JP6982967B2 - Filament for 3D printer modeling - Google Patents

Description

The present invention relates to a filament for modeling a three-dimensional printer and a model formed using the filament.

Conventionally, thermoplastic resins such as acrylonitrile / butadiene / styrene copolymer (ABS resin) and polylactic acid (PLA resin) have been proposed as a molding material of a heat-melting lamination method from the viewpoint of fluidity and molding property (PLA resin). See Patent Documents 1 and 2).

However, in the case of ABS resin, there is a problem that a pungent odor is generated at the time of molding, and in the case of PLA resin, the odor at the time of molding is relatively less than that of ABS resin, but the sweet odor peculiar to the resin is still generated. Further, the PLA resin has a hydrolyzable property, and when the resin itself absorbs moisture, the toughness of the filament is lowered and there is a problem that the filament is easily broken, which may make modeling difficult. Further, since ABS resin and PLA resin are high specific gravity and hard materials, the characteristics of the obtained shaped products are limited, and there is a problem that it is difficult to meet the needs for weight reduction and soft shaped products, for example. be.

Japanese Patent No. 5911564 Japanese Unexamined Patent Publication No. 2016-215502

An object of the present invention is to provide a filament for modeling a three-dimensional printer, which has a small odor during modeling, a very small decrease in toughness due to hydrolysis, and can produce a lightweight and flexible modeled product.

When polypropylene is used, a material that has less odor during molding and does not hydrolyze can be expected, but there is a problem that the molding shrinkage rate is large and the accuracy of the shape and dimensions of the obtained molded product is low. Therefore, it is also an object of the present invention to provide a filament for modeling a three-dimensional printer, which is made of a material having a small molding shrinkage rate and high accuracy in the shape and dimensions of the obtained modeled product, and has excellent formability.

The filament for modeling a three-dimensional printer of the present invention contains a structural unit derived from propylene and a structural unit derived from an α-olefin having 2 to 20 carbon atoms other than propylene, and has the following requirements (a), ( It is characterized by comprising a propylene-based resin composition containing a propylene-based copolymer satisfying b), (c) and (d).
(A) The ultimate viscosity [η] measured in decalin at 135 ° C. is in the range of 0.1 to 5.0 dl / g.
(B) The ratio (molecular weight distribution; Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is in the range of 1.0 to 3.5. It is in.
(C) The melting point (Tm) measured by differential scanning calorimetry (DSC) is 100 ° C. or higher and lower than 165 ° C., or is substantially not observed.
(D) The density measured by the density gradient tube method according to JIS K7112 (1999) is in the range of ^{810 to 880 kg / m 3.}

According to the present invention, by using a specific propylene-based resin composition, a three-dimensional printer capable of producing a lightweight and flexible modeled product having less odor during modeling, extremely small decrease in toughness of the filament due to hydrolysis, and so on. A molding filament can be provided. Further, according to the present invention, by using a specific propylene-based resin composition, it is possible to provide a filament for modeling a three-dimensional printer having excellent formability.

Hereinafter, the present invention will be described in detail.
The three-dimensional printer modeling filament (hereinafter, also simply referred to as “filament”) according to the present invention contains a structural unit derived from propylene and a structural unit derived from an α-olefin having 2 to 20 carbon atoms other than propylene. Moreover, it is characterized by comprising a propylene-based resin composition containing a propylene-based copolymer satisfying the following requirements (a), (b), (c) and (d).

(A) The ultimate viscosity [η] measured in decalin at 135 ° C. is 0.1 to 5.0 dl / g, preferably 0.5 to 4.0 dl / g, more preferably 1.0 to 3.0 dl. It is in the range of / g. When the ultimate viscosity [η] is within the above range, the stickiness of the modeled product is reduced because the number of low molecular weight substances is small, and it is advantageous in terms of moldability and formability.

(B) The ratio (molecular weight distribution; Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is preferably 1.0 to 3.5. Is in the range of 1.3 to 3.0, more preferably 1.6 to 2.8. When the molecular weight distribution is within the above range, the appearance of the modeled object is excellent.

(C) The melting point (Tm) measured by differential scanning calorimetry (DSC) is 100 ° C. or higher and lower than 165 ° C., or is substantially not observed. When the melting point (Tm) is the above-mentioned condition, it is possible to form at high speed and the formability is excellent.

(D) The density measured by the density gradient tube method according to JIS K7112 (1999) is in the range of 810 to 880 kg / m ³ , preferably 820 to 878 kg / m ³ , more preferably 830 to 876 kg / m ³ . be. When the density is within the above range, a lightweight and flexible modeled product can be obtained.

[Propene-based resin composition]
The propylene-based resin composition used in the present invention contains a propylene-based polymer that satisfies the above requirements (a), (b), (c) and (d).

<Propene-based copolymer>
The propylene-based polymer used in the present invention contains a structural unit derived from propylene and a structural unit derived from an α-olefin having 2 to 20 carbon atoms other than propylene, and the above requirements (a), ( b), (c) and (d) are satisfied. By using such a propylene-based polymer, it is possible to produce a lightweight and flexible molded product having less odor during molding and extremely small decrease in toughness due to hydrolysis. Further, by using such a propylene-based polymer, it is made of a material having a small molding shrinkage rate and high accuracy in the shape and dimensions of the obtained modeled product, and is excellent in formability.

