JP2023124604A - Composition for three-dimensional molding, filament for three-dimensional molding, and molded body - Google Patents

Abstract

To provide a composition for three-dimensional molding with suppressed deformation caused by heat shrinkage of a thermoplastic resin to such an extent that can produce a highly accurate molded body.SOLUTION: A composition for three-dimensional molding includes: 45-75 pts. mass of 4-methyl-1-pentene-based polymer (A) which satisfies (A-a) and (A-b); and 25-55 pts.mass of 4-methyl-1-pentene-based polymer (B) which satisfies (B-a) and (B-b) (provided that the total of 4-methyl-1-pentene-based polymer (A) and 4-methyl-1-pentene-based polymer (B) is 100 pts.mass.), where the tensile elastic modulus is 10-1,000 MPa. (A-a): (A) comprises 90-100 mol% of a constitutional unit (i) derived from 4-methyl-1- pentene, and 0-10 mol% of a constitutional unit (ii) derived from C5-20 α-olefin (excluding 4-methyl-1-pentene) (provided that the total of the constitutional unit (i) and the constitutional unit (ii) is 100 mol%). (A-b): The melting point (Tm) measured by a differential scanning calorimeter (DSC) is within a range of 200-250°C. (B-a): (B) comprises 60-78 mole% of a constitutional unit (iii) derived from 4-methyl-1-pentene, and 22-40 mol% of a constitutional unit (iv) derived from C2-4 α-olefin (provided that the total of the constitutional unit (iii) and the constitutional unit (iv) is 100 mol%). (B-b): the melting point (Tm) measured by a differential scanning calorimeter (DSC) is not observed.SELECTED DRAWING: None

Description

The present invention relates to a composition for three-dimensional modeling, a filament for three-dimensional modeling, and a modeled body.

2. Description of the Related Art In recent years, as one of efficient modeling techniques, a method of modeling a modeled object using a manufacturing apparatus for three-dimensional modeling (three-dimensional printer) has attracted attention. Among the methods of forming a modeled body, the method of melting and laminating thermoplastic resins allows the use of a wide range of materials and is advantageous in terms of cost.

Thermoplastic resins such as acrylonitrile-butadiene-styrene copolymer (ABS resin) and polylactic acid (PLA resin) have conventionally been proposed as materials for forming a modeled body from the viewpoint of fluidity and formability. (See Patent Documents 1 and 2). However, since these resins have a high specific gravity and are hard materials, it is difficult to reduce the weight of the shaped body, and it is difficult to manufacture a soft shaped body.

Therefore, as a modeling material that does not cause the above problems that occur when ABS resin and PLA resin are used, Patent Document 3 discloses that the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.1 to 5.0 dl / g, the molecular weight distribution (Mw / Mn) is 1.0 to 3.5, and the melting point measured by differential scanning calorimetry is 100 ° C. or higher and lower than 165 ° C., or is substantially not observed and a filament for three-dimensional printer modeling containing a propylene-based copolymer having a density in the range of 810 to 880 kg/m ³ .

Japanese Patent No. 5911564 JP 2016-215502 A JP 2018-158451 A

However, even when any of the modeling materials described in Patent Documents 1 to 3 is used, due to thermal contraction when the molten modeling material extruded from the nozzle solidifies as a three-dimensional model, modeling In some cases, the body is deformed, and a highly accurate shaped body cannot be obtained. It has been proposed to add a filler with a low coefficient of thermal expansion to the molding material to suppress deformation due to thermal contraction. In some cases, the toughness of the steel was deteriorated.

An object of the present invention is to provide a composition for three-dimensional modeling in which deformation due to heat shrinkage of a thermoplastic resin is suppressed to the extent that a highly accurate modeled object can be manufactured.

As a result of the studies conducted by the present inventors, a 4-methyl-1-pentene polymer (A) that satisfies specific requirements and a 4-methyl-1-pentene copolymer (B) that satisfies specific requirements in a specific proportion and having a tensile modulus within a specific range, the inventors have found that the above problems can be solved, and have completed the present invention.

That is, the present invention has, for example, the following items [1] to [8].

[1] 45 to 75 parts by mass of a 4-methyl-1-pentene polymer (A) that satisfies the following requirements (Aa) and (Ab);
Contains 25 to 55 parts by mass of a 4-methyl-1-pentene copolymer (B) that satisfies the following requirements (Ba) and (Bb) (however, a 4-methyl-1-pentene polymer ( The total of A) and the 4-methyl-1-pentene copolymer (B) is 100 parts by mass.),
A three-dimensional modeling composition having a tensile modulus of 10 to 1000 MPa.
Requirement (Aa) 90 to 100 mol% of structural units (i) derived from 4-methyl-1-pentene and α-olefins having 5 to 20 carbon atoms (excluding 4-methyl-1-pentene) Consists of 0 to 10 mol % of derived structural unit (ii) (provided that the total of structural unit (i) and structural unit (ii) is 100 mol %).
Requirement (Ab) Melting point (Tm) measured by differential scanning calorimeter (DSC) is in the range of 200 to 250°C.
Requirement (Ba) 60 to 78 mol % of the structural unit (iii) derived from 4-methyl-1-pentene and 22 to 40 mol of the structural unit (iv) derived from an α-olefin having 2 to 4 carbon atoms % (provided that the total of structural unit (iii) and structural unit (iv) is 100 mol %).
Requirement (Bb) No melting point (Tm) measured by differential scanning calorimeter (DSC) is observed.

[2] The three-dimensional modeling composition according to [1], wherein the 4-methyl-1-pentene polymer (A) further satisfies requirements (Ac).
Requirement (A-c) Melt flow rate (MFR) at 260° C. under 5 kg load is in the range of 0.01 g/10 min to 250 g/10 min.

[3] The 4-methyl-1-pentene copolymer (B) satisfies at least one requirement selected from the group consisting of the following requirements (Bc), (Bd) and (Be): The composition for three-dimensional modeling according to [1] or [2].
Requirement (Bc) The intrinsic viscosity [η] measured in decalin at 135°C is in the range of 0.5 to 4.0 dl/g.
Requirement (Bd) The molecular weight distribution (Mw/Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC), It ranges from 1.0 to 3.5.
Requirement (Be) density is in the range of 825-860 kg/m ³ .

[4] The composition for three-dimensional modeling according to any one of [1] to [3], which has a Shore D hardness of 50 to 90 as measured according to JIS K6253.

[5] A filament for three-dimensional modeling containing the composition for three-dimensional modeling according to any one of [1] to [4].

[6] A modeled body containing the composition for three-dimensional modeling according to any one of [1] to [4].

[7] A method for producing a three-dimensional modeling filament using the three-dimensional modeling composition according to any one of [1] to [4].

[8] A method for manufacturing a modeled object using the composition for three-dimensional modeling according to any one of [1] to [4].

