Olefin polymer particles for three-dimensional modeling, method for producing olefin polymer particles for three-dimensional modeling, and olefin polymer particle-containing composition

Abstract

Provided are olefin polymer particles for three-dimensional modeling that satisfy the following requirements (p1)-(p3). (p1) The volume average particle size is 10 μm to 200 μm. (p2) The pore volume at a pore diameter of from 0.001 μm to less than 1 μm is 50 mm3 / g to 300 mm3 / g. (p3) The pore volume at a pore diameter of 1 μm to 10 μm is 5 mm3 / g to 60 mm3 / g. (In requirements (p2) and (p3), the pore diameter and the pore volume are measured with a mercury porosimeter.)

Description

Olefin polymer particles for three-dimensional shaping, method for producing olefin polymer particles for three-dimensional shaping, and composition containing olefin polymer particles

[0001] The present invention relates to olefin polymer particles for three-dimensional shaping, a method for producing olefin polymer particles for three-dimensional shaping, and a composition containing olefin polymer particles.

[0002] Representative examples of 3D printing methods using thermoplastic resins include material extrusion (MEX) and powder bed fusion (PBF), which uses powder materials. The PBF method has high modeling accuracy and is capable of producing finely molded objects, so various methods have been proposed.

[0003] For the particles contained in the powder material used in the PBF method, polyamide 12 is used because the wider the difference between its melting point (Tm) and crystallization temperature (Tc), the easier it is to handle and because of its laser absorbency. On the other hand, polypropylene resin has also attracted attention because of its wide difference between its melting point (Tm) and crystallization temperature (Tc) and its wide range of applications.

[0004] For example, a resin powder for 3D shaping containing ethylene-propylene copolymer particles, which has good tensile strength and excellent elongation at break, and a method for producing a 3D object by the PBF method using the resin powder for 3D shaping have been proposed (see Patent Documents 1 and 2). Conventional olefin polymer powders for 3D shaping are obtained by pulverizing the particles by a freeze-grinding method, and then preferably subjecting the particles to a spheronization treatment to adjust the shape.

[0005] It is known that when producing the above-mentioned three-dimensional objects, various liquid additives are sometimes used in combination with the above-mentioned olefin polymer powder in order to improve the flowability and melt moldability.

[0006] Patent Document 1: International Publication No. 2020 / 213586 Patent Document 2: International Publication No. 2024 / 106234

[0007] As described above, the present inventors have considered that, for example, when various liquid additives are used in combination, it may be important for the components to be finely dispersed, fixed, or easily penetrated into the polypropylene resin. On the other hand, the present inventors have also considered that, because hydrocarbon polymers such as polypropylene resins are generally non-polar or are often crystalline resins, the dispersibility and other functions of the main components may be insufficient.

[0008] Furthermore, since hydrocarbon polymers (particles) such as polypropylene resins are generally non-polar, it is considered necessary to efficiently melt the polymers, integrate them, and crystallize them during cooling in order to obtain molded articles that are excellent in rigidity, appearance after molding, etc.

[0009] The present invention has been made in view of the above, and aims to provide olefin polymer particles for three-dimensional shaping that are expected to have a configuration that can improve the dispersibility of liquid additives, a method for producing olefin polymer particles for three-dimensional shaping, and an olefin polymer particle-containing composition.

[0010] As a result of investigations conducted by the present inventors to solve the above problems, they found that olefin polymer particles having a specific structure are suitable for dispersing liquid compounds, and thus completed the present invention. The present invention is characterized by the following features.

[0011] <1> Olefin polymer particles for three-dimensional shaping, which satisfy the following requirements (p1) to (p3): (p1) a volume average particle diameter of 10 μm to 200 μm; (p2) a pore volume of 50 mm3 or more at pore diameters of 0.001 μm or more and less than 1 μm; ３ / g to 300 mm ３ / g (p3) The pore volume at pore diameters of 1 μm to 10 μm is 5 mm ３ / g to 60mm ３ / g (In the requirements (p2) and (p3), the pore diameter and pore volume are measured by a mercury porosimeter.) <2> The olefin polymer particles for three-dimensional shaping according to <1>, further satisfying the following requirement (p3-2): (p3-2) The pore volume of pores with diameters of 1 μm to 4 μm is 1 mm ３ / g~13mm ３<3> Olefin polymer particles for 3D shaping according to <1> or <2>, further satisfying the following requirement (p4): (p4) the circularity is 0.70 to 0.95 <4> Olefin polymer particles for 3D shaping according to any one of <1> to <3>, further satisfying the following requirement (p5): (p5) the decane soluble component content is 0.1% by mass to 40% by mass <5> A method for producing olefin polymer particles for 3D shaping, comprising the step of polymerizing an olefin in the presence of an olefin polymerization catalyst comprising a solid titanium catalyst component (I) containing (a) a liquid magnesium compound, (b) a liquid titanium compound, and (c) an electron donor, an organometallic compound catalyst component (II), and an electron donor (III), to obtain olefin polymer particles that satisfy the following requirements (p1) to (p3): (p1) The volume average particle diameter is 10 μm to 200 μm. (p2) The pore volume at pore diameters of 0.001 μm or more and less than 1 μm is 50 mm ３ / g to 300 mm ３ / g (p3) The pore volume at pore diameters of 1 μm to 10 μm is 5 mm ３ / g to 60mm ３ / g (In the requirements (p2) and (p3), the pore diameter and pore volume are measured by a mercury porosimeter.) <6> The method for producing olefin polymer particles for three-dimensional shaping according to <5>, wherein the electron donor (c) is an aromatic monocarboxylic acid ester. <7> (α) A method for producing olefin polymer particles for three-dimensional shaping according to the following requirements (p1) to (p3): (p1) a volume average particle diameter of 10 μm to 200 μm; (p2) a pore volume of 50 mm3 at pore diameters of 0.001 μm or more and less than 1 μm. ３ / g to 300 mm ３ / g (p3) The pore volume at pore diameters of 1 μm to 10 μm is 5 mm ３ / g to 60mm ３ / g (In the requirements (p2) and (p3), the pore diameter and pore volume are measured by a mercury porosimeter.) An olefin polymer particle-containing composition comprising either (β) a dissolution promoter or (γ) a surface modifier.

[0012] According to the present invention, there are provided olefin polymer particles for 3D shaping, which have a configuration expected to improve the dispersibility of liquid additives, a method for producing olefin polymer particles for 3D shaping, and an olefin polymer particle-containing composition. The olefin polymer particles of the present invention are particles having a specific pore shape, unlike particles obtained by the conventionally known freeze-pulverization method, and are therefore expected to be able to effectively exhibit the functions of the additives when used in combination with various liquid additives.

[0013] In the present invention, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in the present invention, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in the present invention, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the Examples. In the present invention, when multiple substances corresponding to each component are present, the amount of each component means the total amount of the multiple substances, unless otherwise specified. In the present invention, two or more preferred embodiments can be combined. In the present invention, each physical property value described in the detailed description of the invention can be measured by each method described in the Examples section. "Olefin polymer particles" may also be simply called "resin powder."

[0014] <Olefin polymer particles> The olefin polymer particles for three-dimensional shaping of the present invention (hereinafter also simply referred to as "olefin polymer particles") satisfy the following requirements (p1) to (p3): (p1) The volume average particle diameter is 10 μm to 200 μm. (p2) The pore volume at pore diameters of 0.001 μm or more and less than 1 μm is 50 mm ３ / g to 300 mm ３ (p3) The pore volume at pore diameters of 1 μm to 10 μm is 5 mm ３ / g to 60mm ３ / g.

[0015] The olefin polymer particles having the above-mentioned structure are particles having a specific pore shape, and therefore when used in combination with various liquid additives, it is expected that the additives will effectively exhibit their functions.

[0016] The volume average particle diameter of the olefin polymer particles for 3D shaping of the present invention is 10 μm to 200 μm. The preferred lower limit of the volume average particle diameter of the olefin polymer particles for 3D shaping of the present invention is 15 μm, more preferably 20 μm, even more preferably 23 μm, and particularly preferably 25 μm. On the other hand, the preferred upper limit is 170 μm, more preferably 150 μm, even more preferably 130 μm, and particularly preferably 120 μm. If the volume average particle diameter is lower than the above range, particle fluidity may decrease. On the other hand, if the volume average particle diameter is higher than the above range, it may be impossible to satisfactorily form a shaped object with a fine shape, or the number of contact points between particles may become relatively small.

[0017] The volume average particle size of the olefin polymer can be determined by a laser PSD measuring device using a laser diffraction scattering method. More specific measuring methods include the following.

[0018] Measurements are carried out using a Beckman Coulter LS-13320 laser PSD measuring instrument, according to the standard method specified for that instrument. The sample used is a slurry prepared by suspending and dispersing 20 to 30 mg of olefin polymer particles in an appropriate amount of commercially available decane. (This method is also used in the examples and comparative examples described later in this specification.)

[0019] The pore volume of the olefin polymer particles for three-dimensional shaping of the present invention with a pore diameter of 0.001 μm or more and less than 1 μm is 50 mm ３ / g to 300 mm ３ / g. If the pore volume value is lower than the above range, the effect of additives such as melting promoters may be insufficient. On the other hand, if the pore volume value is higher than the above range, the particles may have a low particle specific gravity, resulting in poor handling properties, or the effect of additives such as melting promoters may be too high, i.e., the particle shape may be deformed by the additives. The preferred lower limit of the pore volume for pore diameters of 0.001 μm or more and less than 1 μm is 52 mm ３ / g, more preferably 53 mm ３ On the other hand, the preferred upper limit is 250 mm ３ / g, more preferably 200 mm ３ / g, more preferably 180 mm ３ / g, particularly preferably 160 mm ３ / g.

[0020] In addition, the olefin polymer particles for three-dimensional shaping of the present invention have a pore volume of 9 mm or less at pore diameters of 0.01 μm or more and less than 0.1 μm. ３ / g to 150 mm ３ A more preferable lower limit of the pore volume for pore diameters of 0.01 μm or more and less than 0.1 μm is 9 mm ３ / g, more preferably 10 mm ３ / g, particularly preferably 11 mm ３ On the other hand, a more preferable upper limit is 130 mm ３ / g, more preferably 110 mm ３ / g, more preferably 100 mm ３ / g, particularly preferably 90 mm ３ / g, particularly preferably 85 mm ３ / g. A more preferable upper limit is 80 mm ３ / g, and particularly preferably 75 mm ３ / g.

[0021] In addition, the olefin polymer particles for three-dimensional shaping of the present invention have a pore volume of 9 mm or less at pore diameters of 0.01 μm or more and less than 0.05 μm. ３ / g to 100mm ３ / g.

[0022] The olefin polymer particles for three-dimensional shaping of the present invention have a specific pore volume value within the above-mentioned specific pore diameter range, and are therefore believed to tend to have excellent thermal conductivity when used in conventional heating and fusing methods. Furthermore, they are expected to be efficiently melted, due to the effects of widening the laser light irradiation range when heated by an infrared laser such as a carbon dioxide laser, and the expected thermal diffusion effect due to the reflection of light rays. Furthermore, since the particles contain many pores with relatively small pore diameters, they are expected to be easily blocked during melting. In other words, they are expected to produce fewer voids. This effect is supported by a comparison of the results of the Examples and Comparative Examples described below.

