Title of the invention: Method for producing 4-methyl-1-pentene polymer particles and 4-methyl-1-pentene resin
Technical field
[0001]
　The present invention relates to a method for producing 4-methyl-1-pentene polymer particles and 4-methyl-1-pentene resin.
Background technology
[0002]
　The 4-methyl-1-pentene / α-olefin copolymer containing 4-methyl-1-pentene as a main constituent monomer has excellent heat resistance, mold release property, and chemical resistance, and is widely used in various applications. Has been done. For example, the film made of the copolymer is used for FPC release film, composite material molding, release film, etc. by taking advantage of its features such as good mold release property, or chemical resistance, water resistance and transparency. It is used in laboratory equipment and mandrel for manufacturing rubber hoses by taking advantage of such features.
[0003]
　On the other hand, a molded product made of a conventional resin composition containing a 4-methyl-1-pentene polymer may be required to have a high melting point but to have lower rigidity and flexibility. For example, the use of transfer release sheets in the production of synthetic leather may require both a high melting point to withstand the curing temperature and flexibility to prevent cracking during deep embossing. Patent Documents 1 and 2 disclose 4-methyl-1-pentene-based polymers having high stereoregularity, high heat of fusion, and excellent heat resistance.
[0004]
　Further, the 4-methyl-1-pentene copolymer can be produced by a polymerization method such as a solution polymerization method, a slurry polymerization method, or a gas phase polymerization method. In the case of solution polymerization, the reaction solvent needs to be heat-separated in order to recover the 4-methyl-1-pentene copolymer from the polymerization solution after the polymerization, but in the case of slurry polymerization, the solid is solid-liquid separated from the slurry. Since the 4-methyl-1-pentene copolymer can be recovered only by itself, the slurry polymerization method is a cost-effective production method.
[0005]
　Patent Documents 3 to 5 disclose a method of copolymerizing 4-methyl-1-pentene with another α-olefin in two steps using a Ziegler catalyst. Patent Document 6 discloses a method of copolymerizing 4-methyl-1-pentene and another α-olefin while changing their ratios using a Ziegler catalyst.
[0006]
　Further, Patent Document 1 discloses a 4-methyl-1-pentene polymer having high stereoregularity and a high calorific value for melting obtained by using a specific metallocene catalyst, and Patent Document 2 discloses the same. A 4-methyl-1-pentene polymer having high stereoregularity and a wide molecular weight distribution has been disclosed using the metallocene catalyst of.
Prior art literature
Patent documents
[0007]
Patent Document 1: International Publication No. 2014/050817
Patent Document 2: International Publication No. 2017/150265
Patent Document 3: Japanese Patent Application
Laid-Open No. 63-63707 Patent Document 4: Japanese Patent Application Laid-Open No. 05-271341
Patent Document 5: Special Publication Kaihei 06-184240
Patent Document 6: JP-A-2006-291020
Outline of the invention
Problems to be solved by the invention
[0008]
　As described above, the 4-methyl-1-pentene polymer and the molded product described in Patent Documents 1 and 2 have high stereoregularity, high heat of fusion, and excellent heat resistance. .. The present inventors have studied a 4-methyl-1-pentene polymer capable of obtaining a molded product having low rigidity, that is, excellent flexibility, without significantly impairing this high stereoregularity and excellent heat resistance. did.
[0009]
　That is, the first object of the present invention is to reduce the rigidity of the 4-methyl-1-pentene polymer without impairing the properties such as high stereoregularity and excellent heat resistance, that is, to improve the flexibility. Is to let.
[0010]
　Further, according to the study by the present inventors, in the method for producing a 4-methyl-1-pentene resin by slurry polymerization, for example, the content of a structural unit derived from a comonomer other than 4-methyl-1-pentene is determined. If it is high, the amount of the solvent-soluble portion of the polymer becomes large, and the solid-liquid separability of the obtained slurry is not good.
[0011]
　That is, the second problem of the present invention is a method for producing a 4-methyl-1-pentene resin by slurry polymerization, in which the obtained slurry has good solid-liquid separability, and the copolymer component comonomer contained therein It is to provide a method which can select a wider range of copolymerization ratios.
Means to solve problems
[0012]
　The present inventors have conducted diligent studies to solve the first problem. As a result, they have found that the above-mentioned problems can be solved by 4-methyl-1-pentene-based polymer particles having a specific composition and a specific property, and have completed the first invention.
