WO2018012539A1

WO2018012539A1 - Three-dimensional molding method and molding material for use with same

Info

Publication number: WO2018012539A1
Application number: PCT/JP2017/025418
Authority: WO
Inventors: 雄俊中谷
Original assignee: ユニチカ株式会社; 雄俊中谷; 金築亮; 本多真理子
Priority date: 2016-07-15
Filing date: 2017-07-12
Publication date: 2018-01-18
Also published as: JP6758666B2; JPWO2018012539A1

Abstract

[Problem] To provide a three-dimensional molding method that allows for the shape of a molded article to be easily altered, and allows for the molded article to be imparted with high strength or rigidity following such alteration. [Solution] In this three-dimensional molding method, a molded article having a three-dimensional shape is produced by melting and layering lines of a material containing primarily a thermoplastic resin. When doing so, a polyester copolymer comprising terephthalic acid as an acid component, and ethylene glycol and 1,4-butanediol as diol components, is used as the thermoplastic resin. Alternatively, a polyester copolymer comprising terephthalic acid and ε-caprolactone as acid components, and ethylene glycol and 1,4-butanediol as diol components, is used. The polyester copolymer has a melting point of 130–200°C, a glass transition temperature of 30–50°C, and a crystallization temperature that is no more than 120°C, but is at least 20°C higher than the glass transition temperature.

Description

Three-dimensional molding method and molding material used therefor

The present invention relates to a three-dimensional molding method for obtaining a molded product with a 3D printer or a 3D pen, and particularly to a three-dimensional molding method for easily changing the shape of the molded product and a molding material used therefor.

In recent years, a three-dimensional molding method for obtaining a three-dimensional molded article based on data such as 3D CAD and 3DCG (three-dimensional computer graphics) has been rapidly spread. In particular, 3D printers that employ a hot melt lamination method (FDM method) using a thermoplastic resin as a molding material are also sold at low cost and are also popular in the home.

High-strength, high-rigidity or heat-resistant resins such as ABS resin, polycarbonate resin or polylactic acid resin are mainly used as the thermoplastic resin used in the hot melt lamination method (Patent Document 1, Claim 11). When the molded product obtained by the three-dimensional molding method is not in the desired shape, it is necessary to change the shape, but if the thermoplastic resin is high strength or high rigidity, it is possible to change the shape at home It was difficult.

Japanese Patent Laying-Open No. 2015-221568

An object of the present invention is to provide a three-dimensional molding method capable of easily changing the shape of a molded article and making the molded article high strength or high rigidity after the change.

The present invention solves the above problems by adopting a specific molding material. That is, the present invention relates to a three-dimensional molding method for creating a three-dimensional shape by melting and laminating filaments mainly composed of a thermoplastic resin, wherein the thermoplastic resin contains terephthalic acid as an acid component, Polyester copolymer containing ethylene glycol and 1,4-butanediol as components (hereinafter referred to as “polyester copolymer A”), or terephthalic acid and ε-caprolactone as acid components, and ethylene glycol and diol components as diol components The present invention relates to a three-dimensional molding method characterized by being a polyester copolymer containing 1,4-butanediol (hereinafter referred to as “polyester copolymer B”). Although ε-caprolactone is a cyclic ester, for the sake of convenience, it is assumed that it belongs to the acid component in this specification.

The molding material used in the present invention is a filamentous material mainly composed of a polyester copolymer A containing terephthalic acid as an acid component and ethylene glycol and 1,4-butanediol as a diol component. Further, it is composed of a linear article mainly composed of a polyester copolymer B containing terephthalic acid and ε-caprolactone as acid components and ethylene glycol and 1,4-butanediol as diol components. Furthermore, it is good also considering the mixture of the polyester copolymers A and B as a main body. The mixing ratio of the polyester copolymer A and the polyester copolymer B is arbitrary. For example, the polyester copolymer A: polyester copolymer B = 1 may be about 0.1 to 10 (mass ratio), preferably Polyester copolymer A: Polyester copolymer B = 1: about 0.5 to 2. Further, a core-sheath type filament having polyester copolymer A as a core component and polyester copolymer B as a sheath component, or conversely, a core having polyester copolymer B as a core component and polyester copolymer A as a sheath component. It may be a sheath type filament.

