JP7610485B2 - Composition for three-dimensional printers, material for three-dimensional printers, and method for producing molded object - Google Patents

Description

The present invention relates to a composition for three-dimensional printers, a material for three-dimensional printers, and a method for manufacturing a model using the composition for three-dimensional printers or the material for three-dimensional printers.

Conventionally, fused deposition modeling, in which resin melted by heat is extruded and layered, is known as a modeling method for 3D printers. Fused deposition modeling 3D printers are relatively inexpensive, so they are used in a variety of fields.

In fused deposition modeling, the filament method is generally used, in which resin molded into a filament shape is introduced, but in recent years, the adoption of the pellet method, in which resin molded into a pellet shape is introduced, is also being considered. The pellet method allows the type and amount of color, filler, additives, etc. to be changed, making prototyping easy, and also has the advantage that even large objects can be manufactured in a short time, as the nozzle diameter can be made larger than with the filament method.

Thermoplastic resins such as acrylonitrile butadiene styrene copolymer (ABS resin) and polylactic acid (PLA resin) are widely known as modeling materials used in fused deposition modeling. However, as described in Patent Document 1, ABS resin and PLA resin emit an odor during modeling. In addition, since PLA resin is hydrolyzable, the resin itself can absorb moisture, reducing its toughness and causing it to break easily, making modeling difficult. Furthermore, since ABS resin and PLA resin are high specific gravity and hard materials, there is a problem that the properties of the resulting modeled product are limited.

Therefore, Patent Document 1 proposes a filament for 3D printer modeling that uses a specific olefin-based thermoplastic elastomer composition, which produces extremely little odor during modeling, does not lose toughness due to hydrolysis, and can produce lightweight and flexible models.

JP 2018-144308 A

However, the object obtained using the molding material of Patent Document 1 has a small breaking point stress in the height direction, and the dimensional accuracy cannot be said to be good.

The present invention was made in consideration of these problems, and aims to provide a composition for 3D printers, a material for 3D printers, and a method for manufacturing a model that can produce a model with relatively excellent breaking point stress in the height direction.

The composition for three-dimensional printers of the present invention contains a propylene polymer (A) that contains a monomer unit derived from propylene and has a content of the monomer unit derived from propylene of 85 mol % or more, and a polymer (B), wherein the crystallization half time T ^IC (A) of the propylene polymer (A) and the crystallization half time T ^IC (B) of the polymer (B) satisfy the following formula (1), and the crystallization half time T ^IC (C) of the composition for three-dimensional printers is 900 seconds or more.
T ^IC (B) > T ^IC (A) (1)

The material for three-dimensional printers of the present invention is a material for three-dimensional printers containing one or more polymers, and contains a component (X) insoluble in orthodichlorobenzene at 60°C and a component (Y) soluble in orthodichlorobenzene at 60°C, wherein the crystallization half time T ^IC (X) of the insoluble component (X) and the crystallization half time T ^IC (Y) of the soluble component (Y) satisfy the following formula (11), and the crystallization half time T ^IC (Z) of the material for three-dimensional printers is 900 seconds or longer.
^TIC (Y)> ^TIC (X) (11)

The method for producing a molded object according to the present invention includes a step of melt-laminating the composition for a three-dimensional printer or the material for a three-dimensional printer using a three-dimensional printer.

The present invention provides a composition for three-dimensional printers, a material for three-dimensional printers, and a method for manufacturing a model that can produce a model with relatively excellent breaking point stress in the height direction.

The following describes an embodiment of the present invention, but the present invention is not limited to the following embodiment.

<Composition for 3D printer>
The composition for three-dimensional printers according to this embodiment contains a propylene polymer (A) that contains a monomer unit derived from propylene and has a content of the monomer unit derived from propylene of 85 mol % or more, and a polymer (B).

(Propylene polymer (A))
The propylene polymer (A) contains a monomer unit derived from propylene. The propylene polymer (A) has a content of the monomer unit derived from propylene of 85 mol % or more, preferably 90 mol % or more, more preferably 95 mol % or more, and is further preferably a propylene homopolymer.

The propylene polymer (A) may be a copolymer with other olefins. Examples of the other olefins include ethylene and α-olefins. Examples of the α-olefins include butene-1, hexene-1, 4-methylpentene-1, and octene-1.

