SUPPORT MATERIAL FOR FUSED DEPOSITION MODELING, AND MANUFACTURING METHOD OF FUSED DEPOSITION MODELED STRUCTURE AND THREE-DIMENSIONAL OBJECT USING SAME

Abstract

Provided is a support material for fused deposition modeling capable of being supplied in the form of filament excellent in flexibility and uniformity of wire diameter. The support material comprises a polyvinyl alcohol-based resin (A) and a polylactone (B) having a specific molecular weight in a specific content. The filamentous support material is excellent in productivity. Moreover, the support material portion after the fused deposition modeling can be removed by washing by use of water. The resulting waste liquid is biodegradable and thus the support material is environmentally friendly.

Claims

1. A support material for fused deposition modeling comprising (A) a polyvinyl alcohol-based resin and (B) a polylactone, wherein the (B) polylactone has a number average molecular weight of 20000 to 70000.

2. A support material for fused deposition modeling comprising (A) a polyvinyl alcohol-based resin and (B) a polylactone, wherein the (B) polylactone is contained in an amount of 27 to 60 parts by weight per 100 parts by weight of the (A) polyvinyl alcohol-based resin.

3. A support material for fused deposition modeling comprising (A) a polyvinyl alcohol-based resin and (B) a polylactone, wherein the (B) polylactone has a number average molecular weight of 20000 to 70000, and wherein the (B) polylactone is contained in an amount of 27 to 60 parts by weight per 100 parts by weight of the (A) polyvinyl alcohol-based resin.

4. The support material for fused deposition modeling according to claim 1, wherein the polyvinyl alcohol-based resin (A) has a saponification degree of 72 to 80 mol %.

5. The support material for fused deposition modeling according to claim 2, wherein the polyvinyl alcohol-based resin (A) has a saponification degree of 72 to 80 mol %.

6. The support material for fused deposition modeling according to claim 1, wherein the polylactone (B) is polycaprolactone.

7. The support material for fused deposition modeling according to claim 2, wherein the polylactone (B) is polycaprolactone.

8. The support material for fused deposition modeling according to claim 1, wherein the polylactone (B) has a melting point of 50 to 80° C. wherein the melting point is measured by differential scanning calorimetry.

9. The support material for fused deposition modeling according to claim 2, wherein the polylactone (B) has a melting point of 50 to 80° C. wherein the melting point is measured by differential scanning calorimetry.

10. The support material for fused deposition modeling according to claim 1, being in the form of filament having a diameter of 1.5 to 3 mm.

11. The support material for fused deposition modeling according to claim 2, being in the form of filament having a diameter of 1.5 to 3 mm.

12. A method of manufacturing a fused deposition modeled structure, the method comprising supplying a molten model material and a support material for fused deposition modeling in a molten state, on top of the previously deposited model material or support material, wherein the support material comprising (A) a polyvinyl alcohol-based resin having a number average molecular weight of 20000 to 70000 and (B) a polylactone.

13. A method of manufacturing a fused deposition modeled structure, the method comprising supplying a molten model material and a support material for fused deposition modeling in a molten state, on top of the previously deposited model material or support material, wherein the support material comprising (A) a polyvinyl alcohol-based resin and (B) a polylactone in an amount of 27 to 60 parts by weight per 100 parts by weight of the (A) polyvinyl alcohol-based resin.

14. A method of manufacturing a three-dimensional object, the method comprising contacting a fused deposition modeled structure with water, wherein the fused deposition modeled structure is produced by the method of claim 12.

15. A method of manufacturing a three-dimensional object, the method comprising contacting a fused deposition modeled structure with water, wherein the fused deposition modeled structure is produced by the method of claim 13.

Description

EXAMPLES

[0068] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist of the invention is not exceeded. In the example, “part” means a weight basis.

[Method for Producing Support Material]

[0069] A PVA-based resin and polycaprolactone were charged to a twin-screw extruder (manufactured by TECHNOVEL CORPORATION., L/D=60, 15 mmϕ) at a predetermined ratio, through a charging port for raw material, and kneaded at 230° C. in an extruder (screw speed: 200 rpm). The kneaded resin composition was discharged in the form of strand, air-dried, and subsequently cutting the strand with a fan cutter, thereby obtaining pellets of the resin composition.

[0070] The pellets produced by the above-mentioned extruder were supplied to a single screw extruder, and melt-kneaded under the conditions shown below, following by extruding in the form of strand having a diameter of 1.75 mm, and air-cooled on a belt. The strand was wound around a reel (spool diameter: 20 cm), thereby obtaining a reel of the filamentous support material.

[0071] Single-screw extruder (TECHNOVEL CORPORATION): 20 mmϕ, L/D=24, “SZW20GT-24MG-STD”

[0072] Extrusion temperature pattern: C1/C2/C3/H/A/D=160/180/190/190/190/190° C.