Polyester copolymers A and B can be produced by a known polycondensation method, and generally can be produced by adding 50 mol% of an acid component and 50 mol% of a diol component and dehydrating and condensing them. What is characteristic of the present invention is that terephthalic acid (with ε-caprolactone if necessary) is used as the acid component, and ethylene glycol and 1,4-butanediol are used as the diol component. Each of these components is used for adjusting the glass transition temperature and the crystallization temperature.

The 1,4-butanediol used in combination with ethylene glycol as the diol component is preferably 30 to 70 mol% in the diol component. When 1,4-butanediol is less than 30 mol% or exceeds 70 mol%, the glass transition temperatures of the polyester copolymers A and B tend to be difficult to decrease. The ε-caprolactone used in combination with terephthalic acid as the acid component is preferably 5 to 20 mol% in the acid component. When ε-caprolactone is used as a copolymerization component, the glass transition temperature of the polyester copolymer B can be further reduced. When ε-caprolactone exceeds 20 mol%, the polyester copolymer B tends to be difficult to crystallize at a predetermined temperature.

The filaments mainly composed of the polyester copolymer A and / or B are continuous filaments having a diameter of about 1 to 3 mm. The filaments are wound around several tens to several hundreds of meters and attached to a 3D printer. It is done. As the filament, a monofilament yarn or a multifilament yarn obtained by arranging a plurality of monofilament yarns is used. When using multifilament yarns, it is preferable in handling that the monofilament yarns are not easily separated by fusing each monofilament yarn after being aligned or twisted. Moreover, as a filament, after monofilament yarn or multifilament yarn is braided with a braiding machine (string making machine) to form a braid, each monofilament yarn is preferably fused. A braid is excellent in handling because it has excellent mechanical properties such as breaking strength and bending strength. Furthermore, it is not limited to the above-described ones, and any material that is a filament can be used as a filament.

In addition to the polyester copolymers A and / or B, other polymers may be added to the filament in order to adjust the strength of the molded product, the shape change of the molded product, and the like. For example, polyacetal resin, polyolefin resin, acrylic resin, vinyl acetate resin, polyester resin, polyamide resin, vinyl chloride resin, vinylidene chloride resin, polytetrafluoroethylene resin, silicone resin or polyurethane resin May be added alone or in admixture. These other polymers may be added to the inside of the filament, or may be added in a state of covering the surface of the filament. The amount of other polymer added is about 1 to 30% by mass. When there is too much addition amount of another polymer, the shape change by the low heating which is the characteristic of the polyester copolymer A and / or B will become difficult.

In addition, various additives may be contained in the filament as desired. For example, a dye or pigment may be added to the filament to obtain a color molding. In particular, in the present invention, if a thermochromic pigment that changes color at the glass transition temperature and the crystallization temperature is added to the filament, it can be determined whether the molded product is deformable or whether the molded product is crystallized, It is preferable. Furthermore, fillers, plasticizers, flame retardants, lubricants, weathering agents, antioxidants, heat-resistant agents, and the like can be added. The additive amount is about 0.01 to 5% by mass.

The monofilament yarn constituting the filament can be obtained by melting a raw material mainly composed of polyester copolymer A and / or B and extruding it from a spinning nozzle. In particular, in the present invention, it is preferable to obtain a monofilament yarn by the following method. That is, it is preferable that the raw material is spun by a melt spinning method and then stretched to crystallize the polyester copolymer A and / or B to obtain a monofilament yarn. It is also preferred to obtain a monofilament yarn by spinning by melt spinning and then heat treating to crystallize the polyester copolymer A and / or B. In addition, it is good to perform the temperature at the time of heat processing in the temperature range mentioned later at which crystallization of the polyester copolymer A and / or B advances. Since the monofilament yarn obtained by such a method has the polyester copolymer A and / or B crystallized, the filaments composed of this monofilament yarn are not easily broken or deformed. Is preferable.

