WO2018123763A1 - Composition de résine, et corps moulé sous forme de filaments - Google Patents

Composition de résine, et corps moulé sous forme de filaments Download PDF

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Publication number
WO2018123763A1
WO2018123763A1 PCT/JP2017/045711 JP2017045711W WO2018123763A1 WO 2018123763 A1 WO2018123763 A1 WO 2018123763A1 JP 2017045711 W JP2017045711 W JP 2017045711W WO 2018123763 A1 WO2018123763 A1 WO 2018123763A1
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Prior art keywords
resin composition
polylactic acid
filament
polyamide
monofilament
Prior art date
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Ceased
Application number
PCT/JP2017/045711
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English (en)
Japanese (ja)
Inventor
あづさ 臼井
彰太 野口
松岡　文夫
雄俊 中谷
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Unitika Ltd
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Unitika Ltd
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Filing date
Publication date
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Priority to JP2018517240A priority Critical patent/JP6359230B1/ja
Publication of WO2018123763A1 publication Critical patent/WO2018123763A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters

Definitions

  • the present invention relates to a resin composition for a modeling material of a hot melt lamination method 3D printer, and a filament-shaped molded body comprising the same.
  • 3D printers that produce 3D objects (3D objects) based on 3D CAD and 3D computer graphics data have been rapidly spreading in recent years, especially for industrial use.
  • 3D printer modeling methods include optical modeling, ink jet, powder gypsum modeling, powder sintering modeling, and hot melt additive modeling.
  • polylactic acid has a melting point of about 170 ° C., has a relatively low melting point among plastics, and melts at a low temperature. Therefore, polylactic acid is suitable as a modeling material for 3D printers for individuals.
  • polylactic acid has better formability than the ABS resin, and the resulting molded article has a small warpage, and therefore, it is desired to use polylactic acid as a modeling material.
  • polylactic acid itself is hard, and a molded article made of polylactic acid may be harder than that of ABS resin, so that there are cases where streaking or surface polishing cannot be performed as a finish after shaping.
  • Patent Document 1 discloses a composition in which polylactic acid is blended with a styrene-based resin, polyester, or the like as a hot-melt lamination type three-dimensional modeling material that is easy to polish the surface. However, this material was not sufficiently improved in abrasiveness.
  • the present invention is intended to solve the above-mentioned problems, and is a resin composition that can be suitably used as a modeling material when a three-dimensional model is obtained by a 3D printer, and is flexible and abrasive. It is an object of the present invention to provide a resin composition that can satisfactorily produce an excellent three-dimensional model and a filament-shaped molded body comprising the same.
  • the inventors of the present invention have arrived at the present invention as a result of studies to solve the above problems. That is, the gist of the present invention is as follows.
  • Hot melt lamination method 3D printer resin composition for molding material which contains polylactic acid (A) and polyamide copolymer (B), and includes polylactic acid (A) and polyamide copolymer (B ) And a mass ratio (A / B) of 90/10 to 25/75.
  • the flexural modulus is 1.5 to 3.2 GPa, and the wear mass during the wear test is 1.2 to 2.0 times the wear mass of polylactic acid (A).
  • the resin composition according to (1) contains (3) The resin composition according to (1) or (2), further comprising a filler (C).
  • Hot melt lamination method 3D printer molding material molded body comprising the resin composition according to any one of (1) to (3) and having a diameter of 0.2 to 5.0 mm A filamentous shaped product characterized by the above.
  • the resin composition of the present invention is obtained by blending an appropriate amount of polylactic acid and a polyamide copolymer, it is possible to obtain a filament-shaped molded body free from thick spots.
