Method for producing ion-exchangeable layered silicate particles, method for producing catalyst components for olefin polymerization, method for producing catalysts for olefin polymerization, and method for producing olefin polymers.

Abstract

To improve catalyst activity, and improve the quality of a polymer.SOLUTION: A method for producing ion-exchanging layered silicate particles includes the following steps 1, 2 and 3. Step 1: a step of preparing a slurry containing a compound [I] containing an ion-exchanging layered silicate, a solvent and aluminum ions, in which in 100 mass% of a solid component contained in the slurry, the compound [I] is 8-80 mass%, and the compound [I] may be one or more kinds, step 2: a step of granulating the slurry prepared in the step 1 by spray and drying, and obtaining ion-exchanging layered silicate composite particles, and a step 3: a step of eluting at least a part of a metal component contained in the ion-exchanging layered silicate composite particles obtained in the step 2.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to a method for producing ion-exchangeable layered silicate particles, a method for producing catalyst components for olefin polymerization, a method for producing catalysts for olefin polymerization, and a method for producing olefin polymers. [Background technology]

[0002] Ion-exchangeable layered silicates, such as clay minerals, are widely used as adsorbents, catalysts, and catalyst supports. While various factors influence performance in these applications, pore volume, pore distribution, and specific surface area have particularly significant effects. For example, Patent Document 1 provides an example of a clay mineral with a specific pore distribution as an adsorbent. Furthermore, it is well known that olefin polymers can be produced by polymerizing olefins in the presence of a catalyst that utilizes clay or clay minerals as a catalyst component for olefin polymerization (for example, Patent Document 2).

[0003] Furthermore, catalysts for olefin polymerization that contain ion-exchangeable layered compounds that have undergone acid treatment or salt treatment as components are also known (for example, Patent Document 3). Patent Document 4 discloses clay minerals with a specific pore distribution as catalysts and catalyst supports for olefin polymerization.

[0004] On the other hand, as a method for controlling the pore distribution of a solid made of ion-exchangeable layered silicate, for example, Patent Document 5 describes controlling the pore structure by amorphousizing the SiO2 crystalline component contained in clay minerals. However, this method involves including an SiO2 component that does not have catalytic activity, raising concerns about a decrease in catalytic activity.

[0005] Patent Document 6 describes a method of controlling the pore structure by drying and granulating a slurry containing substantially insoluble salts such as calcium carbonate, magnesium carbonate, and calcium hydroxide, and then reacting it with an acid to generate carbon dioxide. In the technique described in Patent Document 6, pore volume measurement by mercury intrusion method confirms an increase in pore volume in the range of pore diameters from 2 μm to 10 μm. However, in the method described in Patent Document 6, the volume of pores in the range of 10 nm to 300 nm hardly changes.

[0006] Patent Document 7 discloses a method for controlling the pore structure by adding fine particle solids of zinc oxide or titania, drying and granulating them, and then dissolving the fine particle solids with acid. However, the technique in Patent Document 7 results in a small specific surface area, which is important for the performance of catalysts and catalyst supports.

[0007] Patent documents 8 and 9 disclose a technique for forming a specific pore structure by utilizing ion-exchangeable layered silicates having a specific composition. Patent Document 10 describes how performance can be improved by eluting the aluminum component of an ion-exchangeable layered silicate granulated to a specific particle size and adjusting it to a specific particle strength. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] International Publication No. 2010 / 032568 [Patent Document 2] Japanese Patent Application Publication No. 5-295022 [Patent Document 3] Japanese Patent Application Publication No. 7-228621 [Patent Document 4] Japanese Patent Publication No. 2002-088114 [Patent Document 5] Japanese Patent Publication No. 2013-082607 [Patent Document 6] Japanese Patent Publication No. 2000-344513 [Patent Document 7] Japanese Patent Publication No. 2003-252923 [Patent Document 8] Japanese Patent Application Laid-Open No. 2015-108138 [Patent Document 9] Japanese Patent Application Laid-Open No. 2018-111841 [Patent Document 10] Japanese Patent Application Laid-Open No. 2019-172958 [Summary of the Invention] [Problems to be Solved by the Invention]

[0009] In the above Patent Documents 1-10, the pore distribution and the like of a solid composed of an ion-exchangeable layered silicate are controlled to improve the performance of the catalyst. However, in the technologies of these documents, the catalytic activity and the quality of the polymer are not always sufficient, and further improvement of the catalytic activity and the quality of the polymer have been desired. The present disclosure has been made in view of the above circumstances, and aims to improve the catalytic activity and the quality of the polymer, and can be realized in the following forms. [Means for Solving the Problems]

[0010] <1> A method for producing ion-exchangeable layered silicate particles including the following steps 1, 2 and 3. Step 1: A step of preparing a slurry containing an ion-exchangeable layered silicate, a solvent, and a compound [I] containing aluminum ions. Among 100% by mass of the solid components contained in the slurry, the compound [I] is 8% by mass to 80% by mass. Note that the compound [I] may be one or more kinds. Step 2: A step of granulating the slurry prepared in Step 1 by spray drying to obtain ion-exchangeable layered silicate composite particles. Step 3: A step of eluting at least a part of the metal components contained in the ion-exchangeable layered silicate composite particles obtained in Step 2. <2> When the amount of aluminum atoms (mol / g) contained in the ion-exchangeable layered silicate composite particles is denoted as [Alb] and the amount of magnesium atoms (mol / g) is denoted as [Mgb], the [Alb / Mgb] (molar ratio) is between 4.0 and 45.0. <1> A method for producing ion-exchange layered silicate particles as described above.

[0011] <3> When the amount of aluminum atoms (mol / g) contained in the ion-exchangeable layered silicate is denoted as [Ala] and the amount of magnesium atoms (mol / g) is denoted as [Mga], the molar ratio [Ala] / [Mga] is 0.3 or greater and less than 3.9. <1> or <2> A method for producing ion-exchange layered silicate particles as described above. <4> The compound [I] is composed of particles with an average particle size of 0.3 μm to 100.0 μm. <1> ~ <3> A method for producing ion-exchange layered silicate particles as described in any one of the items. <5> The compound [I] is a salt containing a hydroxide. <1> ~ <4> A method for producing ion-exchange layered silicate particles as described in any one of the items. <6> The compound [I] is characterized in that it is aluminum hydroxide. <1> ~ <5> A method for producing ion-exchange layered silicate particles as described in any one of the items.

[0012] <7> Step 3 involves bringing the ion-exchangeable layered silicate composite particles obtained in Step 2 into contact with acids. <1> ~ <6> A method for producing ion-exchange layered silicate particles as described in any one of the items. <8> <1> ~ <7> A method for producing a catalyst component for olefin polymerization, using ion-exchange layered silicate particles obtained by the manufacturing method described in any one of the items. <9> Claim <1> ~ <7> Ion-exchange layered silicate particles obtained by the manufacturing method described in any one of the items, A method for producing an olefin polymerization catalyst, comprising the step of contacting the following components [B] and [C]. Component [B]: Transition metal compound Ingredients [C]: Organoaluminum compounds <10> <9> A method for producing an olefin polymer, comprising carrying out olefin polymerization in the presence of an olefin polymerization catalyst obtained by the manufacturing method described above. [Effects of the Invention]

[0013] According to this disclosure, catalytic activity is improved, and the quality of the polymer is improved. [Brief explanation of the drawing]

[0014] [Figure 1] Figure 1 shows the sum of pore volumes from 10 nm to 300 nm, measured by mercury intrusion, plotted against the BET specific surface area m2 / g obtained by nitrogen adsorption / desorption for the ion-exchangeable layered silicate particles described in the Examples and Comparative Examples. [Figure 2] Figure 2 shows the polymerization activity of propylene homopolymerization using the olefin polymerization catalysts described in the Examples and Comparative Examples, plotted against the MFR of the obtained polymer. [Figure 3] Figure 3 shows the results of two-stage polymerization of propylene-ethylene using the olefin polymerization catalysts described in the Examples and Comparative Examples, plotting the number of fisheyes contained in the sheet against the molecular weight ratio of the obtained polymers (the molecular weight of the second polymer divided by the molecular weight of the first polymer). [Figure 4] Figure 4 shows the mercury intrusion and exit curves measured by the mercury intrusion method for the ion-exchange layered silicate particles described in the examples. [Modes for carrying out the invention]

[0015] The following provides a detailed explanation of this disclosure. In this specification, when numerical ranges are described using "~", unless otherwise specified, both the lower limit and the upper limit are included. For example, the description "10~20" includes both the lower limit "10" and the upper limit "20". In other words, "10~20" has the same meaning as "10 or more and 20 or less".

[0016] 1. Development History The inventors conducted intensive research to achieve the above objectives and found that when producing ion-exchangeable layered silicate particles, they first mixed a specific amount of ion-exchangeable layered silicate with a compound [I] containing aluminum ions (hereinafter sometimes referred to as "compound [I]") to form composite particles, and then dissolved compound [I] from these composite particles to control the pore structure. They then discovered that the specific ion-exchangeable layered silicate particles obtained in this way improve catalytic activity and polymer quality.

[0017] When a specific amount of compound [I] is added to a slurry of ion-exchangeable layered silicate and granulated, it is thought that the primary silicate particles in the resulting composite particles become loosely bonded due to compound [I]. Subsequently, by chemically treating the composite particles, the surface area of ​​the ion-exchangeable layered silicate increases, and compound [I] dissolves from the composite particles into the solvent, creating appropriate voids within the particles, which is presumed to allow control of the pore size of the silicate particles.

[0018] The pore structure in porous catalysts affects performance aspects such as catalyst activity and strength, and consequently, economic efficiency, operability, and product quality. Through diligent research, the inventors discovered that novel ion-exchangeable layered silicate particles can be obtained that have a large specific surface area and a large pore volume of 10 nm to 300 nm in diameter, as measured by mercury intrusion. They also found that using such ion-exchangeable layered silicate particles improves catalytic activity and polymer quality. More specifically, the ion-exchangeable layered silicate particles obtained from the manufacturing method of this disclosure can be used as a catalyst component for olefin polymerization to produce olefin polymers that exhibit high polymerization activity and have low levels of fish-eye particles (poor dispersion of incompatible components, gels, or catalyst residues) in the product, which can degrade the appearance of the product. This disclosure provides a novel method for producing ion-exchangeable layered silicate particles that exhibit these effects, a method for producing a catalyst component for olefin polymerization containing these ion-exchangeable layered silicate particles, and a method for producing a catalyst for olefin polymerization.

[0019] Conventional methods for producing ion-exchangeable layered silicate particles include, for example, a method described in Japanese Patent Publication No. 6136852, which uses smectite with a large Mg / Al ratio, corresponding to the isomorphic substitution amount of the octahedral layer of montmorillonite, which is classified as an ion-exchangeable layered silicate, and performs a specific chemical treatment. It is said that a highly active catalyst component for olefin polymerization with a large specific surface area can be obtained from this production method. However, it has been found that using ion-exchangeable layered silicate particles obtained from this production method results in the generation of numerous fish eyes (Comparative Examples P18 and P19 in Table 4-1). The method for producing ion-exchangeable layered silicate particles described herein not only improves activity but also improves monomer diffusion within the particles. This reduces the variation in activity between active sites, thereby decreasing the number of active sites that produce extremely high molecular weight polymers, and enabling the production of ion-exchangeable layered silicate particles with appropriate strength. Therefore, it is presumed that the method for producing ion-exchangeable layered silicate particles described herein makes it possible to produce catalyst components and catalysts for olefin polymerization that facilitate the formation of uniform polymers and produce olefin polymers with fewer fish eyes in the product.

[0020] 2. Method for producing ion-exchangeable layered silicate particles, and characteristics of ion-exchangeable layered silicate particles (1) Method for producing ion-exchange layered silicate particles The method for producing ion-exchange layered silicate particles according to this disclosure comprises the following steps 1, 2, and 3. Step 1: This step involves preparing a slurry containing an ion-exchangeable layered silicate, a solvent, and a compound [I] containing aluminum ions. Of the 100% by mass of solid components in this slurry, the compound [I] is present in an amount of 8% to 80% by mass. Note that there may be one or more types of compound [I]. Step 2: This step involves granulating the slurry prepared in Step 1 by spray drying to obtain ion-exchangeable layered silicate composite particles. Step 3: This step involves eluting at least a portion of the metal components contained in the ion-exchangeable layered silicate composite particles obtained in Step 2.

[0021] (1.1) Process 1 Step 1 is a step of preparing a slurry containing an ion-exchangeable layered silicate, a solvent, and a compound [I] containing aluminum ions. This slurry contains 8% to 80% by mass of compound [I] out of 100% by mass of solid components in the slurry.

[0022] (1.1.1) Ion-exchange layered silicates The method for producing ion-exchangeable layered silicate particles described herein uses ion-exchangeable layered silicate as a raw material. Ion-exchangeable layered silicate is a type of layered silicate compound that has a crystalline structure in which planes formed by ionic bonds, etc., are stacked parallel to each other with weak bonding forces, and is not limited to naturally occurring materials but may also be artificially synthesized. Specific examples of ion-exchangeable layered silicates include the following minerals, as described in, for example, "Clay Mineralogy" by Haruo Shiramizu, Asakura Shoten (1995). i) Minerals with a 1:1 layer as the main constituent layer include kaolin group minerals such as deckite, nacrite, kaolinite, and nacrite, serpentine group minerals such as chrysotile, lizardite, and antigorite, and serpentine-related minerals such as amethyst and Al lizardite. ii) Examples of smectite group silicates such as montmorillonite, beiderite, nontronite, saponite, hectorite, and stevensite, whose main constituent layer is a 2:1 layer; vermiculite group silicates such as vermiculite; mica group silicates such as mica, illite, sericite, and erythritol; attapulgite, sepiolite, palygorskite, and chlorite groups. These may form mixed layers. Many smectites occur naturally as mixtures of clay minerals and therefore often contain impurities (such as quartz, cristobalite, opal, and carbonates), but these may also be present. Examples of such impurities include bentonite and acid clay, which are clays mainly composed of montmorillonite. The ion-exchangeable layered silicates of this disclosure are preferably layered silicates having a 2:1 structure. More preferably, they are smectite group silicates, and even more preferably, montmorillonite. These ion-exchange layered silicates may be used individually or in combination of two or more types.

[0023] In the method for producing ion-exchangeable layered silicate particles according to this disclosure, the compositional analysis of the ion-exchangeable layered silicate, the ion-exchangeable layered silicate composite particles, and the ion-exchangeable layered silicate particles is performed by the measurement method described later.

[0024] These natural products may be purified by elutriation or efflux. Elutration or efflux removes impurities such as quartz and feldspar, which have a high specific gravity, as well as silicates that do not swell, thereby obtaining desirable ion-exchangeable layered silicates. Conventional methods can be used for elutriation or efflux. Drying or grinding may be performed before purification. Grinding methods include dry grinding and wet grinding. Grinding machines include jaw crushers, gyratory crushers, roll crushers, edge runners, hammer mills, ball mills, bead mills, and jet mills.

[0025] Furthermore, ion exchange treatment using a very small amount of sodium carbonate or the like may be performed beforehand. Examples of such treatments include the conversion of Ca-type bentonite to Na-type activated bentonite (Customs Central Laboratory Bulletin No. 56, p. 85; Clay Science Vol. 21 No. 1 1-13 (1981) Review). This makes it easier to disperse smectite during elutriation, allowing coarse quartz and other particles to be quickly separated by sedimentation based on particle size differences. Known substances may also be added as dispersants, such as sodium silicate and sodium pyrophosphate.

[0026] In the method for producing ion-exchangeable layered silicate particles of this disclosure, the ion-exchangeable layered silicate preferably used is such that, from the viewpoint of catalytic activity, the amount of aluminum atoms contained in the ion-exchangeable layered silicate is [Ala] and the amount of magnesium atoms (mol / g) is [Mga], and the [Ala] / [Mga] (molar ratio) is preferably 0.3 or more and less than 3.9. The lower limit is more preferably 1.0 or more, even more preferably 1.5 or more, and particularly preferably 2.0 or more, and the upper limit is more preferably 3.7 or less, even more preferably 3.5 or less, and particularly preferably 3.2 or less. When the ion-exchangeable layered silicate is a smectite group silicate, the trivalent aluminum constituting the octahedron is replaced with divalent magnesium, and it has a negative layer charge. This negative layer charge is thought to act as a counteranion in the metallocene catalyst to stabilize the cation species of the metallocene transition metal compound (complex), which is the active site precursor, thereby enhancing the stability of the olefin polymerization catalyst. It is believed that a highly active olefin polymerization catalyst can be obtained when [Ala] / [Mga] is within the above range.

[0027] In the method for producing ion-exchangeable layered silicate particles of this disclosure, the ion-exchangeable layered silicate preferably used is subjected to granulation and chemical treatment as described later. Furthermore, in this disclosure, if a silicate has ion-exchangeability and a layered structure before chemical treatment, even if its physical and chemical properties change as a result of the treatment and it no longer has ion-exchangeability or a layered structure, it will still be treated as an ion-exchangeable layered silicate.

[0028] The type of interlayer cation (cation contained between the layers of the ion-exchangeable layered silicate) that is preferably used in the method for producing ion-exchangeable layered silicate particles of this disclosure is not particularly limited. The interlayer cation is preferably one of alkali metals of Group 1 of the periodic table such as lithium and sodium, alkaline earth metals of Group 2 of the periodic table such as calcium and magnesium, or transition metals such as aluminum, silicon, iron, cobalt, copper, nickel, zinc, ruthenium, rhodium, palladium, silver, iridium, platinum, and gold, as these are relatively easily available as industrial raw materials. The term "main component" refers to a substance with a content (mass%) of 51% or more by mass.

[0029] (1.1.2) Raw material slurry The method for producing ion-exchangeable layered silicate particles according to this disclosure uses a slurry (hereinafter sometimes referred to as raw material slurry) containing an ion-exchangeable layered silicate, a solvent, and an aluminum ion-containing compound [I] as raw materials.

[0030] The ion-exchangeable layered silicate preferably used in the method for producing ion-exchangeable layered silicate particles of this disclosure is not particularly limited in its shape before slurrying. The shape before slurrying may be the shape obtained from naturally occurring particles, the shape at the time of artificial synthesis, or an ion-exchangeable layered silicate whose shape has been processed by operations such as crushing, granulation, or classification may be used. Alternatively, a slurry obtained by purification operations such as elutriation may be used as is. Furthermore, it may contain impurities (such as quartz, cristobalite, opal, and carbonates). The concentration of the ion-exchangeable layered silicate in the slurry is not particularly limited. The concentration is preferably 0.5% to 60% by mass, more preferably 0.7% to 40% by mass, even more preferably 0.8% to 20% by mass, and especially preferably 1% to 10% by mass.

[0031] The above-mentioned ion-exchangeable layered silicate may have a particle size of 2 μm or less when measured after dispersion in a solvent, preferably 1 μm or less, more preferably 0.7 μm or less, and even more preferably 0.5 μm or less. Any combination of upper and lower limits can be adopted. Here, particle size refers to the volume-based median diameter determined from the spherical equivalent particle size distribution, measured using a HORIBA LA-960 laser diffraction / scattering particle size distribution analyzer, under the following conditions: distilled water as the dispersion solvent, a real refractive index of 1.490, an imaginary refractive index of 0.100, a real refractive index of 1.333 for the dispersion solvent, a transmittance (R) of 85% to 99%, and a transmittance (B) of 85% to 90%, after ultrasonic treatment for 2 minutes at an ultrasonic intensity of "7" inside the instrument.