[0023] The olefin polymer particles for 3D shaping of the present invention are basically used in combination with various additives without undergoing processes such as melt pelletizing. Therefore, it may be difficult to uniformly disperse various additives and the olefin polymer particles. The olefin polymer particles for 3D shaping of the present invention have pores that satisfy the above-mentioned requirements, which are expected to facilitate the penetration of additives such as heat stabilizers (described below), liquids (slurries) such as melt promoters and surface modifiers, and components that are in a molten or solution state at molding temperatures, into the particles and effectively demonstrate their functions. In particular, depending on the shape of the pores, a permeation effect due to capillary action may be expected. On the other hand, pores smaller than 0.001 μm may be less effective in achieving the above-mentioned effects. Therefore, when the olefin polymer particles of the present invention are used in 3D shaping methods such as 3D printers, structural defects such as voids are expected to be less likely to occur in the resulting molded product. In particular, in an embodiment that satisfies the above-mentioned requirement of a pore diameter of 0.01 μm or more and less than 0.1 μm, or 0.01 μm or more and less than 0.05 μm, it is expected that a more preferable effect will be exhibited.

[0024] Conventionally, olefin polymer particles used as olefin polymer particles for three-dimensional shaping have often been obtained by melt-molding the polymer to obtain pellets, which are then freeze-pulverized to obtain particles with the small particle size described above. Because the particles obtained by such a method undergo a melt-molding process, pores tend not to be formed easily (see the comparative examples described below). Therefore, it is thought that the effects of additives such as melt promoters and surface modifiers may be insufficient.

[0025] The pore volume of the olefin polymer particles for three-dimensional shaping of the present invention with a pore diameter of 1 μm to 10 μm is 5 mm ３ / g to 60mm ３ The preferred lower limit is 8 mm ３ / g, more preferably 10 mm ３ / g, more preferably 12 mm ３ On the other hand, the preferred upper limit is 55 mm ３ / g, more preferably 50 mm ３ / g, more preferably 45 mm ３ / g, particularly preferably 40 mm ３ / g.

[0026] The pore volume of the pores of the olefin polymer particles for three-dimensional shaping of the present invention having a diameter of 1 μm to 4 μm is ３ / g~13mm ３ / g (requirement (p3-2)). A more preferable lower limit is 2 mm ３ / g, more preferably 3 mm ３ On the other hand, a more preferable upper limit is 11 mm ３ / g, more preferably 10 mm ３ / g, particularly preferably 9 mm ３ / g.

[0027] Particles that satisfy the above requirements for the pore volume at pore diameters of 1 μm to 10 μm and the pore volume at pore diameters of 1 μm to 4 μm are expected to be olefin polymer particles with particularly few interparticle voids and good packing properties. Olefin polymer particles with even fewer interparticle voids are more suitable as olefin polymer particles for three-dimensional shaping.

[0028] Considering the particle size of the olefin polymer for 3D shaping of the present invention, it can be assumed that the measured pore volume values ​​for pore diameters of 1 μm or more (including the range of 1 μm to 10 μm) are largely attributable to the gaps between particles. In other words, the olefin polymer particles for 3D shaping of the present invention are particles capable of forming particle aggregates with relatively few gaps. Therefore, when used as binder resin particles for 3D printers, 3D shaped objects obtained using these olefin polymer particles are expected to have excellent moldability with little generation of defects such as voids. This effect will be further described in the examples below.

[0029] On the other hand, conventionally known olefin polymer particles for 3D shaping are often freeze-ground products, and therefore are likely to have irregular particle shapes and surface properties, and tend to be aggregates of particles with many gaps (this is supported by the measured values ​​in the comparative examples of the present application described later). In other words, the olefin polymer particles for 3D shaping of the present invention have favorable properties.

[0030] The pore size and pore volume of the olefin polymer are determined by measurement using a mercury porosimeter. More specifically, they are obtained by measurement using a conventional method using a mercury porosimeter (trade name: PoreMaster 60GT, manufactured by Quantachrome). The obtained data can be analyzed using analysis software (trade name: PoreMaster for Windows) attached to the device to determine the cumulative value of pore volume within a predetermined pore size range. The data described in the examples below are also values ​​measured by the above method.

[0031] The specific surface area of ​​the olefin polymer particles for three-dimensional shaping of the present invention is 30 m ２ / g~150m ２ / g. A more preferred lower limit is 35m ２ / g, more preferably 38m ２ / g, particularly preferably 40m ２ On the other hand, the more preferable upper limit is 100 m ２ / g, more preferably 80m ２ / g, particularly preferably 60m ２ / g, particularly preferably 55m ２ When the specific surface area is within the above range, the moldability and the physical properties of the resulting molded body tend to be excellent. The specific surface area value can be determined by measurement using a mercury porosimeter, similar to the pore volume.

[0032] The olefin polymer particles for 3D shaping of the present invention preferably have a circularity of 0.70 to 0.95. The upper limit is more preferably 0.92, more preferably 0.90. On the other hand, the lower limit is more preferably 0.75, more preferably 0.80. Olefin polymer particles for 3D shaping of having a circularity in such a range may be preferable from the viewpoints of particle flowability, small interparticle gaps, and prevention of voids in the 3D shaping object.

[0033] The circularity of the present invention can be determined using, for example, a particle shape image analyzer, product name PITA-3 or PITA-04, manufactured by Seishin Enterprise Co., Ltd. This device captures images of a particle suspension with a CCD camera and can perform various analyses from the particle image, such as circularity, equivalent circle diameter, aspect ratio, etc. In the present invention, a suspension of about 300 milligrams of olefin polymer particles suspended in isopropyl alcohol is used as a sample, and the circularity is determined by a conventional method using measurement conditions according to the manual for the device depending on the particle shape of the polymer particles.

[0034] The physical properties such as rigidity and impact resistance of the olefin polymer used in the present invention are preferably in the following ranges: Tensile modulus of elasticity: 1200 MPa to 3000 MPa Charpy impact strength measured at -30°C: 2.0 kJ / m ２ The tensile modulus is preferably 1400 MPa to 3000 MPa, more preferably 1500 MPa to 2800 MPa. The Charpy impact strength at -30°C is 2.0 kJ / m or more. ２ ~10 kJ / m ２ is preferred, and 3.0 kJ / m ２ ~8kJ / m ２ is more preferred.

[0035] The melting point of the olefin polymer particles for three-dimensional shaping of the present invention, as measured by DSC, is preferably 150°C to 170°C, more preferably 155°C to 168°C, and even more preferably 157°C to 165°C.

[0036] The resin powder of the present invention preferably has a heat distortion temperature (HDT) measured in accordance with JIS K7191 of 105°C or higher, more preferably 110°C to 150°C, and even more preferably 115°C to 140°C.

[0037] (Propylene-based polymer) The olefin polymer particles for three-dimensional shaping of the present invention contain an olefin polymer. The olefin polymer is not particularly limited, but is preferably a propylene-based polymer. More specific examples of such propylene-based polymers include propylene homopolymers, propylene random copolymers containing structural units derived from propylene and structural units derived from an olefin monomer other than propylene, and propylene-based block copolymers.

[0038] The propylene-based copolymer may be a block copolymer, a random copolymer, or a graft copolymer. From the viewpoints of the heat resistance, mechanical properties, and low-temperature impact resistance of the polymer, a propylene homopolymer or a block copolymer is preferred. From the viewpoint of the heat resistance of the resin powder, the melting point (Tm) measured by DSC is preferably 150°C to 170°C, more preferably 155°C to 170°C, and even more preferably 155°C to 169°C. Furthermore, from the viewpoints of the heat resistance, mechanical properties, and low-temperature impact resistance of the resin powder, the propylene-based polymer is preferably a propylene homopolymer or a propylene-based block copolymer. A propylene-based block copolymer is particularly preferred.

[0039] In the propylene polymer powder, the stereoregularity of the portion where propylene-derived structural units are repeatedly bonded may be either an isotactic structure or a syndiotactic structure, and from the viewpoint of the rigidity and heat resistance of the resin powder, an isotactic structure is preferred.

[0040] The propylene-based block copolymer has a skeleton derived from propylene as an essential skeleton and is composed of skeletons derived from ethylene and one or more olefins selected from α-olefins having 4 to 20 carbon atoms. Examples of α-olefins having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, and 4-methyl-1-hexene.

[0041] The olefin polymer may contain a component soluble in decane at 23° C. (hereinafter, may be referred to as a decane-soluble component). Generally, an olefin homopolymer has a low content of decane-soluble components, while an olefin random copolymer or an olefin block copolymer has a high content of decane-soluble components.

[0042] The olefin polymer of the present invention preferably contains a decane-soluble component. The decane-soluble component content is preferably in the range of 0.1% by mass to 40% by mass. The lower limit is more preferably 0.50% by mass, even more preferably 0.80% by mass, and particularly preferably 1.0% by mass. On the other hand, the upper limit is more preferably 37% by mass, even more preferably 35% by mass, and particularly preferably 33% by mass.

[0043] When the decane-soluble component content of the olefin polymer is within the above range, the balance of performances such as impact resistance improvement, tackification, moldability, etc. can be improved and adjusted within an appropriate range by controlling the amount, and preferably the composition, molecular weight, etc.

[0044] Preferred examples of the olefin polymer containing the decane-soluble component include a propylene homopolymer, a propylene random copolymer, and a propylene-based block copolymer, with a propylene-based block copolymer being particularly preferred.

[0045] When the olefin polymer is a propylene homopolymer, the decane-soluble component content is preferably 0.1% by mass to 10% by mass, with the lower limit being more preferably 0.50% by mass, even more preferably 0.80% by mass, and particularly preferably 1.0% by mass, while the upper limit being more preferably 9% by mass, even more preferably 8% by mass, and particularly preferably 7% by mass.

[0046] When the olefin polymer is a propylene random polymer, the decane-soluble component content is preferably 3% by mass to 13% by mass, with the lower limit being more preferably 3.3% by mass, even more preferably 3.5% by mass, and particularly preferably 3.8% by mass, and the upper limit being more preferably 12% by mass, even more preferably 10% by mass, and particularly preferably 8% by mass.

[0047] The above-mentioned value of the content of the decane-soluble component is a value when the total amount of the olefin polymer is taken as 100% by weight, including the case of the propylene-based block copolymer described later.

[0048] When the propylene-based copolymer is a propylene-based block copolymer, the propylene-based block copolymer contains structural units derived from one or more olefins selected from ethylene and α-olefins having 4 to 20 carbon atoms, and the total content of the olefins other than propylene is preferably 0.5 mol% to 45 mol% from the viewpoint of the mechanical properties and low-temperature impact resistance of the resin powder. The lower limit is more preferably 2 mol%, even more preferably 2.5 mol%, and particularly preferably 3 mol%. On the other hand, the upper limit is more preferably 42 mol%, even more preferably 425 mol%, and particularly preferably 38 mol%.

[0049] The melt flow rate of the propylene polymer measured in accordance with ASTM D-1238 at 230°C under a load of 2.16 kg is preferably 0.05 g / 10 min to 150 g / 10 min, more preferably 5 g / 10 min to 150 g / 10 min, and even more preferably 18 g / 10 min to 100 g / 10 min, from the viewpoint of the mechanical properties and low-temperature impact resistance of the resin powder. For example, the melt flow rate can be adjusted by mixing two or more types of resin powders having different propylene polymer compositions, adjusting the weight-average molecular weight of the propylene polymer, or the like.

[0050] The weight-average molecular weight of the 23°C n-decane insoluble portion (Dinsol) of the propylene polymer contained in the resin powder is not particularly limited. The weight-average molecular weight can be calculated from the polystyrene (PS) equivalent molecular weight distribution by gel permeation chromatography (GPC). The molecular weight distribution (weight-average molecular weight: Mw / number-average molecular weight: Mn) is preferably 1.0 to 10, more preferably 2.0 to 10, and even more preferably 3.0 to 10.