  • the filament-shaped molded object which consists of a resin composition of this invention is suitable as a modeling material of 3D printer, and it is possible to produce the three-dimensional molded item excellent in the softness
  • the resin composition of the present invention is a resin composition containing polylactic acid (A) and a polyamide copolymer, and is a mass ratio (A / B) of polylactic acid (A) and polyamide copolymer (B). ) Is 90/10 to 25/75.
  • poly (L-lactic acid), poly (D-lactic acid), a mixture thereof, and a copolymer containing two or more copolymerization components can be used.
  • poly (L-lactic acid) is preferably the main component.
  • the polylactic acid (A) mainly composed of poly (L-lactic acid) preferably has a D-lactic acid content of 10 mol% or less, and more preferably 6 mol% or less.
  • Polylactic acid (A) preferably has a melt flow rate (MFR) of 0.3 to 15 g / 10 min at a temperature of 190 ° C. and a load of 2.16 kg from the viewpoint of moldability and performance.
  • MFR melt flow rate
  • Examples of commercially available products of polylactic acid include “4032D” (D-lactic acid content: 1.4 mol%, MFR 3 g / 10 min), “3001D” (D-lactic acid content: 1.4 mol%, MFR 10 g) manufactured by NatureWorks. / 10 minutes), or “4060D” (D-lactic acid content 10 mol%, MFR 3.5 g / 10 minutes). These may be used in combination.
  • the resin composition of the present invention needs to contain a polyamide copolymer (B).
  • a polyamide copolymer (B) By blending polyamide with polylactic acid (A), the resin composition is improved in flexibility, and when the polyamide is a copolymer containing a copolymer component, Abrasiveness and yarn production are also improved.
  • the mass ratio (A / B) of the polylactic acid (A) and the polyamide copolymer (B) needs to be 90/10 to 25/75, and in particular, 90/10 to 50/50. Preferably, it is 75/25 to 50/50.
  • the proportion of the polyamide copolymer (B) is less than 10% by mass, the resulting molded article has low flexibility and polishing properties.
  • the filament-shaped molded body foams when melted by the 3D printer. Satisfactory shaped objects cannot be obtained. In addition, the resulting molded article also has poor polishing properties. Furthermore, the filament-shaped molded body is likely to have a variation in diameter, and when the variation becomes large, the filament supply amount (discharge amount) in the 3D printer may fluctuate, and a satisfactory shaped product may not be obtained.
  • the copolymer component constituting the polyamide copolymer (B) in the present invention is not particularly limited as long as it has a polyamide-forming ability, and examples thereof include polyamide 6, polyamide 11, polyamide 12, polyamide 66, and polyamide 69. , Polyamide 610, polyamide 612, polyamide 613, and polyamide 10T.
  • the polyamide copolymer (B) containing two or more of the above copolymerization components has flexibility, good compatibility with polylactic acid (A), close melting point to polylactic acid (A), Because it is easy to mix with lactic acid (A), polyamide 6/66 copolymer, polyamide 6/12 copolymer, polyamide 6/66/12 copolymer, isophthalic acid / adipic acid / 1,6-hexamethylenediamine A polycondensate of / bis (3-methyl-4-aminocyclohexyl) methane is preferred.
  • polyamide copolymers examples include “5023” (6/66 copolymer, melting point 196 ° C.), “7034” (6/12 copolymer, melting point 201 ° C.), or “ 6434 ”(6/66/12 copolymer, melting point 188 ° C.) and“ CX1004 ”manufactured by Unitika (isophthalic acid / adipic acid / 1,6-hexamethylenediamine / bis (3-methyl-4-aminocyclohexyl) ) Polycondensate of methane, melting point 210 ° C.).
  • the polyamide copolymer (B) as described above has a very good compatibility with the polylactic acid (A) and is sufficiently compatible even in the absence of a compatibilizing agent.
  • a filament-shaped molded body having no spots can be obtained, but the resin composition of the present invention does not prevent the usual compatibilizing agent from being contained.
  • the compatibilizing agent include Alfon series manufactured by Toa Gosei Co., Ltd., Modiper A series manufactured by NOF Corporation, SAG series manufactured by Trendsign Co., Ltd., and JONCRYL ADR series manufactured by BASF.
  • the compatibilizing agent containing a functional group having reactivity such as an epoxy group or an allyl group may react with the polylactic acid (A) and the polylactic acid (A) may be easily gelled.