[0032] The type of solvent that makes up the slurry is not particularly limited. Preferred solvents are water and organic solvents such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, and xylene, with water being more preferred. These solvents may be used individually or in combination of two or more.

[0033] The aluminum ion-containing compound [I] preferably used in the method for producing ion-exchangeable layered silicate particles of this disclosure can be selected from among salts containing aluminum ions (including inorganic hydroxides and inorganic oxides). Furthermore, it may be solid at 20°C and, at the temperature of slurry formation with the ion-exchangeable layered silicate and solvent, preferably 20°C, it may be sparingly soluble or almost insoluble in the liquid in the slurry. Here, "spaciously soluble or almost insoluble" means that the amount of solvent in the slurry required to dissolve 1 g of solid is 100 mL or more. Moreover, compound [I] is not particularly limited as long as it can be dissolved by chemical treatment in step 3 described later. From the viewpoint of easy control of pore size, the salts exemplified below are preferred for compound [I].

[0034] The salts of compound [I] only need to contain an aluminum ion as a cation, and may further contain inorganic cations containing metal ions other than aluminum ions, or organic cations. The anions constituting the salts are not particularly limited. The anions may be selected from the group consisting of organic anions and inorganic anions containing metal ions, or they may be selected from the group consisting of organic anions and inorganic anions containing halide ions. For example, the salts may contain an aluminum ion as a cation, and may also contain a cation containing at least one atom selected from groups 1 to 14 of the periodic table other than aluminum ions, and may contain at least one anion selected from the group consisting of halogen anions, inorganic Brønsted acid anions, and organic Brønsted acid anions. As such salts, inorganic salts containing at least one anion selected from inorganic Brønsted acid anions and halogen anions as anions are more preferred. Other cations besides aluminum ions include alkali metal ions such as lithium ions, sodium ions, and potassium ions; alkaline earth metal ions such as magnesium ions and calcium ions; iron ions, strontium ions, cobalt ions, copper ions, nickel ions, zinc ions, ruthenium ions, rhodium ions, palladium ions, silver ions, iridium ions, platinum ions, and ammonium ions. Anions include inorganic acid ions such as sulfate ions, nitrate ions, chloride ions, hydrobromide ions, hydroiodide ions, phosphate ions, pyrophosphate ions, perchlorate ions, molybdate ions, hexafluorosilicate ions, and carbonate ions; organic acid ions such as acetate ions, citrate ions, oxalate ions, formate ions, methanesulfonate ions, trifluoromethanesulfonate ions, toluenesulfonate ions, and taurine ions; and oxygen ions (oxide ions) and hydroxide ions. From the viewpoint of availability and handling, suitable compounds [I] include, for example, aluminum hydroxide, aluminum sulfate, potassium aluminum sulfate (and its hydrate), aluminum ammonium sulfate (and its hydrate), aluminum phosphate, and aluminum metaphosphate. In particular, since the solvent of the raw material slurry is often water, compounds that are poorly soluble in water or practically insoluble in water are preferred, and aluminum hydroxide, aluminum phosphate, and aluminum metaphosphate are preferred, with aluminum hydroxide being particularly preferred from the standpoint of easy industrial wastewater treatment.

[0035] The compound [I] preferably used in the method for producing ion-exchangeable layered silicate particles of this disclosure has an average particle size of 0.3 μm to 100.0 μm when dispersed in water. The lower limit is more preferably 0.4 μm or more, even more preferably 0.5 μm or more, and particularly preferably 0.8 μm or more, and the upper limit is more preferably 50.0 μm or less, even more preferably 20.0 μm or less, and particularly preferably 10.0 μm or less. Any combination of the upper and lower limits can be adopted. When the average particle size of compound [I] is within the above range, ion-exchangeable layered silicate particles having the characteristics of this disclosure can be obtained. It is preferable that the particle size is within the above range from the viewpoint of maintaining appropriate particle strength, suppressing particle crushing, and suppressing the generation of fine powder, etc. The particle size of the above compound [I] can be measured using, for example, a laser diffraction / scattering particle size distribution analyzer LA-960 manufactured by Horiba, Ltd., with distilled water as the dispersion solvent, and appropriate dispersion treatment if necessary.

[0036] The aluminum ion-containing compound [I] preferably used in the method for producing ion-exchangeable layered silicate particles of this disclosure may be used alone or in combination of two or more compounds. It is preferable to add this aluminum ion-containing compound [I] in an amount of 8% to 80% by mass relative to the solid components in the 20°C slurry (assuming the solid components in the slurry make up 100% by mass). This ratio is preferred because it makes it easier to obtain the properties of the ion-exchangeable layered silicate particles of this disclosure. In other words, the amount of compound [I] added is 8% to 80% by mass relative to the total amount of ion-exchangeable layered silicate, compound [I], and other components (components different from ion-exchangeable layered silicate and compound [I]) in a slurry at 20°C (100% by mass of solid components contained in the slurry). The amount of compound [I] added can be appropriately selected within the above range to control the pore distribution. The amount of compound [I] added is more preferably 10% to 70% by mass, even more preferably 12% to 60% by mass, and particularly preferably 15% to 50% by mass. By having compound [I] within the above range, the characteristics of the ion-exchangeable layered silicate particles of this disclosure are easily obtained. If the upper limit exceeds 80% by mass, the strength of the granulated solid may decrease, and fine powder may be more likely to be generated. If it falls below 8% by mass, the properties of the ion-exchangeable layered silicate particles described herein may not be obtained.

[0037] When compound [I] is a carbonate, it is preferable not to use a carbonate alone as compound [I] because the gas generated when the carbonate reacts with an acid affects the pore structure. When compound [I] is used in combination with a carbonate and a compound other than a carbonate, the amount of carbonate added is preferably 0% to 75% by mass, more preferably 0% to 50% by mass, and even more preferably 0% to 30% by mass, based on 100% by mass of the total amount of compound [I] containing the carbonate. Furthermore, the amount of carbonate added as described above includes carbonates originally contained as impurities in the ion-exchangeable layered silicate that is suitably used in the method for producing ion-exchangeable layered silicate particles of this disclosure, and sodium carbonate used to ion-exchange the ion-exchangeable layered silicate to the sodium type (ion-exchangeable layered silicate having sodium ions in the interlayer ions), if such sodium carbonate is present.

[0038] Furthermore, when calculating these additive amounts, salts containing adducts that are liquid on their own, such as hydration water, should be calculated as if they were anhydrous or otherwise without adducts.

[0039] In the method for producing ion-exchangeable layered silicate particles according to the present disclosure, a binder may be added for purposes such as improving the shape during granulation. Examples of binders include sugar, dextrose, corn syrup, gelatin, glue, carboxymethylcellulose, polyvinyl alcohol, water glass, alcohols, glycol, starch, casein, latex, polyethylene glycol, polyethylene oxide, tar, pitch, silica gel, gum arabic, and sodium alginate. Furthermore, viscosity modifiers may be added to adjust the pH, viscosity, etc., of the slurry. It is well known that the pH of an ion-exchange layered silicate slurry affects the viscosity of the slurry, and in order to adjust these, in addition to the binders mentioned above, acids such as sulfuric acid, nitric acid, hydrochloric acid, or alkalis such as lithium hydroxide, sodium hydroxide, and potassium hydroxide may be added. Furthermore, known substances may be added as dispersants or flocculants, such as sodium silicate and sodium pyrophosphate. These binders, viscosity modifiers, dispersants, flocculants, etc., do not contain compound [I] which is preferably used in the method for producing ion-exchangeable layered silicate particles of the present disclosure.

[0040] In step 1, the order in which the ion-exchangeable layered silicate, solvent, and compound [I] are mixed is not particularly limited. For example, the ion-exchangeable layered silicate and compound [I] may be added to the solvent sequentially or simultaneously. Alternatively, the ion-exchangeable layered silicate and compound [I] may be dispersed in the solvent separately before being mixed. There are no limitations on the mixing order when adding binders, dispersants, flocculants, or viscosity modifiers.

[0041] Furthermore, the temperature during mixing is not particularly limited. The mixing temperature is preferably below the boiling point of the solvent, and when water is used, it is preferably 0°C to 80°C, more preferably 10°C to 70°C, and even more preferably 20°C to 60°C. There are no particular limitations on the mixing method. Known methods can be used for mixing. Examples of mixing methods include mixing with a stirrer, a static mixer, etc. In particular, to improve dispersibility, high-speed stirrers, media mills, high-pressure homogenizers, ultrasonic dispersers, thin-film swirling high-speed stirrers, etc., can be used. Multiple of these devices may be combined. Stirrers, high-speed stirrers, bead mills, and high-pressure homogenizers are particularly preferred.

[0042] The viscosity of the slurry prepared in step 1 is not particularly limited. The viscosity of the slurry may be 5 Pa·s to 5000 Pa·s, preferably 8 Pa·s to 3000 Pa·s. The viscosity here refers to the value that can be measured using a B-type viscometer (BROOKFIELD DV-I Viscometer) with an LV-1, LV-2, or LV-3 spindle depending on the viscosity, at 12 rpm and 20°C.

[0043] (1.2) Process 2 Step 2 is a step in which the slurry prepared in Step 1 is granulated by spray drying to obtain ion-exchangeable layered silicate composite particles. In step 2, solid-liquid separation such as drying, concentration, filtration, or decantation may be performed as needed. In step 2, granulation and separation from the solvent may be performed separately or simultaneously. The method and order of granulation and separation from the solvent are not particularly limited. In step 2, it is necessary to include a soluble compound within the granulated particles. Methods for obtaining ion-exchangeable layered silicate composite particles as a preferred granule include, for example, stirring granulation, spray granulation, rolling granulation, briquetting, compacting, extrusion granulation, fluid bed granulation, liquid granulation, emulsification granulation, and compression molding granulation. Preferably, methods include spray drying granulation, spray cooling granulation, fluid bed granulation, jet bed granulation, liquid granulation, and emulsification granulation, with spray drying granulation and spray cooling granulation being particularly preferred.

[0044] When performing spray granulation, the spraying method is not particularly limited. For example, rotary atomizers, single-fluid nozzles, two-fluid nozzles, ultrasonic nozzles, etc., can be used for spraying. The drying medium is also not particularly limited. Examples of drying mediums include nitrogen, argon, and air. The temperature at which the drying medium is supplied during spray drying granulation is not particularly limited. The temperature at which the drying medium is supplied varies depending on the dispersion medium, but in the case of water, it can be 70°C to 260°C, preferably 80°C to 240°C.

[0045] The particle size distribution of ion-exchangeable layered silicate composite particles is not particularly limited. The particle size distribution can be adjusted by manufacturing conditions such as the atomizer, drying medium temperature, and flow rate. The particle size distribution may also be adjusted using known classification techniques such as sieving or air classification.

[0046] The average particle diameter of the ion-exchangeable layered silicate composite particles is not particularly limited. The average particle diameter is preferably 2 μm to 500 μm, more preferably 3 μm to 200 μm, even more preferably 8 μm to 100 μm, and most preferably 10 μm to 70 μm. Although there are various definitions and measurement methods for particle diameter, the average particle diameter here refers to the volume-based median diameter obtained from the spherical equivalent particle diameter distribution measured by laser diffraction, similar to the average particle diameter of the ion-exchangeable layered silicate particles described above.

[0047] Ion-exchangeable layered silicate composite particles are particles containing ion-exchangeable layered silicate and compound [I]. When the amount of aluminum atoms (mol / g) contained in these ion-exchangeable layered silicate composite particles is [Alb] and the amount of magnesium atoms (mol / g) is [Mgb], it is preferable that the [Alb / Mgb] (molar ratio) is 4.0 or more and 45.0 or less. The lower limit is more preferably 4.2 or more, even more preferably 4.5 or more, and particularly preferably 5.0 or more, and the upper limit is more preferably 40.0 or less, even more preferably 30.0 or less, and particularly preferably 15.0 or less. Any combination of the upper and lower limits can be adopted. Here, [Alb] is simply the sum of the aluminum atoms derived from the ion-exchangeable layered silicate ([Alb']) and the aluminum atoms derived from compound [I] ([Alb'']). However, it is not possible to separate the aluminum content from each and quantify them individually from compositional analysis by X-ray fluorescence measurement. Therefore, if you want to know the amounts of [Alb'] and [Alb''] of the ion-exchangeable layered silicate composite particles, you can calculate them from the respective compositions and blending ratios of the ion-exchangeable layered silicate and compound [I] used. Alternatively, if compound [I] does not contain silicon atoms, then assuming that the composition of the ion-exchangeable layered silicate does not change before and after the granulation process, you can calculate [Alb'] and [Alb''] based on the silicon content. For example, in Example 1 described later, the ion-exchangeable layered silicate used had silicon atoms ([Sia]): 11.25 mmol / g and aluminum atoms ([Ala]): 3.77 mmol / g. The ion-exchangeable layered silicate composite particles, prepared by granulating this ion-exchangeable layered silicate with aluminum hydroxide in a solid content ratio of 65:35, have silicon atoms ([Sib]): 8.26 mmol / g and aluminum atoms ([Alb]): 7.93 mmol / g. By applying these compositional values ​​to the following formula (3), we can determine that [Alb''] = 7.03 mmol / g. Here, [Sia] and [Ala] are as defined above. Equation (3): ([Alb''])={([Alb])×([Sia]) / ([Sib])}-([Ala])

[0048] (1.3) Process 3 Step 3 is a step in which at least a portion of the metal components contained in the ion-exchangeable layered silicate composite particles obtained in Step 2 are eluted. By appropriately chemically treating the ion-exchangeable layered silicate composite particles, at least a portion of the metal component is removed from the ion-exchangeable layered silicate composite particles. In this process, at least a portion of the metal component is removed from the ion-exchangeable layered silicate composite particles by the dissolution of some or all of the ion-exchangeable layered silicate and compound [I]. As for the chemical treatment, a treatment method that can dissolve the metal components contained in the ion-exchangeable layered silicate composite particles can be appropriately selected and used. Examples of chemical treatments include acid treatment by contacting with acids, base treatment by contacting with bases, salt treatment by contacting with salts, elution treatment (washing) with a suitable solvent that dissolves the soluble compound (for example, a mixed solvent of alcohol and water), and other chemical treatments. These chemical treatments may be performed multiple times individually, or multiple types of treatments may be combined. In particular, acid treatment is preferred because it improves the specific surface area, which affects the strength, catalytic activity, and adsorption performance of the particles, and it is even more preferable to perform base treatment or salt treatment after acid treatment. Hereinafter, ion-exchangeable layered silicate composite particles and ion-exchangeable layered silicate particles that have undergone a process to elute the aluminum-containing compound [I] of the ion-exchangeable layered silicate composite particles are sometimes collectively referred to as ion-exchangeable layered silicate (composite) particles. Ion-exchangeable layered silicate (composite) particles refer to ion-exchangeable layered silicate composite particles or ion-exchangeable layered silicate particles.

[0049] (1.3.1) Preferred embodiment of step 3 (acid treatment) In step 3, it is preferable to perform acid treatment on the ion-exchangeable layered silicate composite particles. Acid treatment can dissolve soluble compounds and impurities, and also facilitates the exchange of cations between the layers of ion-exchangeable layered silicate composite particles. Acid treatment can alter the properties of the pore structure and increase the specific surface area by eluting some or all of the cations such as Al, Fe, and Mg that constitute the crystalline structure of the ion-exchangeable layered silicate composite particles. Acid treatment also contributes to increasing the acid strength of the ion-exchangeable layered silicate composite particles and increasing the amount of acid per unit mass.

[0050] Examples of acids used in acid treatment include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, benzoic acid, stearic acid, propyrionic acid, fumaric acid, maleic acid, and phthalic acid, as well as organic acids. Among these, inorganic acids are preferred, with hydrochloric acid, nitric acid, and sulfuric acid being more preferred. Even more preferred are hydrochloric acid and sulfuric acid, and particularly preferred is sulfuric acid.

[0051] From the viewpoint of efficiently and uniformly reacting, the acid treatment of ion-exchangeable layered silicate composite particles is preferably carried out by contacting the ion-exchangeable layered silicate composite particles with a solution of acids. When the acids are solid, the solvent used to dissolve them is not particularly limited. Furthermore, when the acids are liquid, they may be used as is or diluted with a solvent; the solvent used in this case is also not particularly limited. Preferred solvents are those that do not react during acid treatment, such as water or organic solvents like methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, and xylene, and more preferably water. These solvents may be used individually or in combination of two or more.

[0052] The acid concentration during acid treatment (the mass percentage of acids relative to the total mass of the slurry during acid treatment) is not particularly limited. The acid concentration is preferably 3% to 50% by mass, more preferably 4% to 40% by mass, and even more preferably 5% to 30% by mass. The temperature during acid treatment is not particularly limited. The temperature is preferably 30°C to 102°C, more preferably 40°C to 100°C, and even more preferably 50°C to 97°C. The concentration of ion-exchangeable layered silicate composite particles in the solvent during acid treatment (the concentration of ion-exchangeable layered silicate composite particles in the slurry, with the entire slurry containing the ion-exchangeable layered silicate composite particles being defined as 100% by mass) is not particularly limited. This concentration is preferably 3% to 50% by mass, more preferably 5% to 30% by mass, and even more preferably 8% to 20% by mass. The duration of the acid treatment is not particularly limited. Preferably, the duration is 5 to 3000 minutes, more preferably 10 to 1500 minutes, and even more preferably 30 to 750 minutes. The degree to which soluble compounds, impurities, cations, etc., are eluted can be adjusted by appropriately selecting the type of acid, the concentration of the acid, the treatment temperature, the treatment time, etc. Furthermore, the acid treatment may be performed in a single step or in multiple steps.

[0053] (1.3.2) Preferred embodiment of step 3 (base treatment) In the method for producing ion-exchangeable layered silicate particles according to the present disclosure, in step 3, instead of the acid treatment described in "(1.3.1) Preferred Embodiment of Step 3" above, the ion-exchangeable layered silicate composite particles may be subjected to base treatment. Alternatively, after performing the acid treatment described in "(1.3.1) Preferred Embodiment of Step 3" above on the ion-exchangeable layered silicate composite particles, a base treatment may be performed by bringing them into contact with bases. Base treatment can dissolve soluble compounds and impurities, and also facilitate the exchange of cations between the layers of ion-exchangeable layered silicate (composite) particles. By eluting some or all of the cations such as Al, Fe, Mg, and Si that constitute the crystal structure of ion-exchangeable layered silicate (composite) particles, base treatment can alter the properties of the pore structure and increase the specific surface area.