Examples of α-olefins having 2 to 20 carbon atoms other than propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and 1-dodecene. , 1-Tetradecene, 1-Hexadecene, 1-Octene, 1-Eikocene and the like, and ethylene or α-olefin having 4 to 10 carbon atoms is preferable.

Specific examples of the propylene-based copolymer include a propylene / ethylene copolymer, a propylene / 1-butene / ethylene copolymer, a 1-butene / propylene copolymer, and a 4-methyl-1-pentene / propylene copolymer. Examples thereof include a coalescence, a 4-methyl-1-pentene / propylene / 1-butene copolymer, a propylene / 1-butene copolymer, and the like.

Commercially available products of the propylene-based copolymer include, for example, Tuffmer (manufactured by Mitsui Chemicals, Inc.), Vistamax TM (manufactured by ExxonMobile Chemical Company), Versify TM (manufactured by The Dow Chemical Company), and the like. Examples thereof include propylene-based copolymers on the market.

The propylene-based polymer may be used alone or in combination of two or more.
Preferred embodiments of the propylene-based polymer include (A) a propylene-based elastomer (propylene / 1-butene / ethylene copolymer) and (B) a 4-methyl-1-pentene / propylene copolymer.

≪Propene-based elastomer (A) ≫
The propylene-based elastomer (A) (hereinafter, also simply referred to as “elastomer (A)”) contains 50 to 85 mol% of structural units derived from propylene and 5 to 25 mol% of structural units derived from 1-butene. It contains 5 to 25 mol% of units derived from ethylene (provided that the total of the constituent units derived from propylene, 1-butene and ethylene is 100 mol%), and the propylene content / ethylene content (molar ratio) is high. It is 90/10 to 70/30, and the glass transition temperature (Tg) is in the range of -15 to -40 ° C.

In the elastomer (A), the content of the structural unit derived from propylene is preferably 60 to 85 mol%, more preferably 65 to 80 mol%.
The content of the building blocks derived from 1-butene is preferably 5 to 22 mol%, more preferably 6 to 18 mol%.
The content of the unit derived from ethylene is preferably 6 to 23 mol%, more preferably 8 to 20 mol%.
The propylene content / ethylene content (molar ratio) is preferably 90/10 to 75/25, and more preferably 90/10 to 80/20. Such a propylene-based elastomer (A) is excellent in transparency and flexibility.

The glass transition temperature (Tg) of the elastomer (A) is preferably in the range of -20 to −35 ° C.
The intrinsic viscosity [η] of the elastomer (A) measured in decalin at 135 ° C. is 0.1 to 5.0 dl / g, preferably 0.5 to 4.0 dl / g, more preferably 1.0. It is in the range of ~ 3.0 dl / g.

The molecular weight distribution (Mw / Mn) obtained by gel permeation chromatography (GPC) of the elastomer (A) is 1.0 to 3.5, preferably 1.3 to 3.2, and more preferably 1. It is in the range of 6 to 3.0.

The melting point (Tm) observed by differential scanning calorimetry (DSC) of the elastomer (A) is 100 ° C. or higher and lower than 120 ° C. or not observed. In addition, "no melting point (Tm) is observed" means that a crystal melting peak having a heat of crystal melting of 1 J / g or more is not observed in the range of −150 ° C. to 200 ° C.

The density of the elastomer (A) measured by the density gradient tube method according to JIS K7112 (1999) is 810 to 880 kg / m ³ , preferably 830 to 878 kg / m ³ , and more preferably 850 to 876 kg / m ^3. Is in the range of.

The elastomer (A) is a transition metal compound (1a) represented by the following general formula (1a) and
With the organoaluminum oxy compound (1b) and / or the compound (2b) that reacts with the transition metal compound (1a) to form an ion pair.
It can be produced by copolymerizing propylene, ethylene and 1-butene in the presence of an olefin polymerization catalyst containing an organoaluminum compound (c), if desired.

式中、Ｒ³は炭化水素基またはケイ素含有基であり、
Ｒ¹、Ｒ²、Ｒ⁴は、水素、炭化水素基またはケイ素含有基であり、それぞれ同一でも異なっていてもよく、
Ｒ⁵〜Ｒ¹⁴は、水素、炭化水素基またはケイ素含有基であり、それぞれ同一でも異なっていてもよく、Ｒ⁵〜Ｒ¹²の隣接した置換基は互いに結合して環を形成してもよく、Ｒ¹³とＲ¹⁴は、互いに結合して環を形成してもよく、
Ｍは第４族遷移金属であり、Ｙは炭素原子であり、Ｑはハロゲン、炭化水素基、アニオン配位子または孤立電子対で配位可能な中性配位子から同一または異なる組合せで選んでもよく、ｊは１〜４の整数である。前記Ｒ¹は、炭化水素基またはケイ素含有基であることが好ましい。

In the formula, R ³ is a hydrocarbon group or a silicon-containing group.
R ¹ , R ² , and R ⁴ are hydrogen, hydrocarbon groups, or silicon-containing groups, which may be the same or different.
R ^{5 to} R ¹⁴ are hydrogen, hydrocarbon groups or silicon-containing groups, which may be the same or different, and ^{adjacent substituents of R 5 to} R ¹² may be bonded to each other to form a ring. , R ¹³ and R ¹⁴ may combine with each other to form a ring.
M is a Group 4 transition metal, Y is a carbon atom, and Q is selected from halogens, hydrocarbon groups, anionic ligands or neutral ligands that can be coordinated with lone electron pairs in the same or different combinations. However, j is an integer of 1 to 4. The R ¹ is preferably a hydrocarbon group or a silicon-containing group.