[0051] The melting point of the propylene polymer measured by DSC is preferably 135° C. to 170° C., more preferably 140° C. to 168° C. The lower limit of the melting point is more preferably 145° C., even more preferably 150° C., and particularly preferably 155° C.

[0052] As described above, the propylene-based block copolymer constituting the propylene-based polymer powder may have a portion soluble in n-decane at 23° C. The “23° C. n-decane soluble portion” refers to a portion of the propylene-based block copolymer that is dissolved in n-decane when the temperature is lowered to 23° C. after heating and dissolving in n-decane at 145° C. for 30 minutes, as described in the Examples below.

[0053] The amount of the 23°C n-decane solubles is preferably 5% to 40% by mass relative to the total amount of the propylene-based block copolymer. A more preferred lower limit is 8% by mass, even more preferably 8% by mass, and particularly preferably 9% by mass. On the other hand, a more preferred upper limit is 35% by mass, even more preferably 30% by mass, and particularly preferably 28% by mass. When the decane-solubles content of the propylene block copolymer is within the above range, controlling the amount and composition thereof may make it possible to improve and adjust the balance of performance, particularly impact resistance improvement, moldability, compatibility with other components described below, dispersibility, and the like, within an appropriate range. In the propylene-based block copolymer, the total amount of the 23°C n-decane solubles and the 23°C n-decane insolubles is 100% by mass.

[0054] The intrinsic viscosity [η] of the n-decane soluble portion at 23° C. is preferably 1.0 dl / g to 10 dl / g, more preferably 1.5 dl / g to 9.0 dl / g, and even more preferably 2.0 dl / g to 8.0 dl / g.

[0055] The 23°C n-decane soluble portion is preferably primarily composed of a copolymer of propylene and one or more olefins selected from ethylene and α-olefins having 4 to 20 carbon atoms. Specifically, a copolymer containing ethylene-derived structural units is preferred from the viewpoint of low-temperature impact resistance, etc. More specifically, examples of such copolymers include those having propylene and ethylene as the main structural units, and those having ethylene and one or more olefins selected from α-olefins having 4 to 20 carbon atoms as the main structural units. In the former case, the preferred range of the content of ethylene-derived structural units is 20 to 90 mol%. The more preferred lower limit is 25 mol%, and even more preferably 28 mol%. Meanwhile, the more preferred upper limit is 85 mol%, and even more preferably 82 mol%. In the latter case, the preferred range of the content of ethylene and olefin-derived structural units selected from 4 to 20 carbon atoms is 95 to 99.5 mol%. Within the above range of the content of structural units derived from ethylene and olefins having 4 to 20 carbon atoms, the content of structural units derived from ethylene is 20 to 90 mol %. The lower limit is more preferably 25 mol %, and even more preferably 28 mol %. On the other hand, the upper limit is more preferably 85 mol %, and even more preferably 82 mol %.

[0056] Of course, the olefin polymer particles for three-dimensional shaping of the present invention can also be used in combination of two or more types of olefin polymer powders.

[0057] The olefin polymer particles for three-dimensional shaping of the present invention may, of course, also include embodiments containing a thermoplastic elastomer, a filler, and the like.

[0058] When the olefin polymer particles for three-dimensional shaping of the present invention contain other components as described above (preferably, when they contain a thermoplastic elastomer and a filler), the content of the olefin polymer particles is preferably 30 parts by mass to 90 parts by mass, more preferably 35 parts by mass to 85 parts by mass, and even more preferably 35 parts by mass to 80 parts by mass, per 100 parts by mass of the total of all components including the olefin polymer particles.

[0059] (Thermoplastic elastomer) The resin powder is preferably a mixture containing a propylene-based polymer powder and a thermoplastic elastomer. When the resin powder contains a thermoplastic elastomer, deformation of a three-dimensional object is effectively suppressed when the resin powder is used to mold the three-dimensional object, and elongation, toughness, and impact resistance at lower temperatures are imparted. The resin powder may contain only one type of thermoplastic elastomer, or may contain two or more types of thermoplastic elastomers.

[0060] Thermoplastic elastomers have rubber-like elasticity. Rubber-like elasticity refers to the property that a resin deforms when a load is applied to it, and tends to return to its original shape when the load is removed. Specifically, a thermoplastic elastomer refers to a thermoplastic resin having a tensile modulus of elasticity of less than 600 MPa at 25°C. In this respect, thermoplastic elastomers are distinguished from thermoplastic resins such as the propylene-based polymers mentioned above.

[0061] Examples of thermoplastic elastomers include ethylene-α-olefin random copolymers, ethylene-α-olefin-non-conjugated polyene random copolymers, hydrogenated block copolymers, other elastic polymers, and mixtures thereof.

[0062] When the thermoplastic elastomer is a copolymer, the thermoplastic elastomer may be a block copolymer, a random copolymer, a graft copolymer, or any other form. From the viewpoint of the heat resistance, mechanical properties, and low-temperature impact resistance of the resin powder, the modulus of elasticity of the thermoplastic elastomer may be less than 500 MPa, and the glass transition temperature of the thermoplastic elastomer measured by DSC may be -30°C or lower. It is preferable that the modulus of elasticity is less than 500 MPa and the glass transition temperature is -40°C or lower.

[0063] When the thermoplastic elastomer is an olefin-based thermoplastic elastomer, the olefin may include structural units derived from ethylene, propylene, or an α-olefin having 4 to 10 carbon atoms. The thermoplastic elastomer may include one type of olefin-derived structural unit alone, or two or more types in combination.

[0064] Specific examples of the α-olefins having 4 to 10 carbon atoms include 1-butene, 1-hexene, and 1-octene. These α-olefins can be used alone or in combination. Among these, 1-butene and 1-octene are particularly preferred.

[0065] The ethylene / α-olefin random copolymer preferably has a molar ratio of ethylene to α-olefin (ethylene / α-olefin) of 95 / 5 to 70 / 30, more preferably 90 / 10 to 75 / 25.

[0066] The ethylene / α-olefin random copolymer preferably has an MFR of 0.05 g / 10 min or more, more preferably 0.05 g / 10 min to 100 g / 10 min, as measured in accordance with ASTM D-1238 at 190°C under a load of 2.16 kg.

[0067] The ethylene / α-olefin random copolymer can be produced by a conventionally known method, or various commercially available products can be used, such as the Tafmer A series and H series manufactured by Mitsui Chemicals, the Engage series manufactured by Dow Chemical Company, and the Exact series manufactured by ExxonMobil.

[0068] The ethylene-α-olefin-non-conjugated polyene random copolymer may be a random copolymer rubber of ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene. Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene. These α-olefins may be used alone or in combination. Of these, propylene, 1-butene, 1-hexene, and 1-octene are particularly preferred. Examples of the non-conjugated polyene include cyclic non-conjugated dienes such as 5-ethylidene-2-norbornene, 5-propylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, and norbornadiene; and chain non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 6-methyl-1,7-octadiene, and 7-methyl-1,6 octadiene.

[0069] The ethylene / α-olefin / non-conjugated polyene random copolymer preferably has a molar ratio of ethylene, α-olefin, and non-conjugated polyene (ethylene / α-olefin / non-conjugated polyene) of 90 / 5 / 5 to 30 / 45 / 25, more preferably 80 / 10 / 10 to 40 / 40 / 20.

[0070] The ethylene-α-olefin-non-conjugated polyene random copolymer preferably has an MFR of 0.05 g / 10 min or more, and more preferably 0.05 g / 10 min to 100 g / 10 min, as measured at 190°C under a load of 2.16 kg in accordance with ASTM D-1238. Specific examples of the ethylene-α-olefin-non-conjugated polyene random copolymer include ethylene-propylene-diene terpolymer (EPDM).

[0071] Examples of the monovinyl-substituted aromatic hydrocarbon constituting the polymer block represented by X in formula (a) or (b) include styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, lower alkyl-substituted styrene, vinylnaphthalene, and other styrenes or derivatives thereof. These may be used alone or in combination of two or more.

[0072] Examples of the conjugated diene constituting the polymer block represented by Y in formula (a) or (b) include butadiene, isoprene, and chloroprene. These may be used alone or in combination of two or more. n is an integer of 1 to 5, preferably 1 or 2.

[0073] Specific examples of hydrogenated block copolymers include styrene-based block copolymers such as styrene-ethylene-butene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), and styrene-ethylene-propylene block copolymer (SEP).

[0074] When butadiene is used as the conjugated diene, the proportion of 1,2-bonds in the polybutadiene block is preferably 20% by mass to 80% by mass, more preferably 30% by mass to 60% by mass.

[0075] Commercially available hydrogenated block copolymers can also be used, and specific examples include Kraton G1657 (trademark, manufactured by Kraton Polymers), Septon 2004 (trademark, manufactured by Kuraray Co., Ltd.), and Tuftec H1052 (trademark, manufactured by Asahi Kasei Corporation).

[0076] The melt flow rate of a thermoplastic elastomer such as an ethylene-α-olefin copolymer or a propylene-α-olefin copolymer is preferably 0.05 g / 10 min to 100 g / 10 min, and more preferably 0.1 g / 10 min to 100 g / 10 min, at 190°C under a load of 2.16 kg, in accordance with ASTM D-1238.

[0077] When the resin powder contains a thermoplastic elastomer, the content of the thermoplastic elastomer is preferably 1 to 40 parts by mass, more preferably 5 to 35 parts by mass, and even more preferably 10 to 35 parts by mass, per 100 parts by mass of the propylene-based polymer powder and other components in total (preferably, 100 parts by mass of the propylene-based polymer powder, the thermoplastic elastomer, and the filler in total).

[0078] When the resin powder of the present invention contains a thermoplastic elastomer, the thermoplastic elastomer preferably contains an ethylene-α-olefin random copolymer. The content of the ethylene-α-olefin random copolymer in the thermoplastic elastomer is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and even more preferably 60% by mass to 90% by mass, based on the total amount of the thermoplastic elastomer.

[0079] When the thermoplastic elastomer contains a hydrogenated block copolymer, the content of the hydrogenated block copolymer in the thermoplastic elastomer is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and even more preferably 60% by mass to 90% by mass. When the thermoplastic elastomer contains an ethylene-α-olefin random copolymer and a hydrogenated block copolymer, the content of the ethylene-α-olefin random copolymer in the thermoplastic elastomer is preferably 50% by mass to 99% by mass, more preferably 60% by mass to 95% by mass, and even more preferably 60% by mass to 90% by mass. The content of the hydrogenated block copolymer in the thermoplastic elastomer is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and even more preferably 10% by mass to 40% by mass.

[0080] (Filler) The resin powder is preferably a mixture containing a propylene-based polymer powder and a filler. As the filler, one type may be used alone, or two or more types may be used in combination. The filler may have an effect overlapping with the effect of other components described later.

[0081] The filler may be dry-blended with the resin powder or may be contained in the resin. By including a filler, the heat resistance, strength, etc. of the resin powder can be improved, and warpage of the resulting three-dimensional molded article tends to be reduced.

[0082] Fillers can be broadly classified into inorganic fillers such as talc, magnesium sulfate fiber, glass fiber, carbon fiber, mica, calcium carbonate, magnesium hydroxide, ammonium phosphate, silicates, carbonates, carbon black, glass beads, fumed silica, hollow glass beads, glass fiber, crushed glass, aluminum oxide, and inorganic oxides, nitrides, borides, and carbides of zirconium, tantalum, titanium, tungsten, boron, aluminum, and beryllium; and organic fillers such as wood flour, cellulose, polyester fiber, nylon fiber, kenaf fiber, bamboo fiber, jute fiber, rice flour, starch, and corn starch. Preferred inorganic fillers include talc, magnesium sulfate, glass, silica, glass fiber, carbon fiber, wood flour, and cellulose. These are described in detail below.