From the viewpoint of improving the transparency and flexibility of the sheet, the propylene polymer (A) is preferably a propylene-ethylene copolymer, a propylene-ethylene-butene-1 copolymer, a propylene-butene-1 copolymer, or a propylene homopolymer, more preferably a propylene-ethylene copolymer having an ethylene-derived structural unit content of 0.1 to 5% by mass, a propylene-butene-1 copolymer having an ethylene-derived structural unit content of 1 to 10% by mass, or a propylene-ethylene-butene-1 copolymer having an ethylene-derived structural unit content of 0.1 to 5% by mass and a butene-1-derived structural unit content of 1 to 10% by mass, or a propylene homopolymer, and even more preferably a propylene homopolymer. These propylene polymers (A) can be obtained, for example, by using a highly active catalyst described in JP-B-64-6211 and JP-B-4-37084, and supplying propylene and, if necessary, other olefins to a polymerization system to carry out polymerization. In addition, the propylene polymer (A) may be polymerized in one of the first and second stages of the multi-stage polymerization method described in JP-A-2004-182981, for example, and the polymer (B) described below may be polymerized in the other stage.

The content of propylene polymer (A) is preferably 60% by mass or more and 90% by mass or less, more preferably 65% by mass or more and 85% by mass or less, and even more preferably 70% by mass or more and 80% by mass or less, relative to 100% by mass, which is the sum of the content of propylene polymer (A) and the content of polymer (B) described below.

The melt flow rate (MFR) of the propylene polymer (A) measured at a temperature of 230°C and a load of 2.16 kg is preferably 1 g/10 min to 100 g/10 min, more preferably 2 g/10 min to 50 g/10 min, and even more preferably 3 g/10 min to 30 g/10 min, from the viewpoint of improving processability. The MFR is measured by the method specified in JIS K7210 Method A.

From the viewpoint of heat resistance, the melting point of the propylene polymer (A) is preferably 120°C or higher and 170°C or lower, and more preferably 130°C or higher and 170°C or lower. The melting point is the temperature at the top of the melting peak obtained by analyzing a differential scanning calorimetry curve obtained by differential scanning calorimetry using a method in accordance with JIS K7121-1987.

(Polymer (B))
The polymer (B) is a polymer having a crystallization half time T ^IC (B) longer than the crystallization half time T ^IC (A) of the propylene polymer (A). That is, the crystallization half time T ^IC (A) of the propylene polymer (A) and the crystallization half time T ^IC (B) of the polymer (B) satisfy the following formula (1).
T ^IC (B) > T ^IC (A) (1)

The crystallization half time is measured at 135°C using a heat flux type differential scanning calorimeter. Specifically, it is calculated from the peak top of the endothermic curve obtained by rapidly cooling each completely dissolved polymer to 135°C and isothermally crystallizing it.

Examples of polymer (B) include propylene homopolymers and copolymers of propylene and other olefins. In the case of copolymers of propylene and other olefins, the content of monomer units derived from propylene is preferably less than 15 mol%, and more preferably 10 mol% or less. Examples of other olefins include ethylene and α-olefins. The α-olefins are preferably α-olefins having 4 to 12 carbon atoms, such as butene-1, hexene-1, 4-methylpentene-1, and octene-1. Polymer (B) may be used alone or in combination of two or more types.

From the viewpoint of improving mechanical properties, the polymer (B) is preferably a propylene-α-olefin copolymer (B1) containing monomer units derived from propylene and monomer units derived from an α-olefin having 4 to 12 carbon atoms, and the content of the monomer units derived from the α-olefin having 4 to 12 carbon atoms is 60 mol% or more. The propylene-α-olefin copolymer (B1) is preferably a propylene-ethylene-butene copolymer or a propylene-butene copolymer, and more preferably a propylene-1-butene copolymer having a content of butene-1-derived structural units of 60 mol% or more, or a propylene-ethylene-1-butene copolymer having a content of ethylene-derived structural units of less than 20 mol% and a content of butene-1-derived structural units of less than 60 mol%. These polymers (B) can be obtained, for example, by using a highly active catalyst described in JP-B-64-6211 and JP-B-4-37084, and feeding propylene alone to a polymerization system, or feeding propylene and another olefin to a polymerization system and carrying out polymerization. Also, the polymer (B) may be polymerized in one of the first and second stages of the multi-stage polymerization method described in JP-A-2004-182981, for example, and the aforementioned propylene polymer (A) may be polymerized in the other stage.