The transition metal compound (1a), the organoaluminum oxy compound (1b), the compound (2b) that reacts with the transition metal compound (1a) to form an ion pair, the organoaluminum compound (c), and the propylene-based compound. Details of the method for producing the elastomer (A) are as described in, for example, Japanese Patent Application Laid-Open No. 2010-163626.

<< 4-Methyl-1-pentene-propylene copolymer (B) >>
The 4-methyl-1-pentene-propylene copolymer (B) (hereinafter, also simply referred to as "copolymer (B)") is a constituent unit derived from 4-methyl-1-pentene in an amount of 15 to 90 mol%. And 10-85 mol% of the constituent units derived from propylene (provided that the total of the constituent units derived from 4-methyl-1-pentene and propylene is 100 mol%), and the glass transition temperature (Tg). ) Is in the range of 10 to 45 ° C.

In the copolymer (B), the structural unit derived from 4-methyl-1-pentene is preferably 40 to 88 mol%, more preferably 60 to 86 mol%, and the structural unit derived from propylene is preferable. Is 12 to 60 mol%, more preferably 14 to 40 mol%. When the composition of the copolymer (B) is in the above range, a molded product having good mechanical properties can be obtained.

The glass transition temperature (Tg) of the copolymer (B) is preferably 15 to 43 ° C, more preferably 20 to 40 ° C.
The ultimate viscosity [η] of the copolymer (B) measured in decalin at 135 ° C. is 0.1 to 5.0 dl / g, preferably 0.5 to 4.0 dl / g, more preferably 0. It is in the range of 8.8 to 2.8 dl / g.

The molecular weight distribution (Mw / Mn) obtained by gel permeation chromatography (GPC) of the copolymer (B) is 1.0 to 3.5, preferably 1.3 to 3.0, more preferably. It is in the range of 1.5 to 2.8.

The melting point (Tm) observed by differential scanning calorimetry (DSC) of the copolymer (B) is 100 ° C. or higher and lower than 165 ° C. or not observed.
The density of the copolymer (B) measured by the density gradient tube method according to JIS K7112 (1999) is 810 to 880 kg / m ³ , preferably 820 to 870 kg / m ³ , more preferably 830 to 850 kg / m 3. It is in the range of m ^3.

The copolymer (B) may be polymerized using a polymerization catalyst. Examples of the polymerization catalyst that can be used in the present invention include conventionally known catalysts such as magnesium-supported titanium catalysts, International Publication No. 01/53369, International Publication No. 01/27124, and JP-A-3-193996. , Or the metallocene catalyst described in JP-A-02-41303 is suitable. As the method for producing the copolymer (B), for example, the methods described in International Publication No. 01/27124, International Publication No. 14/050817, and the like can be adopted.

<Other ingredients>
In the propylene-based resin composition, if necessary, a softener, a heat-resistant stabilizer, an anti-aging agent, a weather-resistant stabilizer, an antistatic agent, a filler, a colorant, etc. Additives such as lubricants can be added.

[Filament for 3D printer modeling]
The filament for modeling a three-dimensional printer of the present invention is produced by melt-spinning the propylene-based resin composition and further stretching it. A known melt spinning method can be adopted for melt spinning. The same applies to stretching.

As a method for producing a filament of the present invention, for example, an extrusion step of extruding a molten strand from a die hole of a single-screw extruder or a twin-screw extruder and guiding the propylene-based resin composition to a cooling water tank to obtain the strand. Examples thereof include a drawing step of stretching the strand and a winding step of winding the stretched filament.

Extrusion is performed at a temperature in the range of melting point (Tm) to melting point (Tm) + 130 ° C. of the propylene resin composition, and the molten strand discharged from the die is immersed in a water tank to be cooled. The water temperature is preferably in the range of 5 to 60 ° C, more preferably 7 to 50 ° C, and even more preferably 10 to 40 ° C, although it depends on the diameter of the target filament. If the water temperature is high, the strands will be insufficiently cooled and will be introduced into the next stretching process while remaining soft, which may cause poor winding on the take-up roll (stretching roll).

Stretching in the present invention refers to an operation in which a filament is mechanically stretched at a temperature equal to or lower than the melting point of a material to orient the molecular chain in parallel with the tensile direction. This operation significantly improves tensile strength and increases toughness. After the stretching step, if it is reheated above the stretching temperature, it tends to shrink to its original dimensions. Therefore, in order to stabilize the dimensions and strength, heat treatment (heat fixing, heat setting) is performed at a temperature slightly lower than the stretching temperature. ) May be done.

In the present invention, the strands obtained in the extrusion step are heated to a specific temperature for stretching. Stretching is performed by the speed ratio (stretching ratio) of the take-up roll on the inlet side and the take-up roll on the outlet side, and the draw ratio at this time is preferably 2 to 15 times. The heating method at the time of stretching may be any of a hot water tank, an oven, a hot roll and the like, and there is no limitation, but a hot water tank is more preferable for more uniform heating and stretching.