[0083] (Other Components) The resin powder of the present invention may be a powder containing other components in addition to the propylene-based polymer and the thermoplastic elastomer, as long as the effects of the invention are not impaired. Examples of other components include resin components such as thermoplastic resins other than the propylene-based polymer, thermosetting resins, and additive components. Biomass-derived raw materials may also be blended into the resin powder.

[0084] Examples of additive components include heat stabilizers, antistatic agents, weather stabilizers, light stabilizers, ultraviolet absorbers, antioxidants, antioxidants, neutralizing agents, fatty acid metal salts, softeners, dispersants, colorants, lubricants, pigments, dyes, brighteners, antistatic agents, solvents, wetting agents, antimicrobial agents, chelating agents, flow aids, reinforcing agents, energy absorption promoters, energy absorption inhibitors, laser absorbers, coalescents, and finish improvers. The other components described above may be used independently, either individually or in combination of two or more.

[0085] The resin powder of the present invention may contain a flow aid. The flow aid is preferably dry-blended with the resin powder. In the present invention, the flow aid refers to a substance that suppresses aggregation of resin powder due to adhesive forces between resin powder particles. By including the flow aid, the fluidity of the resin powder can be improved, and the resin powder is packed evenly when forming a three-dimensional molded body. As a result, the warpage of the obtained three-dimensional molded body is likely to be reduced.

[0086] Examples of flow aids include silica (silicon dioxide) such as fused silica, crystalline silica, and amorphous silica; alumina (aluminum oxide), alumina colloid (alumina sol), and alumina white; calcium carbonate such as light calcium carbonate, heavy calcium carbonate, finely powdered calcium carbonate, and special calcium carbonate fillers; nepheline syenite fine powder, calcined clay such as montmorillonite and bentonite; clay (aluminum silicate powder) such as silane-modified clay; silicic acid-containing compounds such as talc, diatomaceous earth, and silica sand; crushed natural minerals such as pumice powder, pumice balloons, slate powder, and mica powder; sulfur; Examples of suitable fillers include minerals such as barium carbonate, lithopone, calcium sulfate, molybdenum disulfide, and graphite, glass fillers such as glass fibers, glass beads, glass flakes, and foamed glass beads, fly ash spheres, hollow volcanic glass, synthetic inorganic hollow bodies, single-crystal potassium titanate, carbon fibers, carbon nanotubes, hollow carbon spheres, fullerenes, anthracite powder, artificial cryolite, titanium oxide, magnesium oxide, basic magnesium carbonate, dolomite, potassium titanate, calcium sulfite, mica, asbestos, calcium silicate, molybdenum sulfide, boron fiber, and silicon carbide fiber. Among these, silica, alumina, calcium carbonate, glass fillers, and titanium oxide are preferred, and silica is more preferred. Commercially available silica products include the fumed silica "AEROSIL" (registered trademark) series manufactured by Nippon Aerosil Co., Ltd., the dry silica "Reolosil" (registered trademark) series manufactured by Tokuyama Corporation, and the sol-gel silica powder X-24 series manufactured by Shin-Etsu Chemical Co., Ltd.

[0087] The resin powder of the present invention may contain an energy absorption accelerator. The energy absorption accelerator is a substance that absorbs electromagnetic radiation. The energy absorption accelerator may also serve as a filler.

[0088] Examples of the energy absorption promoter include pigments, carbon black, carbon fibers, copper hydroxyphosphate, near-infrared absorbing dyes, near-infrared absorbing pigments, metal nanoparticles, polythiophene, poly(p-phenylene sulfide), polyaniline, poly(pyrrole), polyacetylene, poly(p-phenylene vinylene), polyparaphenylene, poly(styrene sulfonate), poly(3,4-ethylenedioxythiophene)-poly(styrene phosphonate) p-diethylaminobenzaldehyde diphenylhydrazone, anti-9-isopropylcarbazole-3-, and conjugated polymers formed from combinations thereof.

[0089] The resin powder of the present invention may contain an energy absorption inhibitor. The energy absorption inhibitor is a substance that does not easily absorb electromagnetic radiation. The energy absorption inhibitor may also serve as a filler.

[0090] Examples of the energy absorption inhibitor include substances that reflect particle electromagnetic radiation, such as titanium, heat insulating powders, such as mica powder and ceramic powder, and water.

[0091] Either the energy absorption promoter or the energy absorption inhibitor may be used alone, or in order to adjust the degree of absorption of electromagnetic radiation, the energy absorption promoter and the energy absorption inhibitor may be used in combination.

[0092] The resin powder of the present invention may contain a coalescent. The coalescent is, for example, a dispersion containing a radiation absorber (e.g., an active material). The active material may be any infrared-absorbing colorant. The solvent for the coalescent may be water or a non-aqueous solvent (e.g., ethanol, acetone, n-methylpyrrolidone, aliphatic hydrocarbons, etc.). For example, the coalescent may be a mixture of the active material and a solvent (preferably a mixture containing no other components). The coalescent may contain, for example, at least one cosolvent; at least one surfactant; at least one anti-kogation agent; at least one chelating agent; at least one buffer; at least one biocide; and water.

[0093] The resin powder of the present invention may contain a finish improver. The finish improver may include a surfactant, a co-solvent, and the balance amount of water. The finish improver may be a mixture of a surfactant, a co-solvent, and the balance amount of water, excluding other ingredients. The finish improver may include a colorant, or may be a mixture of a colorant, a surfactant, a co-solvent, and the balance amount of water, excluding other ingredients. The finish improver may include one or more ingredients such as an anti-kogation agent, an antimicrobial agent, a chelating agent, etc.

[0094] The resin powder of the present invention and the propylene-based polymer powder contained therein may be coated with any surface-active coating. Examples of the surface-active coating include coatings containing surfactants, acidic polymers, salts of acidic polymers, inorganic particles, etc., and the coating may be one of these, or two or more of these.

[0095] Examples of surfactants used in the surface-active coating include anionic surfactants, nonionic surfactants, cationic surfactants, etc. Examples of anionic surfactants include sodium lauryl sulfate, linear or branched alkylbenzene sulfonates, etc.

[0096] The surface-active coating may be an inorganic particulate coating using inorganic particles, such as fumed metal oxide nanoparticles. Examples of inorganic particles used in the inorganic particulate coating include silicon dioxide, such as AEROSIL® 200, aluminum oxide, such as AEROXIDE® AluC, and aqueous dispersions thereof, such as AERODISP® W1824 and AERODISP® W440.

[0097] The surface-active coating may be applied using any suitable method, such as spray coating, pan coating, air or gas suspension coating, liquid phase coating, liquid dispersion coating, dipping, etc. Additionally, a reaction such as polymerization may be carried out after coating.

[0098] The resin powder of the present invention is used for molding a three-dimensional molded article. When used for molding a three-dimensional molded article, the resin powder of the present invention may be used alone or in combination with other components.

[0099] Three-dimensional molded products that can be molded using the resin powder of the present invention are not particularly limited, and examples thereof include molded products for automobiles (for example, console parts, switch parts, door trim parts, instrument panel parts, clips, covers, engine peripheral parts, grip parts, bumpers, back doors, radiator parts, battery parts, etc.), molded products for electrical appliances (parts and housings of electrical appliances, etc.), furniture members, building materials, construction materials, aircraft parts, toys, shoes, sporting goods, ornaments, cases, etc.

[0100] <Olefin polymer particle-containing composition> The olefin polymer particle-containing composition of the present invention comprises: (α) olefin polymer particles that satisfy the following requirements (p1) to (p3): (p1) a volume average particle diameter of 10 μm to 200 μm; (p2) a pore volume of 50 mm3 or more at pore diameters of 0.001 μm or more and less than 1 μm; ３ / g to 300 mm ３ / g (p3) The pore volume at pore diameters of 1 μm to 10 μm is 5 mm ３ / g to 60mm ３ / g (In the requirements (p2) and (p3), the pore diameter and pore volume are measured by a mercury porosimeter.) The olefin polymer particle-containing composition comprises either (β) a dissolution promoter or (γ) a surface modifier. The above requirements (p1), (p2), and (p3) are all the same as those of the olefin polymer particles for 3D shaping, and their preferred embodiments and expected effects are also the same as those explained for the olefin polymer particles for 3D shaping.

[0101] The (β) dissolution promoter and (γ) surface modifier can be any known component without limitation. When electromagnetic waves such as lasers or microwaves are used, preferred examples of the (β) dissolution promoter are components that absorb the electromagnetic waves and generate heat. Specific preferred examples include carbon and carbon black. In addition, pigments corresponding to the wavelength of the electromagnetic waves can also be used. Multiple types of these components can also be used in combination. The (β) dissolution promoter is preferably used in an amount ranging from 0 to 3 parts by weight per 100 parts by weight of the (α) polymer particles. The lower limit is more preferably 0.5 parts by weight, and even more preferably 0.8 parts by weight. Meanwhile, the upper limit is more preferably 2.5 parts by weight, and even more preferably 2.3 parts by weight.

[0102] The (γ) surface modifier can be a flow agent used in combination to enhance particle fluidity. The flow agent may be any material with a small coefficient of friction and self-lubricating properties. Examples of such flow agents include silicon dioxide and boron nitride. Silica is preferred. A plurality of types of these flow agents can be used in combination. Additionally, known antistatic agents can also be used in combination.

[0103] The surface modifier (γ) is preferably used in an amount of 0 to 3 parts by weight per 100 parts by weight of the polymer particles (α). The lower limit is more preferably 0.5 parts by weight, and even more preferably 0.8 parts by weight. The upper limit is more preferably 2.5 parts by weight, and even more preferably 2.3 parts by weight.

[0104] It is also possible to use known additives such as the antistatic agents introduced in the description of the olefin polymer particles for three-dimensional shaping.

[0105] The olefin polymer particle-containing composition of the present invention is suitable as a material for three-dimensional modeling, such as a binder resin for 3D printers. In such a composition, the (β) dissolution promoter, (γ) surface modifying medium, and various additives can be separated from the (α) olefin polymer particles using the following method.

[0106] Solid components such as silica and carbon in an olefin polymer particle-containing composition can be separated from the olefin polymer particles by using ultrasonic treatment, air blowing, etc. Furthermore, since additives such as heat stabilizers in olefin polymers are often polar compounds, they can be separated from the olefin polymer particles by solvent fractionation using a polar solvent, typical examples of which are alcohols such as methanol and ethanol.

[0107] Therefore, by analyzing the particle size and pores of the olefin polymer particles after separating the components, it is possible to obtain information about the pores and other properties of the (α) olefin polymer particles even after preparing the olefin polymer particle-containing composition.

[0108] <Three-dimensional molded product> The three-dimensional molded product related to the present invention is molded using a resin powder. Examples of the three-dimensional molded product include the above-mentioned molded products for automobiles and other molded products. The three-dimensional molded product related to the present invention may be a sintered body or a molten body of the above-mentioned resin powder.

[0109] The three-dimensional molded article related to the present invention can be produced by three-dimensional molding using the above-mentioned resin powder by powder bed fusion bonding.