[0013]
　The present inventors have studied to solve the above-mentioned second problem. As a result, they have found that the above-mentioned problems can be solved by the method for producing 4-methyl-1-pentene resin (X) described below, and have completed the second invention.
[0014]
　The first and second inventions relate to, for example, the following [1] to [16].
[0015]
　[1] 4-Methyl-1-pentene polymer particles (X) satisfying the following requirements (Xa), (Xb) and (Xc).
[0016]
　(X-a) The content of the structural unit derived from 4-methyl-1-pentene of the 4-methyl-1-pentene polymer constituting the particle (X) is 30.0 to 99.7 mol%. Yes, the content of the structural unit derived from ethylene and at least one olefin selected from α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 0.3 to 70.0 mol%. Is.
[0017]
　(Xb) When measured by a cross fractionation chromatograph (CFC) using an infrared spectrophotometer in the detection unit, at least one peak A of the amount of eluted components is present in the range of 100 to 140 ° C. In addition, at least one peak B of the amount of eluted components is present below 100 ° C.
[0018]
　(Xc) 13 The mesodiad fraction (m) measured by C-NMR is in the range of 95.0 to 100%.
[0019]
　[2] 4-Methyl-1-pentene polymer (x1) 10.0 to 95.0 parts by mass that satisfies the following requirement (x1-a) and 4-methyl-1- that satisfies the following requirement (x2-a). The above-mentioned [, which contains 5.0 to 90.0 parts by mass of the penten copolymer (x2) (however, the total amount of the polymer (x1) and the copolymer (x2) is 100 parts by mass). 1]. 4-Methyl-1-pentene polymer particles (X).
[0020]
　The content of the structural unit derived from (x1-a) 4-methyl-1-pentene is 80.0 to 100 mol%, and ethylene and α-olefin having 3 to 20 carbon atoms (4-methyl-1-pentene). The content of the structural unit derived from at least one olefin selected from (excluding) is 0 to 20.0 mol%.
[0021]
　The content of the structural unit derived from (x2-a) 4-methyl-1-pentene is 20.0 to 98.0 mol%, and ethylene and α-olefin having 3 to 20 carbon atoms (4-methyl-1). -The content of the structural unit derived from at least one olefin selected from (excluding pentene) is 2.0 to 80.0 mol%, but ethylene and 3 to 3 carbon atoms in the polymer (x1). It is greater than the content of the building blocks derived from at least one olefin selected from 20 α-olefins (excluding 4-methyl-1-pentene).
[0022]
　[3] The ultimate viscosity [η] of the polymer (x1) measured in decalin at 135 ° C. is in the range of 0.5 to 20 dl / g, and the melting point (Tm) measured by DSC is 210 to 260 ° C. The ultimate viscosity [η] of the copolymer (x2) measured in decalin at 135 ° C. is in the range of 0.5 to 20 dl / g, and the melting point (Tm) measured by DSC is 220. The 4-methyl-1-pentene polymer particle (X) according to the above [2], which is in the range of less than ° C. or does not show a peak indicating a melting point in DSC measurement.
[0023]
　[4] 4-Methyl-1 according to any one of the above [1] to [3], wherein the ultimate viscosity [η] measured in decalin at 135 ° C. is in the range of 0.5 to 10.0 dl / g. -Pentene-based polymer particles (X).
[0024]
　[5] The 4-methyl-1- according to any one of the above [1] to [4], wherein the mesodiad fraction (m) is in the range of 98.0 to 100% in the requirement (X-c). Pentene-based polymer particles (X).
[0025]
　[6] A resin made of the 4-methyl-1-pentene polymer particles (X) according to any one of the above [1] to [5].
[0026]
　[7] A resin composition containing the resin according to the above [6].
[0027]
　[8] The 4-methyl-1-pentene polymer particles (X) according to any one of [1] to [5], the resin according to the above [6], or the resin according to the above [7]. A molded product molded from the composition.
[0028]
　[9] The 4-methyl-1-pentene polymer (x1) satisfying the following requirement (x1-a) is produced by slurry polymerization using a metallocene catalyst (1) and obtained in the above step (1). In the presence of the polymer (x1), a 4-methyl-1-pentene copolymer (x2) satisfying the following requirement (x2-a) is obtained from the polymer (x1) and the copolymer (x2). The step (2) of producing by slurry polymerization using a metallocene catalyst in the range where the amount of the copolymer (x2) is 5.0 to 90.0 parts by mass when the total amount is 100 parts by mass. A method for producing a 4-methyl-1-pentene resin (X).