Stretching using a hot water tank can be realized by arranging a water tank having a length and depth that can adjust the water temperature and a take-up roll before and after the water tank. Stretching using an oven can be realized by arranging an electric heater (infrared heater) as a heat source in the take-up direction to control the temperature, and arranging a take-up roll in front of and behind it. .. In addition, stretching using a thermal roll is realized by installing multiple take-up rolls whose temperature is controlled by water pipes, oil pipes, and an electric heater placed inside, and adjusting the rotation speed of the rolls. It is possible.

The temperature conditions during stretching are almost the same regardless of which device and method are selected, such as a hot water tank, an oven, and a thermal roll, and the surface temperature of the filament before stretching is the glass transition temperature of the olefin-based thermoplastic elastomer composition. The range from (Tg) to melting point (Tm) is preferable, the range from Tg to Tm-30 ° C is more preferable, and the range from Tg to Tm-60 ° C is even more preferable. If the surface temperature is less than Tg, stretch breakage may occur or stretching more than twice may not be possible. On the contrary, when it exceeds Tm, the effect of strength development by stretching is reduced.

The draw ratio is usually 2 to 15 times, preferably 3 to 12 times, and more preferably 4 to 10 times. If the stretching ratio is less than 2 times, the strength development by the stretching operation may be insufficient. On the other hand, if the draw ratio exceeds 15 times, problems such as stretch breakage, voids and whitening, and filaments tending to crack in the vertical direction may occur.

As a method of stretching 2 to 15 times, in addition to the method of stretching in one step, these are appropriately combined to form a two-step, three-step to multi-step structure, and stretching is performed at a small magnification in each step, and the whole is stretched. A method of setting the draw ratio to 2 to 15 times may also be used.

In the case of multi-stage stretching, the stretching ratio is sequentially changed, for example, 1.1 to 10 times in the first stage and 1.5 to 12 times in the second stage, and the overall stretching ratio is 2. It is preferable that the temperature is increased to about 15 times, and at the same time, the heating temperature condition is the lowest in the first stage in the above temperature range, and the temperature is gradually increased as the number of stages is increased.

In the present invention, the stretched filament can be further heat-treated (heat-fixed) to suppress changes in physical properties (for example, shrinkage) at high temperatures. As a method of heat-treating the olefin-based thermoplastic elastomer composition at a temperature between the glass transition temperature (Tg) and the melting point (Tm), a heating tank set to preferably 20 to 140 ° C., more preferably 30 to 120 ° C. Examples thereof include a method of guiding, performing heat treatment (heat fixing), and then cooling in a cooling tank. As in the case of the stretching operation, any method such as a water tank, an oven, or a heat roll may be used for the heat treatment, and there is no limitation. Further, the cooling may be either water cooling or air cooling, and there is no limitation.
Finally, the stretched filament can be wound up in the form of a dedicated cartridge, bobbin and cone by a winder to obtain a wound filament.

The diameter of the filament for 3D printer modeling of the present invention depends on the design specifications of the fused deposition modeling method and the system capability used for modeling, but is usually 1.0 mm or more, preferably 1.5 mm or more, more preferably 1.5 mm or more. It is 1.6 mm or more. On the other hand, the upper limit is 4.0 mm or less, preferably 3.5 mm or less, and more preferably 3.0 mm or less.

The roundness of the filament for modeling a three-dimensional printer of the present invention is 0.93 or more, preferably 0.95 or more, and the upper limit is 1.0. The roundness in the present invention is measured by the method described in Examples described later.
Since the filament having the diameter and roundness as described above is excellent in formability, it is possible to stably produce a modeled product having excellent appearance, surface texture and the like.

[Model]
The modeled object of the present invention is modeled by a three-dimensional printer using the filament of the present invention. By using the filament of the present invention, it is possible to produce a molded product that has extremely little odor during molding, is lightweight and flexible, has excellent aesthetics and surface smoothness, and is less likely to cause delamination between layers.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.
<Filament spinning equipment and filament manufacturing conditions>
The apparatus and manufacturing conditions when the filaments were manufactured in Examples and Comparative Examples are as follows.
Single shaft extruder with a diameter of 30 mm Die hole diameter: 3.0 mm
Cylinder set temperature:
Examples 1-4; 240-260 ° C.
Comparative Example 1: 200 to 220 ° C.
Comparative Example 2; 220 to 240 ° C.
Comparative Example 3; 180-200 ° C.
Comparative Example 4; 190-210 ° C.
Screw rotation speed: 20 rpm
Gear pump rotation speed: 5.0 to 12.0 rpm (2.2 cc / min),
Discharge amount is determined by the rotation speed of the gear pump Cooling tank temperature: 10 ° C (chiller water circulation)
Hot water tank temperature:
Examples 1-4; 20 ° C.
Comparative Examples 1 to 4; 40 ° C.
Stretching ratio: Set by the difference in the roll speed to be connected Heat fixation: Determined by the difference in the roll speed before the final stage to the roll speed in the final stage (= relaxation rate,%)
Heat fixing temperature: By hot air oven for threading between the roll before the final stage and the roll at the final stage (℃)
<Evaluation>
The methods for measuring and evaluating various physical properties in Examples and Comparative Examples are as follows.