[0054] The bases used in base treatment are not particularly limited as long as they act as Brønsted bases. Bases are substances that react with protons to produce water (neutralization reaction). Preferred bases include hydroxides of metals selected from the group consisting of alkali metals, alkaline earth metals, and metals of groups 3 to 14 of the periodic table. More preferably, the bases are hydroxides of alkali metals, alkaline earth metals, Mn, Fe, Ni, Cu, Zn, Al, Sn, and Pb, and even more preferably hydroxides of alkali metals, alkaline earth metals, Mg, Zn, and Al. Preferred examples of bases include LiOH, NaOH, KOH, CsOH, RbOH, Be(OH)2, Mg(OH)2, Ca(OH)2, Sr(OH)2, Mn(OH)2, Cu(OH)2, Cu(OH)3, Zn(OH)2, Al(OH)3, Sn(OH)4, Pb(OH)2, Ni(OH)2, Li2CO3, Na2CO3, K2CO3, Cs2CO3, Rb2CO3, BeCO3, MgCO3, CaCO3, MnCO3, CuCO3, Al2(CO)3, ZnCO3, PbCO3, LiHCO3, NaHCO3, RpHCO3, CsHCO3, Ca(HCO3)2, Mg(HCO3)2, etc. However, the bases are not limited to these specific examples. Bases may be used individually or in combination. There are no particular restrictions on their use. The state of the bases when they come into contact with ion-exchangeable layered silicate (composite) particles can be either dissolved in a solvent or in solid form. When dissolved in a solvent, there is no limit to the concentration, but it is preferable that the upper limit be below the saturation concentration.

[0055] From the viewpoint of efficiently and uniformly performing the base treatment, it may be carried out by contacting ion-exchangeable layered silicate (composite) particles with a solution of bases. If the base treatment is performed after acid treatment, it may be carried out by contacting a slurry of ion-exchangeable layered silicate (composite) particles with the base. When the bases are solid, the solvent used to dissolve them is not particularly limited. Furthermore, when the bases are liquid, they may be diluted with a solvent before use, and the solvent used in this case is also not particularly limited. Moreover, the solvent used to form the slurry of ion-exchangeable layered silicate (composite) particles is not particularly limited. Examples of solvents include water or organic solvents such as alcohols, preferably ethanol, methanol, ethylene glycol, glycerin, or water, and more preferably water. These solvents may be used individually or in combination of two or more.

[0056] The amount of bases used varies depending on the amount of acid contained in the slurry of ion-exchangeable layered silicate (composite) particles before base treatment, and the purpose of the treatment. In the case of base treatment performed after acid treatment, it is preferable to use an amount of ion-exchangeable layered silicate (composite) particle slurry in which the pH is 8 or less from the time of base addition until the end of base treatment, and the pH at the end of base treatment is 4.5 to 8. Water is used as the solvent for this base treatment.

[0057] The temperature during base treatment is not particularly limited. The temperature is preferably -20°C to 120°C, more preferably 0°C to 105°C, and even more preferably 10°C to 80°C. The concentration of bases in the solution during base treatment is not particularly limited, but is preferably 1% to 50% by mass, more preferably 2% to 30% by mass, and even more preferably 3% to 20% by mass. The concentration in this case refers to the mass percentage of the bases relative to the total mass of the base treatment solution. The duration of the base treatment is not particularly limited. Preferably, the duration is 1 to 600 minutes, more preferably 5 to 300 minutes, and even more preferably 10 to 120 minutes. The degree to which soluble compounds, impurities, cations, etc., are eluted can be adjusted by appropriately selecting the type of base, the concentration of the base, the treatment temperature, the treatment time, etc. Furthermore, the base treatment may be performed in a single step or in multiple steps.

[0058] (1.4) Other chemical treatments In the method for producing ion-exchangeable layered silicate particles according to this disclosure, the ion-exchangeable layered silicate (composite) particles may be subjected to other chemical treatments in addition to acid treatment and base treatment. Alternatively, ion-exchangeable layered silicate composite particles may be subjected to acid treatment or base treatment, followed by further chemical treatment.

[0059] Other chemical treatments include contact treatment with treatment agents containing salts, oxidizing agents, reducing agents, or compounds that can interlate between the layers of ion-exchangeable layered silicate (composite) particles, as well as washing with solvents. Intercalation refers to the process of introducing another substance between layers of a layered material, and the introduced substance is called a guest compound. Furthermore, intercalation and chemical treatment with salts (salt treatment) can form ionic complexes, molecular complexes, organic derivatives, etc., thereby altering the surface area and interlayer distance. By utilizing ion exchange, it is also possible to obtain layered materials with expanded interlayers by substituting exchangeable ions between layers with other large, bulky ions. In other words, the bulky ions play a supporting role for the layered structure and are called pillars. Specific examples of treatment agents are shown below.

[0060] Examples of salts used in salt treatment include salts composed of a cation selected from the group consisting of organic cations and inorganic cations including metal ions, and an anion selected from the group consisting of organic anions and inorganic anions including halide ions. For example, a compound composed of a cation containing at least one atom selected from groups 1 to 14 of the periodic table and at least one anion selected from the group consisting of halogen anions, inorganic Brønsted acids, and organic Brønsted acid anions is a preferred example. Particularly preferred are compounds in which the anion consists of an inorganic Brønsted acid or a halogen.

[0061] Specific examples of such salts include LiCl, LiBr, Li2SO4, Li3(PO4), LiNO3, Li(OOCCH3), NaCl, NaBr, Na2SO4, Na3(PO4), NaNO3, Na(OOCCH3), KCl, KBr, K2SO4, K3(PO4), KNO3, K(OOCCH3), CaCl2, CaSO4, Ca(NO3)2, Ca3(C6H5O7). 2, Ti(OOCCH3)4, Ti(CO3)2, Ti(NO3)4, Ti(SO4)2, TiF4, TiCl4, TiBr4, TiI4, Zr(OOCCH3)4, Zr(CO3)2, Z r(NO3)4, Zr(SO4)2, ZrF4, ZrCl4, ZrBr4, ZrI4, ZrOCl2, ZrO(NO3)2, ZrO(ClO4)2, ZrO(SO4), Hf(OOCCH3) 4, Hf(CO3)2, Hf(NO3)4, Hf(SO4)2, HfOCl2, HfF4, HfCl4, HfBr4, HfI4, CuCl2, CuBr2, Cu(NO3)2, CuC2O4 , Cu(ClO4)2, CuSO4, Cu(OOCCH3)2, Zn(OOCH3)2, Zn(CH3COCHCOCH3)2, ZnCO3, Zn(NO3)2, Zn(ClO4)2, Zn3 Examples include (PO4)2, ZnSO4, ZnF2, ZnCl2, nBr2, ZnI2, AlF3, AlCl3, AlBr3, AlI3, Al2(SO4)3, Al2(C2O4)3, Al(CH3COCHCOCH3)3, Al(NO3)3, AlPO4, GeCl4, Sn(OOCCH3)4, Sn(SO4)2, SnF4, SnCl4, etc., but are not limited to these.

[0062] Examples of organic cations include those derived from ammonium compounds such as trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, dodecylammonium, N,N-dimethylanilinium, N,N-diethylanilinium, N,N-2,4,5-pentamethylanilinium, N,N-dimethyloctadecylammonium, octadodecylammonium, N,N-2,4,5-pentamethylanilinium, N,N-dimethyl-pn-butylanilinium, N,N-dimethyl-p-trimethylsilylanilinium, N,N-dimethyl-1-naphthylanilinium, N,N,2-trimethylanilinium, and 2,6-dimethylanilinium. Examples of cations include, but are not limited to, cations derived from nitrogen-containing aromatic compounds such as pyridinium, quinolinium, N-methylpiperidinium, 2,6-dimethylpyridinium, and 2,2,6,6-tetramethylpiperidinium; cations derived from oxonium compounds such as dimethyloxonium, diethyloxonium, diphenyloxonium, furanium, and oxolanium; cations derived from phosphonium compounds such as triphenylphosphonium, tri-o-tolylphosphonium, tri-p-tolylphosphonium, and trimesitylphosphonium; and cations derived from phosphorus-containing aromatic compounds such as phosphabenzonium and phosphanaphthalenium. Examples of anions include, but are not limited to, those composed of boron compounds and phosphorus compounds, such as hexafluorophosphate, tetrafluoroborate, and tetraphenylborate. Furthermore, these salts may be used individually or in combination of two or more types. In the method for producing ion-exchangeable layered silicate particles according to the present disclosure, the other chemical treatment is preferably a salt treatment with salts containing lithium ions.

[0063] Furthermore, it may be used in combination with acids, bases, oxidizing agents, reducing agents, compounds that interlate between the layers of ion-exchangeable layered silicates, etc. These combinations may be used in combination with treatment agents added at the start of the process, or in combination with treatment agents added during the process.

[0064] The salt treatment described above may be carried out by using a suitable solvent and dissolving the treatment agent in it to form a treatment agent solution, or the treatment agent itself may be used as the solvent. Suitable solvents include water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, ethers, ketones, aldehydes, furans, amines, dimethyl sulfoxide, and dimethylformamide. Preferably, the solvents are water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, and ethers; more preferably, water, alcohols, aliphatic hydrocarbons, and ethers; and most preferably, water and alcohols. Furthermore, the concentration of the treatment agent in the treatment solution is preferably 0.1% to 100% by mass, and more preferably 5% to 50% by mass, relative to the mass of the solution. A benefit of this concentration range is that the processing time is shortened, enabling more efficient production.

[0065] The amount of salt used varies depending on the amount of acid contained in the slurry of ion-exchangeable layered silicate (composite) particles before salt treatment and the purpose of the treatment, but is preferably 0.01 mmol to 100 mmol per 1 g of ion-exchangeable layered silicate (composite) particles, more preferably 0.05 mmol to 70 mmol, and more preferably 0.1 mmol to 50 mmol.

[0066] The temperature during salt treatment is not particularly limited. The temperature is preferably -20°C to 120°C, more preferably 0°C to 105°C, and even more preferably 10°C to 80°C. The concentration of ion-exchangeable layered silicate (composite) particles in the solvent during salt treatment (the concentration of ion-exchangeable layered silicate (composite) particles in the slurry, with the entire slurry containing ion-exchangeable layered silicate (composite) particles being defined as 100% by mass) is not particularly limited. This concentration is preferably 3% to 50% by mass, more preferably 5% to 30% by mass, and even more preferably 8% to 20% by mass. The salt treatment time is not particularly limited. Preferably, the time is 1 minute to 600 minutes, more preferably 5 minutes to 300 minutes, and even more preferably 10 minutes to 120 minutes. Furthermore, the salt treatment may be performed in a single step or in multiple steps.

[0067] Furthermore, it is preferable to perform washing with a solvent as a chemical treatment. Washing can dissolve soluble compounds and impurities. Washing not only exchanges cations present between the layers of the ion-exchangeable layered silicate, but can also remove any remaining acids, bases, salts, or solvents from the aforementioned treatment with acids, bases, or salts.

[0068] Examples of solvents used for washing include water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, ethers, ketones, aldehydes, furans, amines, dimethyl sulfoxide, and dimethylformamide. Two or more of these may be used in mixture form. Preferably, the solvents are water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, and ethers; more preferably, water, alcohols, aliphatic hydrocarbons, and ethers; more preferably, water, alcohols, and mixed solvents thereof; particularly preferably, water. Furthermore, the temperature during washing is not particularly limited. The washing temperature is preferably 0°C to 100°C, more preferably 50°C to 95°C, and even more preferably 10°C to 60°C. There are no particular restrictions on the concentration of ion-exchangeable layered silicate particles during washing, but it is preferably 3% to 50% by mass, more preferably 5% to 40% by mass, and even more preferably 8% to 30% by mass relative to the mass of the solution. The washing time is not particularly limited. Preferably, the washing time is 1 minute to 3000 minutes, more preferably 3 minutes to 1500 minutes, and even more preferably 5 minutes to 750 minutes.

[0069] In the chemical treatments and washing described in section (1.4) "Other Chemical Treatments," the method of solid-liquid separation for separating the solvent from the ion-exchangeable layered silicate (composite) particles is not particularly limited. Examples of solid-liquid separation methods include sedimentation separation, filtration separation, centrifugal sedimentation separation using centrifugal force, and centrifugal filtration. These may be performed multiple times, or multiple methods may be combined. The cleaning rate is preferably 1 / 5 to 1 / 10000, and more preferably 1 / 10 to 1 / 1000. Here, the cleaning rate represents the percentage of solvent remaining at the start of cleaning. For example, if cleaning is performed by contacting 100 L of solvent with the solid and then removing 90 L of solvent, the cleaning rate will be (100-90) / 100 = 1 / 10. Furthermore, the supernatant liquid, which indicates the amount of remaining ions, can be washed until its electrical conductivity is preferably 1000 mS / cm or less, more preferably 100 mS / cm or less, even more preferably 10 mS / cm or less, and most preferably 1 mS / cm or less.

[0070] (1.5) Other processes Other steps may be performed after step 3. For example, it is preferable to dry the obtained ion-exchangeable layered silicate (composite) particles after step 3. The drying method is not particularly limited. Various methods can be used. It is preferable to dry the material in a way that does not cause structural damage to the ion-exchangeable layered silicate (composite) particles. The drying temperature can generally be 100°C to 800°C, preferably 150°C to 600°C, and particularly preferably 180°C to 300°C. The drying time is usually 1 minute to 24 hours, preferably 5 minutes to 4 hours. The atmosphere during drying is preferably dry air, dry nitrogen, dry argon, or reduced pressure.

[0071] Since the properties of ion-exchangeable layered silicate (composite) particles change depending on the drying temperature, even without structural breakdown, it is preferable to change the drying temperature according to the application. When using the ion-exchangeable layered silicate (composite) particles as a component of an olefin polymerization catalyst, when the water content after removal is 0% by mass when the water content after dehydration for 2 hours under the conditions of a temperature of 200 °C and a pressure of 1 mmHg, it is preferably 3% by mass or less, more preferably 1% by mass or less.

[0072] (2) Characteristics of ion-exchangeable layered silicate particles The ion-exchangeable layered silicate particles obtained by the method for producing ion-exchangeable layered silicate particles of the present disclosure may have the following characteristics (i), (ii) and (iii). Characteristic (i): The specific surface area is 250 m 2 / g or more and 700 m 2 / g or less. Characteristic (ii): The pore volume at a pore diameter of 10 nm to 300 nm measured by the mercury intrusion method exceeds 0.128 mL / g and is 0.600 mL / g or less. Characteristic (iii): When the content (mol / g) of silicon atoms is [Si] and the content (mol / g) of aluminum atoms is [Al], the following formula (1) is satisfied. Formula (1): 0.10 ≤ ([Al] / [Si]) ≤ 0.30

[0073] (2.1) Specific surface area (Characteristic (i)) The ion-exchangeable layered silicate particles obtained by the production method of the present disclosure may have a specific surface area of 250 m 2 / g or more and 700 m 2 / g or less. In the ion-exchangeable layered silicate particles, the lower limit value of the specific surface area is preferably 280 m 2 / g or more, more preferably 300 m 2 / g or more, still more preferably 330 m 2 / g or more, and the upper limit value is preferably 600 m 2 / g or less, more preferably 550 m 2 / g or less, and particularly preferably 500 m 2 / g or less. The upper limit value and the lower limit value can adopt any combination. Generally, increasing the specific surface area increases the amount of active components in the catalyst, or increases the amount of active components that can be supported, thus increasing its activity. On the other hand, if the specific surface area is too large, the pore size may decrease, which can lead to a decrease in the diffusion rate of reaction substrates such as monomers and metallocene complexes, resulting in a decrease in catalytic activity or a decrease in adsorption performance as an adsorbent. Therefore, from these viewpoints, the above-mentioned preferred range of specific surface area is selected. In this disclosure, specific surface area refers to the value calculated by BET multipoint analysis (Rouquerol transformation) from adsorption isotherm data measured using nitrogen gas in the gas adsorption method. The method for measuring specific surface area by the gas adsorption method is described, for example, in JIS Z8830.

[0074] (2.2) Pore volume (characteristics (ii)) The ion-exchangeable layered silicate particles obtained by the manufacturing method of this disclosure may have a pore volume at pore diameters of 10 nm to 300 nm, measured by mercury intrusion, that is greater than 0.128 mL / g and less than or equal to 0.600 mL / g. In the ion-exchangeable layered silicate particles of this disclosure, the lower limit of the pore volume at pore diameters of 10 nm to 300 nm, measured by mercury intrusion, is preferably 0.135 mL / g or more, more preferably 0.150 mL / g or more, and even more preferably 0.170 mL / g or more, while the upper limit may be preferably 0.550 mL / g or less, and more preferably 0.500 mL / g or less. It is presumed that when the pore volume of ion-exchangeable layered silicate particles with a pore diameter of 10 nm to 300 nm, as measured by mercury intrusion, falls within the above range, the diffusion rate of reaction substrates such as monomers and metallocene complexes into the ion-exchangeable layered silicate particles increases. Furthermore, because the particle strength is moderately reduced, it is thought that polymerization activity is improved in olefin polymerization catalysts that require the dispersion and disintegration of the support within the polymer generated during polymerization. In addition, these effects are thought to reduce fish eyes in polymer products. Moreover, because catalyst crushing and other issues are less likely to occur during polymerization, the generation of fine powder and clumps is suppressed, and plant operation performance is stabilized. Therefore, from the above viewpoints, the pore volume of pore diameters of 10 nm to 300 nm is selected within the above preferred range. The pore volume measured by the mercury intrusion method in this specification is a value measured based on the mercury intrusion method in accordance with JIS R 1655:2003 "Method for testing pore distribution of molded bodies of fine ceramics by mercury intrusion method," and is a value calculated from the pore distribution on the pressurized (mercury intrusion) side. The specific measurement method is shown in the examples.

[0075] Furthermore, it is assumed that the pore shape of ion-exchangeable layered silicate particles is such that the diameter of the portion deeper inside the pore is larger than the opening (entrance), in other words, it has an ink bottle shape. This can be inferred from the following facts. This will be explained using phenomena observed in the manufacturing method of the present disclosure. For example, after forming composite particles by mixing an ion-exchangeable layered silicate with compound [I] containing aluminum ions with an average particle size of 0.3 μm to 100 μm, compound [I] is dissolved from the composite particles to control the pore structure and produce ion-exchangeable layered silicate particles. In this case, it is thought that pore distribution measurements by mercury intrusion would detect pores with a diameter of approximately 0.3 μm to 100 μm, corresponding to the elution traces of compound [I]. However, in reality, an increase in pores smaller than the diameter of the added compound [I], i.e., pores in the range of 10 nm to 300 nm, is detected. From this fact, it is inferred that the pores have an ink bottle shape, and that the pore distribution measurements by mercury intrusion are observing the diameter of the opening of pores with an ink bottle shape. In other words, it is thought that the pores corresponding to the compound elution traces are ink bottle shaped pores, and pores smaller than the actual pore diameter are being measured. Thus, the ion-exchangeable layered silicate particles obtained by the manufacturing method of this disclosure have relatively large pores inside the particles, but because the entrance diameter of these pores is small, the particle surface maintains appropriate strength, and collapse from the particle surface is suppressed even during polymerization, which is thought to contribute to the operational stability of the plant. Furthermore, because the pores are ink bottle-shaped, monomers and metallocene complexes that enter the pores are less likely to flow out from the inside of the particles to the outside, and it is presumed that this contributes to the high activation of the catalyst by efficiently absorbing monomers and efficiently supporting metallocene complexes. Japanese Patent Publication No. 2-261837 discloses a reference technique for making it difficult for monomers and metallocene complexes that have entered the pores to flow out to the outside.