[0073] Rotation speed: 20 rpm

[0074] Discharge rate: 1.0 kg/hour

[Evaluation Method]

(1) Deviation of Filament Fluctuation

[0075] The filament produced above was measured with respect to its diameter and the maximum deviation (±mm) from 1.75 mm in the diameter along a length of 20 m of the filament was determined. The smaller the maximum deviation, the more stable diameter the filamentous support material had.

(2) Flexibility

[0076] The filament of the support material drawn from the reel of the filament was manually wound 10 times around a tube having a diameter of 15 mm. The number of tears in the filament after the winding operation was counted.

(3) Water Solubility

[0077] The filaments produced above was cut into pellets each having a length of 5 mm. The resulting pellets 5 g were immersed in 500 ml of water (80° C.) and stirred with a stirrer. The time period (minutes) until the pellets could not be visually confirmed was measured. The shorter the time, the better water solubility the support material has. In addition, the case where the insoluble matter was remained even after stirring for 1 hour was assessed as “insoluble”.

[Manufacturing of Support Material]

[0078] The compounds used as components contained in the composition are as follows.

(1) PVA-Based Resin

[0079] Unmodified polyvinyl alcohol having a saponification degree of 79 mol % and an average polymerization degree of 370 was used.

(2) Polylactone

[0080] Five types of polycaprolactones each having a number average molecular weight of 10000, 25000, 37000, 50000 or 80000 were used.

Support Material Nos. 1 Through 13

[0081] Filamentous support material Nos. 1 through 13 were prepared from a resin composition obtained by mixing 100 parts by weight of PVA-based resin with polycaprolactone at the ratio shown in Table 1, based on the production method described above.

[0082] The support material prepared were measured and evaluated with respect to deviation of filament diameter, flexibility, and water solubility according to the early mentioned evaluation method. The results are shown in Table 1.

TABLE-US-00001 TABLE 1 polycaprolactone evaluation number deviation average amount (part) of filament water molecular per 100 parts diameter flexibility solubility No weight of PVA (mm) (count) (min) 1 50000 43 ±0.04 0 44 2 80000 43 ±0.06 0 insoluble 3 10000 43 ±0.06 10 60 4 25000 43 ±0.04 0 40 5 37000 43 ±0.04 0 38 6 50000 11 ±0.02 10 35 7 50000 18 ±0.04 10 45 8 50000 25 ±0.04 10 44 9 50000 33 ±0.04 0 40 10 50000 50 ±0.03 0 39 11 50000 60 ±0.04 0 39 12 50000 67 ±0.02 1 insoluble 13 50000 82 ±0.04 0 insoluble

[0083] As can be seen from the comparison among Nos. 1 through 5, when the polycaprolactone had a number average molecular weight of 20000 to 70000 (Nos. 1, 4 and 5), the fluctuation range of the filament diameter was ±0.05 mm or less, which means excellent diameter stability. In addition, the flexibility was excellent, and the time period for dissolution using water was less than 45 minutes.

[0084] On the other hand, when the number average molecular weight of the polycaprolactone exceeded 70000 (No. 2), the filament diameter deviation was large, and the undissolved support material was remained even after being left for 1 hour. When the polycaprolactone had a number average molecular weight of less than 20000 (No. 3), the deviation of the filament diameter became large. Although the support material could be dissolved in water, it took a longer period to dissolve than the support material containing polycaprolactone having a number average molecular weight of 20000 to 70000. In addition, the filament flexibility was impaired.

[0085] As can be seen from the comparison among Nos. 1 and 6 through 13, the support material Nos. 1 and 9 through 11, each of which contained polycaprolactone at an amount of 27 to 60 parts by weight per 100 parts by weight of the PVA-based resin, were excellent in filament diameter stability and flexibility. The time period for dissolution using water was also less than 45 minutes.

[0086] When the content of polycaprolactone was reduced (Nos. 6 through 8), the filament diameter stability and the time period for immersion in water did not get worse, in fact, the time period tended to be shortened. However, even with polycaprolactone having a number average molecular weight of 20000 to 70000, the flexibility of filaments was impaired when the blending amount was small (Nos. 6 through 8).

[0087] When the polycaprolactone content was high (Nos. 12 and 13), the filament diameter stability and flexibility were not recognized to be lowered. However, even with polycaprolactone having a number average molecular weight of 20000 to 70000, the increase in the amount of the caprolactone impaired the water solubility.

INDUSTRIAL APPLICABILITY

[0088] The support material of the present invention may be provided in the form of long filament of filamentous support material with excellent dimensional accuracy and flexibility. Furthermore, since the support material can be removed by washing with use of water after the fused deposition modeling, the productivity of the intended three-dimensional object is excellent. Moreover, the generated waste liquid is a biodegradable aqueous solution, so that the waste liquid treatment is simple. Accordingly, the support material is useful.