When polymer (B) contains monomer units derived from propylene, the melt flow rate (MFR) of polymer (B) measured at a temperature of 230°C and a load of 2.16 kg is preferably 0.1 g/10 min to 100 g/10 min, more preferably 0.3 g/10 min to 70 g/10 min, and even more preferably 0.5 g/10 min to 50 g/10 min, from the viewpoint of improving mechanical properties. The MFR is measured by the method specified in JIS K7210 Method A.

The polymer (B) may be an ethylene-α-olefin copolymer. The ethylene-α-olefin copolymer is a copolymer of ethylene and an α-olefin having 4 to 12 carbon atoms, containing 50% or more by mass of ethylene-derived structural units. From the viewpoint of improving mechanical properties, the ethylene-α-olefin copolymer preferably has a content of ethylene-derived structural units of 55% by mass or more, more preferably 60% by mass or more, and particularly preferably 65% by mass or more. Examples of the α-olefin include butene-1, 4-methylpentene-1, hexene-1, octene-1, and decene-1. From the viewpoint of improving the impact resistance of the sheet, the α-olefin is preferably butene-1 or hexene-1. These ethylene-α-olefin copolymers may be a mixture of multiple ethylene-α-olefin copolymers having different molecular weights, types of α-olefins, and contents.

When the polymer (B) is an ethylene-α-olefin copolymer, the melt flow rate (MFR) of the polymer (B) measured at a temperature of 230°C and a load of 2.16 kg is preferably 0.1 g/10 min to 100 g/10 min, more preferably 0.5 g/10 min to 70 g/10 min, even more preferably 1 g/10 min to 50 g/10 min, and even more preferably 2 g/10 min to 20 g/10 min. If the MFR is less than 0.1 g/10 min, the dispersed particle size may become too large, resulting in poor transparency of the sheet. If the MFR is more than 100 g/10 min, the impact resistance of the sheet may decrease. The MFR is measured by the method specified in the A method of JIS K7210.

When the polymer (B) is an ethylene-α-olefin copolymer, the density of the polymer (B) is preferably 865 kg/m ³ or more and 898 kg/m ³ or less, more preferably 868 kg/m ³ or more and 897 kg/m ³ or less, and even more preferably 870 kg/m ³ or more and 896 kg/m ³ or less, from the viewpoint of improving the transparency and impact resistance of the sheet. If the density is less than 865 kg/m ³ , the transparency of the sheet may decrease. If the density exceeds 896 kg/m ³ , the impact resistance of the sheet may decrease. The density is measured according to JIS K6760-1981.

Examples of methods for producing ethylene-α-olefin copolymers include the method described in JP-A-3-234717, in which ethylene and α-olefin are polymerized in the presence of a catalyst (metallocene catalyst) containing a transition metal compound having a group with a cyclopentadiene-type anion skeleton. Examples of polymerization methods include known polymerization methods such as the solution method, slurry method, gas phase method, and high-pressure ion method.

From the viewpoint of extending the semi-crystallization time, the melting point of polymer (B) is preferably 0°C or higher and 90°C or lower, and more preferably 20°C or higher and 80°C or lower. The melting point is the temperature at the apex of the melting peak obtained by analyzing a differential scanning calorimetry curve obtained by differential scanning calorimetry using a method in accordance with JIS K7121-1987.

The crystallization half time T ^IC (B) of polymer (B) can be made longer than the crystallization half time T ^IC (A) of propylene polymer (A) by using a polymer having a content of monomer units derived from propylene of less than 15 mol% or an ethylene-α-olefin copolymer as polymer (B).

The content of polymer (B) is preferably 10% by mass or more and 40% by mass or less, more preferably 15% by mass or more and 35% by mass or less, and even more preferably 20% by mass or more and 30% by mass or less, relative to 100% by mass, which is the total content of propylene polymer (A) and polymer (B). When two or more types of polymer (B) are included, the above content is the total content of polymer (B).

The composition for three-dimensional printers according to this embodiment may further contain additives such as neutralizing agents, antioxidants, heat stabilizers, weathering agents, UV absorbers, antistatic agents, dispersants, antibacterial agents, fluorescent brighteners, dyes, and pigments, fillers such as talc, calcium carbonate, and mica, glass fibers, and carbon fibers, to the extent that the effects of the present invention are not impaired.