¡Linear items attached to a 3D printer are fed into an extruder by a feeder. The extruder includes an extrusion nozzle and a heating device that heats the extrusion nozzle. The filament is melted in the heating device and discharged from the extrusion nozzle. The extruder moves based on the data, and the discharged melt is laminated to obtain a three-dimensional shaped molding. When laminating the melt, it may be heated or cooled as necessary, but laminating at room temperature is sufficient. Also in the case of heating, it is preferable that the crystallization is not promoted. Moreover, when cooling, since there is little possibility that a molded article will crystallize, it may carry out arbitrarily. In addition to the filament used in the present invention, a conventionally known filament may be attached to the 3D printer to obtain a molded article. And you may shape only the specific site | part of a molded article with the filament used by this invention. Moreover, in this case, in order to improve the adhesiveness between the part molded with the filamentous material used in the present invention and the part molded with the conventionally known filamentous material, the filamentous material used in the present invention or molded Various processing such as plasma processing may be performed on the part. Furthermore, while obtaining a molding mainly composed of conventionally known filaments, the support material may be molded by the filaments used in the present invention. In the case where the support material is molded with the filamentous material used in the present invention, the support material is easily deformed by heating, and can be easily removed from the main molded object. Moreover, if it is in the state softened by heating, it is also possible to easily remove the support material with a tool such as a cutter, nipper, engraving knife, scissors, or cutting tools.

The polyester copolymer A and / or B used in the present invention has a melting point of 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 130 to 200 ° C. The glass transition temperature is 50 ° C. or less, preferably 30 to 50 ° C. Furthermore, the crystallization temperature is 120 ° C. or lower, preferably 20 ° C. or higher than the glass transition temperature. The crystallization temperature is a temperature at which crystallization of the polyester copolymer A and / or B is most accelerated. The obtained molded product is in a state of having a lot of amorphous regions without being promoted for crystallization unless it is heat-treated near the crystallization temperature during melt lamination. For this reason, when the molding is heated to a temperature higher than the glass transition temperature, the shape can be easily changed. For example, when the glass transition temperature is about 30 to 50 ° C., the shape can be easily changed by immersing in bath water or holding it with fingers. And after shape change, when it heat-processes at crystallization temperature, crystallization will advance and it can be set as a highly strong or highly rigid molded article. For example, if the crystallization temperature is about 100 ° C., crystallization proceeds and a molded article with high strength or high rigidity is obtained when immersed in boiling water. In addition, when it cools to about room temperature, without performing heat processing after shape change, although crystallization has not progressed, it becomes a molded article fixed in the state which changed shape. When the molded product is heated to a temperature higher than the glass transition temperature, the shape can be changed again.

When the three-dimensional molding method according to the present invention is adopted, the shape of the molded product obtained by melt lamination can be changed by heating, and the molded product can be made to have high strength or high rigidity by heat treatment after the change. There is an effect that can be done. In particular, the shape can be changed at about 30 to 50 ° C., and the heat treatment can be performed at about 100 ° C., so that the shape of the molded product can be easily changed at home, and the molded product can be easily made with high strength or high strength at home. There is an effect that it can be made rigid.

Example 1
Polyester copolymer A was obtained by copolymerizing 50 mol% terephthalic acid, 25 mol% ethylene glycol and 25 mol% 1,4-butanediol by dehydration condensation. This polyester copolymer A had a melting point of 180 ° C., a glass transition temperature of 45 ° C., a crystallization temperature of 110 ° C., and a specific gravity of 1.38. This polyester copolymer A was melt-spun with an extruder-type spinning machine and drawn to obtain a filament made of monofilament yarn having a diameter of 1.75 mm.

Example 2
Polyester copolymer B was obtained by copolymerizing 43 mol% terephthalic acid, 7 mol% ε-caprolactone, 25 mol% ethylene glycol and 25 mol% 1,4-butanediol by dehydration condensation. This polyester copolymer B had a melting point of 160 ° C., a glass transition temperature of 30 ° C., a crystallization temperature of 75 ° C., and a specific gravity of 1.38. This polyester copolymer B was melt-spun with an extruder-type spinning machine and drawn to obtain a filament made of monofilament yarn having a diameter of 1.75 mm.