[0110] <Method for manufacturing a three-dimensional molded article> A method for manufacturing a three-dimensional molded article related to the present invention is a method for manufacturing a three-dimensional molded article by powder bed fusion using the resin powder of the present invention described above. A three-dimensional molded article can be manufactured by the same method as the conventional powder bed fusion method, except that the resin powder of the present invention described above is used.

[0111] For example, a method for producing a three-dimensional molded product related to the present invention may include step 1 of forming a thin layer of resin powder, step 2 of selectively irradiating the preheated thin layer with laser light to form a shaped object layer in which the propylene-based polymer contained in the resin powder is melt-bonded, and step 3 of repeating steps 1 and 2 in this order to stack the shaped object layers.

[0112] One model layer constituting the three-dimensional molded product is formed through steps 1 and 2, and the model layers are sequentially stacked to produce the three-dimensional molded product by repeating steps 1 and 2. From the viewpoint of achieving high-precision modeling, the method for producing a three-dimensional molded product related to the present invention preferably includes step 4 of preheating the thin layer of resin powder before irradiating it with the laser in step 2.

[0113] Each of the above-mentioned steps may be carried out with reference to, for example, the method for producing a three-dimensional molded body described in International Publication No. 2020 / 213586, HP Multi Jet Fusion technology, and three-dimensional printing using the molding material described in Patent No. 7071532.

[0114] <Method for producing olefin polymer particles for 3D shaping> The olefin polymer particles for 3D shaping of the present invention can be produced by known olefin polymerization methods. Among these, it is preferable to produce them using an olefin polymerization catalyst containing a solid titanium catalyst component such as those described below. Another preferred example is an olefin polymerization catalyst containing a specific metallocene compound.

[0115] An example of the use of the solid titanium catalyst component is a method for obtaining olefin polymer particles that satisfy the following requirements by polymerizing olefins in the presence of an olefin polymerization catalyst comprising a solid titanium catalyst component (I) containing (a) a liquid magnesium compound, (b) a liquid titanium compound, and (c) an electron donor, an organometallic compound catalyst component (II), and an electron donor (III): (p1) a volume average particle diameter of 10 μm to 200 μm, and (p2) a pore volume of 50 mm3 at pore diameters of 0.001 μm or more and less than 1 μm. ３ / g to 300 mm ３ / g (p3) The pore volume at pore diameters of 1 μm to 10 μm is 5 mm ３ / g to 60mm ３ In the above requirements (p2) and (p3), the pore diameter and pore volume are measured by a mercury porosimeter.

[0116] By including the above steps, the olefin polymer particles for three-dimensional shaping of the present invention can be obtained.

[0117] Specific examples of magnesium compounds that can be used as a raw material for the above-mentioned (a) liquid magnesium compound include known magnesium compounds such as magnesium halides such as magnesium chloride and magnesium bromide; alkoxymagnesium halides such as methoxymagnesium chloride, ethoxymagnesium chloride and phenoxymagnesium chloride; alkoxymagnesiums such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium and 2-ethylhexoxymagnesium; aryloxymagnesiums such as phenoxymagnesium; and magnesium carboxylates such as magnesium stearate.

[0118] These magnesium compounds may be used alone or in combination of two or more kinds. Furthermore, these magnesium compounds may be complex compounds or double compounds with other metals, or mixtures with other metal compounds.

[0119] Among these, halogen-containing magnesium compounds are preferred. Magnesium halides, especially magnesium chloride, are preferred. Alkoxymagnesium compounds such as ethoxymagnesium are also preferred. The magnesium compounds may also be derived from other substances, such as those obtained by contacting an organomagnesium compound, such as a Grignard reagent, with a titanium halide, silicon halide, or alcohol halide. Liquid magnesium compounds can be used as they are. Solid magnesium compounds can be used in a liquid form, such as a hydrocarbon solution, by combining them with known compounds capable of solubilizing the magnesium compound at temperatures ranging from room temperature to approximately 300°C. Preferred solubilizing compounds include alcohols, aldehydes, amines, carboxylic acids, and mixtures thereof. Examples of these compounds include those described in detail in Patent Documents 1 and 2.

[0120] More specific examples of the alcohol capable of solubilizing a magnesium compound include aliphatic alcohols such as methanol, ethanol, propanol, butanol, isobutanol, ethylene glycol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol, and dodecanol; alicyclic alcohols such as cyclohexanol and methylcyclohexanol; aromatic alcohols such as benzyl alcohol and methylbenzyl alcohol; and aliphatic alcohols having an alkoxy group such as n-butyl cellosolve.

[0121] Examples of the carboxylic acid include organic carboxylic acids having 7 or more carbon atoms, such as caprylic acid and 2-ethylhexanoic acid. Examples of the aldehyde include aldehydes having 7 or more carbon atoms, such as capric aldehyde and 2-ethylhexyl aldehyde.

[0122] Examples of the amine include amines having 6 or more carbon atoms, such as heptylamine, octylamine, nonylamine, laurylamine, and 2-ethylhexylamine.

[0123] As the compound capable of solubilizing the magnesium compound, the above-mentioned alcohols are preferred, with ethanol, propanol, butanol, isobutanol, hexanol, 2-ethylhexanol, decanol and the like being particularly preferred.

[0124] The liquid titanium compound (b) may be, for example, a compound represented by the general formula: Ti(OR') ｇ X ４－ｇ (wherein R' is a hydrocarbon group, X is a halogen atom, and g is 0≦g≦4) More specifically, TiCl ４ , TiBr ４ titanium tetrahalides such as Ti(OCH ３ ) Cl ３ , Ti(OC ２ H ５ ) Cl ３ , Ti(O-n-C ４ H ９ ) Cl ３ , Ti(OC ２ H ５ )Br ３ , Ti(O-iso-C ４ H ９ )Br ３ Alkoxy titanium trihalides such as Ti(OCH ３ ) ２ Cl ２ , Ti(OC ２ H ５ ) ２ Cl ２ Alkoxy titanium dihalides such as Ti(OCH ３ ) ３ Cl, Ti(O-n-C ４ H ９ ) ３ Cl, Ti(OC ２ H ５ ) ３ Monohalogenated alkoxy titanium compounds such as Br; Ti(OCH ３ ) ４ , Ti(OC ２ H ５ ) ４ , Ti(OC ４ H ９ )４ , Ti(O-2-ethylhexyl) ４ Examples of suitable tetraalkoxy titanium compounds include:

[0125] Among these, titanium tetrahalides are preferred, with titanium tetrachloride being particularly preferred. These titanium compounds may be used alone or in combination of two or more.

[0126] Examples of the electron donor (c) include known compounds such as aromatic carboxylic acid esters and compounds having two or more ether bonds via a plurality of carbon atoms.

[0127] Specific examples of the aromatic carboxylic acid esters include aromatic carboxylic acid monoesters such as benzoic acid esters and toluic acid esters, as well as aromatic polycarboxylic acid esters such as phthalic acid esters. Among these, aromatic monocarboxylic acid esters are preferred, and specific examples include benzoic acid esters, toluic acid esters, and the like. More specific examples include methyl benzoate, ethyl benzoate, butyl benzoate, methyl p-toluate, ethyl p-toluate, and butyl p-toluate.

[0128] More specifically, the polyether compound includes a compound represented by the following formula (3).

[0129]

[0130] In the above formula (3), m is an integer of 1≦m≦10, more preferably an integer of 3≦m≦10, and R １１ , R １２ , R ３１ ~R ３６ are each a hydrogen atom or a substituent having at least one element selected from carbon, hydrogen, oxygen, fluorine, chlorine, bromine, iodine, nitrogen, sulfur, phosphorus, boron and silicon.

[0131] When m is 2 or more, there are multiple R １１ and R １２ may be the same or different. １１ , R １２, R ３１ ~R ３６ , preferably R １１ and R １２ may cooperate to form a ring other than a benzene ring. Of these, 1,3-diethers are preferred, and 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, and 2,2-bis(cyclohexylmethyl)1,3-dimethoxypropane are particularly preferred. These compounds may be used alone or in combination of two or more.

[0132] The solid titanium catalyst component (I) can be produced by any known method without any limitation using the above compound. Specific examples of such methods include those disclosed in JP-A-56-811, JP-A-58-83006, EP-A-585869, EP-A-583953, etc.

[0133] The method of producing a solid titanium catalyst component using (a) a liquid magnesium compound and (b) a liquid titanium compound, as typified by the above-mentioned method, is known to be capable of easily producing a solid titanium catalyst component with a relatively small particle size. It is also known that the method of producing a solid component using (a) a liquid magnesium compound allows the particle size to be adjusted by, for example, the stirring speed during the reaction (see, for example, International Publication No. 2006 / 054696). Intentionally producing a solid titanium catalyst component with a small particle size using such a method and using it to polymerize an olefin is advantageous for obtaining an olefin polymer with a small particle size. The pore structure of the solid titanium catalyst component can also be adjusted by, for example, adjusting the reaction conditions between (a) the liquid magnesium compound and (b) the liquid titanium compound. It is believed that this method of producing a solid titanium catalyst component involves aggregation of solid fine particles produced during the contact and reaction between (a) the liquid magnesium compound and (b) the liquid titanium compound, resulting in particle growth. In this case, the electron donor is thought to exert a binder effect on the aggregation. The gaps between the solid fine particles likely form pores. Therefore, for example, increasing the reaction rate facilitates pore formation. It is thought that the pores, pore volume, and particle surface area can be controlled by changing the particle structure, such as pore structure, through the selection of the electron donor, or by adjusting the size and quantity of the pores through the amount of electron donor used. Generally, the structure of the solid titanium catalyst component tends to be inherited by the structure of the resulting olefin polymer (commonly known as the replica rule). For this reason, controlling the structure of the solid titanium catalyst component to have pores is advantageous for producing olefin polymer particles with pores. From the above perspectives, a method of producing a solid titanium catalyst component using the components, including (a) a liquid magnesium compound and (b) a liquid titanium compound, and then using the resulting component to produce olefin polymer particles (described below) is often suitable as a method for producing olefin polymer particles for three-dimensional shaping of the present invention.

[0134] The olefin polymerization catalyst may also include a metallocene compound. Preferred examples of the specific metallocene compound include the metallocene compounds disclosed in International Publication No. 2014 / 050816. More specifically, metallocene compounds disclosed in the examples of the publication or compounds with different central metals (in other words, zirconocene compounds, titanocene compounds, hafnocene compounds, etc.) are preferred.

[0135] These compounds, as well as compounds having so-called olefin polymerization catalytic activity, such as the solid titanium catalyst component, are preferably supported on a known porous inorganic oxide such as silica. Supported solid aluminoxane compounds, as described below, are also preferred. Selecting and using compounds having appropriate particle sizes and pores as the porous inorganic oxides or solid aluminoxanes is advantageous in utilizing the replica rule to produce olefin polymer particles that satisfy the particle size and pore structure requirements of the present invention. (The porous inorganic oxides described above are commercially available in particles with various particle sizes and pore structures, and may be useful in the present invention.)

[0136] <Organometallic Compound Catalyst Component (II)> The organometallic compound catalyst component (II) contained in the olefin polymerization catalyst can be a compound containing a metal of Group 13 of the periodic table, such as an organoaluminum compound, an alkylated complex of a metal of Group 1 with aluminum, or an organometallic compound of a metal of Group 2. Among these, organoaluminum compounds are preferred. Specific preferred examples of the organometallic compound catalyst component (II) include the organometallic compound catalyst components described in known documents such as the aforementioned European Patent Publication No. 585869.