The crystallization half time T ^IC (C) of the composition for three-dimensional printers according to this embodiment is 900 seconds or more, and preferably 900 seconds or more and 1400 seconds or less. The crystallization half time T ^IC (C) can be adjusted to 900 seconds or more and 1400 seconds or less by adjusting the content of the structural unit contained in the propylene polymer (A), the structural unit contained in the polymer (B), and the propylene polymer (A) and the polymer (B). The crystallization half time is calculated from the peak top of the endothermic curve obtained by isothermally crystallizing the completely dissolved composition by quenching it to 135°C.

The Young's modulus of the composition for three-dimensional printers according to this embodiment is preferably 900 MPa or more, and more preferably 900 MPa or more and 1500 MPa or less. The Young's modulus of the composition for three-dimensional printers can be adjusted to 900 MPa or more and 1500 MPa or less by adjusting the content of the structural units contained in the propylene polymer (A), the structural units contained in the polymer (B), and the content of the propylene polymer (A) and the polymer (B).

The composition for three-dimensional printers according to this embodiment may have a filament or pellet shape.

The method for forming the composition for three-dimensional printers according to this embodiment into pellets includes adjusting the blending ratio of each of the above-mentioned components so that they fall within the range of the requirements of the present invention, further blending the above-mentioned additives, etc. as necessary, and mixing them uniformly by the following method, and then melt-kneading them by various known methods.

Examples of the equipment used to mix the above-mentioned components include a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, etc. Examples of the equipment used to melt-knead include a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, a roll mill, etc.

As a method for forming the composition for three-dimensional printers according to this embodiment into a filament shape, there is a method in which the composition for three-dimensional printers is melt-spun and then stretched. A known melt-spinning method can be used for melt spinning. Also, a known stretching method can be used for stretching.

Specifically, for example, the composition for three-dimensional printers can be produced by a method including an extrusion process in which a molten strand is extruded from the die hole of a single-screw extruder or a twin-screw extruder and guided into a cooling water tank to obtain a strand, a drawing process in which the strand is drawn, and a winding process in which the drawn filament is wound up.

Drawing is the process of mechanically stretching the filament at a temperature below the melting point of the material, orienting the molecular chains parallel to the pulling direction. This operation significantly improves tensile strength and toughness. After the drawing process, if the material is reheated to a temperature above the drawing temperature, it will tend to shrink back to its original dimensions, so in order to ensure stability of dimensions and strength, it may be heat-treated (heat-fixed, heat-set) at a temperature slightly lower than the drawing temperature.

The strand obtained in the extrusion process is heated to a specific temperature and stretched. The stretching is performed by adjusting the speed ratio (stretching ratio) between the take-up roll on the inlet side and the take-up roll on the outlet side, and the stretching ratio at this time is preferably 2 to 15 times. The heating method during stretching is not particularly limited, and a hot water bath, oven, heated roll, etc. can be used, but it is preferable to use a hot water bath from the viewpoint of more uniform heating and stretching.

The diameter of the filament depends on the design specifications of the fused deposition modeling method and the system capabilities used for modeling, but is preferably 1.0 mm or more, more preferably 1.5 mm or more, and even more preferably 1.6 mm or more. On the other hand, the diameter of the filament is preferably 4.0 mm or less, more preferably 3.5 mm or less, and even more preferably 3.0 mm or less.

<Materials for 3D printers>
The material for three-dimensional printers according to this embodiment is a material for three-dimensional printers that contains one or more polymers, and contains a component (X) that is insoluble in orthodichlorobenzene at 60°C and a component (Y) that is soluble in orthodichlorobenzene at 60°C.

The insoluble component (X) is a component mostly composed of the above-mentioned propylene polymer (A), and the soluble component (Y) is a component mostly composed of the above-mentioned polymer (B). The soluble component (Y) is a component whose crystallization half time T ^IC (Y) is longer than the crystallization half time T ^IC (X) of the insoluble component (X). That is, the crystallization half time T ^IC (X) of the insoluble component (X) and the crystallization half time T ^IC (Y) of the soluble component (Y) satisfy the following formula (11).
^TIC (Y)> ^TIC (X) (11)

The crystallization half time T ^IC (Z) of the material for three-dimensional printers is 900 seconds or more, and preferably 900 seconds or more and 1400 seconds or less. The crystallization half time T ^IC (Z) can be adjusted to 900 seconds or more and 1400 seconds or less by adjusting the type of insoluble component (X), the type of soluble component (Y), and the contents of insoluble component (X) and soluble component (Y).