[0029]
　The content of the structural unit derived from (x1-a) 4-methyl-1-pentene is 80.0 to 100 mol%, and ethylene and α-olefin having 3 to 20 carbon atoms (4-methyl-1-pentene). The content of the structural unit derived from at least one olefin selected from (excluding) is 0 to 20.0 mol%.
[0030]
　The content of the structural unit derived from (x2-a) 4-methyl-1-pentene is 20.0 to 98.0 mol%, and ethylene and α-olefin having 3 to 20 carbon atoms (4-methyl-1). -The content of the structural unit derived from at least one olefin selected from (excluding pentene) is 2.0 to 80.0 mol%, but ethylene and 3 to 3 carbon atoms in the polymer (x1). It is greater than the content of the building blocks derived from at least one olefin selected from 20 α-olefins (excluding 4-methyl-1-pentene).
[0031]
　[10] The ultimate viscosity [η] of the polymer (x1) measured in decalin at 135 ° C. is in the range of 0.5 to 20 dl / g, and the melting point (Tm) measured by DSC is 210 to 260 ° C. The ultimate viscosity [η] of the copolymer (x2) measured in decalin at 135 ° C. is in the range of 0.5 to 20 dl / g, and the melting point (Tm) measured by DSC is 220. The method for producing a 4-methyl-1-pentene resin (X) according to the above [9], wherein the temperature is in the range of less than ° C. or the peak indicating the melting point does not appear in the DSC measurement.
[0032]
　[11] The 4-methyl-1-pentene resin according to the above [9] or [10], wherein the polymerization temperatures in the step (1) and the step (2) are independently in the range of 0 to 100 ° C. The manufacturing method of (X).
[0033]
　[12] The above-mentioned [9] to [11], wherein the metallocene catalyst is a particulate catalyst containing the metallocene compound (A) and having a D50 in the volume statistical value in the range of 1 to 500 μm. A method for producing a 4-methyl-1-pentene resin (X).
[0034]
　[13] The metallocene catalyst contains a metallocene compound (A) and a carrier (B), the carrier (B) contains 20% by mass or more of aluminum atoms, and D50 in the volume statistical value is in the range of 1 to 500 μm. The method for producing a 4-methyl-1-pentene resin (X) according to any one of [9] to [12] above, which is a particulate carrier.
[0035]
　[14] The 4-methyl-1-pentene resin (X) obtained by the method for producing the 4-methyl-1-pentene resin (X) according to any one of [9] to [13] above.
[0036]
　[15] A resin composition containing the 4-methyl-1-pentene resin (X) according to the above [14].
[0037]
　[16] A molded product molded from the 4-methyl-1-pentene resin (X) according to the above [14] or the resin composition according to the above [7].
The invention's effect
[0038]
　According to the first invention, a 4-methyl-1-pentene polymer particles, a resin, and a resin composition capable of obtaining a molded product having low rigidity while maintaining high stereoregularity and excellent heat resistance. And a molded body can be provided.
[0039]
　According to the second invention, in the method for producing a 4-methyl-1-pentene resin by slurry polymerization, the obtained slurry has good solid-liquid separability, and the 4-methyl-1-pentene resin (4-methyl-1-pentene resin) The manufacturing method of X) can be provided. In particular, 4-methyl-1-pentene in a region containing a copolymer component having a high content of a constituent unit derived from a comonomer other than 4-methyl-1-pentene and in which slurry polymerization was difficult with the conventional production method. It is possible to provide a method for producing a 4-methyl-1-pentene resin, which can also produce a based resin.
A brief description of the drawing
[0040]
FIG. 1 is a diagram in which the tensile elastic modulus (MPa) is plotted against a melting point (° C.) for the polymers obtained in Examples and Comparative Examples.
FIG. 2 is a transmission electron microscope (TEM) image of Example 1A.
FIG. 3 is a transmission electron microscope (TEM) image of Example 2A.
FIG. 4 is a transmission electron microscope (TEM) image of Example 3A.
FIG. 5 is a transmission electron microscope (TEM) image in Comparative Example 8A.
Mode for carrying out the invention
[0041]
　Hereinafter, specific embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and is carried out with appropriate modifications within the scope of the object of the present invention. be able to.
[0042]
　As used herein, the term "polymer" is used to include homopolymers and copolymers. Therefore, for example, the 4-methyl-1-pentene polymer (x1) described later may be a 4-methyl-1-pentene homopolymer or a 4-methyl-1-pentene copolymer. Good. Similarly, the term "polymerization" is used to include homopolymerization and copolymerization.