ADVANTAGE OF THE INVENTION The present invention provides a composition for three-dimensional modeling in which deformation caused by thermal contraction of a thermoplastic resin is suppressed to the extent that a highly accurate modeled object can be manufactured.

<<Composition for 3D modeling>>
The composition for three-dimensional modeling of the present invention comprises a 4-methyl-1-pentene polymer (A) that satisfies specific requirements, and a 4-methyl-1-pentene copolymer (B) that satisfies specific requirements. in a specific proportion, and has a tensile modulus in the range of 10 to 1000 MPa.

<4-methyl-1-pentene polymer (A)>
The 4-methyl-1-pentene polymer (A) contained in the composition for three-dimensional modeling of the present invention satisfies the following requirements (Aa) and (Ab), and preferably further requirements ( A polymer satisfying at least one selected from the group consisting of Ac) to requirements (Ah). In the following description, the 4-methyl-1-pentene polymer (A) may be simply referred to as "polymer (A)".

<Requirement (A-a)>
In the polymer (A), the structural unit derived from 4-methyl-1-pentene is "structural unit (i)", α-olefin having 5 to 20 carbon atoms (excluding 4-methyl-1-pentene ) is referred to as a “structural unit (ii)”, the amount of the structural unit (i) is 90 to 100 mol%, preferably 92 to 99 mol%, and the structural unit (ii) The amount is 0 to 10 mol %, preferably 1 to 8 mol % (provided that the total of structural unit (i) and structural unit (ii) is 100 mol %).

When the content of the structural unit (i) in the polymer (A) is 90 mol% or more, heat resistance suitable as a composition for three-dimensional modeling is obtained, and elastic modulus and flexibility suitable for handling are obtained. It has the advantage of being flexible.

Examples of α-olefins having 5 to 20 carbon atoms other than 4-methyl-1-pentene that form the structural unit (ii) of the polymer (A) include 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-eicosene and the like.

The α-olefin forming the structural unit (ii) is preferably an α-olefin having 8 to 18 carbon atoms from the viewpoint of imparting an appropriate elastic modulus and flexibility to the composition for three-dimensional modeling. Specifically, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene and 1-octadecene are more preferred, and 1-hexadecene, 1-heptadecene and 1-octadecene are particularly preferred. These α-olefins can be used singly or in combination of two or more.

The polymer (A) is a structural unit (i) derived from 4-methyl-1-pentene and a structure derived from an α-olefin other than 4-methyl-1-pentene, as long as the effects of the present invention are not impaired. It may contain structural units other than unit (ii). The content of other structural units is, for example, 0 to 10 mol % (provided that the total content of structural units (i) and (ii) is 100 mol %).

The value of the content (mol%) of each structural unit in the polymer (A) is similar to the content of each structural unit in the 4-methyl-1-pentene copolymer (B) described later, carbon 13C nuclear magnetic It is calculated by a measurement method using resonance (hereinafter sometimes referred to as ¹³ C-NMR). A specific measuring method will be described in Examples below.

<Requirements (A-b)>
The polymer (A) has a melting point (Tm) measured by a differential scanning calorimeter (DSC) in the range of 200 to 250°C, preferably 200 to 245°C, more preferably 200 to 240°C. If the melting point of the polymer (A) is within the above range, the resulting three-dimensional modeling composition will have appropriate heat resistance. A specific method for measuring the melting point (Tm) will be described in Examples below.

<Requirements (A-c)>
The melt flow rate (MFR) of the polymer (A) measured at 260° C. under a load of 5.0 kg according to ASTM D1238 is usually 0.01 g/10 min to 250 g/10 min, preferably 5 g/10 min. ~230 g/10 min, more preferably 10 g/10 min to 220 g/10 min, more preferably 15 g/10 min to 200 g/10 min.

When the MFR of the polymer (A) is within the above range, it can be easily mixed with the 4-methyl-1-pentene copolymer (B) described later by melt-kneading, and the resulting three-dimensional modeling composition can be molded. is easy.

<Requirements (A-d)>
The polymer (A) has an intrinsic viscosity [η] measured at 135°C in a decalin solvent of preferably 1.0 to 4.0 dl/g, more preferably 1.0 to 3.5 dl/g, and further It is preferably in the range of 1.0 to 3.0 dl/g.

When the intrinsic viscosity [η] of the polymer (A) is within the above range, the composition for three-dimensional modeling has good fluidity and excellent moldability. A specific method for measuring the intrinsic viscosity [η] is as described in Examples below.

<Requirements (Ae)>
The polymer (A) has a molecular weight distribution (Mw/Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC), preferably 1.5. It ranges from 0 to 7.0. The molecular weight distribution (Mw/Mn) is more preferably 2.0 to 6.0, still more preferably 2.5 to 5.0.

When the molecular weight distribution (Mw/Mn) is within the above range, the influence of the composition distribution and the low molecular weight polymer can be suppressed, which is advantageous for expressing the mechanical properties, moldability and wear resistance of the polymer (A). and can suppress stickiness. Therefore, a composition for three-dimensional modeling containing a polymer (A) having a molecular weight distribution (Mw/Mn) within the above range tends to be excellent in moldability and abrasion resistance, and easily prevent stickiness. In addition, there is a tendency that the mechanical properties and wear resistance of a modeled article made of the composition for three-dimensional modeling containing the polymer (A) are improved.

<Requirements (Af)>
The polymer (A) preferably has a density in the range of 820-850 kg/m ³ , more preferably 825-845 kg/m ³ . When the density of the polymer (A) is within the above range, it is possible to produce a lightweight and strong modeled object using the three-dimensional modeling composition containing the polymer (A). The details of the density measurement conditions, etc., are as described in Examples below.

<Requirements (A-g)>
Polymer (A) has a temperature range of -40 to 150 ° C., torsion mode, frequency of 10 rad / s (1.6 Hz), dynamic viscoelasticity measurement with a strain setting of 0.1%. The value is preferably in the range of 0.01 to 5.0, more preferably 0.1 to 3.0, still more preferably 0.1 to 2.0. In the following description, the maximum value of loss tangent tan δ may be referred to as "tan δ peak value".

Here, the loss tangent tan δ is the ratio (G″/G′) of the storage elastic modulus G′ and the loss elastic modulus G″ measured by dynamic viscoelasticity, and is used for evaluating stress relaxation. The storage elastic modulus G' is an elastic component that retains the stress by storing the energy inside when stress is applied. On the other hand, the loss elastic modulus G″ is a viscous component that converts the energy into heat and releases it (diffuses to the outside) when stress is applied. Therefore, the loss tangent tan δ under a specific temperature environment is The higher the material, the easier it is to absorb the impact, and the higher the stress relaxation.

When the tan δ peak value of the polymer (A) alone is 0.1 or more, deformation of the modeled body due to stress absorption can be suppressed.

