terephthalate resin has a certain degree of crystallinity, even when the melt of the crystalline resin composition is laminated to be modeled, it is easy to model with high density while suppressing warping. As a result, thermal collapse is suppressed.

[0013] Hereinafter, "crystalline polyethylene terephthalate resin having an intrinsic viscosity of 0.81 dl / g or more" will also be referred to as "specific crystalline polyethylene terephthalate resin" for convenience.

[0014] Since the crystalline resin composition for three-dimensional modeling of the present disclosure contains a polyethylene terephthalate resin, the molded object is less likely to warp and has excellent mechanical strength compared to ABS and the like.

[0015] [Specific crystalline polyethylene terephthalate resin] The specific crystalline polyethylene terephthalate resin is a crystalline polyethylene terephthalate resin having an intrinsic viscosity of 0.81 dl / g or more.

[0016] Examples of the specific crystalline polyethylene terephthalate resin include unmodified polyethylene terephthalate resin (PET) and modified polyethylene terephthalate resin. Examples of modified polyethylene terephthalate resins include glycol-modified polyethylene terephthalate resins (PETG), amino-modified polyethylene terephthalate resins, silicone-modified polyethylene terephthalate resins, polyether-modified polyethylene terephthalate resins, acid-modified polyethylene terephthalate resins, etc. Among the above, the specific crystalline polyethylene terephthalate resins are more preferably unmodified polyethylene terephthalate resins (PET), glycol-modified polyethylene terephthalate resins (PETG), and acid-modified polyethylene terephthalate resins, from the viewpoint of further suppressing thermal collapse.

[0017] In the present disclosure, a polyethylene terephthalate resin refers to a polymer having at least a structural unit derived from terephthalic acid and a structural unit derived from ethylene glycol.

[0018] In the present disclosure, "crystalline" refers to the property of having a heat of crystallization (ΔHc) when measured at a heating rate of 10° C. / min in differential scanning calorimetry (DSC). In the present disclosure, "amorphous" refers to a property in which the heat of crystallization (ΔHc) is 0 J / g when measured at a heating rate of 10° C. / min in differential scanning calorimetry (DSC).

[0019] The specific crystalline polyethylene terephthalate resin may further have other constituent units than the constituent units derived from terephthalic acid and the constituent units derived from ethylene glycol, from the viewpoint of suitably adjusting the intrinsic viscosity and the degree of crystallinity and further suppressing the thermal collapse. The specific crystalline polyethylene terephthalate resin may further have, for example, a constituent unit derived from a diacid monomer other than terephthalic acid, or may further have a constituent unit derived from a diacid monomer other than terephthalic acid and a constituent unit derived from a diol monomer other than ethylene glycol.

[0020] Examples of the constituent units derived from diacid monomers other than terephthalic acid include aromatic dicarboxylic acid components derived from isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid, 4,4-biphenyl dicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethane dicarboxylic acid, 5-Na sulfoisophthalic acid, ethylene-bis-p-benzoic acid, etc., and aliphatic dicarboxylic acid components derived from adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc. Among these, aromatic dicarboxylic acid components such as isophthalic acid and 2,6-naphthalenedicarboxylic acid are preferred. From the viewpoints of economy and industrial availability, the constituent units derived from diol monomers other than ethylene glycol are preferably at least one selected from the group consisting of diethylene glycol, s-glycol, trans-tetramethyl-1,3-cyclobutanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, spiroglycol, propylene glycol, octanediol, decanediol, and neopentyl glycol; alicyclic diols, such as 1,4-cyclohexanedimethanol; aromatic diols, such as bisphenol A, bisphenol S, and the like, or ethylene oxide adducts thereof; or triols thereof, such as trimethylolpropane and polytetramethylene glycol. Particularly preferred are trans-tetramethyl-1,3-cyclobutanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, spiroglycol, bisphenol A, bisphenol S, and the like, or ethylene oxide adducts thereof.