  • the polylactic acid (A) is gelled, it becomes difficult to obtain a filament-shaped molded body with good spinning properties, and the molded product obtained using the filament-shaped molded body has a gelled portion on the surface, Quality may be degraded.
  • the resin composition of the present invention can improve the polishing properties by further containing a filler (C).
  • a filler C
  • fillers glass beads, glass fiber powder, wollastonite, mica, synthetic mica, sericite, talc, clay, zeolite, bentonite, kaolinite, dronite, silica, potassium titanate, finely divided silicic acid, shirasu balloon, Calcium carbonate, magnesium carbonate, barium sulfate, aluminum oxide, magnesium oxide, calcium oxide, titanium oxide, aluminum silicate, zirconium silicate, gypsum, graphite, montmorillonite, carbon black, calcium sulfide, zinc oxide, boron nitride, cellulose fiber, etc. Is mentioned.
  • the particle diameter of the filler (C) is preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less, in order to obtain a filament-shaped molded body with good yarn forming properties.
  • the particle size of the filler (C) exceeds 100 ⁇ m, the filter of the spinning machine may be clogged and the filtration pressure may increase during the production of the filament-shaped molded body. Moreover, the filament-shaped molded body obtained may become rough and may deteriorate in quality.
  • the content of the filler (C) in the resin composition is preferably 30% by mass or less, and more preferably 20% by mass or less.
  • the content of the filler (C) exceeds 30% by mass in the resin composition, the yarn-forming property is lowered, and the resulting filament-shaped molded body may have large diameter variations and large surface roughness. May be.
  • the mass ratio (talc / calcium carbonate) is preferably 80/20 to 20/80 from the viewpoint of yarn-making properties and the smoothness of the filament-shaped molded body, and 70/30 More preferably, it is ⁇ 30 / 70.
  • the nozzle may be easily contaminated during production of the filament-shaped molded body and modeling with a 3D printer. Therefore, when the resin composition of this invention contains a filler (C), it is preferable to also contain an antifouling agent.
  • an antifouling agent a metal soap, a fluorine-based lubricant, a lubricant mainly composed of a fatty acid amide or the like can be used.
  • Metal soap refers to fatty acid salts of metals other than alkali metals, and examples of main metals include magnesium, calcium, zinc, copper, lead, aluminum, iron, cobalt, chromium, and manganese.
  • fluorine-based lubricant examples include perfluoroalkane, perfluorocarboxylic acid ester, perfluoro organic compound, and fluorinated polymer.
  • aliphatic amide examples include oleic acid amide, ethylenebisstearic acid amide, and the like. .
  • a fluorine-based lubricant, vinylidene fluoride / hexafluoropropylene copolymer is preferable because of its great effect.
  • commercially available products examples include PPA series manufactured by Daikin Industries.
  • the resin composition of the present invention is a colorant containing a dye or a pigment, an antistatic agent, a terminal blocking agent, an anti-ultraviolet agent, a light stabilizer, an antifogging agent, and an antifog, as long as the object of the present invention is not impaired Agents, plasticizers, flame retardants, anti-coloring agents, antioxidants, mold release agents, moisture-proofing agents, oxygen barrier agents, crystal nucleating agents, and the like. Moreover, you may contain 2 or more types of these. However, the particle diameter of these additives is preferably 100 ⁇ m or less in order to obtain a filament-shaped molded body with good yarn forming properties.
  • the resin composition of the present invention is excellent in flexibility because the polyamide copolymer (B) is blended with the polylactic acid (A), and the flexural modulus, which is an index indicating flexibility, is 3.2 GPa or less.
  • the flexural modulus is preferably 1.5 to 3.2 GPa.
  • the resin composition of the present invention contains a suitable amount of the polyamide copolymer (B) in the polylactic acid (A), details are unknown, but it is excellent in abrasiveness.