<Requirements (A-h)>
The polymer (A) has a loss tangent tan δ value obtained by dynamic viscoelasticity measurement in a temperature range of -40 to 150 ° C., torsion mode, frequency 10 rad / s (1.6 Hz), strain setting 0.1%. is in the range of preferably -30 to 100°C, more preferably 0 to 50°C, still more preferably 10 to 50°C. In the following description, the temperature at which the loss tangent tan δ becomes maximum may be referred to as "tan δ peak temperature".

Furthermore, in the composition for three-dimensional modeling according to the present invention, when the tanδ peak temperature of the polymer (A) alone is in the range of -30 to 100°C, the composition for three-dimensional modeling and the composition for three-dimensional modeling It becomes easy to relax the stress such as distortion and deformation generated in the shaped body obtained from, and the composition has excellent shaping accuracy. A specific method for measuring tan δ will be described in Examples below.
The tan δ peak value and tan δ peak temperature can be adjusted by the composition ratio of structural unit (i)/structural unit (ii) in the polymer (A).

<<Method for producing polymer (A)>>
Polymer (A) can be produced, for example, by polymerizing 4-methyl-1-pentene and optionally an α-olefin having 5 to 20 carbon atoms (excluding 4-methyl-1-pentene). . It may also be produced by thermally decomposing a high-molecular-weight 4-methyl-1-pentene polymer. Further, the polymer (A) may be purified by a method such as solvent fractionation for fractionation based on the difference in solubility in a solvent, or molecular distillation for fractionation based on the difference in boiling point.

The polymer (A) is a conventionally known catalyst for olefin polymerization, such as a vanadium-based catalyst, a titanium-based catalyst, a magnesium-supported titanium catalyst, International Publication No. 01/53369, International Publication No. 01/27124, JP-A-3 -193796, or using a metallocene catalyst described in JP-A-2-41303, 4-methyl-1-pentene and, if necessary, an α-olefin having 5 to 20 carbon atoms (4-methyl -1-pentene) can be obtained by polymerizing.
Moreover, a commercial item can be used for the polymer (A), for example, TPX (registered trademark) manufactured by Mitsui Chemicals, Inc. can be mentioned.

<4-methyl-1-pentene copolymer (B)>
The 4-methyl-1-pentene copolymer (B) contained in the composition for three-dimensional modeling of the present invention satisfies the following requirements (Ba) and (Bb), and preferably further requirements ( At least one requirement selected from the group consisting of Bc) to (Bh) is satisfied. For example, 4-methyl-1-pentene copolymer (B) satisfies requirements (Ba) and (Bb), and further requirements (Bc), (Bd), and (B- It may satisfy at least one requirement selected from the group consisting of e). In the following description, the 4-methyl-1-pentene copolymer (B) may be simply referred to as "copolymer (B)".

<Requirement (B-a)>
In the copolymer (B), the structural unit derived from 4-methyl-1-pentene is "structural unit (iii)", and the structural unit derived from α-olefin having 2 to 4 carbon atoms is "structural unit (iv )”, the amount of the structural unit (iii) is 60 to 78 mol%, and the amount of the structural unit (iv) is 22 to 40 mol% (provided that the structural unit (iii) and the structural unit (iv) shall be 100 mol %).

Since the content of the structural unit (iii) in the copolymer (B) is 60 mol % or more and 78 mol % or less, the composition containing the copolymer (B) and the shaped article formed from the composition Can provide stress relaxation.
Since the content of the structural unit (iv) in the copolymer (B) is 22 mol % or more and 40 mol % or less, the composition containing the copolymer (B) and the shaped article formed from the composition Can provide stress relaxation.

The content (mol %) of each structural unit in the copolymer (B) is calculated based on the results obtained by ¹³ C-NMR measurement, as in the case of the polymer (A). A specific measuring method will be described later in Examples.

The content of the structural unit (iii) in the copolymer (B) is preferably 65 to 75 mol%, more preferably 68 to 75 mol%, still more preferably 70, from the viewpoint of facilitating expression of stress relaxation properties. It is in the range of ~75 mol%.

The content of the structural unit (iv) in the copolymer (B) is preferably 25 to 35 mol%, more preferably 25 to 32 mol%, still more preferably 25, from the viewpoint of ease of expression of stress relaxation properties. It is in the range of ~30 mol%.

Examples of the α-olefin having 2 to 4 carbon atoms forming the structural unit (iv) in the copolymer (B) include ethylene, propylene and 1-butene. These can be used singly or in combination of two or more as long as the effects of the present invention are not impaired. Among these, propylene is particularly preferable, and compatibility with the polymer (A) used in the composition for three-dimensional modeling can be obtained.

<Requirement (Bb)>
Copolymer (B) has no melting point (Tm) observed by differential scanning calorimeter (DSC). The value of the melting point (Tm) varies depending on the stereoregularity of the copolymer (B) and the α-olefin used as the structural unit (iv). The value of the melting point (Tm) and the presence or absence of the melting point (Tm) of the copolymer (B) can be adjusted by controlling the desired composition using an olefin polymerization catalyst, which will be described later. The details of the melting point (Tm) measurement conditions and the like are as described in Examples described later.

<Requirements (Bc)>
Copolymer (B) has a limiting viscosity [η] measured at 135°C in a decalin solvent of preferably 0.5 to 4.0 dl/g, more preferably 0.6 to 3.5 dl/g, More preferably, it is in the range of 0.8 to 3.0 dl/g.

When the intrinsic viscosity [η] of the copolymer (B) is within the above range, the composition for three-dimensional modeling and the modeled object obtained from the composition for three-dimensional modeling are not sticky due to the small amount of low-molecular-weight components. is reduced, and molding of the shaped body is facilitated. A specific method for measuring the intrinsic viscosity [η] is as described in Examples below.

<Requirements (B-d)>
The copolymer (B) preferably has a molecular weight distribution (Mw/Mn), which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC), to 1. .0 to 3.5. The molecular weight distribution (Mw/Mn) is more preferably 1.2 to 3.0, still more preferably 1.5 to 2.5.

When the molecular weight distribution (Mw/Mn) is 3.5 or less, the effect of the low molecular weight and low stereoregular polymer derived from the composition distribution is small, and the composition for three-dimensional modeling and the composition obtained from the composition for three-dimensional modeling are The stickiness of the shaped body to be applied is reduced, and molding of the shaped body is facilitated.

<Requirements (Be)>
The copolymer (B) preferably has a density in the range of 825-860 kg/m ³ , more preferably 830-850 kg/m ³ . When the density is within the above range, uniform and good dispersibility can be obtained for the polymer (A) contained in the composition for three-dimensional modeling, which is preferable. In addition, the obtained composition for three-dimensional modeling is advantageous because it can be formed into uniform filaments. The details of the density measurement conditions, etc., are as described in Examples below.

<Requirements (Bf)>
Copolymer (B) has a loss tangent tan δ peak determined by dynamic viscoelasticity measurement in a temperature range of -40 to 150 ° C., torsion mode, frequency 10 rad / s (1.6 Hz), strain setting 0.1% The value is preferably in the range of 0.5-5.0, more preferably 0.6-4.5, still more preferably 0.7-4.0.

