JP7328679B2 - RESIN COMPOSITION AND FILAMENTAL MOLDED PRODUCT CONSISTING THE SAME - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition for a modeling material for a fused layer deposition method 3D printer, and a filament-like molded article made of the resin composition.

In recent years, 3D printers, which produce three-dimensional objects (three-dimensional objects) based on three-dimensional CAD and three-dimensional computer graphics data, have rapidly spread mainly for industrial use. Modeling methods for 3D printers include methods such as stereolithography, inkjet, powder gypsum modeling, powder sintering modeling, and hot-melt layered modeling.

In recent years, many low-priced 3D printers for personal use have adopted the fused layer deposition method. In this hot melt deposition method 3D printer, a filament-shaped molded body is used as a modeling material, and polylactic acid resin and ABS resin are often used as a resin constituting the modeling material. Polylactic acid resin has a melting point of about 170° C., which is relatively low among plastics and melts at a low temperature, so it is suitable as a molding material for personal 3D printers. In addition, polylactic acid resin has better moldability than ABS resin, and the resulting molded article has less warpage. Therefore, it is desired to use polylactic acid resin as a molding material. However, polylactic acid resin itself is hard, and a modeled object made of polylactic acid resin is hard and fragile in comparison with ABS resin, so it has sometimes been impossible to perform streak engraving, surface polishing, etc. after modeling.

As a hot-melt lamination type three-dimensional modeling material whose surface can be easily polished, for example, Patent Document 1 discloses a material obtained by blending polylactic acid resin with styrene-based resin, polyester, or the like.

International Publication No. 2015/037574 Pamphlet

In view of such prior art, the present invention is a resin composition that can be suitably used as a modeling material when obtaining a three-dimensional model with a 3D printer, and is excellent in flexibility and polishability. An object of the present invention is to provide a resin composition that can be produced and a filament-like molded article made from the same.

The present inventors have conducted studies to solve the above problems, and have found that the above objects can be achieved by blending an appropriate amount of an ionomer resin into a polylactic acid resin, and have completed the present invention.
That is, the gist of the present invention is as follows.
(1) A resin composition for a modeling material for a fused lamination method 3D printer, containing a polylactic acid resin (A) and an ionomer resin (B), wherein the mass ratio of (A) and (B) [(A )/(B)] is 95/5 to 60/40, and the melt flow rate (MFR) value of (A) is higher than the MFR value of (B).
(2) It has a flexural modulus of 1.4 to 3.0 GPa, and the wear mass during the wear test is 1.5 to 2.5 times the wear mass of the polylactic acid resin (A). The resin composition according to (1).
(3) The resin composition according to (1) or (2), further comprising a filler (C).
(4) The resin composition according to (3), which further contains an antifouling agent.
(5) A molding material for a fused layer deposition method 3D printer, which is composed of the resin composition according to any one of (1) to (4) and has a diameter of 0.2 to 5.0 mm. A filamentous shaped article characterized by:

Since the resin composition of the present invention is obtained by blending an appropriate amount of an ionomer resin with a polylactic acid resin, it is possible to obtain a filament-like molded article having a uniform diameter. The filamentous molded article made of the resin composition of the present invention is suitable as a modeling material for 3D printers, and can be used to produce a three-dimensionally shaped article with excellent flexibility and polishability.

It is explanatory drawing of "Luke" produced in order to evaluate formability. FIG. 4 is an explanatory diagram of an "anchor" produced for evaluating dimensional stability.

The resin composition of the present invention comprises a polylactic acid resin (A) and an ionomer resin (B).

Examples of the polylactic acid resin (A) include poly(L-lactic acid) resin, poly(D-lactic acid) resin, mixtures thereof, and copolymer resins containing two or more copolymer components. A polylactic acid resin mainly composed of poly(L-lactic acid) resin is preferable from the viewpoint of spinning properties. The polylactic acid resin mainly composed of poly(L-lactic acid) resin preferably has a D-lactic acid content of 10 mol % or less, more preferably 6 mol % or less.

From the viewpoint of spinning properties, the polylactic acid resin (A) preferably has a melt flow rate (MFR) of 0.3 to 15 g/10 minutes at a temperature of 190° C. and a load of 2.16 kg, and preferably 5 to 12 g/10 minutes. minutes, more preferably 8 to 12 g/10 minutes.