  • the wear mass at the time of the wear test which is an index indicating the abrasiveness, is 1.2 of the wear mass in the case of polylactic acid (A) alone not blended with the polyamide copolymer (B). It is preferably at least twice, more preferably at least 1.3 times, and even more preferably at least 1.4 times.
  • the upper limit of the wear mass is preferably 2.0 times the wear mass in the case of polylactic acid (A) alone in order to prevent the molded article from being deformed.
  • the resin composition of the present invention can be produced by mixing the polylactic acid (A) and the polyamide copolymer (B).
  • a general kneader such as a single screw extruder, a twin screw extruder, a roll kneader, or a Brabender can be used. It is preferred to use an extruder.
  • the resin composition is prepared by, for example, a method in which these resins are melt-kneaded and extruded under conditions of a cylinder temperature of 160 to 230 ° C. and a die temperature of 180 to 240 ° C., and the strand is cooled and then cut into a pellet size. Is preferred. If a biaxial spinning device is used, a filament-shaped molded body is produced as it is without producing pellets of the resin composition from the melt-kneaded polylactic acid (A) and the polyamide copolymer (B). It is also possible.
  • the filamentary molded product of the present invention is composed of the resin composition of the present invention.
  • a resin composition By making a resin composition into the shape of a filament, it can be used suitably as a modeling material of a hot melt lamination method 3D printer.
  • the filament shaped article may be monofilament or multifilament, but monofilament is preferred. These may be unstretched or stretched.
  • the filament shaped body preferably has a diameter of 0.2 to 5.0 mm, more preferably 1.5 to 3.2 mm, and even more preferably 1.6 to 3.1 mm.
  • the diameter of the filament-shaped molded body is an average of the maximum major axis and the minimum minor axis in a cross section cut perpendicular to the longitudinal direction of the filament-shaped molded body. If the diameter of the filament-shaped molded body is less than 0.2 mm, the filament-shaped molded body may become too thin and may not be suitable for a general-purpose hot-melt lamination method 3D printer.
  • the upper limit of the diameter of the filament-shaped molded object suitable for a general purpose hot melt lamination method 3D printer is about 5.0 mm.
  • the resin composition of the present invention is melted at 170 to 270 ° C., extruded from a nozzle hole with a metering supply device, and this is placed in a liquid bath at 20 to 80 ° C.
  • the method include a method in which after cooling and solidification, the material is taken up at a spinning speed of 1 to 50 m / min and wound on a bobbin or the like.
  • the monofilament may be drawn after winding the monofilament after spinning once, or the monofilament may not be taken up after spinning and may be drawn continuously after spinning.
  • the film is stretched, if it is subjected to appropriate heat stretching and heat treatment, a more stable filament is formed, and the formed filament increases in filament strength and improves the smoothness and bending resistance of the filament surface.
  • Gas chromatography (Hewlett Packard, HP-6890) uses helium (He) as a carrier gas at a flow rate of 1.8 ml / min, an oven program held at 90 ° C. for 3 minutes, and at 50 ° C./min at 220 ° C. The temperature was raised to 1 minute and maintained for 1 minute.
  • the column was DB-17 (30 m ⁇ 0.25 mm ⁇ 0.25 ⁇ m) manufactured by J & W, the detector was FID (temperature 300 ° C.), and the internal standard method was used for measurement. The ratio (%) of the peak area of D-lactic acid methyl ester to the total peak area of methyl lactate was calculated, and this was defined as the D-form content (mol%).
  • MFR Melt flow rate of polylactic acid
  • the mass of the disk before and after the wear test was measured, and the difference in mass before and after that was taken as the wear mass.
  • the abrasion mass was evaluated by dividing the abrasion mass of the disk made of each resin composition by the abrasion mass of the disk of Comparative Example 1 composed only of polylactic acid.