≪Resin physical characteristics≫
1) Extreme Viscosity The ultimate viscosity [η] was measured at 135 ° C. in a decalin solvent using a Ubbelohde viscometer as a measuring device. Specifically, about 20 mg of a powdery resin composition was dissolved in 25 ml of decalin, and then the specific viscosity η _sp was measured in an oil bath at 135 ° C. using a Ubbelohde viscometer. After adding 5 ml of decalin to this decalin solution and diluting it, the specific viscosity η _sp was measured in the same manner as above. _{This diluted solution was repeated twice more, and the value of η sp} / C when the concentration (C) was extrapolated to 0 was determined as the ultimate viscosity [η] (unit: dl / g) (see Equation 1 below). ).
[Η] = 1im (η _sp / C) (C → 0) ・ ・ ・ Equation 1

2) Molecular weight distribution (Mw / Mn)
The molecular weight distribution (Mw / Mn) was measured as follows using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters.
The separation columns are two TSKgel GNH6-HT (manufactured by Tosoh) and two TSKgel GNH6-HTL (manufactured by Tosoh), and the column sizes are 7.5 mm in diameter and 300 mm in length, and the column temperature is high. The temperature was 140 ° C., o-dichlorobenzene (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the mobile phase, and BHT (dibutylhydroxytoluene, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.025% by mass was used as the antioxidant, and 1.0 ml / The sample was moved in minutes, the sample concentration was 15 mg / 10 mL, the sample injection volume was 500 microliters, and a differential refraction meter was used as a detector. As the standard polystyrene, Tosoh Co., Ltd. was used for the molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and Pressure Chemical Co., Ltd. was used for 1000 ≦ Mw ≦ 4 × 10 ^6.

3) Melting point (Tm) and glass transition temperature (Tg)
The melting point (Tm) was measured using a differential scanning calorimeter (DSC220C manufactured by Seiko Instruments Inc.) as a measuring device. About 5 mg of the resin composition was sealed in a measuring aluminum pan and heated from 30 ° C. to 10 ° C./min to 200 ° C. The resin composition was held at 200 ° C. for 5 minutes and then cooled to −150 ° C. at 10 ° C./min to completely melt the resin composition. After standing at −150 ° C. for 5 minutes, the second heating was performed at 10 ° C./min to 200 ° C. The peak temperature (° C.) in this second heating was defined as the melting point (Tm) of the resin composition.
The glass transition temperature (Tg) was measured using the same measuring device as above. Find the intersection of the tangents at the inflection point where the baseline moves downward due to the change in the original baseline and the specific heat (the point where the upwardly convex curve changes to the downwardly convex curve), and the glass transition temperature (Tg). ).

4) Density Density was measured by the density gradient tube method according to JIS K7112 (1999).

≪Filament characteristics≫
1) Diameter The filaments were measured at 20 points at 10 cm intervals and the diameter was measured with a caliper and used as the average value.

2) Roundness Filaments were measured at 20 points at 10 cm intervals, and the major axis and minor axis were measured with a caliper, and the ratio of minor axis / major axis was obtained for each measurement point. The average value of the ratio of the minor axis / the major axis at the measured 20 points was taken as the roundness. The closer the roundness is to 1.0, the closer the cross section of the filament is to a perfect circle.

3) Bending resistance After adjusting the filament under the conditions of 23 ° C, 45% relative humidity, and 23 ° C, 90% relative humidity for 2 weeks, grasp both ends of a length of 20 cm with both hands so that both ends overlap. It was bent 180 degrees from the center point to form an elliptical filament. After that, the part where both ends overlapped was fixed with the left hand, and the upper / lower filaments were pressed with the right hand so that the upper and lower filaments overlapped from the overlapping part to the center point. Before the two filaments were lined up in a straight line, it was measured whether the filaments broke at the center point or other points and separated into two filaments. The above measurement was repeated 10 times, and the number of times the filament was broken was defined as bending resistance.

In the above measurement method, when the number of times the filament adjusted under the conditions of 23 ° C. and 90% relative humidity is broken exceeds the number of times the filament adjusted under the conditions of 23 ° C. and 90% relative humidity is broken. This suggests a phenomenon in which the toughness of the resin composition is reduced by hydrolysis.

4) Tensile modulus The filament is adjusted under the conditions of 23 ° C and 45% relative humidity, and measurement is performed in accordance with JIS K7161-1 using a tensile tester (Autograph AG-500C manufactured by Shimadzu Corporation). rice field. The test speed is 300 mm / min, the distance between checks is 100 mm, the distance between marked lines is 50 mm, and a graph (Stress-Streen curve) showing the relationship between normal stress (unit: N) and normal strain (unit:%) is shown. It was prepared and the tensile elastic modulus (unit: MPa) was determined. The measurement was performed 5 times and used as the average value. Generally, it can be said that a resin material having a lower tensile elastic modulus (for example, 100 MPa or less) has a flexibility characteristic.

≪Modeling evaluation≫
1) Odor A sensory evaluation was performed on the presence or absence of an odor generated during modeling. Those with odor were evaluated as "present", and those with no odor were evaluated as "absent".

2) Threading The obtained modeled product was visually observed. Those without fine thread-like (fiber) resin adhering to the surface of the modeled product were evaluated as "none", and those with fine thread-like (fiber) resin adhering to the surface of the modeled product were evaluated as "presence".

3) The molded product obtained by burning was visually observed. If no black spots or kogation caused by burning of the resin is found on the surface of the modeled product, it is judged as "None", and if black spots or kogation caused by burning of the resin is confirmed on the surface of the modeled product, it is judged as "Yes". evaluated.