[0021] From the viewpoint of suitably adjusting the intrinsic viscosity and degree of crystallinity and further suppressing thermal collapse, the specific crystalline polyethylene terephthalate resin preferably contains 30 mol% or more and 55 mol% or less of structural units derived from terephthalic acid and ethylene glycol, respectively, relative to the total structural units constituting the specific crystalline polyethylene terephthalate resin, more preferably 40 mol% or more and 55 mol% or less, and even more preferably 47 mol% or more and 50 mol% or less. From the viewpoint of suitably adjusting the intrinsic viscosity and degree of crystallinity and further suppressing thermal collapse, the specific crystalline polyethylene terephthalate resin preferably contains 0 mol % or less than 20 mol % of structural units derived from diacid monomers other than terephthalic acid and structural units derived from diols other than ethylene glycol, relative to the total structural units constituting the specific crystalline polyethylene terephthalate resin, more preferably 0 mol % or 10 mol % or less, and even more preferably 0 mol % or less than 3 mol %.

[0022] In one embodiment, from the viewpoint of suitably adjusting the intrinsic viscosity and degree of crystallinity and further suppressing thermal collapse, the specific crystalline polyethylene terephthalate resin is preferably a copolymer in which, relative to all constituent units constituting the specific crystalline polyethylene terephthalate resin, constituent units derived from terephthalic acid account for 47 mol% or more and 50 mol% or less, constituent units derived from diacid monomers other than terephthalic acid are 0 mol% or less than 3 mol%, and constituent units derived from ethylene glycol are 47 mol% or more and 50 mol% or less. In another embodiment, from the same viewpoint as above, the specific crystalline polyethylene terephthalate resin is preferably a copolymer in which, relative to all the constituent units constituting the crystalline polyethylene terephthalate resin, the constituent units derived from terephthalic acid account for 47 mol% or more and 50 mol% or less, the constituent units derived from diacid monomers other than terephthalic acid and the constituent units derived from diols other than ethylene glycol are each 0 mol% or less than 3 mol%, and the constituent units derived from ethylene glycol are 47 mol% or more and 50 mol% or less.

[0023] From the viewpoint of further suppressing thermal collapse, the specific crystalline polyethylene terephthalate resin has an intrinsic viscosity of 0.81 dl / g or more, more preferably 0.81 dl / g or more and 1.40 dl / g or less, and even more preferably 0.82 dl / g or more and 1.20 dl / g or less.

[0024] The intrinsic viscosity [η] is a value calculated from the solution viscosity measured at 25°C after the sample to be measured is dissolved in 100 ml of a mixed solution of tetrachloroethane / phenol = 50 / 50 (mass % / mass %) by heating and cooling.

[0025] The specific method for adjusting the intrinsic viscosity to the above range is not particularly limited, but examples thereof include a method in which solid-phase polymerization is carried out after a polycondensation reaction.

[0026] The degree of crystallinity is calculated from the heat of fusion resulting from the melting of the main component in the heat flow curve obtained using a differential scanning calorimeter (DSC). Approximately 5 mg of polymer is sealed in an aluminum pan for measurement of a PerkinElmer DSC8500 and heated from room temperature to 300°C at 10°C / min. In order to completely melt the polymer, it is held at 300°C for 5 minutes and then cooled to 23°C at 10°C / min. After leaving it at -23°C for 5 minutes, it is heated a second time to 300°C at 10°C / min, and the heat of fusion during this second heating is taken as ΔH.

[0027] The specific method for adjusting the degree of crystallinity to the above range is not particularly limited, but examples thereof include a method for adjusting the amount of monomers other than terephthalic acid and ethylene glycol in the crystalline polyethylene terephthalate resin.

[0028] From the viewpoint of further suppressing thermal degradation, the specific crystalline polyethylene terephthalate resin preferably has a melting point, and the melting point is more preferably 240°C or higher and 280°C or lower, even more preferably 240°C or higher and 270°C or lower, and particularly preferably 240°C or higher and 260°C or lower.

[0029] The melting point is a value determined as the temperature Tm at the melting peak position that appears on the endothermic curve by differential scanning calorimetry (DSC). The sample is packed into an aluminum pan and heated from room temperature to 300°C at 10°C / min. In order to completely melt the polymer, it is held at 300°C for 5 minutes and then cooled to 23°C at 10°C / min. After leaving it at -23°C for 5 minutes, it is heated a second time to 300°C at 10°C / min. The melting point is determined from the peak top of the endothermic curve during this second heating.

[0030] There are no particular limitations on the specific method for adjusting the melting point to be within the above range, but examples include a method of adjusting the amounts of monomers other than terephthalic acid and ethylene glycol in the crystalline polyethylene terephthalate resin.