When the tan δ peak value of the copolymer (B) alone is 0.5 or more, stress such as strain and deformation generated in the composition for three-dimensional modeling and the modeled object obtained from the composition for three-dimensional modeling is alleviated. It becomes easy to form, and it becomes a composition excellent in molding accuracy.

<Requirements (B-g)>
Copolymer (B) has a loss tangent tan δ peak determined by dynamic viscoelasticity measurement in a temperature range of -40 to 150 ° C., torsion mode, frequency 10 rad / s (1.6 Hz), strain setting 0.1% The maximum temperature is preferably in the range of -30 to 60°C, more preferably -20 to 50°C, still more preferably 10 to 50°C.

Further, in the composition for three-dimensional modeling according to the present invention, when the tan δ peak temperature of the copolymer (B) alone is in the range of -30 to 60°C, the composition for three-dimensional modeling and the composition for three-dimensional modeling It becomes easy to relax stress such as distortion and deformation generated in a shaped body obtained from an object, and the composition has excellent shaping accuracy. A specific method for measuring tan δ will be described in Examples below.
The tan δ peak value and tan δ peak temperature can be adjusted by the composition ratio of structural unit (iii)/structural unit (iv) in the copolymer (B).

<Requirements (Bh)>
The melt flow rate (MFR) of the copolymer (B) measured at 230° C. under a load of 2.16 kg according to ASTM D1238 is preferably 4.0 to 30 g/10 min, more preferably 6.0 to 15 g/10 min, more preferably in the range of 7.0 to 13 g/10 min.

When the MFR of the copolymer (B) is within the above range, a composition for three-dimensional modeling with excellent moldability can be easily obtained.

<<Method for producing copolymer (B)>>
The method for producing the copolymer (B) is not particularly limited. For example, by polymerizing 4-methyl-1-pentene and the aforementioned α-olefin having 2 to 4 carbon atoms in the presence of an appropriate polymerization catalyst such as a magnesium supported titanium catalyst or a metallocene catalyst, a copolymer can be obtained. (B) is produced.

Polymerization catalysts that can be used in the production of the copolymer (B) include conventionally known catalysts such as magnesium-supported titanium catalysts, International Publication No. 01/53369, International Publication No. 01/27124, and JP-A-3. -193796, or the metallocene catalysts described in JP-A-2-41303, WO 2011/055803, WO 2014/050817, and the like. Polymerization can be carried out by appropriately selecting from a liquid phase polymerization method including solution polymerization and suspension polymerization, a gas phase polymerization method, and the like.

In the liquid phase polymerization method, an inert hydrocarbon solvent can be used as a solvent that constitutes the liquid phase. Examples of said inert hydrocarbons include aliphatic hydrocarbons including propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, and the like. aromatic hydrocarbons, including benzene, toluene, and xylene; and halogenated hydrocarbons, including ethylene chloride, chlorobenzene, dichloromethane, trichloromethane, and tetrachloromethane, and mixtures thereof. included.

Further, in the liquid phase polymerization method, the monomer corresponding to the structural unit (iii) derived from the above-mentioned 4-methyl-1-pentene (that is, 4-methyl-1-pentene), the above-mentioned Bulk polymerization can also be carried out using the monomer corresponding to the structural unit (iv) derived from the α-olefin (that is, the aforementioned α-olefin having 2 to 4 carbon atoms) itself as a solvent.

The 4-methyl-1-pentene and the α-olefin having 2 to 4 carbon atoms are copolymerized step by step to form the copolymer (B). - The composition distribution of the pentene structural unit (iii) and the C 2-4 α-olefin structural unit (iv) can be controlled appropriately.

The polymerization temperature for polymerizing the copolymer (B) is preferably -50 to 200°C, more preferably 0 to 100°C, and even more preferably 20 to 100°C. The polymerization pressure for polymerizing the copolymer (B) is preferably normal pressure to 10 MPa gauge pressure, more preferably normal pressure to 5 MPa gauge pressure.

Hydrogen may be added during the polymerization of the copolymer (B) for the purpose of controlling the molecular weight and polymerization activity of the resulting polymer. The amount of hydrogen to be added is appropriately about 0.001 to 100 NL per 1 kg of the amount of 4-methyl-1-pentene and the amount of α-olefin having 2 to 4 carbon atoms. be.

<Composition for three-dimensional modeling>
The composition for three-dimensional modeling of the present invention contains 45 to 75 parts by mass, preferably 50 to 70 parts by mass, more preferably 50 to 65 parts by mass, still more preferably 55 to 65 parts by mass of the polymer (A). Furthermore, the copolymer (B) is added in an amount of 25 to 55 parts by mass, preferably 30 to 50 parts by mass, more preferably 35 to 50 parts by mass, more preferably 35 to 45 parts by mass (however, the polymer (A ) and the copolymer (B) is 100 parts by mass).
In the composition for three-dimensional modeling of the present invention, deformation due to heat shrinkage of the thermoplastic resin is suppressed. Therefore, it is possible to use the composition for three-dimensional modeling without adding a component (such as a filler) that suppresses the deformation of the three-dimensional modeled object produced from the composition for three-dimensional modeling.

By containing the polymer (A) within the above range, the three-dimensional modeling composition according to the present invention has heat resistance higher than that of a resin composition containing a polymer (A) content less than the above range. Excellent. In addition, the composition for three-dimensional modeling according to the present invention contains the polymer (A) within the above range, so that compared with a resin composition having a polymer (A) content larger than the above range, Improves adhesion to materials.
The composition for three-dimensional modeling according to the present invention contains the copolymer (B) within the above range, so that compared with a resin composition having a content of the copolymer (B) less than the above range, Since the stress relaxation property is high, the balance between the elastic modulus and the stress relaxation property is good, and it becomes easy to produce a modeled object from the composition for three-dimensional modeling. The composition for three-dimensional modeling according to the present invention contains the copolymer (B) within the above range, so that compared with a resin composition containing a larger content of the copolymer (B) than the above range, Since the elastic modulus increases, it becomes easier to produce a modeled object from the composition for three-dimensional modeling.

The composition for three-dimensional modeling according to the present invention has a tensile modulus measured in accordance with JIS K7161-2:2014 of 10 to 1000 MPa, preferably 100 to 800 MPa, more preferably 150 to 750 MPa, further preferably 200. ~400 MPa. When the tensile modulus of the composition for three-dimensional modeling is within the above range, the residual stress contained in the modeled object can be reduced, and warping of the modeled object can be suppressed.