[0076] (2.3) Metal atomic ratio ([Al] / [Si]) (characteristic (iii)) The ion-exchangeable layered silicate particles obtained by the manufacturing method of this disclosure may satisfy the following formula (1), considering their use as a co-catalyst and support, when the silicon atom content (mol / g) is [Si] and the aluminum atom content (mol / g) is [Al]. Equation (1): 0.10≦([Al] / [Si])≦0.30 The left side of equation (1) may preferably be 0.11, more preferably 0.13, even more preferably 0.15, and particularly preferably 0.18, and the right side of equation (1) may preferably be 0.28, more preferably 0.27, and even more preferably 0.26. Any combination of the left and right sides can be adopted. When [Al] / [Si] is within this range, it is thought that there is an appropriate pore volume and specific surface area, resulting in a large number of active sites and a highly active, good quality product.

[0077] (2.4) Metal atomic ratio ([Al] / [Mg], etc.) (characteristics (v)) In light of its use as a co-catalyst and carrier, the ion-exchangeable layered silicate particles obtained by the manufacturing method of this disclosure may further satisfy the following formula (2), where the magnesium atom content (mol / g) is [Mg], and [Si], [Al], and [Mg] satisfy the following formula (2). Formula (2): -3.0×([Al] / [Si])+4.2≦([Al] / [Mg]) ≤ -3.0 × ([Al] / [Si]) + 5.8 The left side of equation (2) may preferably be -3.0 × ([Al] / [Si]) + 4.3, more preferably -3.0 × ([Al] / [Si]) + 4.4, and the right side of equation (2) may preferably be -3.0 × ([Al] / [Si]) + 5.4, more preferably -3.0 × ([Al] / [Si]) + 5.2, and even more preferably -3.0 × ([Al] / [Si]) + 5.0. Any combination of the left and right sides can be adopted.

[0078] If [Al] / [Mg] is smaller than the left side of equation (2), a decrease in catalytic activity is a concern for the following reasons. For example, when producing the ion-exchangeable layered silicate particles of this disclosure, magnesium ions (Mg) eluted during the acid treatment may be lost. 2+ The concentration of ) increases in the reaction system, and Mg is released to the acid sites formed on the end face of the ion-exchange layered silicate. 2+It is anticipated that re-adsorption will occur. As a result, acid sites composed mainly of aluminum atoms will become acid sites composed mainly of magnesium atoms with lower acid strength, which may result in active sites that cannot activate the metallocene complex, potentially leading to a decrease in catalytic activity. Therefore, in the ion-exchange layered silicate particles obtained by the manufacturing method of this disclosure, Mg 2+ The above formula (2) may also be satisfied so that re-adsorption is suppressed.

[0079] Furthermore, calcium ions may be adsorbed to acid sites or inhibit exchange with cations other than calcium during the aforementioned salt treatment. The calcium content is preferably 0.000 mmol / g or more and may be 0.100 mmol / g or less. The lower limit may more preferably be 0.001 mmol / g or more, and the upper limit may more preferably be 0.070 mmol / g or less, even more preferably 0.050 mmol / g or less, and particularly preferably 0.030 mmol / g or less. Any combination of the upper and lower limits can be adopted.

[0080] Furthermore, when the iron atom content (mol / g) is denoted as [Fe], the molar ratio of iron atoms to silicon atoms ([Fe] / [Si]) may be preferably 0.000 to 0.045, more preferably 0.001 to 0.035, even more preferably 0.010 to 0.030, and particularly preferably 0.012 to 0.025, from the viewpoint of ion exchangeability. Furthermore, the molar ratio of magnesium atoms to silicon atoms ([Mg] / [Si]) may be preferably 0.018 to 0.091, more preferably 0.028 to 0.085, even more preferably 0.041 to 0.075, and even more preferably 0.044 to 0.065, from the viewpoint of ion exchangeability.

[0081] (2.5) Lithium atom content (characteristics (iv)) There are no particular restrictions on the lithium atom content contained in the ion-exchangeable layered silicate particles obtained by the manufacturing method of this disclosure. From the viewpoint of catalytic activity, the lithium atom content may preferably be 0.10 mmol / g or more and 5.00 mmol / g or less. The lower limit of the lithium atom content may preferably be 0.30 mmol / g or more, more preferably 0.40 mmol / g or more, even more preferably 0.50 mmol / g or more, and particularly preferably 0.56 mmol / g or more, and the upper limit may preferably be 3.00 mmol / g or less, more preferably 2.00 mmol / g or less, and even more preferably 1.00 mmol / g or less. Any combination of the upper and lower limits can be adopted. When the lithium atom content is within the above preferred range, high polymerization activity is exhibited. The above components can be determined by the method described later.

[0082] (2.6) Particle size (characteristic (vi)) The particle size of the ion-exchangeable layered silicate particles obtained by the manufacturing method of this disclosure is not particularly limited. The average particle size of the ion-exchangeable layered silicate particles of this disclosure may be 2 μm or more and 500 μm or less. In the ion-exchangeable layered silicate particles of this disclosure, the lower limit of the average particle diameter may more preferably be 3 μm or more, even more preferably 8 μm or more, and particularly preferably 10 μm or more, and the upper limit may preferably be 200 μm or less, more preferably 100 μm or less, even more preferably 70 μm or less, even more preferably 60 μm or less, and particularly preferably 55 μm or less. Any combination of the upper and lower limits can be adopted. Generally, if the particle size is too small, when used as an adsorbent or decolorizing agent, it may reduce the efficiency of solid-liquid separation such as filtration, and when used as a catalyst support, it may cause adhesion inside the reactor or blockage of piping and filters. On the other hand, if the particle size is too large, when used as an adsorbent, decolorizing agent, or catalyst support, it may cause poor dispersion in liquid (slurry state) or during gas-phase reactions. Here, the average particle diameter of the ion-exchangeable layered silicate particles of this disclosure refers to the volume-based median diameter obtained from the spherical equivalent particle diameter distribution, measured using a LA-960 laser diffraction / scattering particle size distribution analyzer manufactured by Horiba, Ltd., under the conditions of ethanol as the dispersion solvent, a real refractive index term of 1.490, an imaginary term of 0.000, and a real refractive index term of 1.360 for the dispersion solvent.

[0083] (2.7) Average crushing strength (characteristic (vii)) The average crush strength of the ion-exchangeable layered silicate particles obtained by the manufacturing method of this disclosure is not particularly limited. Considering their application as catalyst supports, it is preferable to maintain the average crush strength within an appropriate range. The crushing strength of a single particle can be measured using the method described in JIS R 1639-5:2007, which specifies the crushing strength of a single particle. Specifically, it can be measured using the method described in the examples below. The average crush strength of the ion-exchangeable layered silicate particles obtained by the manufacturing method of this disclosure may preferably be 1.0 MPa or more and 25.0 MPa or less, the lower limit may more preferably be 3.0 MPa or more, even more preferably 5.0 MPa or more, the upper limit may more preferably be 20.0 MPa or less, even more preferably 15.0 MPa or less, and particularly preferably 13.5 MPa or less. Any combination of the upper and lower limits can be adopted. If the average crushing strength is within the above range, it is possible to suppress particle breakage and fine powder generation during catalyst preparation, and the material is considered to exhibit suitable performance as a support for olefin polymerization catalysts.

[0084] (3) Applications of ion-exchangeable layered silicate particles The ion-exchangeable layered silicate particles obtained by the manufacturing method of this disclosure have a specific pore distribution and specific surface area, and are therefore widely used as supports for olefin polymerization catalysts, catalysts for organic chemical reactions, dehydration, decolorization, and purification of petroleum and oils, as well as as drying agents, adsorbents, and bleaching agents.

[0085] 3. Method for producing catalyst components for olefin polymerization The method for producing the catalyst component for olefin polymerization uses ion-exchangeable layered silicate particles obtained by the above-described production method. The catalyst component for olefin polymerization includes ion-exchangeable layered silicate particles obtained by the manufacturing method described above. Catalyst components for olefin polymerization can be used as catalyst components for olefin polymerization or copolymerization. Ion-exchangeable layered silicate particles function as catalyst supports, co-catalysts, etc. When ion-exchange layered silicate particles obtained by the manufacturing method of this disclosure are used as a catalyst component for olefin polymerization, it is possible to produce olefin polymers that exhibit high polymerization activity and have fewer fish-eyes in the product that degrade the product's appearance.

[0086] The methods for using the catalyst component for olefin polymerization obtained by the manufacturing method of this disclosure are not particularly limited. Examples of usage methods include those described in Japanese Patent Application Publication No. 2002-053611 and Japanese Patent Application Publication No. 2009-280443. In particular, when used as a catalyst for olefin polymerization, as described later, catalytic performance tends to improve.

[0087] 4. Method for producing catalysts for olefin polymerization The method for producing the olefin polymerization catalyst of this disclosure is characterized by mixing (contacting) the following components [A], [B], and [C]. Ingredients [A]: Ion-exchangeable layered silicate particles obtained by the manufacturing method described above. Component [B]: Transition metal compound Ingredients [C]: Organoaluminum compounds

[0088] (1) Each component (1.1) Component [A] Component [A] is the ion-exchangeable layered silicate particles described above. A detailed explanation of the ion-exchangeable layered silicate particles is the same as the explanation in section "2. Ion-exchangeable layered silicate particles," and the description in that section applies as is.

[0089] (1.2) Component [B] Component [B] is a transition metal compound. Among transition metal compounds, transition metal compounds of Group 4 of the periodic table are preferred. An example of a Group 4 transition metal compound is a metallocene compound having at least one conjugated five-membered ring ligand. Compounds represented by the following general formulas (1) to (4) are preferably exemplified as such transition metal compounds.

[0090] [ka] [In the above general formulas (1) to (4), A and A' represent conjugated five-membered ring ligands which may have substituents (A and A' may be the same or different within the same compound), Q represents a bonding group that bridges two conjugated five-membered ring ligands at any position, Z represents a ligand containing a nitrogen atom, oxygen atom, silicon atom, phosphorus atom, or sulfur atom, hydrogen atom, halogen atom, or hydrocarbon group, and Z' represents a ligand containing a nitrogen atom, oxygen atom, silicon atom, phosphorus atom, or sulfur atom, or hydrocarbon group. Q' represents a bonding group that bridges Z at any position on the conjugated five-membered ring ligand, M represents a metal atom selected from Group 4 of the periodic table, and X and Y represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group, or a silicon-containing hydrocarbon group (X and Y may be the same or different within the same compound).

[0091] Examples of conjugated five-membered ring ligands for A and A' include substituents derived from cyclopentadiene, indene, tetrahydroindene, fluorene, azulene, and tetrahydroazulene, which may be unsubstituted or substituted. Among these, substituted or unsubstituted indenyl groups or azulenyl groups are particularly preferred.

[0092] Substituents on the conjugated five-membered ring ligand include hydrocarbon groups having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, hydrocarbon groups having 1 to 30 carbon atoms substituted with halogens such as fluorine, chlorine, and bromine, halogen atom groups such as fluorine, chlorine, and bromine, and alkoxy groups having 1 to 12 carbon atoms, for example, -Si(R 1 )(R 2 )(R 3 Silicon-containing hydrocarbon groups represented by ), -P(R 1 )(R 2 A phosphorus-containing hydrocarbon group represented by ), or -B(R 1 )(R 2 Examples include boron-containing hydrocarbon groups represented by ). If there are multiple substituents, each substituent may be the same or different. The above R 1 , R 2 , R 3 These may be the same or different, and represent an alkyl group having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms. Furthermore, the substituents on the conjugated five-membered ring ligand may have at least one group 15-16 element (i.e., a heteroatom). Preferred substituents include monocyclic or polycyclic substituents containing a heteroatom selected from the group consisting of oxygen, sulfur, nitrogen, and phosphorus atoms in a five-membered or six-membered ring. More preferably, the substituents are derived from a heteroaromatic compound that may be substituted, and particularly preferably, a substituted furyl group or a substituted thienyl group. In the case of a compound having a bridging group represented by general formula (2) or (4), these substituents are not particularly limited, but are preferably located at the α-position (relative to the bonding site with the bridging group) on the conjugated five-membered ring ligand.

[0093] Q represents a bonding group that bridges two conjugated five-membered ring ligands at any position, and Q' represents a bonding group that bridges any position of a conjugated five-membered ring ligand with the group indicated by Z. The following are specific examples of Q and Q'. <1> Alkylene groups such as methylene group, ethylene group, isopropylene group, phenylmethylmethylene group, diphenylmethylene group, and cyclohexylene group. <2> Silylene groups such as dimethylsilylene group, diethylsilylene group, dipropylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methyl-t-butylsilylene group, disylylene group, tetramethyldisylylene group, and silaciclobutylene group. <3> Germanium atoms, phosphorus atoms, nitrogen atoms, boron atoms, or aluminum atoms substituted with hydrocarbon groups

[0094] More specifically, these include groups represented by (CH3)2Ge, (C6H5)2Ge, (CH3)P, (C6H5)P, (C4H9)N, (C6H5)N, (C4H9)B, (C6H5)B, (C6H5)Al, and (C6H5O)Al. Preferably, alkylene groups or silylene groups.

[0095] Furthermore, M represents a metal atom, specifically a transition metal atom selected from Group 4 of the periodic table, such as titanium, zirconium, and hafnium. Zirconium and hafnium are particularly preferred. Furthermore, Z represents a ligand containing a nitrogen atom, oxygen atom, silicon atom, phosphorus atom, or sulfur atom, a hydrogen atom, a halogen atom, or a hydrocarbon group, and Z' represents a ligand containing a nitrogen atom, oxygen atom, silicon atom, phosphorus atom, or sulfur atom, or a hydrocarbon group. Preferred specific examples of Z and Z' include oxygen-containing hydrocarbon groups having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms; sulfur-containing hydrocarbon groups having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms; silicon-containing hydrocarbon groups having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms; nitrogen-containing hydrocarbon groups having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms; phosphorus-containing hydrocarbon groups having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms; and hydrocarbon groups having 1 to 20 carbon atoms. Further preferred specific examples of Z include hydrogen atoms, chlorine atoms, and bromine atoms.

[0096] X and Y are, respectively, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an amino group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, such as a diphenylphosphono group, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, such as a trimethylsilyl group or a bis(trimethylsilyl)methyl group. X and Y may be the same or different. Of these, halogen atoms, hydrocarbon groups having 1 to 10 carbon atoms, and amino groups having 1 to 12 carbon atoms are particularly preferred.

[0097] Examples of compounds represented by general formula (1) include: (1) Bis(methylcyclopentadienyl)zirconium dichloride, (2) Bis(n-butylcyclopentadienyl)zirconium dichloride, (3) Bis(1,3-dimethylcyclopentadienyl)zirconium dichloride, (4) Bis(1-n-butyl-3-methylcyclopentadienyl)zirconium dichloride, (5) Bis(1-methyl-3-trifluoromethylcyclopentadienyl)zirconium dichloride, (6) Bis(1-methyl-3-trimethylsilylcyclopentadienyl)zirconium dichloride, (7) Bis(1-methyl-3-phenylcyclopentadienyl)zirconium dichloride, (8) Bis(indenyl)zirconium dichloride, (9) Bis(tetrahydroindenyl)zirconium dichloride, (10) Bis(2-methyl-tetrahydroindenyl) zirconium dichloride, These are some examples.

[0098] Examples of compounds represented by general formula (2) include: (1) Dimethylsilylenebis{1-(2-methyl-4-isopropyl-4H-azlenyl)}zirconium dichloride, (2) Dimethylsilylenebis{1-(2-methyl-4-phenyl-4H-azlenyl)}zirconium dichloride, (3) Dimethylsilylenebis[1-{2-methyl-4-(4-fluorophenyl)-4H-azlenyl}]zirconium dichloride, (4) Dimethylsilylenebis[1-{2-methyl-4-(2,6-dimethylphenyl)-4H-azlenyl}]zirconium dichloride, (5) Dimethylsilylenebis{1-(2-methyl-4,6-diisopropyl-4H-azlenyl)}zirconium dichloride, (6) Diphenylsilylenebis{1-(2-methyl-4-phenyl-4H-azlenyl)}zirconium dichloride, (7) Dimethylsilylenebis{1-(2-ethyl-4-phenyl-4H-azlenyl)}zirconium dichloride, (8) Ethylenebis{1-[2-methyl-4-(4-biphenylyl)-4H-azlenyl]}zirconium dichloride, (9) Dimethylsilylenebis{1-[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azlenyl]}zirconium dichloride, (10) Dimethylsilylenebis{1-[2-methyl-4-(2',6'-dimethyl-4-biphenylyl)-4H-azlenyl]}zirconium dichloride, (11) Dimethylsilylene {1-[2-methyl-4-(4-biphenylyl)-4H-azlenyl]}{1-[2-methyl-4-(4-biphenylyl)indenyl]} zirconium dichloride, (12) Dimethylsilylene {1-(2-ethyl-4-phenyl-4H-azlenyl)}{1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride, (13) Dimethylsilylenebis{1-(2-ethyl-4-phenyl-7-fluoro-4H-azlenyl)}zirconium dichloride, (14) Dimethylsilylenebis{1-(2-ethyl-4-indolyl-4H-azlenyl)}zirconium dichloride, (15) Dimethylsilylenebis[1-{2-ethyl-4-(3,5-bistrifluoromethylphenyl)-4H-azlenyl}]zirconium dichloride, (16) Dimethylsilylenebis{1-(2-methyl-4-phenyl-4H-azlenyl)}zirconium bis(trifluoromethanesulfonic acid), (17) Dimethylsilylenebis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride, (18) Dimethylsilylenebis{1-(2-methyl-4,5-benzoindenyl)}zirconium dichloride, (19) Dimethylsilylenebis[1-{2-methyl-4-(1-naphthyl)indenyl}]zirconium dichloride, (20) Dimethylsilylenebis{1-(2-methyl-4,6-diisopropylindenyl)}zirconium dichloride,

[0099] (21) Dimethylsilylenebis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride, (22) Ethylene-1,2-bis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride, (23) Ethylene-1,2-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride, (24) Isopropylidenebis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride, (25) Ethylene-1,2-bis{1-(2-methyl-4-phenyl-4H-azlenyl)}zirconium dichloride, (26) Isopropylidenebis{1-(2-methyl-4-phenyl-4H-azlenyl)}zirconium dichloride, (27) Dimethylgermylenebis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride, (28) Dimethylgermylenebis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride, (29) Phenylphosphinobis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride, (30) Dimethylsilylenebis[3-(2-furyl)-2,5-dimethylcyclopentadienyl]zirconium dichloride, (31) Dimethylsilylenebis[2-(2-furyl)-3,5-dimethylcyclopentadienyl]zirconium dichloride, (32) Dimethylsilylenebis[2-(2-furyl)-indenyl]zirconium dichloride, (33) Dimethylsilylenebis[2-(2-(5-methyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride, (34) Dimethylsilylenebis[2-(2-(5-trimethylsilyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride, (35) Dimethylsilylene bis[2-(2-thienyl)-indenyl]zirconium dichloride, (36) Dimethylsilylene [2-(2-(5-methyl)furyl)-4-phenylindenyl] [2-methyl-4-phenylindenyl] zirconium dichloride, (37) Dimethylsilylene bis(2,3,5-trimethylcyclopentadienyl) zirconium dichloride, (38) Dimethylsilylenebis(2,3-dimethyl-5-ethylcyclopentadienyl)zirconium dichloride, (39) Dimethylsilylenebis(2,5-dimethyl-3-phenylcyclopentadienyl)zirconium dichloride, (40) Silacylbutylenebis[2-(2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride,