[0043]
　 [4-Methyl-1-pentene-based polymer particles (X)]
　The 4-methyl-1-pentene-based polymer particles (X) of the first invention (hereinafter, also referred to as "the present invention 1") (simply "particles"). (Also referred to as “X)”) satisfies the requirements (Xa), (Xb) and (Xc) described below.
[0044]
　
　(X-a) The content of the structural unit derived from 4-methyl-1-pentene of the 4-methyl-1-pentene polymer constituting the particle (X) is 30. The content of the structural unit derived from at least one olefin selected from ethylene and α-olefin (excluding 4-methyl-1-pentene) having 3 to 20 carbon atoms, which is 0 to 99.7 mol%, is 0. It is 3 to 70.0 mol%.
[0045]
　The content of the structural unit derived from 4-methyl-1-pentene is preferably 40.0 to 99.5 mol%, more preferably 50.0 to 99.0 mol%, still more preferably 70.0 to 70.0 to 99.0 mol%. It is 97.0 mol%, 75.0-96.0 mol%, or 80.0-95.0 mol%. The content of the structural unit derived from ethylene and at least one olefin selected from α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is preferably 0.5 to 60. 0 mol%, more preferably 1.0 to 50.0 mol%, even more preferably 3.0 to 30.0 mol%, 4.0 to 25.0 mol%, or 5.0 to 20.0 mol. %.
[0046]
　Examples of the olefin include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene and 1-eicosen. Can be mentioned. The olefin can be appropriately selected depending on the use of the particles (X) and the required physical characteristics. For example, as the olefin, an α-olefin having 8 to 18 carbon atoms is preferable from the viewpoint of imparting an appropriate elastic modulus, excellent flexibility, flexibility and stretchability, and 1-octene. At least one selected from 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene and 1-octadecene is more preferable. When the carbon number of the olefin is in the above range, the stretchability of the resin or the resin composition becomes better, and as a result, the appearance due to cracks or cracks at the edges when the resin or resin composition is released from the roll or mold during molding. Defects tend to be less likely to occur.
[0047]
　The 4-methyl-1-pentene polymer is a structural unit other than the structural unit derived from 4-methyl-1-pentene and the structural unit derived from the olefin, as long as the effects of the present invention are not impaired (hereinafter, "" It may also have "other structural units"). The content of the other structural units is, for example, 0 to 10.0 mol%.
[0048]
　Examples of the monomer leading to other constituent units include cyclic olefins, aromatic vinyl compounds, conjugated diene, non-conjugated polyenes, functional vinyl compounds, hydroxyl group-containing olefins, and halogenated olefins. Examples of the cyclic olefin, aromatic vinyl compound, conjugated diene, non-conjugated polyene, functional vinyl compound, hydroxyl group-containing olefin and halogenated olefin are described in paragraphs [0035] to [0041] of JP2013-169685A. Compounds can be used.
[0049]
　When the 4-methyl-1-pentene polymer has other structural units, only one type of other structural units may be contained, or two or more types may be contained.
[0050]
　
　(X-b) When measured with a cross-separation chromatograph device (CFC) using an infrared spectrophotometer for the detection unit, the peak amount of eluted components is in the range of 100 to 140 ° C. At least one A is present, and at least one peak B of the amount of eluted components is present in the range of less than 100 ° C., preferably 0 ° C. or higher and lower than 100 ° C. The peak A may be a single peak or a plurality of peaks. Further, the peak B may be a single peak or a plurality of peaks.
[0051]
　By using the polymer particles in which the peaks A and B of the elution component amounts are present in the above range, it is excellent in that a molded product having low rigidity (high flexibility) can be obtained while maintaining high heat resistance.
[0052]
　For example, in the method for producing particles (X) described later, peak A is derived from the polymer (x1) produced in step (1), and peak B is derived from the copolymer (x2) produced in step (2). To do.
[0053]
　Further, in the CFC measurement, the cumulative mass percentage of the components eluted at 0 ° C. or lower is preferably less than 2.0% by mass, more preferably 1.5% by mass or less, still more preferably 1.0% by mass or less. , Particularly preferably 0.5% by mass or less.