Commercially available polylactic acid resins include, for example, NatureWorks "4032D" (D-lactic acid content: 1.4 mol%, MFR: 3 g/10 min), "3001D" (D-lactic acid content: 1.4 mol %, MFR: 10 g/10 min) and "4060D" (D-lactic acid content: 10 mol %, MFR: 3.5 g/10 min). You may mix and use the said commercial item.

The resin composition of the present invention must contain an ionomer resin (B). By blending the ionomer resin (B) with the polylactic acid resin (A), the flexibility is improved, and the polishability and spinnability are improved. The ionomer resin (B) is a resin in which the molecules of a copolymer of an α-olefin and an α,β-unsaturated carboxylic acid are intermolecularly bonded with metal ions. Examples of α-olefins include polyethylene and polypropylene. Examples of α,β-unsaturated carboxylic acids include acrylic acid, methacrylic acid and itaconic acid. Examples of metal ions include sodium ion, Potassium ions, calcium ions, zinc ions and aluminum ions can be mentioned. Among the ionomer resins (B), ionomer resins in which the metal ions are sodium ions are preferable because they have good compatibility with the polylactic acid resin (A) and have high spinning properties.

From the viewpoint of spinning properties, the ionomer resin (B) preferably has an MFR at a temperature of 190°C and a load of 2.16 kg of 8 g/10 minutes or less, more preferably 4 g/10 minutes or less, and 2 g/10 minutes or less. It is more preferably 10 minutes or less.

In the present invention, the MFR value of polylactic acid resin (A) must be greater than the MFR value of ionomer resin (B). When the MFR value of (A) is smaller than the MFR value of (B), the spinning property is lowered, filaments with a uniform diameter cannot be collected, and the filament supply amount (discharge amount) in the 3D printer fluctuates. However, it is not preferable because it may not be possible to obtain a model with accurate dimensions.

In addition, in the resin composition of the present invention, whether or not the MFR value of the polylactic acid resin (A) is higher than the MFR value of the ionomer resin (B) can be verified by the following procedure.
MFR1 is the value obtained by measuring the resin obtained by vacuum-drying pellets of the resin composition for modeling material at 70° C. for 24 hours at a temperature of 190° C. and a load of 2.16 kgf. On the other hand, pellets of the resin composition for molding materials were placed in a hot 8% aqueous sodium hydroxide solution (80°C x 12 hours treatment) at a bath ratio of 1:100 to elute the polylactic acid component, wash the remaining insoluble components with water, and dry the resin component. is measured under the same measurement conditions as above, and is defined as MFR2. When these measured values satisfy MFR1>MFR2, it can be determined that polylactic acid resin (A)>ionomer resin (B).

Examples of commercial products of the ionomer resin (B) include "Himilan 1706" ( zinc ion-neutralized ethylene methacrylic acid copolymer resin, MFR: 0.9 g/10 min) and "Himilan 1855" manufactured by Mitsui-DuPont Polychemicals. (MFR: zinc ion-neutralized ethylene methacrylic acid copolymer resin, 1.0 g/10 min).

The mass ratio [(A)/(B)] of the polylactic acid resin (A) and the ionomer resin (B) must be 95/5 to 60/40, preferably 90/10 to 70/30. preferably 85/15 to 75/25. If the content of (B) with respect to the total of (A) and (B) is less than 5% by mass, it is not preferable because the flexibility and polishability of the resulting shaped article will be low. If the amount exceeds 40% by mass, the diameter of the filament-like formed article becomes uneven, which is not preferable.

The resin composition of the present invention may further contain a filler (C) in order to improve the dimensional stability of the resulting shaped article. Fillers (C) include, for example, glass beads, glass fiber powder, wollastonite, mica, synthetic mica, sericite, talc, clay, zeolite, bentonite, kaolinite, doronite, silica, potassium titanate, fine silicon powder, 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, nitriding Examples include boron and cellulose fibers, with talc being more preferred.

The average particle size of the filler (C) is preferably 100 µm or less, more preferably 50 µm or less, in order to obtain a filament-like compact with good spinning properties. If the average particle size of (C) exceeds 100 μm, the filter of the spinning machine may be clogged during the production of the filament-shaped compact, resulting in an increase in filtration pressure. In addition, the surface of the filament-like molded product obtained becomes rough, and the quality of the product may deteriorate. The average particle size of (C) is a value defined by the particle size value when the mass accumulation is 50% when the particle size distribution is measured using a particle size distribution analyzer such as a laser diffraction/scattering particle size distribution meter. be. The measurement is usually carried out after adjusting the suspension by adding (C) to water or alcohol so that the measurement allowable concentration is obtained, and dispersing it with an ultrasonic disperser.