The crystallization half time T ^IC (X) of the insoluble component (X) is preferably 700 seconds or more and 1400 seconds or less. The crystallization half time T ^IC (X) can be adjusted to 700 seconds or more and 1400 seconds or less by adjusting the type and content of the insoluble component (X).

In addition, the crystallization half time T ^IC (X) of the insoluble component (X), the crystallization half time T ^IC (Y) of the soluble component (Y), and the crystallization half time T ^IC (Z) of the material for a 3D printer are calculated from the peak top of the endothermic curve obtained by rapidly cooling each completely dissolved component or material to 135°C and isothermally crystallizing it.

The insoluble component (X) and the soluble component (Y) can be separated by precipitating the insoluble component (X) in orthodichlorobenzene in the dissolution tank of the automatic separation device, and then discharging the solution containing the soluble component (Y) in orthodichlorobenzene out of the dissolution tank.

<Method of manufacturing a molded object>
The method for producing a shaped object according to this embodiment includes a step of melt-laminating the above-mentioned composition for three-dimensional printers or the above-mentioned material for three-dimensional printers using a three-dimensional printer.

In the above process, for example, the nozzle temperature can be 160 to 250°C, the discharge diameter can be 0.2 to 0.6 mm, the layer pitch can be 0.05 to 0.6 mm, and the table temperature can be 60 to 100°C.

The above-mentioned method makes it possible to obtain a molded object that is relatively excellent in terms of breaking point stress in the height direction. In addition, the molded object has very little odor during molding, is not subject to a decrease in toughness due to hydrolysis, and is lightweight and flexible. The composition for three-dimensional printers or the material for three-dimensional printers according to this embodiment contains two types of components with different half-crystallization times, and the half-crystallization time is a specific value or more. When the composition for three-dimensional printers or the material for three-dimensional printers according to this embodiment is melt-laminated using a three-dimensional printer, the upper layer is laminated while the lower layer is in a moderately solidified state (not completely solidified), so that the adhesion between the lower layer and the upper layer is strong. Therefore, a molded object that is relatively excellent in terms of breaking point stress in the height direction can be obtained.

The composition for 3D printers, the material for 3D printers, and the method for manufacturing a modeled object according to the present embodiment are not limited to the above embodiment, and various modifications are possible without departing from the gist of the present invention. In addition, the configurations and methods of embodiments other than those described above may be arbitrarily adopted and combined, and the configurations and methods of one embodiment described above may be applied to the configurations and methods of the other embodiments described above.

The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples. The measured values of each item in the examples and comparative examples were measured by the following methods.

(1) Melt flow rate (MFR, unit: g/10 min)
The melt flow rate was measured according to the method specified in JIS K7210, Method A, under conditions of a temperature of 230° C. and a load of 2.16 kg.

(2) Melting point (unit: °C)
The melting point was measured using a thermal analysis device, a differential scanning calorimeter (Q100 manufactured by TA Instruments). Under a nitrogen gas atmosphere, an aluminum pan containing about 5 mg of a sample (a sample obtained by crushing polymer pellets) was (a) held at 220°C for 5 minutes, (b) cooled from 220°C to -90°C at a rate of 10°C/min, (c) heated from -90°C to 220°C at a rate of 10°C/min, (d) cooled from 220°C to -90°C at a rate of 10°C/min, (e) held at -90°C for 5 minutes, and (f) heated from -90°C to 60°C at a rate of 2°C/min (modulation amplitude ±0.16°C, modulation period 3 seconds). The differential scanning calorimeter curve obtained by the calorimetry in (c) above was analyzed by a method conforming to JIS K7121-1987. The temperature at the apex of the melting peak obtained was taken as the melting point of the sample.