  • Diameter of monofilament The obtained monofilament was cut perpendicularly to the longitudinal direction of the monofilament every 20 cm to obtain 30 measurement samples. In each sample, the maximum major axis and the minimum minor axis in the cross section were measured using a micrometer, and the average was taken as the diameter of each sample. The diameter of all 30 samples was averaged to calculate the monofilament diameter.
  • the various raw materials used for the Example and the comparative example are as follows.
  • Polylactic acid ⁇ Polylactic acid resin (“3001D” manufactured by NatureWorks, D-lactic acid content: 1.4 mol%, MFR: 10 g / 10 min) ⁇ Polylactic acid resin (“4060D” manufactured by NatureWorks, D-lactic acid content 10 mol%, MFR 3.5 g / 10 min) ⁇ polyamide ⁇ ⁇ Polyamide 6/66/12 copolymer (“6434B” manufactured by Ube Industries, Ltd., for extrusion molding, melting point 188 ° C.) ⁇ Polyamide 6/12 copolymer (“7034B” manufactured by Ube Industries, Ltd., for extrusion molding, melting point 201 ° C.) ⁇ Polyamide 6/66 copolymer (“5023B” manufactured by Ube Industries, Ltd., for extrusion molding, melting point 196 ° C.) ⁇ Polyamide copolymer (“CX1004" manufactured by Unitika Ltd., melting point 210
  • the mixture was kneaded and extruded under the conditions of a temperature of 200 ° C., a screw rotation speed of 120 rpm, and a discharge rate of 7 kg / h. Subsequently, the strand discharged from the tip of the extruder was cooled by a cooling bath, then taken up by a pelletizer and cut to obtain a master batch pellet (M) of an antifouling agent.
  • M master batch pellet
  • Example 1 Using a twin screw extruder (Ikegai Co., Ltd., PCM-30, screw diameter 29 mm, L / D30, die diameter 3 mm, hole number 3), 90 parts by mass of polylactic acid (A) and polyamide copolymer (B) 10 parts by mass of polyamide 6/66/12 copolymer was blended and fed to an extruder. The mixture was kneaded and extruded under the conditions of a temperature of 215 ° C., a screw rotation speed of 120 rpm, and a discharge rate of 7 kg / h.
  • A polylactic acid
  • B polyamide copolymer
  • the strand discharged from the tip of the extruder was cooled by a cooling bath, then taken up by a pelletizer and cut to obtain a pellet of a resin composition.
  • the obtained pellets of the resin composition were dried under the conditions of 65 ° C. ⁇ 48 hr to make the moisture content 0.01%.
  • the dried resin composition pellets were obtained by using a spinning tester (manufactured by Fuji Filter Industry Co., Ltd., screw diameter: 30 mm, melt extrusion zone: 1000 mm), and the resulting monofilament diameter was 1.75 mm at a spinning temperature of 205 ° C.
  • the amount of discharge was adjusted so that the diameter of the monofilament was 5 mm, and it was extruded from a spinneret having a round cross section having one hole with a monofilament hole diameter of 5 mm. Subsequently, the extruded monofilament was immersed in 50 ° C. cooling water 20 cm below the spinneret and taken out while adjusting with a cooling time of 1 minute to obtain a monofilament (monofilament production method A).
  • Examples 3 to 4 Resin composition pellets having a moisture content of 0.01% were obtained in the same manner as in Example 2 except that the kneading temperature was changed to 210 ° C.
  • the dried resin composition pellets were subjected to a monofilament production apparatus (single screw extruder (manufactured by Nippon Steel Works, screw diameter 60 mm, melt extrusion zone 1200 mm)) at a spinning temperature of 220 ° C. Then, the discharge amount was adjusted so that the diameter of the obtained monofilament was 1.74 mm, and the monofilament was extruded from a spinneret having a round cross section having a hole diameter of 5 mm.
  • Example 4 the extruded monofilament was immersed in 50 ° C. cooling water 20 cm below the spinneret and taken out while adjusting at a take-up speed of 30 m / min to obtain a monofilament.
  • the cooling time was about 1 minute (monofilament production method B (stretch ratio 1)).
  • Example 4 spinning and stretching were performed continuously. That is, under the same conditions as in Example 3, the discharge amount was adjusted so that the diameter of the obtained monofilament was 1.75 mm, and the resin composition was extruded from the spinneret, and then taken out. The cooling time was about 1 minute. Further, the film was stretched 3 times in a warm bath at 70 ° C. and then further heat treated at a temperature of 180 ° C. to obtain a monofilament (monofilament production method B (stretching ratio: 3)).