The content of the filler (C) is preferably 30 parts by mass or less and 20 parts by mass or less with respect to 100 parts by mass of the total amount of the polyarylate resin (A) and the ionomer resin (B). is more preferable. If the content of (C) exceeds 30 parts by mass, the filamentous molded article may have a reduced diameter, resulting in a roughened surface.

Since the resin composition of the present invention contains the filler (C) as described above, dirt tends to adhere to the nozzle during the production of the filament-shaped molding and during the modeling with a 3D printer. be. Therefore, when the resin composition of the present invention contains (C), it is preferable to contain an antifouling agent. Antifouling agents include, for example, metal soaps, fluorine-based lubricants, and lubricants containing fatty acid amides as main components. Metal soaps refer to fatty acid salts of metals other than alkali metals, and main metals include magnesium, calcium, zinc, copper, lead, aluminum, iron, cobalt, chromium, manganese, and the like. Examples of fluorine-based lubricants include perfluoroalkanes, perfluorocarboxylic acid esters, perfluoroorganic compounds, and fluorinated polymers. Examples of aliphatic amides include oleic acid amide and ethylenebisstearic acid amide. . Among them, a vinylidene fluoride-hexafluoropropylene copolymer is preferable because of its high effect of preventing adhesion of dirt. Examples of commercially available products include the PPA series manufactured by Daikin Industries, Ltd.

The resin composition of the present invention may contain coloring agents such as dyes and pigments, antistatic agents, terminal blocking agents, UV inhibitors, light stabilizers, anti-fogging agents, anti-fogging agents, as long as the objects of the present invention are not impaired. , a plasticizer, a flame retardant, an anti-coloring agent, an antioxidant, a release agent, a moisture-proof agent, an oxygen barrier agent, a crystal nucleating agent, a compatibilizer, and the like. One of the above additives may be used alone, or two or more thereof may be used in combination. The particle size of the additive is preferably 100 μm or less, since a filament-like formed article can be obtained with good spinning properties.

The resin composition of the present invention is obtained by blending an appropriate amount of the ionomer resin (B) with the polylactic acid resin (A), and is therefore excellent in flexibility. The flexural modulus, which is an index of flexibility, is preferably 3.0 GPa or less, more preferably 1.4 to 3.0 GPa.

Since the resin composition of the present invention is obtained by blending an appropriate amount of the ionomer resin (B) with the polylactic acid resin (A), it is excellent in polishability. The wear mass in the wear test, which is an index of abrasiveness, is preferably 1.5 times or more the wear mass in the case of polylactic acid resin (A) alone that does not contain ionomer resin (B). It is more preferably 0.7 times or more, more preferably 2.0 times or more. Further, the upper limit of the wear mass is preferably 2.5 times the wear mass in the case of polylactic acid (A) alone, in order to prevent the shape of the molded product from collapsing.

The resin composition of the present invention can be produced by mixing the polylactic acid resin (A) and the ionomer resin (B). For mixing both resins, a general kneader such as a single screw extruder, a twin screw extruder, a roll kneader, and a Brabender can be used. It is preferable to use a machine. The resin composition is produced by, for example, melt-kneading and extruding these resins under conditions of a cylinder temperature of 160 to 230° C. and a die temperature of 180 to 240° C., cooling the strands, and cutting them into pellet sizes. is preferred. If a biaxial spinning device is used, a filament-shaped compact can be produced from the melt-kneaded polylactic acid resin (A) and ionomer resin (B) without producing pellets of the resin composition. is also possible.

The filamentous molded article of the present invention is composed of the resin composition of the present invention. By forming the resin composition into a filament shape, it can be suitably used as a modeling material for a fused layer deposition method 3D printer. The filament-like molded article may be a monofilament or a multifilament, but a monofilament is preferred. Further, these may be unstretched or stretched.

The diameter of the filamentous compact is preferably 0.2 to 5.0 mm, more preferably 1.5 to 3.2 mm, even more preferably 1.6 to 3.1 mm. The diameter of the filamentous molded article is the average of the maximum major axis and the minimum minor axis in a cross section cut perpendicular to the longitudinal direction of the filamentous molded article. If the diameter of the filamentous molded body is less than 0.2 mm, it may become too thin and not suitable for a general-purpose fused layer deposition method 3D printer. In addition, the upper limit of the diameter of the filament-shaped compact suitable for a general-purpose fused layer deposition method 3D printer is about 5.0 mm.