[0137] In addition to the above, known aluminoxane compounds and boron-containing compounds can also be used. Preferred examples of such compounds include the compounds disclosed in International Publication No. 2014 / 050816. Preferred examples include the solid aluminoxane compounds described in International Publication No. 2014 / 123212 and International Publication No. 2010 / 055565552. More preferred examples include the solid methylaluminoxanes described in the above publications.

[0138] <Electron Donor (III)> The olefin polymerization catalyst contains the solid titanium catalyst component (I), the organometallic compound catalyst component (II), and an electron donor (III). A preferred example of the electron donor (III) is an organosilicon compound. An example of this organosilicon compound is a compound represented by the following general formula (4): R Ｓ ｎ Si(OR″) ４－ｎ ...(4) In formula (4), R Ｓ and R″ is a hydrocarbon group, and n is an integer of 0<n<4.

[0139] Specific examples of the organosilicon compound represented by the general formula (4) include diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, phenyltriethoxysilane, cyclohexyltrimethoxysilane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, and cyclopentyldimethylethoxysilane.

[0140] Of these, vinyltriethoxysilane, diphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, and dicyclopentyldimethoxysilane are preferably used.

[0141] Furthermore, a silane compound represented by the following formula (5) described in WO 2004 / 016662 is also a preferred example of the organosilicon compound: Si(OR ａ ) ３ (NR ｂ R ｃ ) ... (5)

[0142] In formula (5), R ａ is a hydrocarbon group having 1 to 6 carbon atoms, and R ａ Examples of the alkyl group include unsaturated or saturated aliphatic hydrocarbon groups having 1 to 6 carbon atoms, and particularly preferred are hydrocarbon groups having 2 to 6 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group, an isopentyl group, a cyclopentyl group, an n-hexyl group, and a cyclohexyl group, and among these, an ethyl group is particularly preferred.

[0143] In formula (5), R ｂ is a hydrocarbon group having 1 to 12 carbon atoms or hydrogen, and R ｂ Examples of the alkyl group include hydrogen and unsaturated or saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms. Specific examples include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group, an isopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, and an octyl group, with an ethyl group being particularly preferred.

[0144] In formula (5), R ｃ is a hydrocarbon group having 1 to 12 carbon atoms, and R ｃExamples of the alkyl group include hydrogen and unsaturated or saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group, an isopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, and an octyl group, with an ethyl group being particularly preferred.

[0145] Specific examples of the compound represented by the above formula (5) include dimethylaminotriethoxysilane, diethylaminotriethoxysilane, diethylaminotrimethoxysilane, diethylaminotriethoxysilane, diethylaminotri-n-propoxysilane, di-n-propylaminotriethoxysilane, methyl-n-propylaminotriethoxysilane, t-butylaminotriethoxysilane, ethyl-n-propylaminotriethoxysilane, ethylisopropylaminotriethoxysilane, and methylethylaminotriethoxysilane.

[0146] Another example of the organosilicon compound is a compound represented by the following formula (6): Ｎ NSi(OR ａ ) ３ ...(6)

[0147] In formula (6), R Ｎ N is a cyclic amino group, and examples of this cyclic amino group include a perhydroquinolino group, a perhydroisoquinolino group, a 1,2,3,4-tetrahydroquinolino group, a 1,2,3,4-tetrahydroisoquinolino group, and an octamethyleneimino group.

[0148] Specific examples of the compound represented by formula (6) include (perhydroquinolino)triethoxysilane, (perhydroisoquinolino)triethoxysilane, (1,2,3,4-tetrahydroquinolino)triethoxysilane, (1,2,3,4-tetrahydroisoquinolino)triethoxysilane, octamethyleneiminotriethoxysilane, etc. These organosilicon compounds can also be used in combination of two or more.

[0149] Other preferred examples of compounds useful as the electron donor (III) include the aromatic carboxylic acid esters and / or the polyether compounds described as examples of compounds having two or more ether bonds via a plurality of carbon atoms (the catalyst component (c)).

[0150] Among these polyether compounds, 1 ， 3-Diethers are preferred, particularly 2-isopropyl-2-isobutyl-1 ， 3-dimethoxypropane, 2 ， 2-diisobutyl-1 ， 3-Dimethoxypropane, 2-isopropyl-2-isopentyl-1 ， 3-dimethoxypropane, 2 ， 2-Dicyclohexyl-1 ， 3-dimethoxypropane, 2 ， 2-bis(cyclohexylmethyl) 1 ， 3-Dimethoxypropane is preferred. These compounds can be used alone or in combination of two or more.

[0151] The combined use of the electron donor (III) as described above often makes it possible to adjust the stereoregularity and molecular weight in particular. Specifically, increasing the ratio of the electron donor (III) used relative to the organometallic compound catalyst component tends to make it easier to obtain a polymer with high stereoregularity and a high molecular weight. On the other hand, decreasing the ratio of the electron donor (III) used tends to make it easier to obtain a polymer with low stereoregularity (for example, a high content of decane-soluble components, as described below) and a low molecular weight.

[0152] In addition to the above-mentioned components, the olefin polymerization catalyst may contain other components useful for olefin polymerization, as needed, such as a carrier such as silica, an antistatic agent, a particle flocculant, a storage stabilizer, etc.

[0153] [Olefin Polymerization Method] The olefin polymerization method according to the present invention is characterized in that olefin polymerization is carried out using an olefin polymerization catalyst. In the present invention, the term "polymerization" may include not only homopolymerization but also copolymerization such as random copolymerization and block copolymerization.

[0154] In the olefin polymerization method according to the present invention, it is also possible to carry out main polymerization in the presence of a prepolymerization catalyst obtained by prepolymerizing an α-olefin in the presence of an olefin polymerization catalyst. This prepolymerization is carried out by prepolymerizing an α-olefin in an amount of 0.1 g to 1000 g, preferably 0.3 g to 500 g, particularly preferably 1 g to 200 g, per 1 g of the olefin polymerization catalyst.

[0155] In the prepolymerization, the catalyst can be used at a higher concentration than that in the main polymerization system. The concentration of the solid titanium catalyst component (I) in the prepolymerization is desirably set to be in the range of usually about 0.001 to 200 mmol, preferably about 0.01 to 50 mmol, and particularly preferably 0.1 to 20 mmol, calculated as titanium atom per liter of the liquid medium.

[0156] The amount of the organometallic compound catalyst component (II) in the prepolymerization may be such that 0.1 g to 1000 g, preferably 0.3 g to 500 g, of polymer is produced per gram of the solid titanium catalyst component (I), and the amount is generally about 0.1 mol to 300 mol, preferably about 0.5 mol to 100 mol, particularly preferably 1 mol to 50 mol, per mol of titanium atom in the solid titanium catalyst component (I).

[0157] In the prepolymerization, the electron donor (III) and the like can be used as needed, and in this case, these components are used in an amount of 0.1 mol to 50 mol, preferably 0.5 mol to 30 mol, and more preferably 1 mol to 10 mol, per mol of titanium atom in the solid titanium catalyst component (I). By adjusting the amount of the electron donor (III), it may be possible to adjust the stereoregularity of the resulting olefin polymer.

[0158] The prepolymerization can be carried out under mild conditions by adding an olefin and the above-mentioned catalyst components to an inert hydrocarbon medium.

[0159] In this case, specific examples of the inert hydrocarbon medium to be used include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cycloheptane, methylcycloheptane, 4-cycloheptane, and methyl 4-cycloheptane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof.

[0160] Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. When an inert hydrocarbon medium is used, it is preferable to carry out the prepolymerization in a batch system.

[0161] On the other hand, the prepolymerization can be carried out using the olefin itself as a solvent, or in the substantial absence of a solvent. In this case, it is preferable to carry out the prepolymerization continuously.

[0162] The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization described below, and specifically, it is preferably propylene.

[0163] The temperature during prepolymerization is usually in the range of about -20°C to +100°C, preferably about -20°C to +80°C, and more preferably 0°C to +40°C.

[0164] Next, the main polymerization, which is carried out after the above-mentioned prepolymerization or without prepolymerization, will be described.

[0165] Examples of olefins that can be used (i.e., polymerized) in this polymerization include α-olefins having 3 to 20 carbon atoms, such as linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene, and branched olefins such as 4-methyl-1-pentene, 3-methyl-1-pentene, and 3-methyl-1-butene, with propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, and 3-methyl-1-butene being preferred. Furthermore, from the viewpoint that the advantages of polymers with a wide molecular weight distribution are easily realized in highly rigid resins, propylene, 1-butene, 4-methyl-1-pentene, and 3-methyl-1-butene are particularly preferred.

[0166] These α-olefins can also be used in combination with aromatic vinyl compounds such as ethylene, styrene, and allylbenzene; and alicyclic vinyl compounds such as vinylcyclohexane and vinylcycloheptane. Furthermore, compounds having polyunsaturated bonds, such as conjugated or non-conjugated dienes, including dienes such as cyclopentene, cycloheptene, norbornene, tetracyclododecene, isoprene, and butadiene, can also be used as polymerization raw materials in combination with ethylene and the α-olefin. These compounds can be used alone or in combination with two or more (hereinafter, olefins used in combination with the above-mentioned ethylene or "α-olefins having 3 to 20 carbon atoms" will also be referred to as "other olefins").

[0167] Among the other olefins, ethylene and aromatic vinyl compounds are preferred. Furthermore, other olefins such as ethylene may be used in combination in a small amount, for example, 10% by weight or less, preferably 5% by weight or less, based on 100% by weight of the total amount of olefins.

[0168] In the present invention, the prepolymerization and main polymerization can be carried out by any of liquid phase polymerization methods such as bulk polymerization, solution polymerization, and suspension polymerization, or gas phase polymerization methods.

[0169] When the main polymerization is carried out in the form of a slurry polymerization reaction, the inert hydrocarbon used in the prepolymerization described above can be used as the reaction solvent, or an olefin that is liquid at the reaction temperature can be used.

[0170] In the main polymerization of the polymerization method of the present invention, the solid titanium catalyst component (I) is typically used in an amount of about 0.0001 to 0.5 millimole, preferably about 0.005 to 0.1 millimole, calculated as titanium atoms per liter of polymerization volume. The organometallic compound catalyst component (II) is typically used in an amount of about 1 to 2,000 moles, preferably about 5 to 500 moles, more preferably 10 to 350 moles, even more preferably 30 to 350 moles, and particularly preferably 50 to 350 moles, per mole of titanium atoms in the prepolymerized catalyst component in the polymerization system. The electron donor (III), if used, is typically used in an amount of 0.001 to 50 moles, preferably 0.01 to 30 moles, and particularly preferably 0.05 to 20 moles, per mole of metal atoms in the organometallic compound catalyst component (II). As mentioned above, the stereoregularity and molecular weight can sometimes be adjusted by adjusting the amount of the electron donor (III) used.

[0171] If the polymerization is carried out in the presence of hydrogen, the molecular weight of the resulting polymer can be controlled, and a polymer having a high melt flow rate can be obtained.

[0172] In the present invention, the polymerization temperature of the olefin is usually about 20°C to 200°C, preferably about 30°C to 100°C, and more preferably 50°C to 90°C. The pressure is usually set at atmospheric pressure to 10 MPa, preferably 0.20 MPa to 5 MPa. In the polymerization method of the present invention, the polymerization can be carried out by any of batch, semi-continuous, and continuous methods. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions. By carrying out such multi-stage polymerization, it is possible to further broaden the molecular weight distribution of the olefin polymer.

[0173] The olefin polymer thus obtained may be any of a homopolymer, a random copolymer, a block copolymer, etc. When olefin polymerization, particularly propylene polymerization, is carried out using the above-mentioned olefin polymerization catalyst, a highly stereoregular propylene polymer having a decane-insoluble component content of 70% or more, preferably 85% or more, particularly preferably 90% or more can be obtained.