4) Surface smoothness The surface of the obtained modeled product was traced with a human nail, and the surface smoothness was evaluated by the following index.
◯; When the surface of the modeled product was traced with a human nail, there was no place to get caught.
×; When the surface of the modeled product was traced with a human nail, a place where it was caught was confirmed.

5) Adhesiveness between layers With respect to the obtained modeled product, peeling between layers was attempted by pulling by hand, and the adhesiveness between layers was evaluated according to the following criteria.
〇; There was no peeling between layers.
X; Peeling between layers was observed.

[Example 1]
<Synthesis of propylene / ethylene / butene copolymer>
To a 1.5 liter autoclave dried under reduced pressure and replaced with nitrogen, 675 ml of heptane was added at room temperature, and then a 1.0 mmol / ml toluene solution of triisobutylaluminum was added to 0.3 mmol in terms of aluminum atom. 0.3 ml was added, 28.5 liters of propylene (25 ° C., 1 atm) and 10 liters of 1-butene (25 ° C., 1 atm) were inserted under stirring, and the temperature was started to reach 60 ° C. .. After that, the inside of the system ^{was pressurized with ethylene to 6.0 kg / cm 2} G, and toluene of rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride synthesized by a known method. Add 7.5 ml of solution (0.001 mM / ml) and 2.3 ml of toluene solution of triphenylcarbenium tetra (pentafluorophenyl) borate (0.001 mM / ml), and copolymerize propylene, ethylene and 1-butene. Was started. The catalyst concentration at this time was 0.001 mmol / liter for rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride and triphenylcarbenium tetra (pentafluorophenyl) for the entire system. The volate was 0.003 mmol / liter. During the polymerization, ethylene was continuously supplied to maintain the ^{internal pressure at 6.0 kg / cm 2 G.} Fifteen minutes after the start of the polymerization, the polymerization reaction was stopped by adding methyl alcohol. After decompression, the polymer solution is taken out, and the polymer solution is washed with a 1: 1 ratio of "an aqueous solution containing 5 ml of concentrated hydrochloric acid to 1 liter of water" to remove the catalyst residue. It was transferred to the aqueous phase. After allowing this catalyst mixed solution to stand still, the aqueous phase was separated and removed, and the mixture was further washed twice with distilled water, and the polymerization liquid phase was separated into oil and water. Next, the oil-water-separated polymer liquid phase was brought into contact with 3 times the amount of acetone under strong stirring to precipitate a polymer, which was thoroughly washed with acetone, and the solid part (copolymer) was collected by filtration. It was dried at 130 ° C. and 350 mmHg for 12 hours under nitrogen flow. The yield of the propylene / butene / ethylene copolymer obtained as described above was 24 g. The physical characteristics of the obtained polymer are shown in Table 1.

<Manufacturing of filament>
As the propylene-based elastomer (A), the propylene / butene / ethylene copolymer obtained above was used to obtain a filament according to the above filament spinning apparatus and manufacturing conditions. The filament physical properties are shown in Table 1.

<Fused Deposition Modeling>
The manufactured filament is attached to "MF-1100" manufactured by Muto Kogyo Co., Ltd. to perform modeling, and a cup-shaped modeled product with a bottom diameter of φ65 mm, a height of 105 mm, an opening diameter of φ95 mm, and a wall surface thickness of 1.3 mm is produced. did. The nozzle temperature was 240 ° C., the discharge diameter was 0.4 mm, the stacking pitch was 0.2 mm, and the table heating temperature was 80 ° C. Table 1 shows the modeling evaluation of the obtained cup-shaped modeled product.

[Example 2]
<Synthesis of propylene / ethylene / butene copolymer>
883 ml of dry hexane, 70 g of 1-butene and triisobutylaluminum (1.0 mmol) were charged at room temperature in a 2000 ml polymerizer fully substituted with nitrogen, and then the temperature inside the polymerizer was raised to 40 ° C. with propylene. After pressurizing the pressure in the system to 0.76 MPa, the pressure in the system was adjusted to 0.8 MPa with ethylene. Next, dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenyl zirconium dichloride 0.001 mmol and methylaluminoxane (manufactured by Toso Finechem) of 0.3 mmol in terms of aluminum atom were contacted with toluene. The solution was added into the polymerizer, polymerized for 30 minutes while maintaining the internal temperature at 40 ° C. and the internal pressure at 0.8 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer weighed 53.1 g. The physical characteristics of the obtained polymer are shown in Table 1.

<Manufacturing of filament>
As the propylene-based elastomer (A), the propylene / butene / ethylene copolymer obtained above was used to obtain a filament according to the above filament spinning apparatus and manufacturing conditions. The filament physical properties are shown in Table 1.

<Fused Deposition Modeling>
The manufactured filament is attached to "MF-1100" manufactured by Muto Kogyo Co., Ltd. to perform modeling, and a cup-shaped modeled product with a bottom diameter of φ65 mm, a height of 105 mm, an opening diameter of φ95 mm, and a wall surface thickness of 1.3 mm is produced. did. The nozzle temperature was 240 ° C., the discharge diameter was 0.4 mm, the stacking pitch was 0.2 mm, and the table heating temperature was 80 ° C. Table 1 shows the modeling evaluation of the obtained cup-shaped modeled product.