The composition for three-dimensional modeling according to the present invention preferably has a Shore D hardness value immediately after the start of contact with an indenter, which is measured in a state in which three press sheets having a thickness of 2 mm are stacked in accordance with JIS K6253. is 50-90, more preferably 52-80, even more preferably 55-75. When the value of the Shore D hardness of the composition for three-dimensional modeling is within the above range, the material can be supplied without problems during three-dimensional modeling using the extrusion lamination method.
As will be described later, in the extrusion lamination method, filaments and pellets are sometimes used as the material for the shaped body. When a filament is used as a material, the filament is delivered by a gear. When the Shore D hardness value of the composition for three-dimensional modeling is within the above range, the composition has a hardness that facilitates delivery by a gear. It has a hardness that can suppress wear of the gear while having the hardness. On the other hand, when pellets are used as the material, the pellets are discharged after melt-kneading with a screw. It is easy and tends to reduce screw wear.

The composition for three-dimensional modeling according to the present invention is obtained by mixing the polymer (A) and the copolymer (B) in the specific ratio. The mixing method is not particularly limited, and various known methods, for example, a method of dry blending the above components with a Henschel mixer, a tumbler blender, a V-blender, etc., after dry blending, a single screw extruder, twin screw extrusion. It can be adjusted by a method of melt-kneading with a machine, a Banbury mixer or the like, a method of stirring and mixing in the presence of a solvent, and the like.

The composition for three-dimensional modeling according to the present invention can contain an antioxidant as necessary within a range that does not impair the effects of the present invention. A known antioxidant can be used as the antioxidant. Specifically, hindered phenol compounds, sulfur-based antioxidants, lactone-based antioxidants, organic phosphite compounds, organic phosphonite compounds, or combinations of several of these can be used.

The composition for three-dimensional modeling according to the present invention contains conventionally known additives such as weather stabilizers, ultraviolet absorbers, antistatic agents, anti-slip agents, anti-blocking agents, and the like, as long as the effects of the present invention are not impaired. Anti-fogging agents, crystal nucleating agents, lubricants, pigments, dyes, anti-aging agents, hydrochloric acid absorbents, inorganic or organic fillers, organic or inorganic foaming agents, cross-linking agents, cross-linking aids, adhesives, softeners , may contain various additives such as flame retardants. Regarding the contents of the various additives described above, the contents of the components other than the polymer (A) and the copolymer (B) in the resin composition (X) are the contents of the polymer (A) and the copolymer (B). It is preferably 5 parts by mass or less, more preferably 3 parts by mass or less with respect to the total of 100 parts by mass.

Moreover, the composition for three-dimensional modeling according to the present invention may also contain a polymer other than the polymer (A) and the copolymer (B). In that case, the content of the components other than the polymer (A) and the copolymer (B) in the three-dimensional modeling composition is , preferably 20 parts by mass or less, more preferably 10 parts by mass or less.

<Form of 3D modeling composition>
The form of the composition for three-dimensional modeling may be a molded article. The molding method for the molded product is not particularly limited, and the molded product may be molded by a known molding method such as extrusion molding. Also, the form of the molded article may be pellets or filaments.
Pellets refer to small amounts of pre-shaped solids.
A filament refers to an elongated string-like elongated object with a uniform cross-section. Filaments are generally used in the form wound on reels.

The composition for three-dimensional modeling may be in the form of pellets or filaments, or may be a mixture of materials in both pellet and filament forms. The form of the composition for three-dimensional modeling is preferably a pellet from the viewpoint of modeling a relatively large shaped object.

When molding the composition for three-dimensional modeling into pellets, the molding method is not limited. Examples of the method of forming pellets include a method of kneading and extruding a three-dimensional modeling composition with a melt extruder (eg, twin screw extruder) and cutting the extruded rod-shaped strands with a pelletizer. Also, the composition for three-dimensional modeling to be fed into the melt extruder may be a dry blend. A dry blend is prepared by previously mixing part or all of the composition for three-dimensional modeling with a Henschel mixer or the like.

≪Filament for 3D modeling≫
The filament for three-dimensional modeling of the present invention is produced by melt-spinning the composition for three-dimensional modeling and further drawing. A known melt spinning method can be employed for melt spinning. Moreover, a well-known method can be employ|adopted also about extending|stretching.

As a method for producing the filament of the present invention, for example, the composition for three-dimensional modeling is extruded as a molten strand through a die hole of a single-screw extruder or a twin-screw extruder, introduced into a cooling water tank, and extruded to obtain a strand. a drawing step of drawing the strands; and a winding step of winding the drawn filaments.

The extrusion is carried out at a temperature in the range of the melting point (Tm) of the polymer (A) to the melting point (Tm)+130° C., and the molten strand extruded from the die is immersed in a water bath and cooled. The water temperature is preferably in the range of 5 to 60°C, more preferably 7 to 50°C, still more preferably 10 to 40°C, depending on the diameter of the filament to be used. If the water temperature is high, the strand will be insufficiently cooled, and the strand will be introduced into the next drawing process while it is still soft, which may cause winding failure on the take-up roll (stretching roll).

Drawing in the present invention means an operation of mechanically drawing a filament at a temperature below the melting point of the material to orient the molecular chains parallel to the drawing direction. This operation significantly improves tensile strength and increases toughness. After the stretching process, if it is reheated above the stretching temperature, it will tend to shrink back to its original dimensions. ).

In the present invention, the strand obtained by the extrusion process is heated to a specific temperature and stretched. Stretching is carried out according to the speed ratio (stretch ratio) between the take-up roll on the entrance side and the take-up roll on the exit side, and the stretch ratio at this time is preferably 2 to 15 times. A hot water bath, an oven, a hot roll, or the like may be used as a heating method during stretching, and there is no limitation, but a hot water bath is more preferable for more uniform heating and stretching.

Stretching using a hot water bath can be realized by arranging a water bath having a length and depth in which the water temperature can be adjusted and take-up rolls in front of and behind the water bath. Stretching using an oven uses an electric heater (infrared heater) as a heat source and is placed in the take-up direction, and can be realized by placing an oven with a length of several meters whose temperature is adjustable and take-up rolls in front of and behind it. be. In addition, stretching using hot rolls can be realized by installing multiple take-up rolls whose temperature is controlled by water pipes, oil pipes, and electric heaters placed inside, and adjusting the rotation speed of the rolls. is.

The temperature conditions during drawing are almost the same regardless of which device and method such as a hot water bath, oven, or hot roll is selected, and the surface temperature of the filament before drawing is the glass transition temperature (Tg) of the polymer (A). to the melting point (Tm), more preferably Tg to Tm-30°C, and even more preferably Tg to Tm-60°C. If the surface temperature is lower than Tg, the stretch may be broken, or the stretch may not be doubled or more. Conversely, if the Tm is exceeded, the effect of strength development by stretching is reduced.

The draw ratio is usually 2 to 15 times, preferably 3 to 12 times, more preferably 4 to 10 times. If the draw ratio is less than 2 times, the strength development by the drawing operation may be insufficient. On the other hand, if the draw ratio exceeds 15 times, troubles such as breakage of drawing, whitening due to voids, and longitudinal cracking of filaments may occur.