[0100] (41) Silacic butylene bis[2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (42) Silacylbutylenebis[2-(4,5-dimethyl-2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloridome, (43) Silacic butylene bis[2-(5-t-butyl-2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (44) Silacic butylene bis[2-(5-phenyl-2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (45) Silacic butylene bis[2-(2-thienyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (46) Silacic butylene bis[2-(5-methyl-2-thienyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (47) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-fluorophenyl)-5-methyl-1-indenyl]zirconium dichloride, (48) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-chlorophenyl)-5-methyl-1-indenyl]zirconium dichloride, (49) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-methylphenyl)-5-methyl-1-indenyl] zirconium dichloride, (50) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-5-methyl-1-indenyl]zirconium dichloride, (51) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(3,5-dimethylphenyl)-5-methyl-1-indenyl] zirconium dichloride, (52) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(3,5-di-t-butylphenyl)-5-methyl-1-indenyl]zirconium dichloride, (53) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(1-naphthyl)-5-methyl-1-indenyl]zirconium dichloride, (54) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(2-naphthyl)-5-methyl-1-indenyl]zirconium dichloride, (55) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-biphenylyl)-5-methyl-1-indenyl]zirconium dichloride, (56) Silacic butylene bis[2-(2-furyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride, (57) Silacic butylene bis[2-(5-methyl-2-furyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride, (58) Silacic butylene bis[2-(4,5-dimethyl-2-furyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride, (59) Silacic butylene bis[2-(5-t-butyl-2-furyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride, (60) Silacic butylene bis[2-(5-phenyl-2-furyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride,

[0101] (61) Silacic butylene bis[2-(2-thienyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride, (62) Silacic butylene bis[2-(5-methyl-2-thienyl)-4-phenyl-5,6-dimethyl-1-indenyl]zirconium dichloride, (63) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-fluorophenyl)-5,6-dimethyl-1-indenyl] zirconium dichloride, (64) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-chlorophenyl)-5,6-dimethyl-1-indenyl] zirconium dichloride, (65) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-methylphenyl)-5,6-dimethyl-1-indenyl] zirconium dichloride, (66) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-5,6-dimethyl-1-indenyl]zirconium dichloride, (67) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(3,5-dimethylphenyl)-5,6-dimethyl-1-indenyl] zirconium dichloride, (68) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(3,5-di-t-butylphenyl)-5,6-dimethyl-1-indenyl]zirconium dichloride, (69) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(1-naphthyl)-5,6-dimethyl-1-indenyl] zirconium dichloride, (70) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(2-naphthyl)-5,6-dimethyl-1-indenyl]zirconium dichloride, (71) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-biphenylyl)-5,6-dimethyl-1-indenyl]zirconium dichloride, (72) Silacylbutylenebis[2-(2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (73) Silacylbutylenebis[2-(5-methyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indasen-1-yl]zirconium dichloride, (74) Silacylbutylenebis[2-(4,5-dimethyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (75) Silacylbutylenebis[2-(5-t-butyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (76) Silacylbutylenebis[2-(5-phenyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indasen-1-yl]zirconium dichloride, (77) Silacylbutylenebis[2-(2-thienyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (78) Silacicbutylenebis[2-(5-methyl-2-thienyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (79) Silacylbutylenebis[2-(5-methyl-2-furyl)-4-(4-fluorophenyl)-1,5,6,7-tetrahydro-s-indasen-1-yl]zirconium dichloride, (80) Silacylbutylenebis[2-(5-methyl-2-furyl)-4-(4-chlorophenyl)-1,5,6,7-tetrahydro-s-indasen-1-yl]zirconium dichloride,

[0102] (81) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-methylphenyl)-1,5,6,7-tetrahydro-s-indasen-1-yl]zirconium dichloride, (82) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-1,5,6,7-tetrahydro-s-indasen-1-yl]zirconium dichloride, (83) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indasen-1-yl]zirconium dichloride, (84) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(3,5-di-t-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (85) Silacylbutylenebis[2-(5-methyl-2-furyl)-4-(1-naphthyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (86) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(2-naphthyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (87) Silacic butylene bis[2-(5-methyl-2-furyl)-4-(4-biphenylyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (88) Silacic butylene bis[2-(2-furyl)-4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indasen-1-yl]zirconium dichloride, (89) Silacylbutylenebis[2-(5-methyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indasen-1-yl]zirconium dichloride, (90) Silacic butylene [2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl] [2,5-dimethyl-4-phenyl-1-indenyl] zirconium dichloride, (91) Silacic butylene [2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl] [2-(2-furyl)-4-phenyl-5-methyl-1-indenyl] zirconium dichloride, (92) Silacic butylene [2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl] [2-(5-t-butyl-2-furyl)-4-phenyl-5-methyl-1-indenyl] zirconium dichloride, (93) Silacic butylene [2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl] [2-(5-methyl-2-furyl)-4-phenyl-1-indenyl] zirconium dichloride, (94) Silacic butylene [2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl] [2-(5-methyl-2-furyl)-4-phenyl-5,6-dimethyl-1-indenyl] zirconium dichloride, (95) Silacic butylene [2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl] [2-(5-methyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indasen-1-yl] zirconium dichloride, (96) Silacycyclopentylenebis[2-(2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (97) Silacycyclopentylenebis[2-(5-methyl-2-furyl)-4-phenyl-5-methyl-1-indenyl]zirconium dichloride, (98) Silacyclopentylenebis[2-(2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride, (99) Silacyclopentylenebis[2-(5-methyl-2-furyl)-4-phenyl-1,5,6,7-tetrahydro-s-indasen-1-yl]zirconium dichloride, (100) Dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)indenyl}zirconium dichloride, (101) Dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4-hydroazlenyl}zirconium dichloride, These are some examples.

[0103] Examples of compounds represented by general formula (3) include: (1) (Tetramethylcyclopentadienyl)titanium (bis-t-butylamide) dichloride, (2) (Tetramethylcyclopentadienyl)titanium(bisisopropylamide)dichloride, (3) (Tetramethylcyclopentadienyl)titanium (biscyclododecylamide) dichloride, (4)(tetramethylcyclopentadienyl)titanium{bis(trimethylsilyl)amide) dichloride, (5) (2-methyl-4-phenyl-4H-azlenyl)titanium {bis(trimethylsilyl)amide}dichloride, (6) (2-methylindenyl)titanium (bis-t-butylamide) dichloride, (7) (Fluorenyl)titanium (bis-t-butylamide) dichloride, (8) (3,6-diisopropylfluorenyl)titanium(bis-t-butylamide)dichloride, (9) (Tetramethylcyclopentadienyl)titanium (phenoxide) dichloride, (10) (Tetramethylcyclopentadienyl)titanium (2,6-diisopropylphenoxide) dichloride, These are some examples.

[0104] Examples of compounds represented by general formula (4) include: (1) Dimethylsilanediyl (tetramethylcyclopentadienyl) (t-butylamide) titanium dichloride, (2) Dimethylsilanediyl (tetramethylcyclopentadienyl) (cyclododecylamide) titanium dichloride, (3) Dimethylsilanediyl (2-methylindenyl)(t-butylamide)titanium dichloride, (4) Examples include dimethylsilanediyl (fluorenyl) (t-butylamide) titanium dichloride.

[0105] Compounds in which the dichloride in these example compounds is replaced with dibromide, difluoride, dimethyl, diphenyl, dibenzyl, bisdimethylamide, bisdiethylamide, etc., are also similarly exemplified. Furthermore, compounds in which zirconium in the example compounds is replaced with hafnium or titanium, and titanium is replaced with hafnium or zirconium, are also similarly exemplified.

[0106] In this disclosure, the transition metal compound represented by general formula (2) is preferred. Furthermore, metallocene compounds can be used individually or in combination of two or more types.

[0107] When using two or more types in combination, you can choose two or more compounds from the group of compounds included in any one of the general formulas (1) to (4) above, or you can choose one or more compounds selected from the group of compounds included in one general formula and one or more compounds selected from the group of compounds included in another general formula.

[0108] (1.3) Component [C] Component [C] is an organoaluminum compound. The component [C] is the general formula (AlR n X 3-n ) m The organoaluminum compounds represented by the formula are preferably used. In the formula, R represents an alkyl group having 1 to 20 carbon atoms, X represents a halogen, hydrogen, alkoxy group, or amino group, n represents an integer from 1 to 3, and m represents an integer from 1 to 2. The organoaluminum compounds can be used individually or in combination of two or more.

[0109] Specific examples of organoaluminum compounds include trimethylaluminum, triethylaluminum, trin-n-propylaluminum, trin-n-butylaluminum, triisobutylaluminum, trin-n-hexylaluminum, trin-n-octylaluminum, trin-n-decylaluminum, diethylaluminum chloride, diethylaluminum sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, and diisobutylaluminum chloride. Of these, the preferred are trialkylaluminum and alkylaluminum hydride with m=1 and n=3. More preferably, R is a trialkylaluminum having 1 to 8 carbon atoms.

[0110] (2)Mixing method etc. The mixing (contact) method is not particularly limited, but contact can be made in the following order. Furthermore, this mixing may be performed not only during catalyst preparation, but also during prepolymerization with olefins or during polymerization of olefins. A solvent may be used in these mixing processes to ensure thorough mixing. 1) Mix component [B] and component [A]. 2) Mix component [B] and component [A], then mix in component [C]. 3) Mix component [B] and component [C], then mix in component [A]. 4) Mix component [A] and component [C], then mix in component [B]. Alternatively, the three components may be mixed simultaneously.

[0111] A preferred mixing method is to mix component [A] and component [C] as described in 4) above, remove any unreacted component [C] by washing or other means, then mix in the minimum necessary amount of component [C] again, and then mix in component [B].

[0112] The molar ratio (Al / M) of Al in component [C] to the transition metal (M) in component [B] is in the range of 0.1 to 1,000, preferably 1 to 100, and more preferably 4 to 50.

[0113] There are no particular restrictions on the mixing temperature, but it is preferably between 0°C and 100°C, more preferably between 10°C and 80°C, and most preferably between 20°C and 60°C.

[0114] Organic solvents are preferred as solvents, with saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene being more preferred, and olefins, as described later, being more preferred. These may be used individually or in combination. There are no restrictions on the concentration of component [B] in the solvent, but it is preferably 3 mM to 50 mM, more preferably 4 mM to 40 mM, and even more preferably 6 mM to 30 mM. The amount of component [B] used is preferably in the range of 0.001 mmol to 10 mmol per 1 g of component [A], more preferably in the range of 0.001 mmol to 1 mmol.

[0115] The olefin polymerization catalyst of this disclosure may undergo a prepolymerization treatment in which a small amount of ethylene or α-olefin is polymerized in contact with it. The α-olefin used is not particularly limited, but propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene, etc. can be used, and ethylene and propylene are particularly preferred. The method for supplying ethylene or α-olefins can be any method, such as supplying ethylene or α-olefins to the reaction vessel at a constant rate or under constant pressure, a combination thereof, or by introducing stepwise changes.

[0116] The pre-polymerization time is not particularly limited, but is preferably in the range of 5 minutes to 24 hours. Furthermore, the amount of prepolymerization is preferably 0.01 to 100 parts by mass, and more preferably 0.1 to 50 parts by mass, per 1 part by mass of component [A] of the prepolymerized polymer. The prepolymerization temperature is not particularly limited, but is preferably 0°C to 100°C, more preferably 10°C to 70°C, especially preferably 20°C to 60°C, and even more preferably 30°C to 50°C. Prepolymerization is preferably carried out in a liquid such as an organic solvent. As solvents used in prepolymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene, and olefins (described later) are more preferred. These may be used individually or in combination. Alternatively, the solvent used when the components are mixed may be used as is. The concentration of the solid catalyst during prepolymerization is not particularly limited, but is preferably 10 g / L to 300 g / L, more preferably 20 g / L to 200 g / L, and even more preferably 25 g / L to 150 g / L.

[0117] The olefin polymerization catalyst may be dried after mixing the components and after prepolymerization. The drying method is not particularly limited, but examples include vacuum drying, heat drying, and drying by circulating a drying gas. These methods may be used individually or in combination of two or more methods. During the drying process, the catalyst may be stirred, vibrated, or allowed to flow, or it may be left to stand still.

[0118] Furthermore, it is possible to include polymers such as polyethylene, polypropylene, and polystyrene, or inorganic oxide solids such as silica and titania, during or after the mixing of the above components. In addition, various surfactants, antistatic agents, and alkoxysilanes, aminosilanes, ethers, phthalates, carboxylic acid esters, etc., which are known as donors in olefin polymerization catalysts, can also be added.

[0119] 5. Method for producing olefin polymers The method for producing an olefin polymer according to this disclosure is characterized by carrying out olefin polymerization in the presence of an olefin polymerization catalyst obtained by the above-described production method. In this disclosure, the term "olefin polymer" also includes "olefin copolymer." To indicate that olefin copolymers are also included, the term "olefin (co)polymer" may also be used. That is, olefin (co)polymer means at least one of a homopolymer and a copolymer. A method for producing an olefin (co)polymer preferably involves homopolymerizing or copolymerizing ethylene or an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst according to the present disclosure. That is, in this production method, one type of ethylene or α-olefin is polymerized, or two or more types of ethylene or α-olefins are copolymerized.

[0120] In copolymerization, the relative amounts of each monomer in the reaction system do not need to remain constant over time. Each monomer may be supplied in a constant mixing ratio. Alternatively, the mixing ratio of the supplied monomers may be changed over time. Furthermore, considering the copolymerization reaction ratio, one of the monomers may be added in portions.

[0121] The polymerizable α-olefins are preferably ethylene or α-olefins having 3 to 20 carbon atoms, specifically including propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, styrene, divinylbenzene, 7-methyl-1, 7-octadiene, cyclopentene, norbornene, and ethylidenenorbornene. Preferably, they are ethylene or α-olefins having 3 to 8 carbon atoms, and more preferably ethylene or propylene.

[0122] In copolymerization, the type of comonomer used can be selected from the above-mentioned ethylene or α-olefins, with one or more types other than the main component being used. The preferred main component of the comonomer is propylene.

[0123] Any polymerization method can be employed, as long as the catalyst component and each monomer are in efficient contact. Specifically, methods such as slurry methods using inert solvents, methods using monomers such as propylene as solvents without substantially using inert solvents, solution polymerization, or gas-phase methods that keep each monomer in gaseous form without substantially using liquid solvents can be employed. Continuous polymerization, batch polymerization, or prepolymerization methods can also be applied.

[0124] In slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene, either alone or in mixtures, are used as polymerization solvents. The polymerization temperature is not particularly limited, but is usually between 0°C and 150°C.

[0125] Hydrogen may also be used as a molecular weight modifier. Furthermore, compounds that deactivate catalysts, such as oxygen or alcohol, may be supplied to adjust the reaction rate. Known additives such as oxygen, alcohol, alkoxysilane, and surfactants may also be added to improve operability. The polymerization pressure is not particularly limited, but is 0 kg / cm². 2 ~2000 kg / cm 2G (≒0MPaG~196.14MPaG), preferably 0kg / cm 2 ~60kg / cm 2 A suitable pressure range is G (approximately 0 MPa G to 5.88 MPa G).

[0126] The olefin(co)polymer obtained by the method for producing olefin(co)polymers is not particularly limited, but suitable examples include ethylene homopolymers, propylene homopolymers, propylene-ethylene block copolymers, propylene-ethylene random copolymers, and propylene / ethylene-α-olefin copolymers.

[0127] The olefin(co)polymers obtained by the manufacturing method of this disclosure have fewer fish-eyes that degrade the appearance of the product. The olefin (co)polymer obtained by the manufacturing method of this disclosure is preferable if it has a low number of fish eyes. Specifically, the number of fish eyes is preferably 0 per 900 mm. 2 ~100pcs / 900mm 2 More preferably 0 pieces / 900mm 2 ~70pcs / 900mm 2 That is the case. Fish eyes in mixtures of immiscible polymers, known as impact copolymers or block copolymers, obtained through multi-stage polymerization or polymer compounding, can occur due to poor dispersion caused by polymer mismatch (composition), mixing ratio, and molecular weight differences (viscosity differences). Generally, fish eyes tend to increase when mismatch is low or when there are large differences in molecular weight and viscosity among the components. The measurement methods for each of the above characteristics will be described later, so they are omitted here. [Examples]

[0128] The present disclosure will now be described in detail with reference to examples, but the present disclosure is not limited by these examples unless it deviates from its essence. The measurement method in these examples is as follows.

[0129] 1.Various physical property measurement methods (1) Compositional analysis of ion-exchangeable layered silicate and ion-exchangeable layered silicate (composite) particles A calibration curve was created in accordance with JIS R2212, and the substance was quantified by X-ray fluorescence measurement. The equipment used was the Rigaku ZSX Primus IV. The sample was prepared by firing it at 1050°C for 1 hour, then separating 0.4g, mixing it with 4g of flux (Li2B4O7) and 15μL of 50% LiBr aqueous solution (release agent), and creating a glass bead.

[0130] (2) Measurement of lithium atom content of ion-exchange layered silicate particles The concentration was determined using an atomic absorption spectrophotometer (AAS). The equipment used was a Hitachi Z-5310. The samples were calcined at 700°C, collected in a platinum crucible, and then heated and decomposed with the addition of sulfuric acid and hydrofluoric acid. After adjusting the volume of the solution, it was measured using an atomic absorption spectrophotometer (AAS).

[0131] (3) Measurement of pore distribution and specific surface area by nitrogen adsorption method Adsorption and desorption isotherms were measured using the nitrogen adsorption method. The specific surface area was determined by performing a BET multipoint analysis (Rouquerol transformation) using the obtained adsorption isotherms. The specific measurement conditions were as follows: Equipment: Anton-Paar Autosorb-iQ3 gas adsorption measurement device Measurement method: Nitrogen gas adsorption method Pretreatment conditions: Heat the sample under reduced pressure (1.3 Pa or less) at 200°C for 2 hours. Sample quantity: approximately 0.2g Gas liquefaction temperature: 77K

[0132] (4) Measurement of pore distribution by mercury intrusion method The measurements were taken in accordance with JIS R 1655:2003, "Method for testing pore distribution of molded fine ceramics by mercury intrusion method." Specifically, the measuring device used was a Micromeritex Autopore IV9520 model. The sample was pre-dried under reduced pressure at 200°C for 2 hours. The reduced-pressure dried powder sample was weighed (approximately 0.4 g) and placed in a dedicated cell, and as a pretreatment, degassing was performed under vacuum (50 μmHg or less for 10 minutes). Subsequently, the pressure was set to 4.0 psia, and mercury was introduced into the cell as the initial pressure. The pressure was increased in steps from 4.0 psia to 40,000 psia, and then decreased to 26 psia. The number of steps during the pressure increase was 79 or more, and the number of steps during the pressure decrease was 39 or more. After an equilibrium time of 10 seconds at each step, the amount of mercury injected was measured. The contact angle of mercury was 140 degrees, and the surface tension of mercury was 485 dynes / cm. For the measurement data on the pressurized (mercury intrusion) side, a cumulative pore volume curve was obtained by plotting pore diameter on the horizontal axis and pore volume on the vertical axis. The pore volume at pore diameters from 10 nm to 300 nm was calculated from the difference in cumulative pore volume at pore diameters of 10 nm and 300 nm.