As a method for producing a filament-shaped molded body made of monofilaments, for example, the resin composition of the present invention is melted at 180 to 220°C, extruded from a nozzle hole with a metering device, and placed in a liquid bath at 20 to 80°C. After cooling and solidification, the fiber is taken up at a spinning speed of 1 to 50 m/min and wound around a bobbin or the like. In addition, when forming a monofilament, it may be stretched at a magnification of more than 1.0 times and 5.0 times or less. The draw ratio is more preferably more than 1.0 times and 3.5 times or less. By drawing, the bending resistance of the obtained filaments can be improved. The monofilament may be drawn after being wound once after spinning, or the monofilament may be drawn continuously after spinning without being wound after spinning. Appropriate heat drawing and heat treatment during drawing form more stable filaments, and the formed filaments have increased filament strength and improved filament surface smoothness.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these.

The evaluation of the resin composition, the filament-shaped molded article and the modeled article was carried out by the following methods.
A. Evaluation method (1) D-form content of polylactic acid resin (A) About 0.3 g of polylactic acid resin (A) was added to 6 ml of a 1N-potassium hydroxide/methanol solution and sufficiently stirred at 65°C to obtain a polylactic resin. was decomposed, 450 μl of sulfuric acid was added and stirred at 65° C. to give lactic acid methyl ester. 5 ml of the obtained lactic acid methyl ester, 3 ml of pure water, and 13 ml of methylene chloride were mixed and shaken. After static separation, about 1.5 ml of the lower organic layer was sampled, filtered through a disk filter for HPLC (pore size 0.45 μm), and measured by gas chromatography.
Gas chromatography (HP-6890, manufactured by Hewlett Packard) was performed using helium (He) as a carrier gas at a flow rate of 1.8 ml/min under an oven program of 90°C for 3 minutes and 50°C/min to 220°C. and maintained for 1 minute. DB-17 (30 m×0.25 mm×0.25 μm) manufactured by J&W was used as a column, FID was used as a detector (temperature: 300° C.), and measurement was performed by an internal standard method. The ratio (%) of the peak area of D-lactic acid methyl ester to the total peak area of methyl lactate was calculated and defined as the D-form content (mol %).

(2) Melt flow rate (MFR) of polylactic acid resin (A) and ionomer resin (B)
It was measured according to JIS K 7210 using a melt indexer F-B01 manufactured by Toyo Seiki Seisakusho. Measurement was performed under the conditions of a test temperature of 190°C and a test load of 2.16 kg.

(3) Abrasiveness Pellets of the obtained resin composition (dried at 65°C for 48 hours to a moisture content of 0.01%) were used in an injection molding machine (manufactured by Nissei Plastics Co., Ltd., NEX-110 type) was used to prepare a disk with a diameter of 10 mm and a thickness of 2 mm under the conditions of a cylinder temperature of 190 to 220°C and a mold temperature of 30 to 40°C.
Using a Taber abrasion tester (Rotary Abrasion Testen manufactured by Toyo Seiki Co., Ltd.), the disk was subjected to an abrasion test according to JIS K7204. The wear wheel used was H-22, the number of rotations was 1000, the rotation speed was 70 rpm, the load was 1.0 kgf, the ambient temperature for measurement was 20° C., and the humidity was 65% RH.
The mass of the disc before and after the wear test was measured, and the difference between the masses before and after was taken as the wear mass. Abrasiveness was evaluated by dividing the wear mass of the disc made of each resin composition by the wear mass of the disc of Comparative Example 1 composed only of the polylactic acid resin.
In the present invention, a value obtained by dividing the wear mass by the wear mass of the disc of Comparative Example 1 composed only of polylactic acid was 1.5 or more, and was judged to pass.

(4) Flexibility Using an injection molding machine (manufactured by Nissei Plastics Co., Ltd., NEX-110 type), under the conditions of cylinder temperature 190 to 220 ° C. and mold temperature 30 to 40 ° C., prepare a test piece (dumbbell piece) for general physical property measurement conforming to ISO, bend span 64 mm, test speed 2 mm / sec was measured.
In the present invention, 3.0 GPa or less was considered acceptable.