[0031] From the viewpoint of further suppressing thermal collapse, the specific crystalline polyethylene terephthalate resin preferably has a half-crystallization time at 180°C in the range of 230 sec to 800 sec, more preferably 250 sec to 750 sec, and even more preferably 270 sec to 700 sec. If the half-crystallization time at 180°C is long, thermal collapse occurs due to insufficient solidification, and if the half-crystallization time is too short, thermal collapse occurs due to a decrease in interlaminar strength.

[0032] From the viewpoint of further suppressing thermal collapse, the specific crystalline polyethylene terephthalate resin preferably has a ratio of the half-crystallization time at 200° C. to the half-crystallization time at 180° C. (200° C. / 180° C.) of 1.65 or less, more preferably 1.6 or less. If the ratio of the half-crystallization time at 180° C. to the half-crystallization time at 200° C. is large, the solidification rate is highly dependent on temperature, and thermal collapse is likely to occur.

[0033] Approximately 5 mg of sample is packed into a special aluminum pan, and using a PerkinElmer DSC8500, the temperature is raised from 30°C to 300°C at 500°C / min, held at 300°C for 10 minutes, and then lowered from that temperature (300°C) to each isothermal crystallization temperature at 500°C / min, and the half-crystallization time is determined from the DSC curve obtained by holding at the isothermal crystallization temperature. The half-crystallization time is the time it takes to reach 50% of the heat, assuming that the area between the DSC heat curve and the baseline during the isothermal crystallization process is the total heat.

[0034] There are no particular limitations on the specific method for setting the crystallization half time within the above range, but examples include a method of adjusting the amounts of monomers other than terephthalic acid and ethylene glycol in the crystalline polyethylene terephthalate resin.

[0035] The method for producing the specific crystalline polyethylene terephthalate resin is not particularly limited. For example, the specific crystalline polyethylene terephthalate resin can be produced by referring to the production methods described in paragraphs 0055 to 0061 of JP 2015-113441 A and paragraph 0063 of WO 2016 / 181995 A.

[0036] [Other materials] The crystalline resin composition for three-dimensional modeling of the present disclosure may further contain other materials other than the crystalline polyethylene terephthalate resin having an intrinsic viscosity of 0.81 dl / g or more, within the range in which the effects of the present disclosure are achieved. The other materials may be used independently, one or more kinds, or two or more kinds may be used in combination. Examples of other materials include aromatic polyester resins having an intrinsic viscosity of less than 0.81 dl / g (such as crystalline polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, polyethylene isophthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, and polytrimethylene terephthalate resin), aliphatic polyester resins (such as polyethylene succinate resin and polybutylene succinate resin), oxyacid polymers (such as polylactic acid resin and polycaprolactone resin), polyester elastomers obtained by copolymerizing aromatic polyesters with polyalkylene glycol, resin components such as thermoplastic resins other than propylene-based polymers, elastomer components (such as propylene-based elastomers such as polyisobutylene, butyl rubber, propylene-ethylene copolymer rubber, propylene-butene copolymer rubber, and propylene-butene-ethylene copolymer rubber, and ethylene-based elastomers such as ethylene-propylene copolymer rubber), and inorganic fillers.

[0037] When the crystalline resin composition for three-dimensional modeling of the present disclosure contains other materials, the ratio of the specific crystalline polyethylene terephthalate resin to the entire crystalline resin composition may be 80% by mass or more and less than 100% by mass, or 90% by mass or more and less than 100% by mass.

[0038] Examples of additive components include diethylene glycol, heat stabilizers, antistatic agents, weather stabilizers, light stabilizers, ultraviolet absorbers, antioxidants, antioxidants, neutralizers, fatty acid metal salts, softeners, dispersants, colorants, lubricants, pigments, dyes, fillers, brighteners, electrostatic agents, solvents, wetting agents, antimicrobial agents, chelating agents, flow aids, reinforcing agents, energy absorption promoters, energy absorption inhibitors, laser absorbers, fusion agents, and finish improvers. When preparing a crystalline resin composition for three-dimensional modeling by mixing other materials, the mixing order is arbitrary, and the materials may be mixed simultaneously, or a multi-stage mixing method in which some components are mixed and then other components are mixed may be used.