[0133] (5) Measurement of average particle size The particle size distribution was measured using a HORIBA LA-960 laser diffraction / scattering particle size distribution analyzer under the following conditions: ethanol as the dispersion solvent, real refractive index term 1.490, imaginary term 0.000, and real refractive index term 1.360 of the dispersion solvent, after ultrasonic dispersion. The average particle size refers to the median diameter based on volume.

[0134] (6) Crushing strength Using the Shimadzu Corporation's "MCT-210" crushing tester, and in accordance with JIS R 1639-5, 20 particles selected to avoid size bias were measured at a temperature of 23°C, humidity of 35%, and a loading speed of 1.9 mN / sec. The crushing strength of the particles was then calculated according to the following formula. S = 2.48·P / (π·d 2 ) (S: Crushing strength (MPa), P: Test pressure at fracture (N), d: Diameter = Average value of the major axis diameter and minor axis diameter of the particle (μm)) Note that 'd' was measured using an optical microscope. The average of the crushing intensities of the 20 obtained particles was defined as the average crushing intensity.

[0135] (7) Particle size of ion-exchange layered silicate (raw material) The volume-based median diameter, determined from the spherical equivalent particle size distribution measured by the following method, was defined as the particle size of the ion-exchange layered silicate (raw material). The particle size distribution was measured using a HORIBA LA-960 laser diffraction / scattering particle size distribution analyzer, under the following conditions: distilled water as the dispersion solvent, real refractive index term 1.490, imaginary term 0.100, real refractive index term of the dispersion solvent 1.333, transmittance (R) 85%~99%, transmittance (B) 85%~90%, and after ultrasonic treatment for 2 minutes at an ultrasonic intensity of "7" inside the instrument.

[0136] (8) MFR (Meltmass Flow Rate) The measurements were taken using a melt indexer manufactured by Takara Corporation, in accordance with the test conditions of JIS K7210, "Plastics - Test methods for melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastic plastics": 230°C, 2.16 kg load.

[0137] (9) Measurement of the number of fisheyes To 20 g of polymer, 10 mg each of pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), tris(2,4-di-tert-butylphenyl) phosphite, and calcium stearate were added. The mixture was kneaded using an Xplore microcompounder (DSM) at 200°C, 50 rpm, and 2 min, and then pressed to a thickness of 0.2 mm at 190°C, 10 MPa to obtain a sheet. The sheet was scanned using a Canon Cano Scan 9000F Mark II as a 1200dpi, 8-bit grayscale image, then the image was binarized and processed into a 30mm x 30mm area (square area: 900mm). 2 The number of fisheyes was measured at three locations, and the average of these three values ​​was used as the number of fisheyes. Points smaller than 3 pixels were considered noise and were excluded from the measurement.

[0138] (10) Method for analyzing polymers containing ethylene-propylene copolymer The analysis was performed using a method that combines the cross-fractionation method and the FT-IR method described in Japanese Patent Publication No. 2015-193605 ([Analysis of Characteristic Values ​​of Polymerized Olefin Polymers] (1)~(6)).

[0139] 2. Production of ion-exchangeable layered silicate particles (1) Example a1 (1.1) Production of ion-exchange layered silicate composite particles As the ion-exchangeable layered silicate, a 5.0% by mass aqueous slurry of "Benclay KK" (main component: smectite group montmorillonite with a 2:1 layered structure), manufactured by Mizusawa Chemical Industries, Ltd., was used. The particle size of the ion-exchangeable layered silicate was 0.457 μm. 1950 g of Benclay KK's aqueous slurry (5.0% by mass) and 217 g of distilled water were added to a 5 L beaker and stirred. 52.5 g of aluminum hydroxide (aluminum ion-containing compound [I]) with an average particle size of 1 μm, manufactured by Nippon Light Metal Co., Ltd., was added to the slurry while stirring. The amount of aluminum hydroxide used was 35% by mass relative to 100% by mass of the solid components in the slurry. After stirring for 2 minutes, the mixture was further stirred for 5 minutes using a high-speed stirrer to prepare the slurry. Using the obtained slurry, spray drying granulation was performed under the following conditions using a spray drying granulator (Okawara Chemical Machinery Co., Ltd. "L-8"). • Atomizer type: M type rotary disc Atomizer rotation speed: 8000 rpm • Cyclone differential pressure: 1.05 kPa • Dry air inlet temperature: 130℃ The slurry supply time was 153 minutes. The granules were collected in the lower part of the granulator body and the lower part of the cyclone. 92 g of the granules obtained in the lower part of the body were passed through a sieve with a mesh size of 75 μm to remove coarse material, and dried at 200°C under reduced pressure for 2 hours to obtain 59.6 g of ion-exchangeable layered silicate composite particles. The results of various analyses of the ion-exchangeable layered silicate, the aluminum ion-containing compound [I], and the ion-exchangeable layered silicate composite particles are shown in Tables 1-1 and 1-2. Here, the following symbols in Table 1-1 for ion-exchange layered silicates mean the following: • "Fea": The amount of iron atoms contained in ion-exchange layered silicate. The following symbols in the ion-exchangeable layered silicate composite particles in Table 1-2 have the following meanings: • "Mgb": The amount of magnesium atoms contained in ion-exchange layered silicate composite particles • "Feb": The amount of iron atoms contained in ion-exchange layered silicate composite particles

[0140] (1.2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) 157.5g of distilled water was added to a 1L flask equipped with a stirring blade and reflux device, and 62.5g of 96% sulfuric acid was added dropwise. The aqueous solution was heated in an oil bath until its internal temperature reached 95°C. Once the target temperature was reached, 30g of the ion-exchangeable layered silicate composite particles prepared in (1.1) above were added, and the mixture was reacted for 180 minutes while maintaining a temperature of 95°C. The reaction was stopped by pouring this reaction solution into 150 mL of distilled water. The resulting slurry was filtered using an apparatus with a Nucche filter and a suction bottle connected to an aspirator, and the filtered cake was rinsed with 300 g of distilled water. This filtered cake was then washed with 300 g of 10% dilute sulfuric acid and rinsed with 300 g of distilled water to obtain a filtered cake with a solid content of 40.0 g.

[0141] (1.3) Chemical treatment of ion-exchangeable layered silicate composite particles (2) 36.0 g of the solids chemically treated in (1.2) above and 46.9 g of distilled water were added to a 200 mL flask and stirred. The slurry was heated to 40°C, and a 1.5 mol / L aqueous lithium hydroxide solution was added dropwise until the pH of the slurry reached 6.50. The amount of lithium hydroxide solution added was 6.2 g. The reaction was allowed to proceed for 120 minutes while maintaining the temperature at 40°C. At the end of the reaction, the pH of the slurry was 5.66. The reaction slurry was filtered using a Nucche filter and a suction bottle with an aspirator connected, and washed twice with 140 g of distilled water. The recovered cake was dried overnight at 110°C. Furthermore, before use as a catalyst component, the dried cake was crushed by lightly pressing it with a spatula, coarse material was removed by passing it through a 75 μm sieve, and it was dried at 200°C under reduced pressure for 2 hours to obtain 13.9 g of ion-exchangeable layered silicate particles. The results of various analyses of ion-exchangeable layered silicate particles are shown in Tables 2-1 and 2-2. The following symbols in Table 2-1 for ion-exchangeable layered silicate particles have the following meanings: • "Na": The amount of sodium atoms contained in ion-exchange layered silicate particles • "K": Amount of potassium atoms contained in ion-exchange layered silicate particles

[0142] Furthermore, in Table 2-1, Examples a1 to a8 satisfy the following formula (2). Formula (2): -3.0×([Al] / [Si])+4.2≦([Al] / [Mg]) ≤ -3.0 × ([Al] / [Si]) + 5.8

[0143] (2) Example a2 (2.1) Production of ion-exchange layered silicate composite particles A slurry was prepared in the same manner as in Example a1(1.1), except that 1800 g of Benclay KK's aqueous slurry, 450 g of distilled water, and 30 g of aluminum hydroxide (aluminum-containing compound [I]) were used. The amount of aluminum hydroxide used was 25% by mass relative to 100% by mass of solid components in the slurry. Using the obtained slurry, spray drying granulation was performed using the same apparatus and conditions as in Example a1(1.1). The slurry supply time was 164 minutes. The granulated product was collected at the lower part of the granulator main body and the lower part of the cyclone. 89.9 g of the granulated product obtained at the lower part of the main body was passed through a sieve with a mesh size of 75 μm to remove coarse materials, and dried at 200 °C under reduced pressure for 2 hours to obtain 38.5 g of ion-exchangeable layered silicate composite particles. The results of various analyses of the ion-exchangeable layered silicate and compound [I] and the obtained ion-exchangeable layered silicate composite particles are shown in Tables 1-1 and 1-2.

[0144] (2.2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) It was carried out in the same manner as in Example a1 (2.2), except that 164.3 g of distilled water, 48.3 g of 96% sulfuric acid, and the ion-exchangeable layered silicate were changed to 29 g of the ion-exchangeable layered silicate composite particles in (2.1) above. The reaction was stopped by pouring the reaction solution into 145 mL of distilled water, and the obtained slurry was filtered using a device with a Buchner funnel and an aspirator connected to a suction flask. The filter cake was rinsed with 290 g of distilled water. Further, this filter cake was washed with 290 g of 10% dilute sulfuric acid, rinsed with 290 g of distilled water, and 45.1 g of solid content was obtained as the filter cake.

[0145] (2.3) Chemical treatment of ion-exchangeable layered silicate composite particles (2) 40.3 g of the solid obtained from (2.2) above and 54.0 g of distilled water were added to a 200 mL flask and stirred. The slurry was heated to 40°C, and a lithium hydroxide aqueous solution prepared to a concentration of 1.5 mol / L was added dropwise until the slurry pH reached 6.50. The amount of lithium hydroxide aqueous solution added was 10.0 g. The reaction was allowed to proceed for 90 minutes while maintaining the temperature at 40°C. At the end of the reaction, the pH of the slurry was 5.93. The reaction slurry was filtered using an apparatus with an aspirator connected to a Nutsch suction bottle and washed twice with 159 g of distilled water. The recovered cake was dried overnight at 110°C. Furthermore, before use as a catalyst component, the dried cake was crushed by lightly pressing it with a spatula, coarse material was removed by passing it through a sieve with a mesh size of 75 μm, and the cake was dried at 200°C under reduced pressure for 2 hours to obtain 12.9 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Tables 2-1 and 2-2.

[0146] (3) Example a3 (3.1) Production of ion-exchange layered silicate composite particles A slurry was prepared in the same manner as in Example a1(1.1), except that 2550 g of Benclay KK's aqueous slurry, 52 g of distilled water, and 22.5 g of aluminum hydroxide (aluminum ion-containing compound [I]) were used. The amount of aluminum hydroxide used was 15% by mass relative to 100% by mass of the solid components contained in the slurry. Spray drying granulation was performed using the obtained slurry with the same apparatus and conditions as in Example a1(1.1). The slurry supply time was 197 minutes. The granules were collected in the lower part of the granulator body and the lower part of the cyclone. 103.8 g of the granules obtained in the lower part of the body were passed through a sieve with a mesh size of 75 μm to remove coarse material, and dried at 200°C under reduced pressure for 2 hours to obtain 49.8 g of ion-exchangeable layered silicate composite particles. The results of various analyses of the ion-exchangeable layered silicate and compound [I] used, and the obtained ion-exchangeable layered silicate composite particles are shown in Tables 1-1 and 1-2.

[0147] (3.2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) The procedure was carried out in the same manner as in Example a1 (2.2), except that 187.0 g of distilled water, 55.0 g of 96% sulfuric acid, and 33 g of the ion-exchangeable layered silicate composite particles described in (3.1) above were used instead. The reaction was stopped by pouring the reaction solution into 165 mL of distilled water. The resulting slurry was filtered using an apparatus with a Nucche filter and a suction bottle connected to an aspirator, yielding 51.8 g of solids as a filtration cake.

[0148] (3.3) Chemical treatment of ion-exchangeable layered silicate composite particles (2) 46.5 g of the solid obtained from (3.2) above and 73.2 g of distilled water were added to a 200 mL flask and stirred. The slurry was heated to 40°C, and a lithium hydroxide aqueous solution prepared to a concentration of 1.5 mol / L was added dropwise until the slurry pH reached 6.50. The amount of lithium hydroxide aqueous solution added was 20.1 g. The reaction was allowed to proceed for 120 minutes while maintaining the temperature at 40°C. At the end of the reaction, the pH of the slurry was 5.68. The reaction slurry was filtered using an apparatus with an aspirator connected to a Nutsch suction bottle and washed twice with 200 g of distilled water. The recovered cake was dried overnight at 110°C. Furthermore, before use as a catalyst component, the dried cake was crushed by lightly pressing it with a spatula, coarse material was removed by passing it through a sieve with a mesh size of 75 μm, and it was dried at 200°C under reduced pressure for 2 hours to obtain 16.4 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Tables 2-1 and 2-2.

[0149] (4) Example a4 (4.1) Production of ion-exchange layered silicate composite particles A slurry was prepared in the same manner as in Example a1(1.1), except that aluminum hydroxide (aluminum ion-containing compound [I]) with an average particle size of 2 μm was used. Using the obtained slurry, spray drying granulation was performed using the same apparatus and conditions as in Example a1(1.1). The slurry supply time was 186 minutes. The granules were collected in the lower part of the granulator body and the lower part of the cyclone. 101.6 g of the granules obtained in the lower part of the body were passed through a sieve with a mesh size of 75 μm to remove coarse material, and dried at 200°C under reduced pressure for 2 hours to obtain 54.9 g of ion-exchangeable layered silicate composite particles. The results of various analyses of the ion-exchangeable layered silicate and compound [I] used, and the obtained ion-exchangeable layered silicate composite particles are shown in Tables 1-1 and 1-2.

[0150] (4.2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) The procedure was carried out in the same manner as in Example a1 (2.2), except that 220.5 g of distilled water, 87.5 g of 96% sulfuric acid, and 42 g of the ion-exchangeable layered silicate composite particles described in (4.1) above were used instead. The reaction was stopped by pouring the reaction solution into 210 mL of distilled water. The resulting slurry was filtered using an apparatus with an aspirator connected to a Nucche suction bottle, and the filtered cake was rinsed with 420 g of distilled water. This filtered cake was then washed with 400 g of 10% dilute sulfuric acid and rinsed with 400 g of distilled water to obtain a filtration cake with a solid content of 54.3 g.

[0151] (4.3) Chemical treatment of ion-exchangeable layered silicate composite particles (2) 48.9 g of the solid obtained from (4.2) above and 71.3 g of distilled water were added to a 200 mL flask and stirred. The slurry was heated to 40°C, and a lithium hydroxide aqueous solution prepared to a concentration of 1.5 mol / L was added dropwise until the slurry pH reached 6.50. The amount of lithium hydroxide aqueous solution added was 10.3 g. The reaction was allowed to proceed for 120 minutes while maintaining the temperature at 40°C. At the end of the reaction, the pH of the slurry was 5.87. The reaction slurry was filtered using an apparatus with an aspirator connected to a Nutsch filter and suction bottle, and washed twice with 200 g of distilled water. The recovered cake was dried overnight at 110°C. Furthermore, before use as a catalyst component, the dried cake was crushed by lightly pressing it with a spatula, coarse material was removed by passing it through a sieve with a mesh size of 75 μm, and it was dried at 200°C under reduced pressure for 2 hours to obtain 15.3 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Tables 2-1 and 2-1.

[0152] (5) Example a5 (5.1) Production of ion-exchange layered silicate composite particles As the ion-exchangeable layered silicate, we used an aqueous slurry (solid content 3.1 wt%, main component being montmorillonite of the smectite group with a 2:1 layered structure) obtained by kneading 3% by mass of sodium carbonate with clay mineral from Nakajo, Niigata Prefecture, manufactured by Mizusawa Chemical Industry Co., Ltd., and then purifying it by elutriation and centrifugation. The particle size of the ion-exchangeable layered silicate was 0.223 μm. A slurry was prepared in the same manner as in Example a1(1.1), except that 3241 g of the above-mentioned ion-exchangeable layered silicate aqueous slurry (3.1% by mass) was used, and the amount of aluminum hydroxide (aluminum ion-containing compound [I]) used was changed to 49.5 g. The amount of aluminum hydroxide used was 35% by mass relative to 100% by mass of the solid components contained in the slurry. Using the obtained slurry, spray drying granulation was performed using the same apparatus and conditions as in Example a1(1-1). The slurry supply time was 186 minutes. The granules were collected in the lower part of the granulator body and the lower part of the cyclone. 91.3 g of the granules obtained in the lower part of the body were passed through a sieve with a mesh size of 75 μm to remove coarse material, and dried at 200°C under reduced pressure for 2 hours to obtain 45.2 g of ion-exchangeable layered silicate composite particles. The results of various analyses of the ion-exchangeable layered silicate and compound [I] used, and the obtained ion-exchangeable layered silicate composite particles are shown in Tables 1-1 and 1-2.

[0153] (5.2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) 141.4g of distilled water, 56.1g of 96% sulfuric acid, and ion-exchangeable layered silicate composite particles The procedure was the same as in Example a1 (2.2), except that 26.9 g of ion-exchangeable layered silicate composite particles as described in (5.1) above were used. The reaction was stopped by pouring the reaction solution into 135 mL of distilled water. The resulting slurry was filtered using an apparatus with a Nucche filter and a suction bottle connected to an aspirator, and the filtered cake was rinsed with 300 g of distilled water. This filtered cake was then washed with 400 g of 10% dilute sulfuric acid and rinsed with 400 g of distilled water to obtain a filtration cake with a solid content of 34.2 g.

[0154] (5.3) Chemical treatment of ion-exchangeable layered silicate composite particles (2) 33.1 g of the solid obtained from (5.2) above and 46.9 g of distilled water were added to a 200 mL flask and stirred. The slurry was heated to 40°C, and a 1.5 mol / L aqueous lithium hydroxide solution was added dropwise until the slurry pH reached 6.50. The amount of lithium hydroxide solution added was 5.8 g. The reaction was allowed to proceed for 90 minutes while maintaining the temperature at 40°C. At the end of the reaction, the pH of the slurry was 5.98. The reaction slurry was filtered using an apparatus with an aspirator connected to a Nutsche filter and suction bottle, and washed twice with 135 g of distilled water. The recovered cake was dried overnight at 110°C. Furthermore, before use as a catalyst component, the dried cake was crushed by lightly pressing it with a spatula, coarse material was removed by passing it through a 75 μm sieve, and it was dried at 200°C under reduced pressure for 2 hours to obtain 11.82 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Tables 2-1 and 2-2.