(5) Spinnability Evaluation was made according to the following two grades based on the number of yarn breakages when a monofilament with a fiber diameter of 1.75 mm was collected at a spinning speed of 10 m/min for 24 hours.
O: Yarn breakage did not occur.
x: Yarn breakage occurred or the filament could not be taken off.

(6) Diameter of monofilament The obtained monofilament was cut perpendicularly to the longitudinal direction of the monofilament every 20 cm to obtain 30 measurement samples. For each sample, the maximum length and minimum width in the cross section were measured using a micrometer, and the average was taken as the diameter of each sample. The diameter of the monofilament was calculated by averaging the diameters of all 30 samples.

(7) Uniformity of diameter of monofilaments Using the maximum value (M1) and minimum value (M2) of the diameters of all samples calculated in (6) above, the uniformity of diameters of monofilaments was calculated.
Diameter uniformity = (M1-M2)/2

(8) Bend resistance of monofilament According to the MIT folding endurance test described in JIS P 8115, using an MIT folding endurance tester manufactured by Mize Tester Co., Ltd., load 5 N, clamp tip R 0.38 mm, grip distance 2 0 mm, a test speed of 175 rpm, and a bending angle of 135 degrees, and the number of folding endurance of the monofilament was measured. For the measurement, a sample was used which had been allowed to stand for 48 hours or longer under standard conditions (room temperature 22±2° C., humidity 50±2%). In the MIT folding endurance test, each monofilament was measured three times and an average value was obtained. The number of folding endurance was evaluated in the following four stages.
⊙: 100 times or more ○: 30 times or more and less than 100 times Δ: 5 times or more but less than 30 times ×: less than 5 times In the present invention, a folding endurance of 5 times or more was regarded as acceptable. The folding endurance is more preferably 30 times or more, and even more preferably 100 times or more.

(9) Nozzle contamination of 3D printer Using the obtained monofilament and a 3D printer (CREATOR PRO manufactured by FLASHFORGE), molding of an ISO dumbbell piece is repeated 10 times under the conditions of a nozzle temperature of 190 to 240 ° C. and a table temperature of 50 ° C. During this time, contamination of the nozzle was observed. If the dirt adhering to the nozzle was also adhered to the shaped ISO dumbbell piece, it was evaluated as "x", and if it was not adhered to the shaped ISO dumbbell piece, it was evaluated in the following two stages.
◯: No dirt adhered to the nozzle.
Δ: Dirt adhered to the nozzle.
In the present invention, "Δ" or higher was regarded as acceptable.

(10) 3D printer formability Using the obtained monofilament, a 3D printer (CREATOR PRO manufactured by FLASHFORGE) was used at a nozzle temperature of 190 to 240 ° C. and a table temperature of 50 ° C. "Luke" in FIG. was modeled. If the resin was not discharged uniformly, or if the warpage was too large and the sample was peeled off from the modeling table, modeling could not be performed, it was evaluated as "x". When the molding was successful, the appearance of 1 (overhang portion) in FIG. 1 was evaluated in the following two stages.
⊚: The shape of the overhang portion was not sagging.
◯: The shape of the overhang portion was sagging.
In the present invention, "O" or better was regarded as acceptable.

(11) Dimensional Stability of Modeled Object Using the obtained monofilament, a 3D printer (CREATOR PRO manufactured by FLASHFORGE) was used to perform the measurement under the conditions of a nozzle temperature of 190 to 240°C and a table temperature of 50°C. sculpted the Anchor. When the warpage was too large and the molded object was separated from the molding table and could not be molded, it was evaluated as "x". If the model can be formed, place the modeled anchor on a smooth leveling board (marble, etc.), place a weight at position 5 in Fig. 2 and fix it, and then the three tip parts of 2 to 4 in Fig. 2. The height from the table was measured with a clearance gauge or vernier caliper, the average value was obtained, and the following three grades were used for evaluation.
◯: The average value was more than 0 mm and less than 1 mm.
(triangle|delta): The average value was 1 mm or more.
In the present invention, "Δ" or higher was regarded as acceptable.