(3) Separation of insoluble component (X) and soluble component (Y) in orthodichlorobenzene The insoluble component (X) and soluble component (Y) in orthodichlorobenzene at 60 ° C. of the composition for three-dimensional printers were separated using an automatic separation device (PREP-mc2, manufactured by Polymer ChAR). 500 mg of sample (a sample obtained by crushing pellets, which are a composition for three-dimensional printers) and 200 mL of orthodichlorobenzene containing 0.05% by mass of dibutylhydroxytoluene were added to the dissolution tank of the automatic separation device, and then heated and stirred at 140 ° C. for 90 minutes to prepare a solution with a concentration of 5.0 mg / mL. The obtained solution was cooled to 100 ° C. at a rate of 20 ° C. / min, held at 100 ° C. for 45 minutes, cooled to 30 ° C. at a rate of 0.5 ° C. / min, and held at 30 ° C. for 60 minutes to precipitate the insoluble component (X) in orthodichlorobenzene.

The obtained solution containing the soluble component (Y) in orthodichlorobenzene was discharged from the dissolution tank over 60 minutes while being kept at 60°C, and then the remaining solution containing the soluble component (Y) in orthodichlorobenzene was discharged from the dissolution tank over 60 minutes while being kept at 60°C, and the obtained discharged liquids were combined, and the solution containing the soluble component (Y) in orthodichlorobenzene was separated.

100 mL of orthodichlorobenzene was then added to the dissolution tank, and the mixture was heated and stirred at 140°C for 60 minutes to dissolve the insoluble component (X) in orthodichlorobenzene again. The resulting solution was discharged from the dissolution tank over 60 minutes while being kept at 140°C, and then allowed to stand at room temperature for 18 hours to separate the mixture containing the insoluble component (X) in orthodichlorobenzene.

The mixture containing the insoluble component (X) in orthodichlorobenzene and the solution containing the soluble component (Y) in orthodichlorobenzene were each poured into about 10 times the amount of methanol. The resulting precipitate was suction filtered using a PTFE membrane with a pore size of 10 μm. The resulting residue was washed with about 200 mL of methanol, and the methanol was removed by suction filtration, and then transferred to an evaporating dish. The precipitate in the evaporating dish was dried for 4 hours on a water bath at 60°C while blowing nitrogen gas onto it, and then dried for 18 hours in a vacuum dryer at room temperature. The resulting solids were designated as the insoluble component (X) in orthodichlorobenzene and the soluble component (Y) in orthodichlorobenzene, respectively.

(4) Crystallization half time (unit: seconds)
The half-crystallization time was measured using a differential scanning calorimeter (DSC8500, manufactured by PerkinElmer Japan Co., Ltd.). Specifically, pellets of each polymer, pellets of a composition (material) for a three-dimensional printer, or insoluble or soluble components in orthodichlorobenzene at 60 ° C. were compressed into a film having a thickness of 500 μm using a compression molding machine to prepare a measurement sample. After setting 10 mg of the measurement sample in the DSC8500, the temperature was raised to 220 ° C. and maintained at 220 ° C. for 5 minutes to completely dissolve the measurement sample. Thereafter, the dissolved measurement sample was quenched to 135 ° C. at a temperature drop rate of 300 ° C. / min to cause isothermal crystallization. The half-crystallization time was calculated from the peak top of the obtained endothermic curve. The shorter the half-crystallization time, the faster the crystallization rate.

(5) Young's modulus (unit: MPa)
A test piece having a width of 20 mm, a length of 120 mm, and a thickness of 2 mm was prepared by press molding. The test piece was used to measure a stress-strain curve under conditions of a grip distance of 60 mm and a tensile speed of 50 mm/min, and the initial elastic modulus was evaluated as Young's modulus.

(6) Breaking stress (unit: MPa)
From a model produced using a 3D printer, a test piece was cut out to a width of 5 mm (Z direction), a length of 30 mm (X direction), and a thickness of 2 mm (Y direction) in the horizontal direction (X direction), and a test piece was cut out to a width of 5 mm (X direction), a length of 30 mm (Z direction), and a thickness of 2 mm (Y direction) in the vertical direction (Z direction). The stress at break was evaluated using a gripping distance of 10 mm and a tensile speed of 50 mm/min.

The ingredients contained in the composition for 3D printers are shown in Table 1.

Propylene homopolymer (a1):
The propylene homopolymer had an MFR of 8.5 g/10 min and a crystallization half time of 803 seconds.