[0155] (6) Example a6 (6.1) Production of ion-exchange layered silicate composite particles A slurry was prepared in the same manner as in Example a5 (5.1), except that 3629 g of ion-exchangeable layered silicate aqueous slurry and 37.5 g of aluminum hydroxide (aluminum ion-containing compound [I]) were used. The amount of aluminum hydroxide used was 25% by mass relative to 100% by mass of solid components in the slurry. Using the obtained slurry, spray drying and granulation were performed using the same apparatus and conditions as in Example a1 (1.1), except that the drying air inlet temperature was set to 140°C. The slurry supply time was 253 minutes. The granules were collected in the lower part of the granulator body and the lower part of the cyclone. 96.4 g of the granules obtained in the lower part of the body were passed through a sieve with a mesh size of 75 μm to remove coarse material, and dried at 200°C under reduced pressure for 2 hours to obtain 42.6 g of ion-exchangeable layered silicate composite particles. The results of various analyses of the ion-exchangeable layered silicate and compound [I] used, and the obtained ion-exchangeable layered silicate composite particles are shown in Tables 1-1 and 1-2.

[0156] (6.2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) Except that 148.5 g of distilled water, 49.5 g of 96% sulfuric acid, and 27.0 g of the ion-exchange layered silicate composite particles of the above (6.1) were used instead of the ion-exchange layered silicate composite particles, the same operations as in Example a1 (2.2) were carried out. The reaction was stopped by pouring the reaction solution into 135 mL of distilled water, and the resulting slurry was filtered using a device with a Buchner funnel and an aspirator flask connected to an aspirator. The filter cake was rinsed with 270 g of distilled water. Further, this filter cake was washed with 300 g of 10% dilute sulfuric acid and rinsed with 300 g of distilled water, and 36.1 g of solid content was obtained as the filter cake.

[0157] (6.3) Chemical treatment (2) of ion-exchange layered silicate composite particles 32.6 g of the solid content obtained from the above (6.2) and 54.5 g of distilled water were added to a 200 mL flask and stirred. This slurry was heated to 40 °C, and an aqueous lithium hydroxide solution prepared to a concentration of 1.5 mol / L was dropped therein until the slurry pH reached 6.50. The dropping amount of the aqueous lithium hydroxide solution was 7.5 g. The reaction was carried out while maintaining 40 °C for 90 minutes. The pH of the slurry at the end of the reaction at this time was 5.34. The reaction slurry was filtered using a device with a Buchner funnel and an aspirator flask connected to an aspirator, and washed twice with 147 g of distilled water. The recovered cake was dried at 110 °C overnight. Further, before using as a catalyst component, the dried cake was crushed while gently pressing with a spatula, and coarse materials were removed through a sieve with a mesh opening of 75 μm, and dried at 200 °C under reduced pressure for 2 hours to obtain 12.3 g of ion-exchange layered silicate particles. The results of various analyses are shown in Tables 2-1 and 2-2.

[0158] (7) Example a7 (7.1) Production of ion-exchange layered silicate composite particles As the ion-exchange layered silicate, an aqueous slurry (solid content 6.7 wt%, main component is smectite montmorillonite of the 2:1 type layer structure) obtained by kneading 3% by mass of sodium carbonate into a clay mineral produced in Nakajo, Niigata Prefecture, manufactured by Mizusawa Chemical Industry Co., Ltd., and then performing water elutriation and centrifugation for purification was used. The particle diameter of the ion-exchange layered silicate was 0.259 μm. A slurry was prepared in the same manner as in Example a1 (1.1), except that the aqueous slurry of ion-exchangeable layered silicate was changed to 1791 g of the above ion-exchangeable layered silicate aqueous slurry (6.7% by mass), 609 g of distilled water, and 40.0 g of aluminum hydroxide (aluminum ion-containing compound [I]). The amount of aluminum hydroxide used at this time was 25% by mass relative to 100% by mass of the total solid components contained in the slurry. After stirring for 2 minutes, the slurry was further stirred for 5 minutes using a high-speed stirrer to prepare the slurry. Using the obtained slurry, spray drying granulation was performed under the following conditions using a spray drying granulator (Okawara Chemical Machinery Co., Ltd. "L-8"). • Atomizer type: M type rotary disc Atomizer rotation speed: 30,000 rpm • Cyclone differential pressure: 1.08 kPa • Dry air inlet temperature: 150℃ The slurry was supplied for 80 minutes. The granulated material was collected in the lower part of the granulator body and the lower part of the cyclone. A total of 158.3 g of granulated material collected in the lower part of the body and the cyclone was passed through a sieve with a mesh size of 53 μm to remove coarse material, and dried at 200°C under reduced pressure for 2 hours to obtain 137.7 g of ion-exchangeable layered silicate composite particles. The results of various analyses of the ion-exchangeable layered silicate, the aluminum ion-containing compound [I], and the ion-exchangeable layered silicate composite particles are shown in Tables 1-1 and 1-2.

[0159] (7.2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) 538.2 g of distilled water was added to a 1 L flask equipped with a stirring blade and reflux device, and 137.5 g of 96% sulfuric acid was added dropwise. The aqueous solution was heated in an oil bath until its internal temperature reached 95°C. Once the target temperature was reached, 110 g of the ion-exchangeable layered silicate composite particles prepared in (7.1) above were added, and the mixture was reacted for 270 minutes while maintaining a temperature of 95°C. The reaction was stopped by pouring this reaction solution into 550 mL of distilled water. The resulting slurry was filtered using an apparatus with a Nucche filter and a suction bottle connected to an aspirator, and the filtered cake was rinsed three times with 300 g of 10% dilute sulfuric acid. This filtered cake was then slurryed with 1100 g of distilled water and washed again by filtration. This washing with distilled water was performed a total of three times. 205.5 g of solids was obtained as the filtered cake.

[0160] (7.3) Chemical treatment of ion-exchangeable layered silicate composite particles (2) A lithium sulfate aqueous solution was prepared by adding 243.2 g of distilled water and 86.4 g of lithium sulfate monohydrate to a 1 L flask and stirring. After raising the temperature of this aqueous solution to 40°C, 205.5 g of the solid components chemically treated in (7.2) above were added to the aqueous solution, and the slurry was stirred for 2 hours. The pH of the slurry at the end of the reaction was 1.79. The reaction slurry was filtered using an apparatus with an aspirator connected to a Nutsche filter and suction bottle, and washed four times with 1605 g of distilled water. The recovered cake was dried overnight at 110°C. Furthermore, before use as a catalyst component, the dried cake was crushed by lightly pressing it with a spatula, coarse material was removed by passing it through a sieve with a mesh size of 53 μm, and the cake was dried at 200°C under reduced pressure for 2 hours to obtain 58.1 g of ion-exchangeable layered silicate particles. The results of various analyses of the ion-exchangeable layered silicate particles are shown in Tables 2-1 and 2-2.

[0161] (8) Example a8 (8.1) Production of ion-exchange layered silicate composite particles A slurry was prepared in the same manner as in Example a7(7.1), except that 1795 g of ion-exchangeable layered silicate aqueous slurry, 610 g of distilled water, and 64.8 g of aluminum hydroxide (aluminum ion-containing compound [I]) were used. The amount of aluminum hydroxide used was 35% by mass relative to 100% by mass of solid components in the slurry. Spray drying granulation was performed using the obtained slurry with the same apparatus and conditions as in Example a7(7.1). The slurry supply time was 80 minutes. The granules were collected in the lower part of the granulator body and the lower part of the cyclone. A total of 176.8 g of granules collected in the lower part of the body and the cyclone were passed through a sieve with a mesh size of 53 μm to remove coarse material, and dried at 200°C under reduced pressure for 2 hours to obtain 154.2 g of ion-exchangeable layered silicate composite particles. The results of various analyses of ion-exchangeable layered silicates, aluminum ion-containing compounds [I], and ion-exchangeable layered silicate composite particles are shown in Tables 1-1 and 1-2.

[0162] (8.2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) The procedure was the same as in Example a7 (7.2), except that 711.1 g of distilled water, 222.6 g of 96% sulfuric acid, and 152 g of ion-exchangeable layered silicate composite particles were used instead of the ion-exchangeable layered silicate composite particles described in (8.1) above. The reaction was stopped by pouring the reaction solution into 760 mL of distilled water, and the resulting slurry was filtered using an apparatus with an aspirator connected to a Nucche and suction bottle. The filtered cake was rinsed three times with 400 g of 10% dilute sulfuric acid. This filtered cake was then slurryed with 1520 g of distilled water and washed again by filtration. This washing with distilled water was performed a total of three times. 265.5 g of solids was obtained as the filtered cake.

[0163] (8.3) Chemical treatment of ion-exchangeable layered silicate composite particles (2) The procedure was the same as in Example a7 (7.3), except that 281.3 g of distilled water, 104.2 g of lithium sulfate monohydrate, and 260.2 g of solids obtained from (8.2) above were used. The pH of the slurry at the end of the reaction was 2.09. The reaction slurry was filtered using an apparatus with an aspirator connected to a Nutsche suction bottle and washed four times with 1937 g of distilled water. The recovered cake was dried overnight at 110°C. Furthermore, before use as a catalyst component, the dried cake was crushed by lightly pressing it with a spatula, coarse material was removed by passing it through a sieve with a mesh size of 53 μm, and the cake was dried at 200°C under reduced pressure for 2 hours to obtain 64.7 g of ion-exchangeable layered silicate particles. The results of various analyses of the ion-exchangeable layered silicate particles are shown in Tables 2-1 and 2-2.

[0164] (9) Comparative Example a1 (9.1) Production of ion-exchange layered silicate composite particles A slurry was prepared in the same manner as in Example a1(1.1), except that 2400 g of Benclay KK's aqueous slurry (5.0% by mass) was used, and distilled water and aluminum hydroxide were not used. Using the obtained slurry, spray drying granulation was performed using the same apparatus and conditions as in Example a1(1.1). The slurry supply time was 181 minutes. The granules were collected in the lower part of the granulator body and the lower part of the cyclone. 105.2 g of the granules obtained in the lower part of the body were passed through a sieve with a mesh size of 75 μm to remove coarse material, and dried at 200°C under reduced pressure for 2 hours to obtain 59.6 g of ion-exchangeable layered silicate composite particles. The results of various analyses of the ion-exchangeable layered silicate and compound [I] used, and the obtained ion-exchangeable layered silicate composite particles are shown in Tables 1-1 and 1-2.

[0165] (9.2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) The procedure was carried out in the same manner as in Example a1 (2.2), except that 204.0 g of distilled water, 60.0 g of 96% sulfuric acid, and 36 g of ion-exchangeable layered silicate composite particles were replaced with the ion-exchangeable layered silicate composite particles described in (9.1) above. The reaction was stopped by pouring the reaction solution into 155 mL of distilled water. The resulting slurry was filtered using an apparatus with an aspirator connected to a Nucche and suction bottle. The filtered cake was rinsed with 310 g of distilled water, yielding a solid content of 51.0 g as the filtered cake.

[0166] (9.3) Chemical treatment of ion-exchangeable layered silicate composite particles (2) 46.4 g of the solid obtained from (9.2) above and 88.7 g of distilled water were added to a 200 mL flask and stirred. The slurry was heated to 40°C, and a 1.5 mol / L aqueous lithium hydroxide solution was added dropwise until the slurry pH reached 6.50. The amount of lithium hydroxide solution added was 9.0 g. The reaction was allowed to proceed for 100 minutes while maintaining the temperature at 40°C. At the end of the reaction, the pH of the slurry was 5.59. The reaction slurry was filtered using an apparatus with an aspirator connected to a Nutsch filter and suction bottle, and washed twice with 228 g of distilled water. The recovered cake was dried overnight at 110°C. Furthermore, before use as a catalyst component, the dried cake was crushed by lightly pressing it with a spatula, coarse material was removed by passing it through a 75 μm sieve, and the mixture was dried at 200°C under reduced pressure for 2 hours to obtain 19.8 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Tables 2-1 and 2-2.

[0167] (10) Comparative example a2 (10.1) Production of ion-exchange layered silicate composite particles As an ion-exchangeable layered silicate, we prepared granulated material (median diameter 33.3 μm) of a water slurry (main component: montmorillonite of the smectite group with a 2:1 layered structure) obtained by purifying clay minerals from Nakajo, Niigata Prefecture, used in Example a5, by elutriation and centrifugation, manufactured by Mizusawa Chemical Industry Co., Ltd. The results of various analyses of this ion-exchangeable layered silicate composite particle are shown in Tables 1-1 and 1-2.

[0168] (10.2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) 585g of distilled water was added to a 1L flask equipped with a stirring blade and reflux device, and 76g of 96% sulfuric acid was added dropwise. This aqueous solution was heated in an oil bath until the internal temperature reached 95°C. At 95°C, 90g of the aforementioned ion-exchangeable layered silicate particles (10.1) were added, and the mixture was reacted for 360 minutes while maintaining the temperature at 95°C. The reaction was stopped by pouring this reaction solution into 900 mL of distilled water. The resulting slurry was filtered by suction, and the solid components were washed three times with 450 mL of distilled water.

[0169] (10.3) Chemical treatment of ion-exchangeable layered silicate composite particles (2) 270.9 g of the solid component described in (10.2) above and 355.1 g of distilled water were added to a 1 L flask and stirred. The slurry was heated to 40°C, and 20.6 g of 4.43 wt% lithium hydroxide aqueous solution was added dropwise. The mixture was then stirred for 90 minutes to allow the reaction to proceed. The slurry pH after 90 minutes was 5.51. The reaction slurry was poured into 800 mL of distilled water and then filtered by suction. The recovered solid was washed three times with 900 mL of distilled water. After washing, it was dried overnight at 110°C, coarse material was removed by passing it through a sieve with a mesh size of 75 μm, and then dried at 200°C under reduced pressure for 2 hours to obtain 68.8 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Tables 2-1 and 2-2.

[0170] (11) Comparative example a3 (11.1) Production of ion-exchange layered silicate particles Comparative ion-exchangeable layered silicate particles were produced in the same manner as in Example 3 of Japanese Patent Publication No. 2019-172958. The results of various analyses are shown in Tables 1-1, 1-2, 2-1, and 2-2.

[0171] (12) Comparative example a4 (12.1) Production of ion-exchange layered silicate composite particles As the ion-exchangeable layered silicate, we used "Kunipia F" manufactured by Kunimine Industries (whose main component is montmorillonite of the smectite group with a 2:1 layered structure). The particle size of the ion-exchangeable layered silicate was 1.23 μm. 2375g of distilled water and 125g of Kunipia F were added to a 5L beaker and stirred for 2 minutes. Then, the mixture was stirred for another 5 minutes using a high-speed stirrer to prepare a slurry. Using the obtained slurry, spray drying granulation was performed using the same apparatus and conditions as in Example a1(1.1). The slurry supply time was 171 minutes. The granulated material was collected in the lower part of the granulator body and the lower part of the cyclone. 62.0 g of the granulated material obtained in the lower part of the body was passed through a sieve with a mesh size of 75 μm to remove coarse material, and dried at 200°C under reduced pressure for 2 hours to obtain 39.6 g of ion-exchangeable layered silicate composite particles. The results of various analyses of these ion-exchangeable layered silicate composite particles are shown in Tables 1-1 and 1-2.

[0172] (12.2) Chemical treatment of ion-exchangeable layered silicate composite particles (1) 181.3g of distilled water was added to a 1L flask equipped with a stirring blade and reflux device, and 53.3g of 96% sulfuric acid was added dropwise. This aqueous solution was heated in an oil bath until the internal temperature reached 95°C. At 95°C, 32g of the ion-exchangeable layered silicate composite particles described in (12.1) above was added, and the mixture was reacted for 360 minutes while maintaining the temperature at 95°C. The reaction was stopped by pouring this reaction solution into 161 mL of distilled water. The resulting slurry was filtered using an apparatus with a Nucche filter and a suction bottle connected to an aspirator, and the filtered cake was rinsed with 270 g of distilled water. The filtered cake was then washed with 300 g of 10% dilute sulfuric acid and rinsed with 300 g of distilled water to obtain a filtered cake with a solid content of 55.6 g.

[0173] (12.3) Chemical treatment of ion-exchangeable layered silicate composite particles (2) 51.7 g of the solid obtained from (12.2) above and 31.7 g of distilled water were added to a 200 mL flask and stirred. The slurry was heated to 40°C, and a lithium hydroxide aqueous solution prepared to a concentration of 1.5 mol / L was added dropwise until the slurry pH reached 6.50. The amount of lithium hydroxide aqueous solution added was 9.4 g. The reaction was allowed to proceed for 100 minutes while maintaining the temperature at 40°C. At the end of the reaction, the pH of the slurry was 5.71. The reaction slurry was filtered using an apparatus with an aspirator connected to a Nutsch suction bottle and washed twice with 200 g of distilled water. The recovered cake was dried overnight at 110°C. Furthermore, before use as a catalyst component, the dried cake was crushed by lightly pressing it with a spatula, coarse material was removed by passing it through a sieve with a mesh size of 75 μm, and the cake was dried at 200°C under reduced pressure for 2 hours to obtain 17.5 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Tables 2-1 and 2-2. However, due to the poor particle shape, crush strength measurements were not performed.

[0174] (13) Comparative Example a5 (13.1) Production of ion-exchange layered silicate particles Comparative ion-exchangeable layered silicate particles were produced in the same manner as described in Japanese Patent Publication No. 2003-252923 [Production of Silicate B]. The results of various analyses are shown in Tables 1-1, 1-2, 2-1, and 2-2.

[0175] (14) Comparative example a6 (14.1) Production of ion-exchange layered silicate composite particles A slurry was prepared in the same manner as in Example a7(7.1), except that 2400 g of Benclay KK's aqueous slurry (5.0 mass%) was used, and distilled water and aluminum hydroxide were not used. Spray drying granulation was performed using the obtained slurry with the same apparatus and conditions as in Example a7(7.1). The slurry supply time was 84 minutes. The granules were collected in the lower part of the granulator body and the lower part of the cyclone. A total of 109.8 g of granules collected in the lower part of the body and the cyclone were passed through a sieve with a mesh size of 53 μm to remove coarse material, and dried at 200°C under reduced pressure for 2 hours to obtain 103.6 g of ion-exchangeable layered silicate particles. The results of various analyses of the ion-exchangeable layered silicate and ion-exchangeable layered silicate particles are shown in Tables 1-1 and 1-2.

[0176] (14.2) Chemical treatment of ion-exchangeable layered silicate particles (1) The procedure was the same as in Example a7 (7.2), except that 231.0 g of distilled water, 91.7 g of 96% sulfuric acid, and 44 g of ion-exchangeable layered silicate composite particles were used instead of the ion-exchangeable layered silicate particles described in (14.1) above. The reaction was stopped by pouring the reaction solution into 220 mL of distilled water, and the resulting slurry was filtered using an apparatus with an aspirator connected to a Nucche and suction bottle. The filtered cake was rinsed once with 440 g of distilled water. This filtered cake was then slurryed with 440 g of distilled water and washed again by filtration. 113.3 g of solids was obtained as the filtered cake.