B. Raw Materials Raw materials used in Examples and Comparative Examples are as follows.
[Polylactic acid resin (A)]
· 3001D (manufactured by NatureWorks, D-lactic acid content: 1.4 mol%, MFR: 11 g / 10 minutes)

[Ionomer resin (B)]
- Himilan 1706 (Mitsui DuPont Polychemicals ionomer, zinc ion-neutralized ethylene methacrylic acid copolymer resin, MFR: 0.9 g/10 minutes)
- Himilan 1855 (manufactured by DuPont Mitsui Polychemicals, ionomer resin, zinc ion-neutralized ethylene methacrylic acid copolymer resin, MFR: 1.0 g/10 minutes)
- Himilan 1702 (manufactured by DuPont Mitsui Polychemicals, ionomer resin, zinc ion-neutralized ethylene methacrylic acid copolymer resin, MFR: 16 g/10 minutes)

[Polymer having the same skeleton as ionomer resin and not substituted with metal ions]
· Nucrel AN4213C (manufactured by Mitsui DuPont Polychemicals, ethylene methacrylic acid copolymer resin, MFR: 10 g / 10 minutes)
[Low density polyethylene]
・ Novatec LD LJ401 (low-density polyethylene manufactured by Japan Polyethylene, MFR: 1.5 g / 10 minutes)

〔filler〕
・ Talc (Hymicron talc HE5 manufactured by Takehara Chemical Industry Co., Ltd., average particle size: 1.6 μm)

[Masterbatch Pellets for Antifouling Agent]
Using a twin-screw extruder (manufactured by Ikegai, PCM-30), 99 parts by mass of polylactic acid resin (3001D) and an antifouling agent (vinylidene fluoride-hexafluoropropylene copolymer, manufactured by Daikin Industries, Ltd. "PPA DA- 310ST”) was blended with 1 part by mass and supplied to the extruder. The mixture was kneaded and extruded under 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 extruded from the tip of the extruder was cooled in a cooling bath, taken up by a pelletizer, and cut to obtain masterbatch pellets (M) of the antifouling agent.

Example 1
Using a twin screw extruder (manufactured by Ikegai, PCM-30, screw diameter 29 mm, L / D 30, die diameter 3 mm, number of holes 3), 95 parts by mass of 3001D as polylactic resin (A) and ionomer resin (B ) was blended with 5 parts by weight of Himilan 1706 and supplied to the extruder. The mixture was kneaded and extruded under 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 extruded from the tip of the extruder was cooled in a cooling bath, taken up by a pelletizer, and cut to obtain pellets of the resin composition. The obtained pellets of the resin composition were dried at 65° C. for 48 hours to a moisture content of 0.01%.
The dried resin composition pellets are processed using a monofilament manufacturing apparatus (single-screw extruder (manufactured by Japan Steel Works, Ltd., screw diameter 60 mm, melt extrusion zone 1200 mm)) at a spinning temperature of 220 ° C. to obtain a monofilament. The discharge rate was adjusted so that the diameter was 1.75 mm, and extruded through a spinneret with a circular cross section having one hole with a hole diameter of 5 mm. Subsequently, the extruded monofilament was immersed in cooled warm water of 50° C. 20 cm below the spinneret, and was taken off at an adjusted take-off speed of 30 m/min to obtain a monofilament. Cooling time was about 1 minute (unstretched).

Examples 2, 3, 5, 6, 8, 9, 11-13, Comparative Examples 2, 6, 7
Except for changing the resin composition described in Table 1, the same operation as in Example 1 was performed to obtain pellets of the resin composition, and then unstretched monofilaments were obtained.

Example 4
Pellets of the resin composition obtained in Example 3 (dried under the conditions of 65 ° C. for 48 hours to have a moisture content of 0.01%) were processed by a monofilament manufacturing apparatus (single screw extruder (Japan Steel Works, Ltd. Co., Ltd., screw diameter 60 mm, melt extrusion zone 1200 mm)))), under the conditions of a spinning temperature of 200 ° C., the discharge rate is adjusted so that the diameter of the monofilament obtained after drawing is 1.75 mm, and the hole diameter is 5 mm. It was extruded through a round cross-section spinneret with one hole. Subsequently, the extruded monofilament was immersed in cooled warm water of 50° C. 20 cm below the spinneret, and taken off while adjusting the take-off speed to 30 m/min to obtain a drawn monofilament (draw ratio=3.0). Cooling time was about 1 minute.

Examples 7 and 10
Pellets of the resin composition were obtained in the same manner as in Example 1, except that the resin composition described in Table 1 was changed and blended. Then, using the obtained pellets of the resin composition, the same operation as in Example 4 was performed to obtain pellets of the resin composition, and then a stretched monofilament was obtained.