[0039] [Characteristics of crystalline resin composition for three-dimensional modeling] The crystalline resin composition for three-dimensional modeling has a Young's modulus in the XY direction at 23° C. of preferably 2300 MPa or more and 3200 MPa or less, more preferably 2350 MPa or more and 3000 MPa or less, and even more preferably 2400 MPa or more and 2900 MPa or less. The XY direction refers to the direction in which the longitudinal direction of the test piece is perpendicular to the lamination direction. The crystalline resin composition for three-dimensional modeling has a Young's modulus in the Z direction at 23° C. of preferably 1700 MPa or more and 2500 MPa or less, more preferably 1750 MPa or more and 2400 MPa or less, and even more preferably 1800 MPa or more and 2300 MPa or less. The Z direction refers to the direction in which the longitudinal direction of the test piece is parallel to the lamination direction.

[0040] When each of the Young's moduli is within the above range, the composition is excellent in resistance to thermal collapse, and when the crystalline resin composition is melted, the ejection properties from a nozzle are improved, resulting in excellent moldability. Each Young's modulus is a value measured using an AG-20kNXDPlus (manufactured by Shimadzu Corporation) in accordance with JIS-7161 (2014).

[0041] In the present disclosure, Young's modulus is an index showing the rigidity of a resin, and the higher the value, the higher the rigidity, and the lower the value, the higher the flexibility. There are no particular limitations on the specific method for making the Young's modulus in each direction within the above range, but an example of this is a method for making the polyethylene terephthalate resin contained in the crystalline resin composition for three-dimensional modeling crystalline.

[0042] Three-dimensional objects that can be molded using the crystalline resin composition for three-dimensional modeling are not particularly limited, and examples thereof include automobile objects (e.g., console parts, switch parts, door trim parts, instrument panel parts, clips, covers, etc.), electrical appliance objects (electrical appliance parts, housings, etc.), furniture members, building members, construction materials, aviation parts, toys, shoes, sporting goods, ornaments, cases, etc. In particular, the crystalline resin composition for three-dimensional modeling according to the present disclosure is suitable for molding automobile objects, building members, and construction materials, since thermal collapse is suppressed when the composition is used for modeling.

[0043] [Mold of crystalline resin composition for three-dimensional modeling] The crystalline resin composition for three-dimensional modeling can be in the form of pellets, filaments, or the like. The pellet refers to a particulate mass of the crystalline resin composition for three-dimensional modeling. A filament refers to a long, linear material such as a thread that is used to output data using a three-dimensional object manufacturing device, and is generally used in a form wound around a reel.

[0044] The crystalline resin composition for three-dimensional modeling may be in the form of pellets or filaments, or may be a mixture of materials in the form of both pellets and filaments. From the viewpoint of producing a relatively large three-dimensional object, the form of the crystalline resin composition for three-dimensional modeling is preferably pellets.

[0045] The crystalline resin composition for three-dimensional modeling may be a molded product or a commercially available product. The molding method for the molded product is not particularly limited, and the molded product may be molded by a known molding method such as extrusion molding. When the crystalline resin composition for three-dimensional modeling is molded into pellets, for example, one type of thermoplastic elastomer may be kneaded and extruded by a melt extruder (e.g., twin-screw extruder), and the extruded rod-shaped strands may be cut by a pelletizer to form pellets. Alternatively, a mixture of multiple types of thermoplastic elastomers, a mixture of a thermoplastic elastomer and a thermoplastic resin, or a mixture of a thermoplastic elastomer and other components may be dry-blended by a Henschel mixer or the like, and then the dry blend may be kneaded and extruded by a melt extruder (e.g., twin-screw extruder), and the extruded rod-shaped strands may be cut by a pelletizer to form pellets.

[0046] <Three-dimensional object> The three-dimensional object of the present disclosure is a three-dimensional structure, i.e., a 3D structure, formed using the crystalline resin composition for three-dimensional modeling of the present disclosure. According to the present disclosure, a three-dimensional object having a three-dimensional structure and suppressed thermal collapse can be obtained. Examples of the applicable three-dimensional object include the three-dimensional object exemplified in the above-mentioned crystalline resin composition for three-dimensional modeling of the present disclosure. The three-dimensional object of the present disclosure may be either a sintered body or a melt of the above-mentioned crystalline resin composition for three-dimensional modeling.

[0047] The three-dimensional object of the present disclosure can be manufactured, for example, by three-dimensional molding using the aforementioned crystalline resin composition for three-dimensional modeling by fused deposition modeling (FDM), in which a molten crystalline resin composition for three-dimensional modeling is extruded from a melting head to form an additive manufacturing process. EXAMPLES

[0048] Hereinafter, the embodiment of the present invention will be described in more detail based on examples. However, the present invention is not limited to these examples, which are one embodiment of the present invention. In the table, blank spaces mean that the corresponding component is not contained.