[0174] Furthermore, according to the olefin polymerization method of the present invention, polyolefins, particularly polypropylene, having a broad molecular weight distribution can be obtained even with a small number of polymerization stages, for example, single-stage polymerization, without requiring multistage polymerization. The olefin polymerization method of the present invention is characterized in that it often produces olefin polymers having a higher proportion of high-molecular-weight components and a lower proportion of low-molecular-weight components (particularly so-called solid components) than conventional olefin polymers having the same melt flow rate (MFR). This characteristic can be confirmed by gel permeation chromatography (GPC) measurements, which will be described later, and polymers having high Mw / Mn and Mz / Mw values ​​can be obtained.

[0175] The olefin polymer particles of the present invention can be produced by using the above-mentioned methods.In addition, if the particle size of the olefin polymer particles obtained by the above-mentioned methods is larger than the range required by the present invention, for example, outside the range required by the present invention, it can be adjusted to within the range required by the present invention by using conventional methods such as pulverization treatment by pulverization methods such as mechanical pulverization or wet pulverization, particle spheroidization treatment, classification treatment, etc.In addition, the above-mentioned various pulverization methods may not provide sufficient pulverization effect depending on the particle shape of the olefin polymer particles used, so it is important to select an appropriate method.

[0176] Hereinafter, the embodiment of the present invention will be described in more detail based on examples, but the present invention is not limited to these examples, which are one embodiment of the present invention.

[0177] <Various Analytical Methods for Polymer Particles> Various physical properties of the polymer particles described below were analyzed by the following methods. (Ethylene Content) The content of structural units derived from ethylene in the propylene-based block copolymer particles or in the n-decane soluble portion at 23°C was measured by measuring the content of structural units derived from ethylene in the propylene-based block copolymer particles or in the n-decane soluble portion at 23°C ... １３ Measurement was performed at 120°C using a C NMR (manufactured by Bruker Biospin, device name AVANCEIII cryo-500), and units derived from ethylene and units derived from propylene were identified by a conventional method, and the units were identified from the absorption intensity ratio.

[0178] (23°C n-decane soluble portion) 200 mL of n-decane was added to 5 g of propylene-based block copolymer particles, and the mixture was heated and dissolved at 145°C for 30 minutes. The mixture was cooled to 20°C over approximately 3 hours and allowed to stand for 30 minutes. Thereafter, the precipitate (α) was filtered off. The filtrate was poured into approximately three times the amount of acetone to precipitate the components dissolved in n-decane. The precipitate (β) (hereinafter referred to as n-decane soluble portion: D ｓｏｌ The precipitate (α), n-decane, and acetone were filtered off, and the precipitate was dried. The filtrate was concentrated to dryness, but no residue was observed. The precipitate (α) was added again to 200 mL of n-decane, heated at 145°C for 30 minutes, and the solution was filtered to remove the filler and other particles. The filtrate was cooled to 20°C over approximately 3 hours and allowed to stand for 30 minutes, after which the precipitate (γ) (hereinafter referred to as the n-decane insoluble portion of the propylene-based block copolymer: D ｉｎｓｏｌ In the n-decane fractionation of the propylene-based block polymer, the precipitate (γ) was separated from the n-decane insoluble portion (D ｉｎｓｏｌ ), the amount of n-decane solubles was calculated as follows: Amount of n-decane solubles (mass%) = [amount of precipitates (β) / (amount of precipitates (γ) + precipitates (β)] × 100

[0179] (Intrinsic viscosity [η] of n-decane soluble part at 23°C) According to JIS K 7367-3 standard, ｓｏｌ The measurement was carried out in a decalin solvent at 135°C. More specifically, the measurement was carried out in the following manner. ｓｏｌ Approximately 20 mg of sample was dissolved in 15 mL of decalin, and the specific viscosity ηｓｐ The decalin solution was diluted with 5 mL of decalin solvent, and the specific viscosity η ｓｐ This dilution procedure was repeated two more times, and the η when the concentration (C) was extrapolated to 0 was measured. ｓｐ The value of / C was calculated as the intrinsic viscosity. [η] = lim (η ｓｐ / C) (C→0)

[0180] (Volume Average Particle Diameter) Using the propylene-based block copolymer particles or propylene polymer particles obtained in the examples as samples, the volume average particle diameter was measured by the standard method specified for the instrument using a laser PSD measuring instrument LS-13320 manufactured by Beckman Coulter, Inc. The sample used was a slurry prepared by suspending and dispersing 20 to 30 mg of olefin polymer particles in an appropriate amount of commercially available decane.

[0181] (Pore diameter, pore volume, specific surface area) The propylene-based block copolymer particles or propylene polymer particles obtained in the examples were used as samples, and measurements of pore diameter and pore volume were carried out by a conventional method using a mercury porosimeter (trade name: PoreMaster 60GT, manufactured by Quantachrome Co., Ltd.). The obtained data was analyzed using analysis software (trade name: Poremaster for Windows) attached to the device, and the cumulative pore volume and specific surface area were calculated for pore diameters of 0.001 μm or more and less than 0.01 μm, 0.01 μm or more and less than 0.05 μm, 0.05 μm or more and less than 0.1 μm, 0.1 μm or more and less than 0.5 μm, 0.5 μm or more and less than 1 μm (0.001 μm or more and less than 1 μm), 1 μm to 10 μm, and 1 μm to 4 μm.

[0182] (Circularity) The propylene-based block copolymer particles or propylene polymer particles obtained in the examples were used as samples, and measurements were carried out in a conventional manner using a PITA-3 (particle shape image analyzer, manufactured by Seishin Enterprise Co., Ltd., sample amount: approximately 300 mg, dispersion medium: isopropyl alcohol, measurement range: 5 to 300 μm, measurement camera magnification: 4x), and the circularity was calculated.

[0183] (Melting Point) The propylene-based block copolymer particles or propylene polymer particles obtained in the examples were used as samples, and measurements were carried out using a differential scanning calorimeter (Perkin-Elmer, DSC8000). Approximately 5 mg of the sample was sealed in an aluminum pan and heated from 30°C to 230°C at 10°C / min. The sample was held at 230°C for 10 minutes to completely melt all crystals, and then cooled to 30°C at 10°C / min. After being left at 30°C for 1 minute, the sample was heated to 230°C at 10°C / min. The peak temperature in this second heating test was taken as the melting point (Tm).

[0184] Example 1 (Preparation of Solid Titanium Catalyst Component) 95.2 g of anhydrous magnesium chloride, 398.1 g of decane, and 306 g of 2-ethylhexyl alcohol were heated and reacted at 140°C for 6 hours to form a homogeneous solution. The solution was then cooled to 50°C, and 17.6 g of ethyl benzoate was added to the solution. The mixture was then stirred and mixed at 130°C for 1 hour. After the homogeneous solution was cooled to room temperature, 50 mL of the homogeneous solution was added dropwise to 200 mL of titanium tetrachloride maintained at 0°C with stirring. The mixture was heated to 80°C over 210 minutes. When the temperature reached 78°C, 2.35 g of ethyl benzoate was added to the reaction solution. Stirring was then continued at 80°C for 2 hours. The solid portion was then collected by hot filtration, resuspended in 200 mL of titanium tetrachloride, and stirred at 90°C for 2 hours. After completion of the reaction, the solid portion was again collected by hot filtration, washed with decane at a temperature of 90°C, and then thoroughly washed with hexane at room temperature until no free titanium compounds were detected in the washings. In this manner, a solid titanium catalyst component (solid titanium catalyst component (I)) was prepared. The solid titanium catalyst component prepared by the above procedure was stored as a decane slurry, and a portion of this was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component thus obtained was 3.1% by mass of titanium, 18% by mass of magnesium, 60% by mass of chlorine, 15.4% by mass of ethyl benzoate, and 1.5% by mass of 2-ethylhexyl alcohol residue.

[0185] (Polymerization) 400 ml of purified heptane was charged into a 1 L stainless steel autoclave (equipped with a stirrer, a pressure gauge, a gas flow meter, a gas supply pipe, and a gas discharge pipe) that had been thoroughly purged with nitrogen, and 60 L / hr of propylene was passed through it at room temperature for 15 minutes to saturate the liquid and gas phases. Subsequently, after raising the temperature to 60°C, 2.5 mmol of triethylaluminum (organometallic compound catalyst component (II)), 1.25 mmol of dicyclopentyldimethoxysilane (an organosilicon compound serving as electron donor (III)), and 0.025 mmol of the solid titanium catalyst component (solid titanium catalyst component (I)) obtained above were charged while propylene was still passing through it at 12 L / hr. (Up to this point, the operation was carried out under normal pressure conditions.) The gas exhaust pipe was sealed, and 120 mL of hydrogen was supplied. The temperature was quickly raised to 70°C, and the total pressure was raised to 0.3 MPa. Propylene polymerization was carried out while maintaining this pressure and temperature. When the amount of propylene supplied after the temperature increase reached 20 L based on normal temperature and normal pressure, the supply of propylene was stopped, the temperature was rapidly cooled to 40°C, and the pressure was released. Nitrogen was supplied while the temperature was being lowered to purge the remaining propylene. Thereafter, nitrogen substitution was repeated several times. When the temperature was cooled to 28°C, 11 L of propylene and then 4.7 L of ethylene were supplied, and propylene / ethylene copolymerization was carried out at 30°C for 15 minutes. After the pressure was released, the resulting solid slurry was filtered and dried under reduced pressure at room temperature overnight. The resulting propylene-based block copolymer particles weighed 29 g, had an ethylene content of 13.2 mol%, a volume average particle size of 63 μm, and a volume of 57 mm with a pore size of 0.001 μm or more and less than 1 μm. ３ / g, and the volume for pore diameters of 1 to 4 μm is 5 mm ３ / g, and the volume for pore diameters of 1 to 10 μm is 30 mm ３ The analytical results of the component soluble in n-decane at 23°C were as follows: Content of component soluble in n-decane: 18.4 wt % Intrinsic viscosity [η]: 6.3 dL / g Content of ethylene-derived structural units: 43 mol % These results are also shown in Tables 1 and 2.

[0186] [Examples 2 and 3] Propylene-based block copolymer particles were produced in the same manner as in Example 1, except that the amount of gas supplied in the propylene / ethylene copolymerization stage was changed to the value shown in Table 1. The results obtained are shown in Tables 1 and 2.

[0187] Comparative Example 1 (Mechanical Pulverization) Pellets obtained by melt extrusion molding of a propylene-based block copolymer (Prime Polypro J707G, manufactured by Prime Polymer Co., Ltd.) were cooled to −120°C with liquid nitrogen and pulverized using a pulverizer (Rinrex Mill, manufactured by Osaka Gas Liquid Co., Ltd.). After pulverization, the pellets were classified using a 106 μm mesh to obtain a powder material consisting of propylene-based block copolymer pellets. The volume average particle size, circularity, and powder material were analyzed using a mercury porosimeter. The results are shown in Table 2.