[0054]
　The small cumulative mass percentage of the components eluted at 0 ° C. or lower indicates that the amount of the low molecular weight polymer contained in the polymer particles (X) is small. When the cumulative mass percentage is within the above range, it is possible to suppress the outflow of low molecular weight components that are contaminating components from the molded product obtained from the resin composition containing the polymer, so that a die at the time of molding or the like can be suppressed. It is possible to effectively suppress contamination of the molding machine, discoloration of the obtained molded product, contamination of the surface of the molded product, and contamination of the contents. Further, when used as a release film or a protective film, it is expected to reduce the transition from the film to the base material. In the present invention, the cumulative mass percentage can be adjusted according to the type of metallocene catalyst described later.
[0055]
　
　(X-c) 13 The mesodiad fraction (m) measured by C-NMR is in the range of 95.0 to 100%. The mesodiad fraction (m) is preferably in the range of 96.0 to 100%, more preferably 97.0 to 100%, even more preferably 98.0 to 100%, and particularly preferably 98.5 to 100%. .. The upper limit is preferably 100%, but can also be 99.9%. Within this range, fish eyes and poor appearance due to eye tar during molding of the particles (X) and the resin or resin composition obtained from the particles (X) are unlikely to occur. It is presumed that this is because the uniformity of the composition distribution is improved by narrowing the melting point distribution.
[0056]
　 The
　particle (X) has an intrinsic viscosity [η] measured in decalin at 135 ° C., preferably 0.5 to 10.0 dl / g, more preferably 0.5 to 5.0 dl / g. g, more preferably in the range of 1.0 to 5.0 dl / g.
[0057]
　The ultimate viscosity [η] of the particles (X) can be adjusted, for example, by the value of [η] of each of the polymer (x1) and the copolymer (x2) described later, and the content ratio.
[0058]
　The particle size (D50) of the particles (X) is usually in the range of 10 to 2000 μm, preferably 30 to 1000 μm, more preferably 50 to 500 μm, and even more preferably 70 to 300 μm. The particle size (D50) of the particles (X) is preferably in the range of 30 to 1800 μm, more preferably 50 to 1500 μm, still more preferably 70 to 1200 μm in one embodiment.
[0059]
　Specifically, the particle size (D50) is a value measured using a laser diffraction / scattering device (LS13320) manufactured by Beckman Coulter, and decan can be used as the dispersion medium of the sample.
[0060]
　The bulk density of the particles (X) is usually 0.1 to 1.0 g / cm 3 , preferably 0.2 to 0.8 g / cm 3 , and more preferably 0.3 to 0.5 g / cm 3 . In range.
[0061]
　The particles (X) of the present invention 1 refer to a state in which the shape of the polymer particles obtained by producing the polymer in the polymerization reaction tank is maintained, and are usually obtained by slurry polymerization described later. It is a polymer particle. More specifically, it refers to polymer particles that have not been treated at a high temperature that cannot retain the shape of the polymer particles. That is, for example, the treatment was performed at a temperature of 260 ° C. or higher, preferably 250 ° C. or higher, more preferably 240 ° C. or higher, further preferably 200 ° C. or higher, particularly preferably 150 ° C. or higher, and particularly preferably 100 ° C. or higher. Means polymer particles without temperature. That is, for example, the resin pellet obtained by melt-kneading the polymer particles does not correspond to the particles (X) of the present invention 1. Further, for the purpose of drying the solvent or the like after the completion of the polymerization reaction, the polymer particles may be heated at a temperature lower than the above temperature while maintaining the shape of the polymer particles.
[0062]
　Details of the measurement conditions for the above requirements will be described in the Examples column.
[0063]
　 The
　particles (X) are 4-methyl-1-pentene polymers (x1) that satisfy the following requirements (x1-a). It is preferable to contain 10.0 to 95.0 parts by mass and 5.0 to 90.0 parts by mass of a 4-methyl-1-pentene copolymer (x2) satisfying the following requirement (x2-a). However, the total amount of the polymer (x1) and the copolymer (x2) is 100 parts by mass. The particles (X) usually contain a polymer (x1) and a copolymer (x2) in the same particles.
[0064]
　The amount of the polymer (x1) is preferably 20.0 to 90.0 parts by mass, more preferably 30.0 to 85.0 parts by mass. The amount of the copolymer (x2) is preferably 10.0 to 80.0 parts by mass, and more preferably 15.0 to 70.0 parts by mass. However, the total amount of the polymer (x1) and the copolymer (x2) is 100 parts by mass.
[0065]
　 <4-Methyl-1-pentene polymer (x1)> The
　4-methyl-1-pentene polymer (x1) (also simply referred to as "polymer (x1)") satisfies the following requirement (x1-a).