[0049] <Preparation of polyethylene terephthalate resin> (Preparation of crystalline polyethylene terephthalate resin (1)) 332g of high-purity terephthalic acid and 143g of ethylene glycol were charged into an autoclave and reacted under a nitrogen atmosphere of 255°C at a pressure of 1.7kg / cm for 2 hours while stirring. Then, the heating temperature was increased to 250°C and the reaction was continued for 6 hours. The water generated by this reaction was constantly distilled out of the system. Next, 0.042g of germanium dioxide and 0.080g of phosphoric acid were added to the reaction system, and the system was heated to 280°C over 1 hour while reducing the pressure in the system to 1 torr. The reaction was continued for another 3 hours, and the unreacted ethylene glycol was distilled out of the system. After the reaction was completed, the reactant was taken out of the reactor in a strand shape, immersed in water, cooled, and then cut into chips by a strand cutter. The polyethylene terephthalate obtained by the above liquid phase polymerization had an intrinsic viscosity of 0.56 dl / g. The polyethylene terephthalate obtained by the liquid phase polymerization was pre-crystallized at 170°C for 2 hours, and then solid-phase polymerized at 205°C for 15 hours in a nitrogen atmosphere. The intrinsic viscosity of the polyethylene terephthalate thus obtained was 1.20 dl / g.

[0050] (Preparation of Crystalline Polyethylene Terephthalate Resins (2) to (5), (C1) to (C3)) In the preparation of the above crystalline polyethylene terephthalate resin (1), the resins of each example were obtained with the same specifications as those for the preparation of the above crystalline polyethylene terephthalate resin (1), except that the mole percentages of isophthalic acid, terephthalic acid, ethylene glycol, and 1,4-cyclohexanedimethanol were as shown in Table 1 or Table 2.

[0051] (Preparation of amorphous polyethylene terephthalate resins (C4) to (C6)) In the preparation of the above amorphous polyethylene terephthalate resin (C1), the resins of each example were obtained under the same specifications as those for the preparation of the above amorphous polyethylene terephthalate resin (C1), except that the mole percentages of isophthalic acid, terephthalic acid, ethylene glycol, and 1,4-cyclohexanedimethanol were as shown in Table 2.

[0052] <Example 1> The crystalline polyethylene terephthalate resin (1) obtained above was used to obtain a crystalline resin composition for three-dimensional modeling, and modeling was performed. Specifically, a measurement square prism (170 mm x 170 mm x height 100 mm) was created using a material extrusion type 3D modeling device ("GEM444D" manufactured by S.Lab Co., Ltd., nozzle diameter: 3 mm) and application software ("Simplify3D" manufactured by Simplify3D). First, the materials shown in Tables 1 and 2 were put into a hopper, and the 3D modeling material was supplied into the cylinder through the hopper. Next, the temperature of the 3D modeling material was heated to 270°C to 300°C by a heater provided in the cylinder to melt it (melting process). Next, the 3D data was sliced ​​into slices using application software to generate 2D data. Based on the 2D data, the application software's setting parameters were set as follows, and modeling was performed using the material extrusion method (MEX). Specifically, based on the 3D coordinate data, the molten 3D modeling material was layered in sequence on a substrate to form a 3D model (modeling process).

[0053] <Examples 2 to 5, Comparative Examples 1 to 6> In Example 1, except that the type of resin was the resin shown in Table 1 or Table 2, the same specifications as in Example 1 were used to obtain a crystalline resin composition for three-dimensional modeling of each example, and modeling was performed.

[0054] The physical properties of the crystalline resin composition for three-dimensional modeling obtained in each example are shown in Tables 1 and 2.

[0055] [Evaluation of formability] -3D data- · 170mm x 170mm x 100mm height cuboid -Setting parameters for measuring rectangular prism model- 2mm nozzle - Build speed: 600mm / min Nozzle temperature: 300℃

[0056] [Evaluation of Young's Modulus] A 2 mm thick rectangular prism was 3D printed, and a test piece (a 1BA dumbbell as specified in JIS K 7161-2:2014) was sampled from the wall. Using the obtained sample, a tensile test was performed in accordance with JIS K 7161-2:2014 at a test temperature of 23°C and a tensile speed of 0.5 mm / min to measure the Young's modulus.