[0177] (14.3) Chemical treatment of ion-exchangeable layered silicate particles (2) 106.5 g of the solid obtained from (14.2) above and 89.9 g of distilled water were added to a 500 mL flask and stirred. The slurry was heated to 40°C, and a 1.5 mol / L aqueous lithium hydroxide solution was added dropwise until the slurry pH reached 6.50. The amount of lithium hydroxide solution added was 16.1 g. The reaction was allowed to proceed for 100 minutes while maintaining the temperature at 40°C. At the end of the reaction, the pH of the slurry was 5.85. The reaction slurry was filtered using an apparatus with an aspirator connected to a Nutsch suction bottle and washed twice with 331 g of distilled water. The recovered cake was dried overnight at 110°C. Furthermore, before use as a catalyst component, the dried cake was crushed by lightly pressing it with a spatula, coarse material was removed by passing it through a 53 μm sieve, and the mixture was dried at 200°C under reduced pressure for 2 hours to obtain 20.3 g of ion-exchangeable layered silicate particles. The results of various analyses are shown in Tables 2-1 and 2-2.

[0178] (15) Comparative example a7 (15.1) Production of ion-exchange layered silicate particles As an ion-exchangeable layered silicate, we prepared granulated material (median diameter 15.2 μm) of a water slurry (main component: montmorillonite of the smectite group with a 2:1 layered structure) obtained by purifying clay minerals from Nakajo, Niigata Prefecture, manufactured by Mizusawa Chemical Industry Co., Ltd., using elutriation and centrifugation. The results of various analyses of these ion-exchangeable layered silicate particles are shown in Tables 1-1 and 1-2.

[0179] (15.2) Chemical treatment of ion-exchangeable layered silicate particles (1) The procedure was the same as in Example a7 (12.2), except that 650.0 g of distilled water, 83.3 g of 96% sulfuric acid, and 100.0 g of ion-exchangeable layered silicate composite particles were used instead of the ion-exchangeable layered silicate particles described in (15.1) above. The reaction was stopped by pouring the reaction solution into 500 mL of distilled water, and the resulting slurry was filtered using an apparatus with an aspirator connected to a Nucche and suction bottle. The filtered cake was rinsed once with 1000 g of distilled water. This filtered cake was then slurryed with 500 g of distilled water and filtered again for washing. This washing with distilled water was performed a total of three times. 286.6 g of solids was obtained as the filtered cake.

[0180] (15.3) Chemical treatment of ion-exchangeable layered silicate particles (2) The procedure was the same as in Example a7 (7.3), except that 132.1 g of distilled water, 52.2 g of lithium sulfate monohydrate, and 139.0 g of solids obtained from (15.2) above were used. The pH of the slurry at the end of the reaction was 2.49. The reaction slurry was filtered using an apparatus with an aspirator connected to a Nutsche suction bottle and washed four times with 970 g of distilled water. The recovered cake was dried overnight at 110°C. Furthermore, before use as a catalyst component, the dried cake was crushed by lightly pressing it with a spatula, coarse material was removed by passing it through a sieve with a mesh size of 53 μm, and the cake was dried at 200°C under reduced pressure for 2 hours to obtain 31.7 g of ion-exchangeable layered silicate particles. The results of various analyses of the ion-exchangeable layered silicate particles are shown in Tables 2-1 and 2-2.

[0181] [Table 1]

[0182] [Table 2]

[0183] [Table 3]

[0184] [Table 4]

[0185] 3. Production of catalysts for olefin polymerization (1) Example b1 10.0 g of ion-exchangeable layered silicate particles obtained in Example a1 and 66 mL of heptane were added to a 1000 mL flask and stirred. Then, 34 mL (24.5 mmol-Al) of triisobutylaluminum (TiBA) heptane solution was added and the mixture was stirred at room temperature for 1 hour. The mixture was then washed with heptane until the residual liquid volume was reduced to 1 / 100, and finally the slurry volume was adjusted to 50 mL. To this, 31 mL (12.2 mmol) of heptane solution of trin-normal octyl aluminum was added. In a separate flask (volume 200 mL), a solution was prepared by mixing 287 μmol of (r)-silacyclobutylenebis[2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-5,6-dimethyl-1-indenyl]zirconium dichloride (synthesis method: see Example 7 of Japanese Patent Publication No. 2015-193605) with 30 mL of toluene. This solution was added to the ion-exchangeable layered silicate particle slurry and stirred at 40°C for 60 minutes. After the above reaction, heptane was added to adjust the total volume to 300 mL, and the mixture was transferred to a 1 L stirring autoclave that had been thoroughly purged with nitrogen. The slurry temperature was set to 40°C, and propylene was supplied at a rate of 10 g / hour for 2 hours. After stopping the supply of propylene, the reaction was continued until the pressure reached 0.025 MPaG. Subsequently, the remaining monomers were purged and the polymerization catalyst slurry was recovered from the autoclave. The recovered polymerization catalyst slurry was allowed to stand, and the supernatant was removed. 8.5 mL (6 mmol) of heptane solution of triisobutylaluminum was added at room temperature, and then the mixture was dried under reduced pressure to obtain a catalyst for olefin polymerization. The preliminary polymerization ratio (catalyst yield for olefin polymerization ÷ (amount of ion-exchangeable layered silicate particles + metallocene complex) - 1) was 2.53 g / g-catalyst.

[0186] (2) Example b2 The procedure was the same as in Example b1, except that the ion-exchange layered silicate particles obtained in Example a2 were used. The pre-polymerization ratio was 2.48 g / g-catalyst.

[0187] (3) Example b3 The procedure was the same as in Example b1, except that the ion-exchange layered silicate particles obtained in Example a3 were used. The pre-polymerization ratio was 2.32 g / g-catalyst.

[0188] (4) Example b4 The procedure was the same as in Example b1, except that the ion-exchange layered silicate particles obtained in Example a4 were used. The pre-polymerization ratio was 2.41 g / g-catalyst.

[0189] (5) Example b5 The procedure was the same as in Example b1, except that the ion-exchange layered silicate particles obtained in Example a5 were used. The pre-polymerization ratio was 2.42 g / g-catalyst.

[0190] (6) Example b6 The procedure was the same as in Example b1, except that the ion-exchange layered silicate particles obtained in Example a6 were used. The pre-polymerization ratio was 2.44 g / g-catalyst.

[0191] (7) Example b7-1 10.0 g of ion-exchangeable layered silicate particles obtained in Example a7 and 66 mL of heptane were added to a 1000 mL flask and stirred. Then 34 mL (24.5 mmol-Al) of triisobutylaluminum (TiBA) heptane solution was added and stirred at room temperature for 1 hour. Afterward, the mixture was washed with heptane until the residual liquid volume was reduced to 1 / 100, and finally, the slurry volume was adjusted to 50 mL. In another flask (volume 200 mL), rac-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}hafnium dichloride (complex I, 54 μmol) (synthesis method: see Synthesis Example 1 in Japanese Patent Publication No. 2012-149160) was dissolved in toluene (9 mL) (Solution 1). Furthermore, in another flask (volume 200 mL), rac-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)indenyl}hafnium dichloride (complex II, 126 μmol) (synthesis method: see Example 7 in Japanese Patent Publication No. 11-240909) was dissolved in toluene (21 mL) (Solution 2). The 1L flask containing the slurry of ion-exchangeable layered silicate particles mentioned earlier was placed in an oil bath heated to 50°C. After 5 minutes, 0.3 mL (0.21 mmol-Al) of triisobutylaluminum heptane solution was added, followed by the addition of the above solution 1 (9 mL), and the mixture was stirred at 50°C for 60 minutes. Subsequently, 4.5 mL (1.76 mmol-Al) of trin-normal octyl aluminum (TnOA) heptane solution was added, followed by the addition of the above solution 2, and the mixture was stirred at 50°C for 20 minutes. After the above reaction, heptane was added to adjust the total volume to 250 mL, and the mixture was transferred to a 1 L stirring autoclave that had been thoroughly purged with nitrogen. The slurry temperature was set to 40°C, and propylene was supplied at a rate of 5 g / hour for 4 hours. After stopping the supply of propylene, stirring was continued for another hour. Subsequently, the remaining monomers were purged and the polymerization catalyst slurry was recovered from the autoclave. The recovered polymerization catalyst slurry was allowed to stand, and the supernatant was removed. 8.5 mL (6 mmol) of heptane solution of triisobutylaluminum was added at room temperature, and then the mixture was dried under reduced pressure to obtain a catalyst for olefin polymerization. The pre-polymerization ratio was 1.97 g / g-catalyst.

[0192] (8) Example b7-2 In Example b7-1, the catalyst for olefin polymerization was produced in the same manner as in Example b7-1, except that the amount of rac-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4-hydroazlenyl}hafnium dichloride (complex I) was changed to 90 μmol and the amount of toluene used to dissolve complex I was changed to 21 mL, and the triisobutylaluminum heptane solution in the "1 L flask containing the slurry of ion-exchangeable layered silicate particles was placed in an oil bath heated to 50°C, and after 5 minutes, the triisobutylaluminum heptane solution was changed to 0.5 mL. The prepolymerization ratio was 2.00 g / g-catalyst.

[0193] (9) Example b8 The procedure was carried out in the same manner as in Example b7-2, except that the ion-exchange layered silicate particles obtained in Example a8 were used. The pre-polymerization ratio was 1.95 g / g-catalyst.

[0194] (10) Comparative Example b1 The procedure was the same as in Example b1, except that the ion-exchange layered silicate particles obtained in Comparative Example a1 were used. The pre-polymerization ratio was 2.31 g / g-catalyst.

[0195] (11) Comparative example b2 The procedure was the same as in Example b1, except that the ion-exchange layered silicate particles obtained in Comparative Example a2 were used. The pre-polymerization ratio was 2.36 g / g-catalyst.

[0196] (12) Comparative Example b3 The procedure was the same as in Example b1, except that ion-exchange layered silicate particles obtained in Comparative Example a3 were used. The pre-polymerization ratio was 2.36 g / g-catalyst.

[0197] (13) Comparative example b4 The procedure was the same as in Example b1, except that the ion-exchange layered silicate particles obtained in Comparative Example a4 were used. The pre-polymerization ratio was 2.06 g / g-catalyst.

[0198] (14) Comparative Example b5 The procedure was the same as in Example b1, except that the ion-exchange layered silicate particles obtained in Comparative Example a5 were used. The pre-polymerization ratio was 2.38 g / g-catalyst.

[0199] (15) Comparative example b6 The procedure was carried out in the same manner as in Example b7-1, except that ion-exchange layered silicate particles obtained in Comparative Example a6 were used. The pre-polymerization ratio was 1.92 g / g-catalyst.

[0200] (16) Comparative Example b7-1 The procedure was carried out in the same manner as in Example b7-1, except that ion-exchange layered silicate particles obtained in Comparative Example a7 were used. The pre-polymerization ratio was 1.47 g / g-catalyst.

[0201] (17) Comparative Example b7-2 The procedure was carried out in the same manner as in Example b7-2, except that ion-exchange layered silicate particles obtained in Comparative Example a7 were used. The pre-polymerization ratio was 0.99 g / g-catalyst.

[0202] 4. Polymer production (1) Example P1 (Propylene homopolymerization) After thoroughly replacing the contents of a 3 L stirring autoclave with propylene, 5.6 mL (4.04 mmol) of heptane solution of triisobutylaluminum (TiBA) was added, followed by the introduction of 316 mL of hydrogen and 750 mL of liquid propylene, and the temperature was raised to 65°C. The olefin polymerization catalyst obtained in Example b1 above was slurryed with heptane, and 11.6 mg (sum of ion-exchangeable layered silicate particles and metallocene complex) was injected under pressure as a solid catalyst to start polymerization. After polymerization at 65°C for 1 hour, 5 mL of ethanol was added to stop the polymerization reaction. After purging the remaining propylene, the polymer was recovered and dried at 90°C for 1 hour. The results are shown in Table 3-1.

[0203] (2) Examples P2-P21 (Propylene homopolymerization) Polymerization was carried out in the same manner as in Example P1, except that the type of catalyst, catalyst amount, and hydrogenation amount for olefin polymerization were as described in Table 3-1. The results are shown in Table 3-1.

[0204] (3) Examples P22-27 (Propylene homopolymerization) Polymerization was carried out in the same manner as in Example P1, except that the polymerization temperature was set to 70°C, and the type, amount, and amount of olefin polymerization catalyst were as described in Table 3-2. The results are shown in Table 3-2.

[0205] (4) Comparative Examples P1-P17 (Propylene Homopolymerization) Polymerization was carried out in the same manner as in Example P1, except that the type of catalyst, catalyst amount, and hydrogenation amount for olefin polymerization were as described in Table 3-1. The results are shown in Table 3-1.

[0206] (5) Comparative Examples P18-23 (Propylene Homopolymerization) Polymerization was carried out in the same manner as in Example P22, except that the type of catalyst, catalyst amount, and hydrogenation amount for olefin polymerization were as described in Table 3-2. The results are shown in Table 3-2.

[0207] [Table 5]

[0208] [Table 6]

[0209] (4) Example P28 (2-stage polymerization: 1st stage - propylene homopolymerization, 2nd stage - ethylene-propylene copolymerization) After thoroughly replacing the contents of a 3 L stirring autoclave with propylene, 5.6 mL (4.04 mmol) of heptane solution of triisobutylaluminum (TiBA) was added, followed by the introduction of 528 mL of hydrogen and 750 mL of liquid propylene, and the temperature was raised to 65°C. The olefin polymerization catalyst obtained in Example b1 above was slurryed with heptane, and 7.1 mg (sum of ion-exchangeable layered silicate particles and metallocene complex) was injected as a solid catalyst to start polymerization. After polymerization at 65°C for 1 hour, the unreacted propylene remaining in the autoclave was purged. A mixed gas of ethylene and propylene was then supplied to the autoclave in a molar ratio of 1:1, and polymerization was carried out at 80°C and 1.9 MPaG for 0.50 hours. The reaction was stopped by injecting 5 ml of ethanol under pressure, and the remaining monomer was purged. The resulting polymer was dried at 90°C for 1 hour. The polymerization conditions and results are shown in Tables 4-1 and 4-2.

[0210] (5) Examples P29~45 (2-stage polymerization: 1st stage - propylene homopolymerization, 2nd stage - ethylene-propylene copolymerization) Polymerization was carried out in the same manner as in Example P28, except that the type of catalyst for olefin polymerization, the amount of catalyst, the amount of hydrogenation, and the copolymerization time of ethylene and propylene were as described in Table 4-1. The polymerization conditions and results are shown in Tables 4-1 and 4-2.

[0211] (6) Comparative Examples P24~33 (2-stage polymerization: 1st stage - propylene homopolymerization, 2nd stage - ethylene-propylene copolymerization) Polymerization was carried out in the same manner as in Example P28, except that the type of catalyst for olefin polymerization, the amount of catalyst, the amount of hydrogenation, and the copolymerization time of ethylene and propylene were as described in Table 4-1. The polymerization conditions and results are shown in Tables 4-1 and 4-2.

[0212] [Table 7]

[0213] [Table 8]

[0214] 5. Results and Discussion Figure 1 shows the sum of pore volumes from 5 nm to 300 nm measured by mercury intrusion for ion-exchange layered silicate particles of Examples a1 to a6 and Comparative Examples a1 to a5, and the BET specific surface area m² measured by nitrogen adsorption / desorption. 2 This figure plots the values ​​against / g. From Figure 1, it can be seen that the ion-exchangeable layered silicate particles of the example have a high specific surface area and a large pore volume in the 5nm to 300nm range. It can be seen that the example achieves a different relationship between pore volume and specific surface area compared to the conventional comparative example. Figure 2 shows the polymerization activity of propylene homopolymerization using olefin polymerization catalysts in Examples b1-b6 and Comparative Examples b1-b5, plotted against the MFR of the obtained polymers. From Figure 2, it can be seen that the catalysts using ion-exchangeable layered silicate particles in the Examples show higher catalytic activity relative to the comparative examples' catalysts. In other words, when compared at similar MFRs, the catalysts in the Examples show higher catalytic activity than the catalysts in the comparative examples. Figure 3 shows the results of two-stage polymerization of propylene-ethylene and propylene using olefin polymerization catalysts in Examples b1-b6 and Comparative Examples b1-b3,b5. The number of fisheyes in the polymer-processed sheets is plotted against the molecular weight ratio of the obtained polymers (the molecular weight of the second-stage polymer divided by the molecular weight of the first-stage polymer). From Figure 3, it can be seen that using the olefin polymerization catalysts of Examples b1-b6 sufficiently suppresses the number of fisheyes in relation to the molecular weight ratio. As described above, the ion-exchangeable layered silicate particles obtained by the manufacturing method of this disclosure are more active than conventional catalysts for olefin polymerization and can be used to produce olefin (co)polymers with a sufficiently suppressed fish-eye number.

[0215] The present invention is not limited to the embodiments detailed above, and various modifications or changes are possible within the scope of the claims of the present invention. [Industrial applicability]

[0216] According to the present invention, it is possible to provide a method for producing ion-exchangeable layered silicate particles having a novel pore structure that improves catalytic activity and polymer quality, a method for producing catalyst components for olefin polymerization, a method for producing catalysts for olefin polymerization, and a method for producing olefin polymers, all of which have high industrial applicability.

Claims

1. A method for producing ion-exchangeable layered silicate particles, comprising the following steps 1, 2, and 3. Step 1: This step involves preparing a slurry containing an ion-exchangeable layered silicate, a solvent, and a compound [I] containing aluminum ions. Of the 100% by mass of solid components contained in the slurry, compound [I] is 8% by mass to 80% by mass. Note that compound [I] may be one or more types. Step 2: This step involves granulating the slurry prepared in Step 1 by spray drying to obtain ion-exchangeable layered silicate composite particles. Step 3: This step involves eluting at least a portion of the metal components contained in the ion-exchangeable layered silicate composite particles obtained in Step 2.

2. A method for producing ion-exchangeable layered silicate particles according to claim 1, wherein when the amount of aluminum atoms (mol / g) contained in the ion-exchangeable layered silicate composite particles is [Alb] and the amount of magnesium atoms (mol / g) is [Mgb], the [Alb / Mgb] (molar ratio) is 4.0 or more and 45.0 or less.

3. A method for producing ion-exchangeable layered silicate particles according to claim 1, wherein when the amount of aluminum atoms (mol / g) contained in the ion-exchangeable layered silicate is [Al] and the amount of magnesium atoms (mol / g) is [Mga], the molar ratio [Al] / [Mga] is 0.3 or more and less than 3.

9.

4. The method for producing ion-exchangeable layered silicate particles according to claim 1, wherein the compound [I] is a particle with an average particle size of 0.3 μm to 100.0 μm.

5. The method for producing ion-exchangeable layered silicate particles according to claim 1, wherein the compound [I] is a hydroxide-containing salt.

6. A method for producing ion-exchangeable layered silicate particles according to claim 1, characterized in that the compound [I] is aluminum hydroxide.

7. The method for producing ion-exchangeable layered silicate particles according to claim 1, wherein step 3 involves contacting the ion-exchangeable layered silicate composite particles obtained in step 2 with acids.

8. A method for producing a catalyst component for olefin polymerization, using ion-exchangeable layered silicate particles obtained by the manufacturing method described in any one of claims 1 to 7.

9. Ion-exchangeable layered silicate particles obtained by the manufacturing method described in any one of claims 1 to 7, A method for producing an olefin polymerization catalyst, comprising the step of contacting the following components [B] and [C]. Component [B]: Transition metal compound Component [C]: Organoaluminum compound

10. A method for producing an olefin polymer, comprising carrying out olefin polymerization in the presence of an olefin polymerization catalyst obtained by the production method described in claim 9.

Images