  • Examples 5-17, 19, 28-29 Resin composition pellets in the same manner as in Example 3 except that the parts of the master batches of polylactic acid, polyamide copolymer, filler and antifouling agent were changed to those shown in Tables 1 and 2 and blended. Got. And the monofilament was obtained with the manufacturing method B like Example 3, 4 using the pellet of the obtained resin composition.
  • Tables 1 and 2 show the evaluation results of the resin compositions and monofilaments obtained in Examples and Comparative Examples.
  • the resin compositions obtained in the examples were excellent in abrasiveness, flexibility, and yarn production, and the obtained monofilaments were excellent in the formability in a 3D printer. For this reason, these resin compositions can be used suitably as a modeling material of a hot melt lamination method 3D printer.
  • the monofilament of Example 4 stretched 3 times using the pellets of the resin composition of Example 3 has improved bending resistance and surface roughness compared to the unstretched monofilament obtained in Example 3. Was also improved.
  • the resin compositions containing the fillers of Examples 5 to 17, 19, 23 to 24, and 28 to 29 had no adverse effect on the yarn forming property and maintained flexibility. Moreover, the obtained monofilament was excellent also in the moldability in 3D printer.
  • the resin composition containing a filler was further improved in abrasiveness and retained flexibility.
  • the monofilament obtained from the resin composition containing a filler can be used more suitably as a modeling material for the hot melt lamination method 3D printer.
  • the monofilaments stretched three times in Examples 7, 12, 15, 17, and 29 had improved bending resistance and improved surface roughness compared to unstretched monofilaments.
  • the monofilaments of Examples 16 and 17 contained a stain preventive agent, the stain did not adhere to the nozzle during modeling by the 3D printer.
  • the resin composition of Comparative Example 1 was only polylactic acid, the elastic modulus was high and the flexibility was poor, and the polishing property was also poor.
  • the resin composition of Comparative Example 2 was inferior in flexibility and polishability because the polyamide copolymer content was too small.
  • the resin composition of Comparative Example 3 was inferior in yarn-making property and polishing property because the polyamide copolymer content was excessive. Since the resin composition of Comparative Example 4 was only a polyamide copolymer, the polishability was poor.
  • the polyamide did not contain a copolymer component and was polyamide 6, it was poor in abrasiveness and inferior in yarn production.
  • the obtained monofilaments had variations in diameter, and could not be shaped without biting into the roller that supplies the filament to the liquefier of the hot melt lamination method 3D printer.
  • the yarn forming property was inferior and a monofilament could not be obtained.
  • the resin composition of Comparative Example 7 does not contain a polyamide copolymer, and since a filler is simply added to polylactic acid, the yarn-making property is slightly inferior, the flexibility is greatly reduced, and the brittleness is obtained. There was no significant improvement in abrasiveness.

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Abstract

L'invention concerne une composition de résine pour matériau de moulage destiné à une imprimante 3D à dépôt de fil fondu. La composition de résine de l'invention est caractéristique en ce qu'elle comprend un acide polylactique (A) et un copolymère de polyamide (B), le rapport (A/B) de l'acide polylactique (A) et du copolymère de polyamide (B) étant compris entre ９０／１０ et ２５／７５.
PCT/JP2017/045711 2016-12-26 2017-12-20 Composition de résine, et corps moulé sous forme de filaments Ceased WO2018123763A1 (fr)

Priority Applications (1)

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JP2018517240A JP6359230B1 (ja) 2016-12-26 2017-12-20 樹脂組成物およびフィラメント状成形体

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JP2016250317 2016-12-26
JP2016-250317 2016-12-26
JP2017182457 2017-09-22
JP2017-182457 2017-09-22

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WO2018123763A1 true WO2018123763A1 (fr) 2018-07-05

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