As a method of stretching 2 to 15 times, in addition to a method of performing a single stage stretching process, a plurality of times of stretching are appropriately combined to form a 2-stage, 3-stage to multi-stage structure, and each stage has a small magnification. A method in which stretching is performed to set the overall stretching ratio to 2 to 15 times may also be used.

When performing multistage stretching, the stretching ratio is changed sequentially, for example, 1.1 to 10 times in the first stage and 1.5 to 12 times in the second stage, so that the overall stretching ratio is 2. 15 times, and at the same time, the heating temperature conditions are preferably such that the first stage is the lowest in the above temperature range, and the temperature is successively increased as the number of stages is increased.

In the present invention, the drawn filaments can be further heat-treated (heat-set) to suppress changes in physical properties (for example, shrinkage) at high temperatures. As a method of heat-treating the polymer (A) at a temperature between the glass transition temperature (Tg) and the melting point (Tm), preferably 20 to 140 ° C., more preferably 30 to 120 ° C. It is introduced into a heating tank, A method of cooling in a cooling bath after heat treatment (heat setting) may be mentioned. As in the case of the stretching operation, any method such as a water bath, an oven, or a hot roll may be used for the heat treatment, and there is no limitation. Moreover, the cooling method may be either water cooling or air cooling, and there is no limitation.
Finally, the drawn filament is wound by a special cartridge, bobbin or cone by a winder to obtain a filament roll.

The diameter of the filament for three-dimensional modeling of the present invention depends on the design specifications of the three-dimensional printer used in the modeling process and the system capacity used for modeling, but it is usually 1.0 mm or more, preferably 1.5 mm or more, or more. Preferably, it is 1.6 mm or more. On the other hand, the upper limit is usually 4.0 mm or less, preferably 3.5 mm or less, more preferably 3.0 mm or less.

The roundness of the filament for three-dimensional modeling of the present invention is usually 0.93 or more, preferably 0.95 or more, and the upper limit is 1.0. The circularity is obtained by measuring the major axis and the minor axis with a vernier caliper at a plurality of points on the filament at predetermined intervals, and averaging the ratio of the minor axis/major axis for each measurement point. can be done. The closer the circularity is to 1.0, the closer the cross section of the filament is to a perfect circle.
A filament having a diameter and a circularity within the above range is excellent in formability, and is therefore suitable for producing a shaped body with excellent appearance, surface properties, and the like.

≪Method for manufacturing model≫
The method for manufacturing a modeled body comprises a melting step of melting the composition for three-dimensional modeling of the present disclosure described above, and extruding the melted composition for three-dimensional modeling from a nozzle of a three-dimensional printer to form a modeled body. and The melting process and the shaping process are performed in this order.

(melting process)
The melting step melts the composition for three-dimensional modeling. A heating means for melting the composition for three-dimensional modeling is not particularly limited, and known heating means can be applied.

In the melting step, it is preferable to use a three-dimensional printer equipped with heating means such as an electric heater.

The temperature for melting the three-dimensional modeling composition is not particularly limited, and may be appropriately set according to the properties of the polymer (A) and copolymer (B) contained in the three-dimensional modeling composition. The temperature for melting the composition for three-dimensional modeling may be, for example, +10° C. to 150° C. based on the melting point or glass transition temperature (Tg) of the polymer (A), whichever is higher.

In the melting step, for example, the composition for three-dimensional modeling may be melted and kneaded. In particular, when the composition for three-dimensional modeling contains glass fibers, it is preferable to melt and knead the composition for three-dimensional modeling in the melting step. By melting and kneading the composition for three-dimensional modeling, the polymer (A) and the copolymer (B) contained in the composition for three-dimensional modeling tend to mix more uniformly. Therefore, it is easy to suppress the occurrence of unevenness in the material of the obtained modeled body. As a result, the deformation of the shaped body tends to be more suppressed.

(Molding process)
In the modeling process, the three-dimensional modeling composition melted in the melting process is extruded from a nozzle to model a modeled body.

In the modeling process, for example, a molten composition for three-dimensional modeling is extruded from a nozzle of a three-dimensional printer, and based on a plurality of two-dimensional data, two-dimensional layers are sequentially laminated on a substrate, thereby forming a modeled body. can be shaped. A plurality of two-dimensional data are generated by slicing the three-dimensional coordinate data of the object to be formed into slices by slicer software.

A material extrusion type three-dimensional printer can be used as the three-dimensional printer. The material extrusion type three-dimensional printer is not particularly limited, and a known device or a known device configuration can be applied.

A three-dimensional printer may be, for example, a device comprising a cylinder, a nozzle and heating means. A composition for three-dimensional modeling is supplied to the cylinder. The nozzle is provided at a portion of the cylinder on the downstream side in the discharge direction of the composition for three-dimensional modeling. The nozzle ejects the composition for three-dimensional modeling. A heating means is provided in the cylinder. The heating means heats and melts the composition for three-dimensional modeling.
A three-dimensional printer extrudes a heated and melted composition for three-dimensional modeling from a nozzle, and laminate-models the composition for three-dimensional modeling extruded from the nozzle. Thereby, a three-dimensional modeled object is modeled.

The cylinder may have a screw inside it. The screw kneads the three-dimensional modeling material.
The three-dimensional printer may further comprise a table device. A table device is arranged opposite the nozzle. A melted composition for three-dimensional modeling extruded from a nozzle is layered on the table device.
The three-dimensional printer may further comprise control means. The control means controls the spatial coordinates of the substrate and the nozzle, and the amount of the three-dimensional modeling composition extruded from the nozzle. The control means controls the ejection of the molten three-dimensional modeling composition extruded from the nozzle, and controls the movement of the nozzle and/or the table device in the X-axis, Y-axis, and Z-axis directions with respect to the reference plane. preferably.

(Other processes)
The method for manufacturing a shaped body according to the present invention may further include, for example, a processing step. In the processing step, the shaped body shaped in the shaping step is processed.

<Modeled body>
A modeled object according to the present invention is a modeled object formed from the composition for three-dimensional modeling. Therefore, deformation due to thermal contraction or the like of the modeled body is suppressed.

The shaped body according to the present invention is not particularly limited as long as it is a shaped body formed from the composition for three-dimensional modeling, and may be shaped by any method. Above all, it is preferable that the shaped body according to the present invention is shaped by the method for manufacturing the shaped body described above.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. Methods for measuring physical properties of polymers, polymers used, methods for preparing test pieces, and methods for evaluation in the following examples and comparative examples are as follows.

≪Method for measuring physical properties of polymer≫
<Constituent unit content>
The 4-methyl-1-pentene content and α-olefin content of each of the polymers used in Examples and Comparative Examples were calculated based on the results of ¹³ C-NMR measurement using the following apparatus and conditions. However, the α-olefin content in this measurement does not include the content of 4-methyl-1-pentene.