[0066]
　The content of the structural unit derived from (x1-a) 4-methyl-1-pentene is 80.0 to 100 mol%, preferably 85.0 to 100 mol%, and more preferably 90.0 to 100 mol. %, More preferably 95.0 to 100 mol%, and at least one olefin selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) (hereinafter, "comonomer 1"). The content of the structural unit derived from (also referred to as) is 0 to 20.0 mol%, preferably 0 to 15.0 mol%, more preferably 0 to 10.0 mol%, still more preferably 0 to 5. It is 0.0 mol%.
[0067]
　As for the content of the structural unit, the total repetitive structural unit amount is 100 mol%.
[0068]
　Examples of comonomer 1 include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-eicosen. Can be mentioned. The comonomer 1 can be appropriately selected depending on the use of the resin (X) and the required physical characteristics. For example, as the comonomer 1, an α-olefin having 8 to 18 carbon atoms is preferable from the viewpoint of imparting an appropriate elastic modulus, excellent flexibility, flexibility and stretchability, and 1-octene. At least one selected from 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene and 1-octadecene is more preferable. When the carbon number of the comonomer 1 is in the above range, the stretchability of the resin or the resin composition becomes better, and as a result, cracks or edge cracks occur during mold release from the roll or mold during molding. Appearance defects tend to be less likely to occur.
[0069]
　When the polymer (x1) has a structural unit derived from the comonomer 1, the structural unit may contain only one type, or may contain two or more types.
[0070]
　The polymer (x1) is a structural unit derived from other monomer 1 other than 4-methyl-1-pentene and comonomer 1 (hereinafter, also referred to as “other structural unit 1”” as long as the effect of the present invention is not impaired. ) May have. The content of the other structural unit 1 is, for example, 0 to 10.0 mol%.
[0071]
　Examples of the other monomer 1 include cyclic olefins, aromatic vinyl compounds, conjugated diene, non-conjugated polyenes, functional vinyl compounds, hydroxyl group-containing olefins, and halogenated olefins. Examples of the cyclic olefin, aromatic vinyl compound, conjugated diene, non-conjugated polyene, functional vinyl compound, hydroxyl group-containing olefin and halogenated olefin are described in paragraphs [0035] to [0041] of JP2013-169685A. Compounds can be used.
[0072]
　When the polymer (x1) has another structural unit 1, the other structural unit 1 may contain only one type, or may contain two or more types.
[0073]
　It is preferable that the 4-methyl-1-pentene polymer (x1) further satisfies the requirement of at least one physical characteristic selected from the physical characteristics ([η], melting point) described below.
[0074]
　The polymer (x1) has an intrinsic viscosity [η] measured in decalin at 135 ° C., preferably in the range of 0.5 to 20 dl / g, more preferably 0.5 to 5.0 dl / g.
[0075]
　The polymer (x1) has a melting point (Tm) measured by a differential scanning calorimetry (DSC), preferably in the range of 210 to 260 ° C, more preferably 220 to 260 ° C, and even more preferably 225 to 260 ° C. When the melting point of the polymer (x1) is in the above range, the obtained particles (X) are excellent in heat resistance. Further, when slurry polymerization is carried out in the second invention described later, when the melting point of the polymer (x1) is within the above range, the slurry properties are excellent and the solid-liquid separability is excellent, and the obtained resin (X) It tends to have excellent heat resistance.
[0076]
　Details of the above configuration, measurement method of physical properties, etc. will be described in the Example column. When slurry polymerization is carried out in the second invention described later, the above constitution, physical properties and the like are for the polymer particles obtained by filtering the slurry.
[0077]
　 <4-Methyl-1-pentene copolymer (x2)> The
　4-methyl-1-pentene copolymer (x2) (also simply referred to as "copolymer (x2)") has the following requirements (x2-a). Meet.
[0078]
　The content of the structural unit derived from (x2-a) 4-methyl-1-pentene is 20.0 to 98.0 mol%, preferably 25.0 to 95.0 mol%, and more preferably 30. 0-95.0 mol%, more preferably 30.0-92.0 mol%, particularly preferably 30.0-90.0 mol%, ethylene and α-olefin (4-] having 3 to 20 carbon atoms. The content of the structural unit derived from at least one olefin (hereinafter, also referred to as “commonomer 2”) selected from methyl-1-pentene) is 2.0 to 80.0 mol%, preferably 5. It is 0 to 75.0 mol%, more preferably 5.0 to 70.0 mol%, still more preferably 8.0 to 70.0 mol%, and particularly preferably 10.0 to 70.0 mol%. However, the content (mol%) of the structural unit derived from the comonomer 2 in the copolymer (x2) is larger than the content (mol%) of the structural unit derived from the comonomer 1 in the polymer (x1).