[0188] [Example 4] (Polymerization) A 1 L stainless steel autoclave (equipped with a stirrer, a pressure gauge, a gas flow meter, a gas supply pipe, and a gas discharge pipe) whose interior air had been thoroughly purged with nitrogen was charged with 400 ml of purified heptane, and propylene was passed through it at room temperature at 60 L / hr for 15 minutes to saturate the liquid and gas phases. Subsequently, after raising the temperature to 60°C, 2.5 mmol of triethylaluminum (organometallic compound catalyst component (II)), 1.25 mmol of dicyclopentyldimethoxysilane (an organosilicon compound serving as electron donor (III)), and 0.025 mmol of the solid titanium catalyst component (solid titanium catalyst component (I)) obtained in Example 1 were added while propylene was still passing through at 12 L / hr. (Up to this point, the operation was carried out under normal pressure conditions.) The gas exhaust pipe was sealed, and 480 mL of hydrogen was supplied. The temperature was quickly raised to 70°C, and the total pressure was raised to 0.3 MPa. Propylene polymerization was carried out while maintaining this pressure and temperature. When the amount of propylene supplied after the temperature increase reached 30 liters at normal temperature and normal pressure, the supply of propylene was stopped, the temperature was rapidly cooled to 40°C, and the pressure was released. While the temperature was being lowered, nitrogen was supplied to purge the remaining propylene. Thereafter, nitrogen substitution was repeated several times. When the temperature was cooled to 28°C, 21 L of propylene and then 9 L of ethylene were supplied, and propylene / ethylene copolymerization was carried out at 30°C for 15 minutes. After the pressure was released, the resulting solid slurry was filtered and dried under reduced pressure at room temperature overnight.

[0189] [Examples 5 and 6] Propylene-based block copolymer particles were produced in the same manner as in Example 1, except that the amount of gas supplied in the propylene / ethylene copolymerization stage was changed to the value shown in Table 1. The obtained results are shown in Tables 1 and 2.

[0190] Example 7 A 1 L stainless steel autoclave (equipped with a stirrer, a pressure gauge, a gas flow meter, a gas supply pipe, and a gas discharge pipe) whose interior was thoroughly purged with nitrogen was charged with 400 ml of purified heptane, and propylene was passed through it at room temperature at 60 L / hr for 15 minutes to saturate the liquid and gas phases. The temperature was then raised to 60°C, and then, while propylene was still passing through it at 12 L / hr, 2.5 mmol of triethylaluminum (organometallic compound catalyst component (II)), 1.25 mmol of dicyclopentyldimethoxysilane (an organosilicon compound serving as electron donor (III)), and 0.025 mmol of the solid titanium catalyst component (solid titanium catalyst component (I)) obtained above were added. (Up to this point, the operation was carried out under normal pressure conditions.) The gas exhaust pipe was sealed, and 480 ml of hydrogen was supplied. The temperature was quickly raised to 70°C, and the total pressure was raised to 0.3 MPa. Propylene polymerization was carried out while maintaining this pressure and temperature. When the amount of propylene supplied after the temperature increase reached 30 liters at normal temperature and normal pressure, the supply of propylene was stopped. After depressurization, the resulting solid slurry was filtered and dried under reduced pressure at 80°C overnight. The yield of the resulting solid phase (white powder) was 44 g, and the melting point was 162°C. Other analytical results are shown in Table 2.

[0191] Example 8 Propylene polymer particles were produced in the same manner as in Example 7, except that the amount of hydrogen supplied in the propylene polymerization stage was changed to 120 mL. The yield of the obtained solid phase (white powder) was 46 g, and the melting point was 162° C. Other analytical results are shown in Table 2.

[0192]

[0193] * Pore volume value for each pore diameter range

[0194] As shown in Table 2, the olefin polymer particles (propylene-based block copolymer particles or propylene polymer particles) of Examples 1 to 8 have larger measured pore volumes at pore diameters of 0.001 μm or more and less than 1 μm than those of Comparative Example 1. This result suggests that the olefin polymer particles of the examples of the present invention are in a form in which the effects of additives such as melt promoters are more likely to be exhibited. On the other hand, the measured pore volumes at pore diameters of 1 μm to 10 μm or 1 μm to 4 μm in Examples 1 to 8 are smaller than those of Comparative Example 1. Since the numerical value in this pore diameter range can mainly serve as an index of the gaps between particles, this suggests that the gaps between particles of the olefin polymer particles of the Examples are smaller than those of the Comparative Examples.

[0195] Next, the olefin polymer particles and the three-dimensional molded articles molded using the olefin polymer particles were subjected to the following measurements and evaluations.

[0196] (Evaluation of Diffusibility of Melt Accelerator into Obtained Polymer Particles) A ​​cylindrical stainless steel container (product number 63-2587-03, manufactured by AS ONE) with a height of 2.3 cm and an inner diameter of 1.55 cm (open at the top) was prepared. Next, 1.5 g of the olefin polymer particles obtained in the above Examples and Comparative Examples was filled to the entire container. The stainless steel container filled with the olefin polymer particles was placed in the center of an MX50-type heating moisture meter manufactured by A&D Corporation, and the olefin polymer particles in the container were heated to 130°C and maintained at this temperature. (The moisture meter was heated at 130°C for at least 2 minutes using the heating function of the moisture meter.) Next, 4 μl of the following melt accelerator was dropped onto the upper center of the olefin polymer particles in the container. The amount dropped was equivalent to one drop, using a TGK Fine Pipette Gene II and Fine Disposable Tip FT-UT micropipette. Immediately after the drop, the container was heated to 150°C and maintained for 2 minutes. The stainless steel vessel was then removed, and the olefin polymer particles in the vessel were taken out, and the molten black mass was separated and its maximum diameter was measured. The above procedure was repeated four times, and the median value of the maximum diameters was used.

[0197] Melting promoter composition: Water 68% by mass, 2-pyrrolidinone 25% by mass, carbon black (average particle size: 60 nm) 5% by mass, other additives 2% by mass

[0198] (Measurement of void ratio of molded body) (Method of preparing molded body) Using a 3D SYSTEMS SINTERSTATION 2500 plus 3D modeling device, a 0.1 mm-thick thin layer of the olefin polymer particles obtained in the Examples and Comparative Examples was formed on a modeling stage (length (X) 360 mm, width (Y) 310 mm) at a recoating speed of 160 mm / sec and a temperature of 150°C. This thin layer was irradiated with a carbon dioxide laser (equipped with a carbon dioxide laser galvanometer scanner) over an area of ​​10 mm wide and 80 mm long to create a molded layer. The process of laminating a molded layer on the molded layer in the same manner as above was repeated to obtain a molded body having a width of 10 mm, a length of 80 mm, and a thickness of 4 mm. The carbon dioxide laser irradiation conditions were as follows: laser output: 50 W, laser light wavelength: 10.6 μm, beam diameter: 500 μm (diameter on the surface of the thin layer), number of lines: 1

[0199] (Method of calculating void ratio) The center of the molded body was cut to obtain a sample piece 10 mm wide, 40 mm long, and 4 mm thick. The density (D) of this sample was determined according to the JIS 7112A standard (underwater displacement method). (Units were g / ml.) Furthermore, using the measured density value and the density of the olefin polymer itself, the void ratio was calculated according to the following formula. (The olefin polymer particles in the Examples and Comparative Examples were propylene polymers, and the calculation was based on 0.90 g / ml.) Void ratio (%) = 100 x (D) / 0.90

[0200] [Example 3P] The diffusivity was measured by the above-mentioned method using the olefin polymer particles obtained in Example 3. The results are shown in Table 3.

[0201] [Example 4P] The diffusivity was measured by the above-mentioned method using the olefin polymer particles obtained in Example 4. The results are shown in Table 3.

[0202] Comparative Example 1P The diffusivity was measured by the above-mentioned method using the olefin polymer particles obtained in Comparative Example 1. The results are shown in Table 3.

[0203]

[0204] The olefin polymer particles obtained in Examples 3 and 7 were dry-blended in a ratio of 3:7 (particles of Example 3:particles of Example 7), and the void ratio was measured by the method described above. The results are shown in Table 4.

[0205] The olefin polymer particles obtained in Examples 4 and 8 were dry-blended in a ratio of 3:7 (particles of Example 4:particles of Example 8), and the void ratio was measured by the method described above. The results are shown in Table 4.

[0206] Comparative Example 1V The void ratio was measured by the method described above using the olefin polymer particles obtained in Comparative Example 1. The results are shown in Table 4.

[0207]

[0208] The results disclosed in Tables 3 and 4 above show that the olefin polymer particles for 3D shaping and the olefin polymer particle composition of the present invention have a high degree of diffusion (dispersibility) of the melting promoter, which is a liquid additive. Furthermore, the void ratio of molded articles using the polymer particles was also low. These findings also demonstrate that the olefin polymer particles for 3D shaping of the present invention and the olefin polymer particle composition containing the olefin polymer particles have properties suitable as base resins for 3D shaping, such as 3D printing. Furthermore, the olefin polymer particles of the examples of the present invention are considered to be less likely to produce voids as particles for 3D shaping used in 3D printers, etc., and to facilitate the production of 3D shaped objects with excellent strength and appearance.

[0209] The disclosure of Japanese Patent Application No. 2024-150354, filed on August 30, 2024, is incorporated herein by reference in its entirety. All publications, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual publication, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. Olefin polymer particles for three-dimensional shaping, which satisfy the following requirements (p1) to (p3): (p1) the volume average particle diameter is 10 μm to 200 μm; (p2) the pore volume at pore diameters of 0.001 μm or more and less than 1 μm is 50 mm ３ / g to 300 mm ３ / g (p3) The pore volume at pore diameters of 1 μm to 10 μm is 5 mm ３ / g to 60mm ３ / g (In the above requirements (p2) and (p3), the pore diameter and pore volume are measured by a mercury porosimeter.) 2. The olefin polymer particles for three-dimensional shaping according to claim 1, further satisfying the following requirement (p3-2): (p3-2) The pore volume of pores with diameters of 1 μm to 4 μm is 1 mm ３ / g~13mm ３ / g 3. The olefin polymer particles for three-dimensional shaping according to claim 1, further satisfying the following requirement (p4): (p4) the circularity is 0.70 to 0.

95.

4. The olefin polymer particles for three-dimensional shaping according to claim 1, further satisfying the following requirement (p5): (p5) the content of decane-soluble components is 0.1% by mass to 40% by mass; 5. A method for producing olefin polymer particles for three-dimensional shaping, comprising the step of polymerizing olefins in the presence of an olefin polymerization catalyst comprising a solid titanium catalyst component (I) containing (a) a liquid magnesium compound, (b) a liquid titanium compound, and (c) an electron donor, an organometallic compound catalyst component (II), and an electron donor (III), to obtain olefin polymer particles that satisfy the following requirements (p1) to (p3): (p1) a volume average particle diameter of 10 μm to 200 μm; (p2) a pore volume of 50 mm3 at pore diameters of 0.001 μm or more and less than 1 μm. ３ / g to 300 mm ３ / g (p3) The pore volume at pore diameters of 1 μm to 10 μm is 5 mm ３ / g to 60mm ３ / g (In the above requirements (p2) and (p3), the pore diameter and pore volume are measured by a mercury porosimeter.) 6. The method for producing olefin polymer particles for three-dimensional shaping according to claim 5, wherein the electron donor (c) is an aromatic monocarboxylic acid ester.

7. (α) Olefin polymer particles that satisfy the following requirements (p1) to (p3): (p1) a volume average particle diameter of 10 μm to 200 μm; (p2) a pore volume of 50 mm3 or more at pore diameters of 0.001 μm or more and less than 1 μm; ３ / g to 300 mm ３ / g (p3) The pore volume at pore diameters of 1 μm to 10 μm is 5 mm ３ / g to 60mm ３ / g (In the requirements (p2) and (p3), the pore diameter and pore volume are measured by a mercury porosimeter.) An olefin polymer particle-containing composition comprising either (β) a dissolution promoter or (γ) a surface modifier.

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