Using a JEOL Ltd. ECP500 type nuclear magnetic resonance apparatus, a mixed solvent of ortho-dichlorobenzene/deuterated benzene (80/20% by volume), a sample concentration of 55 mg/0.6 ml, a measurement temperature of 120° C., and an observation nucleus of ¹³ C. (125 MHz), sequence is single pulse proton decoupling, pulse width is 4.7 μs (45° pulse), repetition time is 5.5 seconds, integration count is 10,000 or more, chemical shift reference value is 27.50 ppm measured as The composition of each polymer was quantified from the obtained ¹³ C-NMR spectrum.

<Melt flow rate (MFR)>
According to ASTM D1238, polymer (A) was measured at a temperature of 260° C. and a load of 5 kg, and copolymer (B) was measured at a temperature of 230° C. and a load of 2.16 kg.

<Melting point (Tm)>
Based on JIS K7121, using a differential scanning calorimeter DSC7000X manufactured by Hitachi High-Tech Science Co., Ltd., the highest temperature of the melting peak apex measured at a heating rate of 10° C./min was taken as the melting point.

<Intrinsic Viscosity>
The intrinsic viscosity was determined at 135° C. in decalin solvent using an Ubbelohde viscometer. First, about 20 mg of a sample was taken from each of the polymers used in Examples and Comparative Examples. The form of the sample may be any of various forms such as polymerized powder, pellets, filaments, and resin lumps. The collected sample was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath heated to 135°C. After diluting this decalin solution with 5 ml of the decalin solvent, the specific viscosity ηsp was measured in the same manner. This dilution operation was repeated twice, and the value of ηsp/C when the concentration (C) was extrapolated to zero was calculated as the intrinsic viscosity (see the formula below).
[η]=lim(ηsp/C) (C→0)

<Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw/Mn value)>
The molecular weight of each of the polymers used in Examples and Comparative Examples was measured by gel permeation chromatography (GPC).
Specifically, a Waters ALC/GPC150-Cplus type (integrated differential refractometer detector) is used as a liquid chromatograph, and two Tosoh GMH6-HT and two GMH6-HTL are used as separation columns. Used in series connection, using o-dichlorobenzene as a mobile phase medium and 0.025% by mass of dibutylhydroxytoluene (manufactured by Takeda Pharmaceutical Company Limited) as an antioxidant, the mobile phase medium was moved at 1.0 ml/min. , the sample concentration was 15 mg/10 ml, the sample injection volume was 500 μL, and a differential refractometer was used as the detector. As standard polystyrene, standard polystyrene manufactured by Tosoh Corporation was used with a weight average molecular weight (Mw) of 1,000 or more and 4,000,000 or less.

By analyzing the obtained chromatogram by creating a calibration curve using a standard polystyrene sample by a known method, the weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn value ) was calculated. The measurement time per sample was 60 minutes.

<Density>
Density was measured using a density gradient tube according to JIS K7112.

≪Synthesis of polymer≫
<Synthesis Example 1: Synthesis of polymer (A-1)>
According to the polymerization method described in Comparative Example 9 of WO 2006/054613, by changing the ratio of 4-methyl-1-pentene, 1-hexadecene, 1-octadecene, and hydrogen, the polymer ( A-1) was obtained. Table 1 shows the measurement results of each physical property.

<Synthesis Example 2: Synthesis of copolymer (B-1)>
300 ml of n-hexane (dried over activated alumina under a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene were placed in a 1.5 L SUS autoclave equipped with a stirring blade that was sufficiently purged with nitrogen at 23°C. entered. The autoclave was charged with 0.75 ml of a 1.0 mmol/ml toluene solution of triisobutylaluminum (TIBAL) and stirred.

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 prepared in advance in terms of aluminum and 0.01 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl)(2,7-di-t-butyl 0.34 ml of a toluene solution containing zirconium dichloride (fluorenyl) was injected into the autoclave with nitrogen to initiate the 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 initiation of polymerization, 5 ml of methanol was injected into the autoclave under pressure with nitrogen to stop the polymerization reaction, and then the pressure inside the autoclave was released to atmospheric pressure. After the pressure was released, the reaction solution was stirred while adding acetone.

The obtained powdery copolymer containing the solvent was dried at 100° C. under reduced pressure for 12 hours. The weight of the product copolymer (B-1) was 36.9 g, the content of 4-methyl-1-pentene in the copolymer (B-1) was 72.4 mol%, and the content of propylene was It was 27.6 mol %. No melting point was observed when measured with a differential scanning calorimeter (DSC). Table 1 shows the measurement results of each physical property.

<Synthesis Example 3: Synthesis of copolymer (CB-1)>
300 ml of n-hexane (dried over activated alumina under a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene were placed in a fully nitrogen-substituted SUS autoclave with a capacity of 1.5 L and equipped with a stirring blade at 23°C. loaded. The autoclave was charged with 0.75 ml of a 1.0 mmol/ml toluene solution of triisobutylaluminum (TIBAL) and stirred.

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 prepared in advance in terms of aluminum and 0.01 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl)(2,7-di-t-butyl 0.34 ml of a toluene solution containing zirconium dichloride (fluorenyl) was injected into the autoclave with nitrogen to initiate the 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 initiation of polymerization, 5 ml of methanol was injected into the autoclave under pressure with nitrogen to stop the polymerization reaction, and then the pressure inside the autoclave was released to atmospheric pressure. After the pressure was released, the reaction solution was stirred while adding acetone.

The obtained powdery polymer containing solvent was dried at 130° C. under reduced pressure for 12 hours. The weight of the product copolymer (CB-1) was 44.0 g, the content of 4-methyl-1-pentene in the copolymer (CB-1) was 84.1 mol%, the content of propylene was was 15.9 mol %. The melting point was 130° C. as measured by a differential scanning calorimeter (DSC). Table 1 shows the measurement results of each physical property.

<Dynamic viscoelasticity measurement of each polymer>
A predetermined amount of each of the polymer (A-1), the copolymer (B-1) and the copolymer (CB-1) obtained by the above method is filled in a SUS mold, and the polymer (A- In the case of 1), the heating plate was set to 270 ° C., and in the case of the copolymer (B-1) and the copolymer (CB-1), the heating plate was set to 200 ° C., and a hydraulic heat press machine (Kansai Roll Co., Ltd. PEWR- 30), preheat for 7 minutes, pressurize at a gauge pressure of 10 MPa for 2 minutes, transfer to a cooling plate set at 20 ° C., compress at a gauge pressure of 10 MPa and cool for 3 minutes, measure a thickness of 2.0 mm A press sheet for

Next, the press sheet for measurement with a thickness of 2.0 mm obtained by the above method was measured by a rheometer (MCR301 manufactured by Anton Paar) in torsion mode, frequency of 10 rad/s (1.6 Hz), strain amount of 0.1. % and a heating rate of 2° C./min. Table 1 shows the results.