Comparative example 1
Except for supplying 3001D alone instead of supplying a blend of 3001D and Himilan 1706, the same operation as in Example 1 was performed to obtain pellets of the resin composition, An undrawn monofilament was obtained.

Comparative example 3
The same operation as in Example 1 was performed except that the resin composition was changed to that shown in Table 1, and after obtaining pellets of the resin composition, an attempt was made to obtain an unstretched monofilament. Since the content of the ionomer resin to be formed was excessive, the spinnability was poor and a monofilament could not be obtained.

Comparative example 4
The same operation as in Example 1 was performed except that the resin composition was changed to that shown in Table 1. After obtaining pellets of the resin composition, an attempt was made to obtain an unstretched monofilament. Since the ionomer resin having an MFR value higher than that of the polylactic acid resin was contained, the spinnability was poor and a monofilament could not be obtained.

Comparative example 5
The same operation as in Example 1 was performed except that the resin composition was changed to that shown in Table 1. After obtaining pellets of the resin composition, an attempt was made to obtain an unstretched monofilament. Since a polymer having the same skeleton as that of the ionomer resin and not substituted with metal ions was contained instead of the ionomer resin, the compatibility between the polylactic acid resin and the polyolefin resin was poor, the spinning property was poor, and a monofilament could not be obtained.

Table 1 shows the properties of the resin compositions obtained in Examples and Comparative Examples, the properties of the monofilaments obtained, the contamination of the nozzle of the 3D printer, the moldability, and the properties of the molded objects obtained.

Since Examples 1 to 13 were resin compositions in which an appropriate amount of ionomer resin was blended with polylactic acid resin, they were excellent in spinnability, polishability, and flexibility. Therefore, these resin compositions can be suitably used as a modeling material for a fused layer deposition method 3D printer.
The shaped articles of Examples 6 and 9 used a resin composition containing talc in addition to the ionomer resin in the polylactic acid resin, and thus had excellent dimensional stability compared to the shaped article of Example 3. .
The shaped objects of Examples 7 and 10 used a resin composition containing talc in addition to the ionomer resin in the polylactic acid resin, and thus had excellent dimensional stability compared to the shaped object of Example 4. .
The modeled article of Example 13 was excellent in dimensional stability compared to the modeled article of Example 11 because the resin composition containing talc in addition to the ionomer resin was used in the polylactic acid resin.
The monofilaments of Examples 4, 7, and 10 were stretched 3 times, and therefore, compared with the monofilaments of Examples 3, 6, and 9, the bending resistance was improved and the surface roughness was improved.
The monofilaments of Examples 9 and 10 used a resin composition containing an antifouling agent, so compared to the monofilaments of Examples 6 and 7, the nozzles were less soiled during modeling with a 3D printer.

The resin composition of Comparative Example 1 was inferior in polishability and flexibility because the polylactic acid resin did not contain an ionomer resin.
The resin composition of Comparative Example 2 was inferior in polishability and flexibility because the content of the ionomer resin contained in the polylactic acid resin was too small.
The resin composition of Comparative Example 6 contained low-density polyethylene in the polylactic acid resin without containing the ionomer resin, and thus was inferior in polishability.
The resin composition of Comparative Example 7 was inferior in flexibility because the polylactic acid resin contained only talc without containing an ionomer resin.

Claims (5)

A molding material for a molding material for a fused lamination method 3D printer, containing a polylactic resin (A) and an ionomer resin (B), wherein the mass ratio of (A) and (B) [(A) / (B )] is 95/5 to 60/40, the melt flow rate (MFR) value of (A) is greater than the MFR value of (B), and the ionomer resin (B) is zinc ion-neutralized ethylene 1. A filament-shaped molded article having a diameter of 0.2 to 5.0 mm, which is composed of a resin composition for modeling material which is a methacrylic acid copolymer resin . The resin composition has a flexural modulus of 1.4 to 3.0 GPa, and an abrasion mass during an abrasion test that is 1.5 to 2.5 times the abrasion mass of the polylactic acid resin (A). 2. The filamentous formed article according to claim 1, characterized in that: 3. The filamentous formed article according to claim 1, wherein the resin composition further contains a filler (C). 4. The filamentous molded article according to claim 3, wherein the resin composition further contains an antifouling agent. The filamentous molded article according to any one of claims 1 to 4, wherein said filamentous molded article is a drawn monofilament.

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