[Example 3]
<Synthesis of 4-methyl-1-pentene-propylene copolymer>
In a stainless steel (SUS) autoclave with a capacity of 1.5 L fully substituted with nitrogen, 300 ml of n-hexane (dried on activated alumina in a dry nitrogen atmosphere) and 450 ml of 4-methyl-1. -Penten was charged at 23 ° C. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum was charged into this autoclave, and the stirrer was rotated. Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure (gauge pressure) was 0.19 MPa. Subsequently, 1 mmol of methylaluminoxane in terms of aluminum (Al) and 0.01 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-dienyl) prepared in advance were subsequently prepared. 0.34 ml of a toluene solution containing -t-butyl-fluorenyldo zirconium dichloride was pressed into an autoclave with nitrogen to initiate a polymerization reaction. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C. After 60 minutes from the start of the polymerization, 5 ml of methanol was press-fitted into the autoclave with nitrogen to stop the polymerization reaction, and then the inside of the autoclave was depressurized to atmospheric pressure. After decompression, acetone was added to the reaction solution while stirring the reaction solution to obtain a polymerization reaction product containing a solvent. Then, the obtained polymerization reaction product containing the solvent was dried under reduced pressure at 100 ° C. for 12 hours to obtain 44.0 g of a powdery 4-methyl-1-pentene-propylene copolymer. Table 1 shows the physical characteristics of the obtained 4-methyl-1-pentene-propylene copolymer.

<Manufacturing of filament>
As the 4-methyl-1-pentene-propylene copolymer (B), the 4-methyl-1-pentene-propylene copolymer obtained above was used, and filaments were obtained by the above-mentioned filament spinning apparatus and manufacturing conditions. .. The filament physical properties are shown in Table 1.

<Fused Deposition Modeling>
The manufactured filament is attached to "MF-1100" manufactured by Muto Kogyo Co., Ltd. to perform modeling, and a cup-shaped modeled product with a bottom diameter of φ65 mm, a height of 105 mm, an opening diameter of φ95 mm, and a wall surface thickness of 1.3 mm is produced. did. The nozzle temperature was 230 ° C., the discharge diameter was 0.4 mm, the stacking pitch was 0.2 mm, and the table heating temperature was 80 ° C. Table 1 shows the modeling evaluation of the obtained cup-shaped modeled product.

[Example 4]
<Synthesis of 4-methyl-1-pentene-propylene copolymer>
300 ml of n-hexane (dried on activated alumina in a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene were placed in a SUS autoclave with a stirring blade having a capacity of 1.5 L and sufficiently nitrogen-substituted. It was charged at 23 ° C. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum was charged into this autoclave, and the stirrer was rotated. Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure (gauge pressure) was 0.40 MPa. Subsequently, 1 mmol of methylaluminoxane and 0.01 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-) prepared in advance in terms of Al were used. 0.34 ml of a toluene solution containing butyl-fluorenyl) zirconium dichloride was pressed into an autoclave with nitrogen to initiate a polymerization reaction. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C. After 60 minutes from the start of the polymerization, 5 ml of methanol was press-fitted into the autoclave with nitrogen to stop the polymerization reaction, and then the inside of the autoclave was depressurized to atmospheric pressure. After decompression, acetone was added to the reaction solution while stirring the reaction solution to obtain a polymerization reaction product containing a solvent. Then, the obtained polymerization reaction product containing the solvent was dried under reduced pressure at 100 ° C. for 12 hours to obtain 36.9 g of a powdery 4-methyl-1-pentene-propylene copolymer. Table 1 shows the physical characteristics of the obtained 4-methyl-1-pentene-propylene copolymer.

<Manufacturing of filament>
As the 4-methyl-1-pentene-propylene copolymer (B), the 4-methyl-1-pentene-propylene copolymer obtained above was used, and filaments were obtained by the above-mentioned filament spinning apparatus and manufacturing conditions. .. The filament physical properties are shown in Table 1.

<Fused Deposition Modeling>
The manufactured filament is attached to "MF-1100" manufactured by Muto Kogyo Co., Ltd. to perform modeling, and a cup-shaped modeled product with a bottom diameter of φ65 mm, a height of 105 mm, an opening diameter of φ95 mm, and a wall surface thickness of 1.3 mm is produced. did. The nozzle temperature was 230 ° C., the discharge diameter was 0.4 mm, the stacking pitch was 0.2 mm, and the table heating temperature was 80 ° C. Table 1 shows the modeling evaluation of the obtained cup-shaped modeled product.

[Comparative Example 1]
A commercially available ABS resin filament ("Verbatim" manufactured by Mitsubishi Chemical Media Co., Ltd., natural) is attached to "MF-1100" manufactured by Muto Kogyo Co., Ltd. to perform modeling, and the bottom diameter is φ65 mm, the height is 105 mm, and the opening diameter is φ95 mm. , A cup-shaped modeled product having a wall surface thickness of 1.3 mm was produced. The nozzle temperature was 230 ° C., the discharge diameter was 0.4 mm, the stacking pitch was 0.2 mm, and the table heating temperature was 80 ° C. Table 2 shows the modeling evaluation of the obtained cup-shaped modeled product.