[0079]
　As for the content of the structural unit, the total repetitive structural unit amount is 100 mol%.
[0080]
　Examples of the comonomer 2 include the olefin exemplified as the comonomer 1 in the requirement (x1-a). The comonomer 2 can be appropriately selected depending on the use and required physical properties of the particles (X) or the resin (X) obtained by the second production method of the present invention described later. For example, as the comonomer 2, an α-olefin having 8 to 18 carbon atoms is preferable from the viewpoint of imparting an appropriate elastic modulus and excellent flexibility, flexibility and stretchability, and 1-octene, At least one selected from 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene and 1-octadecene is more preferable. When the carbon number of the comonomer 2 is in the above range, the stretchability of the resin or the resin composition becomes better, and as a result, cracks or edge cracks occur when the resin or resin composition is released from the roll or mold during molding. Appearance defects tend to be less likely to occur.
[0081]
　In the copolymer (x2), only one type of structural unit derived from the comonomer 2 may be contained, or two or more types may be contained. Further, when the polymer (x1) has a structural unit derived from the comonomer 1, the comonomer 1 of the polymer (x1) and the comonomer 2 of the copolymer (x2) may be the same or different.
[0082]
　The copolymer (x2) is a structural unit derived from other monomer 2 other than 4-methyl-1-pentene and comonomer 2 (hereinafter, also referred to as “other structural unit 2”” as long as the effect of the present invention is not impaired. May have). The content of the other structural unit 2 is, for example, 0 to 10.0 mol%.
[0083]
　Examples of the other monomer 2 include compounds exemplified as the other monomer 1 in the polymer (x1). When the copolymer (x2) has another structural unit 2, the other structural unit 2 may contain only one type, or may contain two or more types.
[0084]
　It is preferable that the 4-methyl-1-pentene copolymer (x2) further satisfies the requirement of at least one physical characteristic selected from the physical characteristics ([η], melting point) described below.
[0085]
　The copolymer (x2) has an intrinsic viscosity [η] measured in decalin at 135 ° C., preferably in the range of 0.5 to 20 dl / g, more preferably 1.0 to 7.0 dl / g.
[0086]
　The copolymer (x2) has a melting point (Tm) measured by a differential scanning calorimeter (DSC) preferably in the range of less than 220 ° C., or a peak indicating the melting point does not appear in the DSC measurement. More preferably, the melting point (Tm) is in the range of less than 210 ° C., or no peak indicating the melting point appears in the DSC measurement. More preferably, the melting point (Tm) is in the range of 120 to 200 ° C., or no peak indicating the melting point appears in the DSC measurement. Particularly preferably, the melting point (Tm) is in the range of 130 to 180 ° C., or no peak indicating the melting point appears in the DSC measurement. Such an embodiment is preferable in that a 4-methyl-1-pentene polymer having a high content of structural units derived from a comonomer can be obtained.
[0087]
　Details of the above configuration, measurement method of physical properties, etc. will be described in the Example column. When the slurry polymerization is carried out in the second invention below, the above constitution, physical properties and the like are for the polymer particles obtained by filtering the slurry. The content, [η] and Tm of the constituent units of the copolymer (x2) are those of the polymer (x1) and the particles (X) (or the resin (X) obtained by the second production method of the present invention below). It can be calculated from the measurement result and the mass ratio of the polymer (x1) and the copolymer (x2).
[0088]
　 [Method for Producing 4-Methyl-1-pentene Polymer Resin (X)]
　The second 4-methyl-1-pentene resin (X) of the present invention (hereinafter, also referred to as "the present invention 2") (simply "" The method for producing the resin (X) ”is a step (1) of producing a 4-methyl-1-pentene polymer (x1) satisfying the requirement (x1-a) by slurry polymerization using a metallocene catalyst. In the presence of the polymer (x1) obtained in the step (1), a 4-methyl-1-pentene copolymer (x2) satisfying the requirement (x2-a) was added to the polymer (x1) and the polymer (x1). When the total amount of the copolymer (x2) is 100 parts by mass, the amount of the copolymer (x2) is in the range of 5.0 to 90.0 parts by mass by slurry polymerization using a metallocene catalyst. It has a manufacturing step (2).