[Example 1]
<Preparation Example 1: Preparation of three-dimensional modeling composition>
60 parts by mass of the polymer (A-1) and 40 parts by mass of the copolymer (B-1) were dry-blended to prepare a composition for three-dimensional modeling.

<Measurement of tensile modulus>
The obtained composition for three-dimensional modeling was hot-press molded under conditions of a heating temperature of 200° C., a pressing pressure of 50 MPa, and a pressing time of 3 minutes to obtain a hot-pressed square plate for measurement with a thickness of 2 mm. This plate was punched into a 1BA test piece shape defined in JIS K7161-2:2014. The total length of the hot pressed product for measurement was 75 mm. The tensile modulus of the obtained heat-pressed product for measurement was measured. Table 2 shows the measurement results.

<Measurement of Shore D hardness>
Three heat-pressed rectangular plates for measurement of the composition for three-dimensional modeling described above were stacked to have a total thickness of 6 mm, and the hardness was measured with a Shore D hardness tester according to JIS K6253. The Shore D hardness was obtained immediately after the start of contact with the indentor. Table 2 shows the results obtained.

<Manufacturing filament>
The composition for three-dimensional modeling was melt-kneaded in a twin-screw extruder, extruded and cooled in a cooling water bath to form a strand. After that, the resulting strand was drawn in a hot water bath to produce a filament with a diameter of 1.75 mm.

<Manufacturing and Evaluation of Modeled Objects>
Using the obtained filament with a diameter of 1.75 mm as a material, modeled bodies A1 to A4 were produced using a 3D printer model "Raise3D Pro2" manufactured by Japan 3D Printer Co., Ltd. At this time, shape data was created by Autodesk's software "Fusion360", and modeling conditions were determined by Simplify3D's software "Simplify3D". An evaluation sample was produced under the molding conditions of a molding table of 40° C., a nozzle temperature of 290° C., a molding speed of 60 mm/s, and an internal filling rate of 100%.

The modeled body A1 has a rectangular plate shape with a length of 40 mm, a width of 20 mm, and a thickness of 2 mm, and the modeled body A2 has a rectangular plate shape with a length of 80 mm, a width of 40 mm, and a thickness of 2 mm.
The shaped body A3 is a toothed shaped body with a bottom diameter of 80 mm and a height of 40 mm. Compared to the modeled bodies A1 and A2, the modeled body A3 has an increased uneven shape, and requires fine modeling to reproduce the alignment of human teeth and gums. As the time increases, strong adhesion is required between the modeling table and the modeled body, so modeling is more difficult than with the modeled bodies A1 and A2.
The shaped body A4 is a boat-shaped shaped body with a bottom length of 40 mm, a width of 10 mm, an overall length of 60 mm, and a height of 50 mm. The boat-shaped body A4 is a modeled body that is more difficult to model than the modeled body A3 because the bow is lifted from the bottom and the upper layer portion is larger than the lower layer portion that serves as a support during layered manufacturing. .

The modeled body was evaluated based on the following evaluation criteria based on whether or not modeling was completed and the shape of the modeled body after being released from the modeling table.
(Evaluation criteria)
◯: Modeling was completed without stopping midway, and the amount of warpage of the modeled body after releasing from the mold was less than 2 mm.
Δ: Modeling was completed without stopping midway, and the amount of warpage of the modeled body after release was 2 mm or more.
x: Modeling stopped in the middle because the model warped during modeling.
XX: The filament cannot be installed in the device.
-: Not modeled.

The warpage of the molded body after releasing from the mold was evaluated by placing the molded body on a surface plate and measuring the lift amount of the bottom surface of the molded body from the surface plate. The maximum value of the amount of floating was defined as the amount of warpage of the modeled body. Each measurement result is shown in Table 2.

<Comparative Examples 1 to 7>
The amounts of the polymer (A-1), copolymer (B-1), and copolymer (CB-1) used to prepare the composition for three-dimensional modeling were changed as shown in Table 2. In the same manner as in Example 1, the composition for three-dimensional modeling was prepared, the tensile modulus of elasticity was measured, the Shore D hardness was measured, the shaped body was produced, and the resulting shaped body was evaluated. Table 2 shows the results obtained.

Claims (8)

45 to 75 parts by mass of a 4-methyl-1-pentene polymer (A) that satisfies the following requirements (Aa) and (Ab);
Contains 25 to 55 parts by mass of a 4-methyl-1-pentene copolymer (B) that satisfies the following requirements (Ba) and (Bb) (however, a 4-methyl-1-pentene polymer ( The total of A) and the 4-methyl-1-pentene copolymer (B) is 100 parts by mass.),
A three-dimensional modeling composition having a tensile modulus of 10 to 1000 MPa.
Requirement (Aa) 90 to 100 mol% of structural units (i) derived from 4-methyl-1-pentene and α-olefins having 5 to 20 carbon atoms (excluding 4-methyl-1-pentene) Consists of 0 to 10 mol % of derived structural unit (ii) (provided that the total of structural unit (i) and structural unit (ii) is 100 mol %).
Requirement (Ab) Melting point (Tm) measured by differential scanning calorimeter (DSC) is in the range of 200 to 250°C.
Requirement (Ba) 60 to 78 mol % of the structural unit (iii) derived from 4-methyl-1-pentene and 22 to 40 mol of the structural unit (iv) derived from an α-olefin having 2 to 4 carbon atoms % (provided that the total of structural unit (iii) and structural unit (iv) is 100 mol %).
Requirement (Bb) No melting point (Tm) measured by differential scanning calorimeter (DSC) is observed. The composition for three-dimensional modeling according to claim 1, wherein the 4-methyl-1-pentene polymer (A) further satisfies requirements (Ac).
Requirement (A-c) Melt flow rate (MFR) at 260° C. under 5 kg load is in the range of 0.01 g/10 min to 250 g/10 min. Claim 1, wherein the 4-methyl-1-pentene copolymer (B) satisfies at least one requirement selected from the group consisting of the following requirements (Bc), (Bd) and (Be): Or the composition for three-dimensional modeling according to 2.
Requirement (Bc) The intrinsic viscosity [η] measured in decalin at 135°C is in the range of 0.5 to 4.0 dl/g.
Requirement (Bd) The molecular weight distribution (Mw/Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC), It ranges from 1.0 to 3.5.
Requirement (Be) density is in the range of 825-860 kg/m ³ . The composition for three-dimensional modeling according to any one of claims 1 to 3, wherein the Shore D hardness of the composition measured according to JIS K6253 is 50 to 90. A filament for three-dimensional modeling containing the composition for three-dimensional modeling according to any one of claims 1 to 4. A modeled object containing the composition for three-dimensional modeling according to any one of claims 1 to 4. A method for producing a three-dimensional modeling filament using the three-dimensional modeling composition according to any one of claims 1 to 4. A method for producing a modeled object using the composition for three-dimensional modeling according to any one of claims 1 to 4.