Example 3
Polyester copolymer A of Example 1 was melt-spun with an extruder-type spinning machine to obtain a monofilament yarn without stretching. Then, this monofilament yarn was introduced into a hot air dryer, heat-treated at 110 ° C. for 5 minutes under no load, and air-cooled to obtain a filament made of monofilament yarn having a diameter of 1.75 mm.

Example 4
Polyester copolymer B of Example 2 was melt-spun with an extruder-type spinning machine to obtain a monofilament yarn without stretching. Then, this monofilament yarn was introduced into a hot air dryer, subjected to heat treatment at 75 ° C. for 5 minutes under no load, and air-cooled to obtain a filament made of monofilament yarn having a diameter of 1.75 mm.

Example 5
Polyester copolymer A of Example 1 was melt-spun with an extruder-type spinning machine and drawn to obtain a 430 dtex monofilament yarn. A braid was obtained by braiding the monofilament yarn with 21 multifilament yarns as the core yarn, and the multifilament yarn with 2 filaments as the side yarns, and braiding with an eight-square punching machine (braiding machine). The obtained braid was subjected to heat treatment at 170 ° C. for 2 minutes to obtain a line product made of a braid having a diameter of 1.75 mm.

Example 6
In the same manner as in Example 5, except that the polyester copolymer B of Example 2 was used and the heat treatment was performed at 150 ° C. for 2 minutes, a filament made of braid having a diameter of 1.75 mm was formed. Obtained.

Example 7
A mixture in which 50% by mass of the polyester copolymer A of Example 1 and 50% by mass of the polyester copolymer B of Example 2 were uniformly mixed was obtained. This mixture was melt-spun with an extruder-type spinning machine and stretched to obtain a filament made of monofilament yarn having a diameter of 1.75 mm.

Example 8
A mixture obtained by uniformly mixing 95% by mass of the polyester copolymer A of Example 1 and 5% by mass of a polyolefin resin (trade name “engage 8200” manufactured by Dow Chemical Co., Ltd.) was obtained. This mixture was melt-spun with an extruder-type spinning machine and stretched to obtain a filament made of monofilament yarn having a diameter of 1.75 mm.

Example 9
A mixture in which 90% by mass of the polyester copolymer B of Example 2 and 10% by mass of a polyester resin (trade name “Elitel UE-3210” manufactured by Unitika Co., Ltd.) were uniformly mixed was obtained. This mixture was melt-spun with an extruder-type spinning machine and stretched to obtain a filament made of monofilament yarn having a diameter of 1.75 mm.

Comparative Example 1
Polylactic acid having a melting point of 165 ° C., a glass transition temperature of 60 ° C., a crystallization temperature of 110 ° C. and a specific gravity of 1.24 is melt-spun with an extruder-type spinning machine, drawn, and made of a monofilament yarn having a diameter of 1.75 mm. Obtained a line item.

Using the filaments obtained in Examples 1 to 9 and Comparative Example 1, 10 types of moldings consisting of a rectangular parallelepiped having a length of 80 mm, a width of 10 mm, and a thickness of 2 mm using a 3D printer (Davinci Pro) manufactured by XYZ printing I got a thing. The sag test of these moldings was performed by the following method. That is, as shown in FIG. 1, the molded product was placed with a double-sided tape on the stand (portion shown in dark ink in FIG. 1), fixed with double-sided tape, and extended 60 mm from the stand. The state was left for 5 minutes. This was performed at 25 ° C. and 50 ° C., and it was measured how many mm (the sag length) the overhanging edge of the molded article sagged from the initial state. The results are shown in Table 1.