Propylene homopolymer (a2):
The propylene homopolymer had an MFR of 13.3 g/10 min and a crystallization half time of 717 seconds.

1-Butene copolymer (b1):
The copolymer is a propylene-1-butene random copolymer having an MFR of 9 g/10 min, a melting point of 58° C., a content of monomer units derived from 1-butene of 72.3 mol %, and a content of monomer units derived from propylene of 27.7 mol %. The crystallization half time of the copolymer was more than 9000 seconds.

1-Butene copolymer (b2):
The ethylene-1-butene random copolymer had an MFR of 9 g/10 min, a melting point of 100° C., a content of monomer units derived from 1-butene of 99.1 mol %, and a content of monomer units derived from ethylene of 0.9 mol %. The crystallization half time of this ethylene-1-butene random copolymer was more than 9,000 seconds.

Amorphous propylene copolymer (b3):
The copolymer is a propylene-1-butene random copolymer having an MFR of 0.8 g/10 min, a content of monomer units derived from propylene of 96 mol %, and a content of monomer units derived from 1-butene of 4 mol %. The crystallization half time of the copolymer was more than 9000 seconds.

Olefin-based thermoplastic elastomer:
The product is Esporex 4785 manufactured by Sumitomo Chemical Co., Ltd. Esporex 4785 contains a propylene polymer, an oil-extended ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber, a crosslinking agent, and a crosslinking aid. Note that since the olefin-based thermoplastic elastomer is a crosslinked body, the MFR could not be measured.

<Example 1: Composition 1 for 3D printer>
70% by mass of the propylene homopolymer (a1) and 30% by mass of the 1-butene copolymer (b1) were kneaded and extruded using a 30 mm single screw extruder at an extrusion rate of about 5 kg/hr, a cylinder temperature of 230° C., and a screw rotation speed of 60 rpm to obtain pellets. The half-crystallization time of the pellets was measured.

The pellets obtained were crushed into samples, which were then separated into insoluble (X) and soluble (Y) components in orthodichlorobenzene at 60°C, and the half-crystallization time for each was measured.

The pellets obtained were then press molded for 5 minutes using a compression molding machine (Model F-37, manufactured by Shinto Metal Industries) at a temperature of 230°C and a pressure of 5 MPa, and then cold pressed for 5 minutes at a temperature of 30°C and a pressure of 5 MPa to obtain a press molded body having a length of 150 mm, a width of 150 mm and a thickness of 2 mm. A test piece having a length of 120 mm, a width of 20 mm and a thickness of 2 mm was cut out from the obtained press molded body, and the Young's modulus was measured. The results are shown in Table 2.

The pellets obtained were then extruded using a 20 mm single screw extruder (die hole diameter 3 mm, 1 hole) at a cylinder temperature of 190-200°C and a screw rotation speed of 15 rpm, and then quenched with water at approximately 4°C. The resulting strand was stretched using a stretching machine at a stretching speed of 8 m/min and a stretching temperature of 25°C to obtain a filament with a thread diameter of approximately 1.7 mm.

The obtained filament was melt-laminated using FT Finetech Products' 3D printer molding machine "FAST System" under conditions of a nozzle temperature of 220°C, an ejection diameter of 0.4 mm, a lamination pitch of 0.2 mm, and a table temperature of 70°C to obtain a square-shaped object with a width, depth, and height of 30 mm and a wall thickness of 2.0 mm. The evaluation results of the breaking stress of the obtained object are shown in Table 2.

<Example 2: Composition 2 for 3D printer>
Except for using the propylene homopolymer (a2) instead of the propylene homopolymer (a1), a press-molded body and a square-shaped shaped object were obtained in the same manner as in Example 1. The Young's modulus of the obtained press-molded body and the evaluation results of the breaking stress of the obtained shaped object are shown in Table 2.

<Example 3: Composition 3 for 3D printer>
Except for using 90% by mass of propylene homopolymer (a1) instead of 70% by mass of propylene homopolymer (a1) and 10% by mass of amorphous propylene copolymer (b3) instead of 30% by mass of 1-butene copolymer (b1), a press-molded body and a square-shaped shaped object were obtained in the same manner as in Example 1. The Young's modulus of the obtained press-molded body and the evaluation results of the breaking stress of the obtained shaped object are shown in Table 2.