[0057] [Evaluation of thermal collapse] Using a material extrusion type three-dimensional object manufacturing device (manufactured by S.Lab Co., Ltd., "GEM444D," nozzle diameter: 3 mm) and application software ("Simplify3D" by Simplify3D), a measurement object as shown in Fig. 1 was manufactured from the crystalline resin composition. Specifically, based on three-dimensional coordinate data, the three-dimensional object was manufactured by sequentially layering the molten crystalline resin composition for three-dimensional modeling on a substrate. -3D data- The model shown in Figure 1 is used to evaluate the thermal collapse of the model. -Setting parameters for the measurement object- 3mm nozzle - Build speed: 600mm / min Nozzle temperature: 300℃ Layer pitch: 1.5mm ·Width: 3mm

[0058] FIG. 1 is a schematic diagram of a model. The molded object was compared with the evaluation model, and the locations where collapse had occurred were confirmed in X1 to X4, and the molded object was evaluated according to the following criteria. The results are shown in Tables 1 and 2. -Evaluation criteria- A: No crumbling B: One collapsed area C: Two collapsed areas D: Collapsed in 3 or more places

[0059] [Evaluation of Warpage] A material extrusion type three-dimensional object manufacturing device ("GEM444D" manufactured by S.Lab Co., Ltd., nozzle diameter: 3 mm) and application software ("Simplify3D" manufactured by Simplify3D) were used to manufacture the object for measurement shown in Fig. 2. Specifically, based on three-dimensional coordinate data, the three-dimensional object was manufactured by successively layering the molten crystalline resin composition for three-dimensional object manufacture on a substrate. -3D data- ·120mm x 350mm x 30mm height cuboid -Setting parameters for the honeycomb structure of the measurement object- 4mm nozzle - Build speed: 600mm / min Nozzle temperature: 300℃ Layer pitch: 2mm ·Width: 4.8mm

[0060] -Evaluation criteria- The amount of lift from the bottom surface was measured at points a1 and a2 in FIG. 2, and the evaluation was based on the average value. A: The amount of lift is 1mm or less. B: The amount of floating is more than 1 mm and 3 mm or less. C: The amount of lift is more than 3 mm. D: Cannot be modeled

[0061] [Table 1]

[0062] [Table 2]

[0063] As shown in Table 1, it was found that the crystalline resin compositions for three-dimensional modeling of the Examples suppressed thermal collapse when producing a three-dimensional object, compared to the crystalline resin compositions for three-dimensional modeling of the Comparative Examples. It was also found that the crystalline resin compositions for three-dimensional modeling of the Examples suppressed the occurrence of warping when producing a three-dimensional object. [Explanation of symbols]

[0064] a1: Amount of lift a2: Amount of lift x1: Check for heat damage x2: Check for heat damage x3: Check for heat damage x4: Check for heat damage

Claims

1. A crystalline resin composition for three-dimensional modeling, comprising a crystalline polyethylene terephthalate resin having an intrinsic viscosity of 0.81 dl / g or more.

2. The crystalline polyethylene terephthalate resin has the following composition relative to all constituent units constituting the crystalline polyethylene terephthalate resin: The content of structural units derived from terephthalic acid is 47 mol % or more and 50 mol % or less, The constituent units derived from the diacid monomer other than terephthalic acid are 0 mol % or less than 3 mol %; The content of structural units derived from ethylene glycol is 47 mol % or more and 50 mol % or less, The crystalline resin composition for three-dimensional modeling according to claim 1, which is a copolymer represented by the formula:

3. The crystalline resin composition for three-dimensional modeling according to claim 1 , wherein the intrinsic viscosity is 0.82 dl / g or more and 1.20 dl / g or less.

4. The crystalline resin composition for three-dimensional modeling according to claim 1 , wherein the crystalline polyethylene terephthalate resin has a half crystallization time range at 180° C. of 230 sec or more and 800 sec or less.

5. The crystalline resin composition for three-dimensional modeling according to claim 1, wherein the crystalline polyethylene terephthalate resin has a ratio of the half-crystallization time at 200°C to the half-crystallization time at 180°C (200°C / 180°C) of 1.6 or less.

6. The crystalline resin composition for three-dimensional modeling according to claim 1 , wherein the crystalline polyethylene terephthalate resin has a melting point of 240° C. or higher and 260° C. or lower.

7. A three-dimensional object produced by using the crystalline resin composition for three-dimensional modeling according to any one of claims 1 to 6.

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