[Comparative Example 2]
A commercially available PLA resin filament (Polymaker's "PolyPulls", white) is attached to Muto Kogyo's "MF-1100" for modeling, and the bottom surface has a diameter of φ65 mm, a height of 105 mm, an opening diameter of φ95 mm, and a wall surface. A cup-shaped model with a thickness of 1.3 mm was produced. The nozzle temperature was 220 ° C., the discharge diameter was 0.4 mm, the stacking pitch was 0.2 mm, and the table heating temperature was 60 ° C. Table 2 shows the modeling evaluation of the obtained cup-shaped modeled product.

[Comparative Example 3]
Using pellets of propylene homopolymer ("J106G" manufactured by Prime Polymer Co., Ltd., MFR: 15 g / min; JIS K7210-1 compliant, 230 ° C., 2.16 kg load), filaments were obtained by the above filament spinning apparatus and manufacturing conditions. .. The filament physical properties are shown in Table 2.

The manufactured filament is attached to "MF-1100" manufactured by Muto Kogyo Co., Ltd. to perform modeling, and a cup-shaped modeled product with a bottom diameter of φ65 mm, a height of 105 mm, an opening diameter of φ95 mm, and a wall surface thickness of 1.3 mm is produced. did. The nozzle temperature was 230 ° C., the discharge diameter was 0.4 mm, the stacking pitch was 0.2 mm, and the table heating temperature was 80 ° C. Table 2 shows the modeling evaluation of the obtained cup-shaped modeled product.

[Comparative Example 4]
Using pellets of propylene random polymer ("J226T" manufactured by Prime Polymer Co., Ltd., MFR: 20 g / min; JIS K7210-1 compliant, 230 ° C., 2.16 kg load), filaments were obtained by the above filament spinning apparatus and manufacturing conditions. .. The filament physical properties are shown in Table 2.

The manufactured filament is attached to "MF-1100" manufactured by Muto Kogyo Co., Ltd. to perform modeling, and a cup-shaped modeled product with a bottom diameter of φ65 mm, a height of 105 mm, an opening diameter of φ95 mm, and a wall surface thickness of 1.3 mm is produced. did. The nozzle temperature was 220 ° C., the discharge diameter was 0.4 mm, the stacking pitch was 0.2 mm, and the table heating temperature was 60 ° C. Table 2 shows the modeling evaluation of the obtained cup-shaped modeled product.

Claims (7)

The olefin polymer contains a structural unit derived from propylene and a structural unit derived from an α-olefin having 2 to 20 carbon atoms other than propylene, and has the following requirements (a), (b) and (c). A filament for modeling a three-dimensional printer, which comprises a propylene-based resin composition containing only a propylene-based copolymer satisfying (d) and (d):
(A) The ultimate viscosity [η] measured in decalin at 135 ° C. is in the range of 0.1 to 5.0 dl / g;
(B) The ratio (molecular weight distribution; Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is in the range of 1.0 to 3.5. It is in;
(C) The melting point (Tm) measured by differential scanning calorimetry (DSC) is greater than or equal to 100 ° C and less than 165 ° C, or is substantially non-observed;
(D) The density measured by the density gradient tube method according to JIS K7112 (1999) is in the range of ^{810 to 880 kg / m 3.} As a resin component, a structural unit derived from propylene and a structural unit derived from an α-olefin having 2 to 20 carbon atoms other than propylene are contained, and the following requirements (a), (b), (c) and A filament for modeling a three-dimensional printer, which comprises a propylene-based resin composition containing only a propylene-based copolymer satisfying (d):
(A) The ultimate viscosity [η] measured in decalin at 135 ° C. is in the range of 0.1 to 5.0 dl / g;
(B) The ratio (molecular weight distribution; Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is in the range of 1.0 to 3.5. It is in;
(C) The melting point (Tm) measured by differential scanning calorimetry (DSC) is greater than or equal to 100 ° C and less than 165 ° C, or is substantially non-observed;
(D) The density measured by the density gradient tube method according to JIS K7112 (1999) is in the range of ^{810 to 880 kg / m 3.} The propylene-based copolymer contains 50 to 85 mol% of a constituent unit derived from propylene, 5 to 25 mol% of a constituent unit derived from 1-butene, and 5 to 25 mol% of a constituent unit derived from ethylene. (However, the total of the structural units derived from propylene, 1-butene and ethylene is 100 mol%.), The propylene content / ethylene content (molar ratio) is 90/10 to 70/30, and the glass transition temperature ( The filament for modeling a three-dimensional printer according to claim 1 or 2 , wherein Tg) is a propylene-based polymer (A) in the range of -15 to -40 ° C. The propylene-based copolymer contains 15 to 90 mol% of the structural unit derived from 4-methyl-1-pentene and 10 to 85 mol% of the structural unit derived from propylene (provided that 4-methyl-1 is contained. -The total of the constituent units derived from pentene and propylene is 100 mol%.), 4-Methyl-1-pentene-propylene copolymer (B) having a glass transition temperature (Tg) in the range of 10 to 45 ° C. The filament for modeling a three-dimensional printer according to any one of claims 1 to 3, wherein the filament is characterized by the above. The three-dimensional printer for modeling according to any one of claims 1 to 4 , wherein the filament has a diameter of 1.0 to 4.0 mm and the roundness of the filament is 0.93 or more. filament. The filament for 3D printer modeling according to any one of claims 1 to 5 , which is used for modeling a 3D printer in a fused deposition modeling method. A model made of the filament for modeling a three-dimensional printer according to any one of claims 1 to 6.