<Comparative Example 1: Composition C1 for three-dimensional printer>
Except for using the 1-butene copolymer (b2) instead of the 1-butene copolymer (b1), a press-molded body and a square-shaped shaped object were obtained in the same manner as in Example 1. The Young's modulus of the obtained press-molded body and the evaluation results of the breaking stress of the obtained shaped object are shown in Table 2.

<Comparative Example 2: Composition C2 for three-dimensional printer>
Except for using 58 mass% of propylene homopolymer (a2) instead of 70 mass% of propylene homopolymer (a1), and 42 mass% of olefin-based thermoplastic elastomer instead of 30 mass% of 1-butene copolymer (b1), a press-molded body and a square-shaped shaped object were obtained in the same manner as in Example 1. The Young's modulus of the obtained press-molded body and the evaluation results of the breaking stress of the obtained shaped object are shown in Table 2.

As can be seen from the results in Table 2, the compositions for three-dimensional printers of the examples that satisfy all of the constituent requirements of the present invention can produce objects that are relatively excellent in terms of breaking point stress in the Z direction (height direction). In addition, the compositions for three-dimensional printers of the examples have a high Young's modulus.

On the other hand, the compositions for 3D printers of each comparative example, in which the semi-crystallization time of the composition for 3D printers is less than 900 seconds, have a small stress at break in the Z direction (height direction). In addition, the composition for 3D printers of Comparative Example 2, which contains an olefin-based thermoplastic elastomer, has a small Young's modulus.

Claims (12)

A propylene polymer (A) containing a monomer unit derived from propylene and having a content of the monomer unit derived from propylene of 85 mol % or more;
A polymer (B) and
The crystallization half time T ^IC (A) of the propylene polymer (A) and the crystallization half time T ^IC (B) of the polymer (B) satisfy the following formula (1),
A composition for three-dimensional printers, the crystallization half time T ^IC (C) of which is 900 seconds or more.
^TIC (B)> ^TIC (A) (1) The composition for three-dimensional printers according to claim 1 , wherein the T ^IC (C) is from 900 seconds to 1400 seconds. The composition for three-dimensional printers according to claim 1 or 2, which has a Young's modulus of 900 MPa or more. The composition for three-dimensional printers according to any one of claims 1 to 3, wherein the Young's modulus is 900 MPa or more and 1500 MPa or less. The composition for three-dimensional printers according to any one of claims 1 to 4, wherein the polymer (B) is a propylene-α-olefin copolymer (B1) that contains monomer units derived from propylene and monomer units derived from an α-olefin having 4 to 12 carbon atoms, and the content of the monomer units derived from the α-olefin having 4 to 12 carbon atoms is 60 mol% or more. The composition for three-dimensional printers according to claim 5, wherein the propylene-α-olefin copolymer (B1) is a propylene-butene copolymer. The composition for three-dimensional printers according to any one of claims 1 to 6, wherein the propylene polymer (A) has a melt flow rate of 1 g/10 min or more and 100 g/10 min or less, measured at a temperature of 230°C and a load of 2.16 kg. With respect to the total content of the propylene polymer (A) and the content of the polymer (B) being 100% by mass,
The content of the propylene polymer (A) is 60% by mass or more and 90% by mass or less,
The composition for three-dimensional printers according to any one of claims 1 to 7, wherein the content of the polymer (B) is 10% by mass or more and 40% by mass or less. The composition for a three-dimensional printer according to any one of claims 1 to 8, which has a filament shape or a pellet shape. A material for a three-dimensional printer comprising one or more polymers,
Contains a component (X) insoluble in orthodichlorobenzene at 60°C and a component (Y) soluble in orthodichlorobenzene at 60°C,
The crystallization half time T ^IC (X) of the insoluble component (X) and the crystallization half time T ^IC (Y) of the soluble component (Y) satisfy the following formula (11):
A material for a three-dimensional printer, the material having a semi-crystallization time T ^IC (Z) of 900 seconds or more.
^TIC (Y)> ^TIC (X) (11) The material for a three-dimensional printer according to claim 10, wherein the T ^IC (X) is 700 seconds or more and 1400 seconds or less. A method for manufacturing a shaped object, comprising a step of melt laminating a composition for a three-dimensional printer according to any one of claims 1 to 9, or a material for a three-dimensional printer according to claim 10 or 11, using a three-dimensional printer.