[Table 1]
━━━━━━━━━━━━━━━━━━━
Sagging length (mm)
━━━━━━━━━━━━━
25 ° C 50 ° C
━━━━━━━━━━━━━━━━━━━
Example 1 0 21
Example 2 1 32
Example 3 0 23
Example 4 1 31
Example 5 0 22
Example 6 1 33
Example 7 1 25
Example 8 0 11
Example 9 1 33
Comparative Example 1 0 2
━━━━━━━━━━━━━━━━━━━

As can be seen from the results in Table 1, the molded products obtained by the methods according to Examples 1 to 9 become soft enough to change the shape when heated to 50 ° C., which is higher than the glass transition temperature. On the other hand, since the molded product obtained by the method according to Comparative Example 1 has a glass transition temperature of polylactic acid of 60 ° C., heating at 50 ° C. does not become soft enough to change the shape. In addition, if it heats above 60 degreeC, the molded article obtained by the method which concerns on the comparative example 1 will also become soft, and a shape change is possible, but if it heats at 60 degreeC or more at home, there exists a danger of a burn. Therefore, it is not preferable.

Next, 10 types of molded articles made of the obtained rectangular parallelepiped were each left to heat treatment at a predetermined temperature for 5 minutes. That is, the molded product obtained by the method according to Examples 1, 3, 5 and 8 was 110 ° C., and the molded product obtained by the method according to Examples 2, 4, 6 and 9 was 70 ° C. The molded product obtained by the method according to Example 7 was heat-treated at 100 ° C., and the molded product obtained by the method according to Comparative Example 1 was heat-treated at 110 ° C. Then, the sag length was measured by the method described above. The results are shown in Table 2.

[Table 2]
━━━━━━━━━━━━━━━━━━━
Sagging length (mm)
━━━━━━━━━━━━━
25 ° C 50 ° C
━━━━━━━━━━━━━━━━━━━
Example 1 0 0
Example 2 0 0
Example 3 0 0
Example 4 0 0
Example 5 0 0
Example 6 0 0
Example 7 0 0
Example 8 0 0
Example 9 0 0
Comparative Example 1 0 0
━━━━━━━━━━━━━━━━━━━

As can be seen from the results in Table 2, the moldings obtained by the methods according to Examples 1 to 9 become soft when heated to the glass transition temperature before the heat treatment, but are heated to the glass transition temperature after the heat treatment. As can be seen from FIG.

It is the side view which showed the protrusion state from the stand of the molded article at the time of measuring drooping length.

Claims

In the three-dimensional molding method of creating a three-dimensional shape by melting and laminating the filaments mainly composed of thermoplastic resin,
A three-dimensional molding method, wherein the thermoplastic resin is a polyester copolymer containing terephthalic acid as an acid component and ethylene glycol and 1,4-butanediol as a diol component.
In the three-dimensional molding method of creating a three-dimensional shape by melting and laminating the filaments mainly composed of thermoplastic resin,
3. A three-dimensional molding method, wherein the thermoplastic resin is a polyester copolymer containing terephthalic acid and ε-caprolactone as acid components and ethylene glycol and 1,4-butanediol as diol components.
The three-dimensional molding method according to claim 1 or 2, wherein 1,4-butanediol is present in an amount of 30 to 70 mol% in the diol component.
The three-dimensional molding method according to claim 2, wherein 5 to 20 mol% of ε-caprolactone is present in the acid component.
The three-dimensional molding according to any one of claims 1 to 4, wherein the filament is a monofilament yarn, a multifilament yarn obtained by aligning a plurality of monofilament yarns, a braided cord obtained by braiding a monofilament yarn or a multifilament yarn. Law.
The melting point of the thermoplastic resin is 200 ° C or lower, the glass transition temperature is 50 ° C or lower, the crystallization temperature is 120 ° C or lower, and the crystallization temperature is 20 ° C or higher than the glass transition temperature. The three-dimensional molding method according to any one of 5.
A three-dimensional molded product obtained by melting and laminating the filaments is heated to a temperature of 50 ° C. or lower, and then subjected to a heat treatment at a temperature of 70 ° C. to 120 ° C. The three-dimensional molding method according to any one of claims 1 to 6, which promotes crystallization of a polymer.
A molding material used in a three-dimensional molding method comprising a linear article mainly composed of a polyester copolymer containing terephthalic acid as an acid component and ethylene glycol and 1,4-butanediol as a diol component.
A molding material used in a three-dimensional molding method comprising a filament mainly composed of a polyester copolymer containing terephthalic acid and ε-caprolactone as acid components and ethylene glycol and 1,4-butanediol as diol components.