[0089]
　The first 4-methyl-1-pentene-based polymer particles (X) of the present invention include, for example, the step (1) of producing the polymer (x1) by slurry polymerization using a metallocene catalyst. In the presence of the polymer (x1) obtained in the step (1), the total amount of the polymer (x2), the polymer (x1) and the copolymer (x2) is 100 parts by mass. In the case where the amount of the copolymer (x2) is in the range of 5.0 to 90.0 parts by mass, preferably by a production method having a step (2) of producing by slurry polymerization using a metallocene catalyst. Can be manufactured.
[0090]
　That is, the production method includes steps (1) and (2) having different polymerization conditions, but the two-stage polymerization of steps (1) and (2) may be used, and in addition to steps (1) and (2). The polymerization may be a three-stage or higher type including further steps.
[0091]
　 In
　step (1), a 4-methyl-1-pentene polymer (x1) satisfying the above requirement (x1-a) is produced by slurry polymerization. In step (1), polymerization is usually carried out using a metallocene catalyst.
[0092]
　The polymer (x1) is described in detail in the <4-Methyl-1-pentene polymer (x1)> column, including the requirements (x1-a), preferred embodiments and monomer species.
[0093]
　When the comonomer 1 is used in the step (1), the supply amount ratios of 4-methyl-1-pentene and the comonomer 1 are set so that the content of the structural unit derived from each is within the above range, and the comonomer 1 is used. Although it depends on the reactivity, for example, the supply amount ratio 4-methyl-1-pentene / comonomer 1 (molar ratio) is 100/0 to 80/20, preferably 100/0 to 90/10, and more preferably 100 /. It is in the range of 0 to 95/5, more preferably 100/0 to 97/3, particularly preferably 100/0 to 98/2, and is a range in which slurry polymerization is possible.
[0094]
　In step (1), a slurry containing the polymer (x1) is obtained. The slurry concentration, that is, the polymer (x1) particle concentration is usually 0.015 to 45% by mass, preferably 0.03 to 35% by mass. The slurry concentration can be calculated by filtering, for example, by the method described in the Example column.
[0095]
　 In
　step (2), a 4-methyl-1-pentene copolymer satisfying the above requirement (x2-a) in the presence of the polymer (x1) obtained in step (1). x2) is produced by slurry polymerization. In step (2), polymerization is usually carried out using a metallocene catalyst.
[0096]
　The copolymer (x2) is described in detail in the <4-Methyl-1-pentene copolymer (x2)> column, including the requirement (x2-a), preferred embodiments and monomer species.
[0097]
　In the step (2), the supply ratios of 4-methyl-1-pentene and comonomer 2 are set so that the content of the constituent units derived from each is within the above range, and varies depending on the reactivity of comonomer 2. For example, the supply amount ratio 4-methyl-1-pentene / comonomer 2 (molar ratio) is 0/100 to 98/2, preferably 20/80 to 98/2, and more preferably 30/70 to 95/5. It is more preferably in the range of 30/70 to 92/8, and particularly preferably in the range of 30/70 to 90/10.
[0098]
　When 4-methyl-1-pentene (monomer) remains after the polymerization in step (1), 4-methyl-1-pentene system without supplying 4-methyl-1-pentene (monomer) to step (2). A copolymer can be obtained.
[0099]
　In the step (2), when the total amount of the polymer (x1) obtained in the step (1) and the copolymer (x2) obtained in the step (2) is 100 parts by mass, the copolymer (x2) The copolymer (x2) is produced in the range of 5.0 to 90.0 parts by mass, preferably 10.0 to 80.0 parts by mass, and more preferably 15.0 to 70.0 parts by mass. To do. When these polymers are produced in such an amount ratio, a 4-methyl-1-pentene polymer having a high content of structural units derived from a comonomer (comonomer 1 and comonomer 2 are collectively referred to as such) Is preferable in that
[0100]
　Further, by producing the polymer (x1) in the step (1) and then producing the copolymer (x2) in the step (2), solution polymerization is likely to occur when the polymerization is performed in the reverse order. In comparison with the above, slurry polymerization is possible in each of the above steps.
[0101]
　In the step (2), the supply amounts of 4-methyl-1-pentene and comonomer 2 are selected so that the amount ratio of the polymer (x1) and the copolymer (x2) is within the above range.
[0102]
　In the step (2), in one embodiment, 4-methyl-1-pentene and comonomer 2 can be added to the slurry containing the polymer (x1) to carry out slurry polymerization of these monomers. If 4-methyl-1-pentene added in step (1) remains, it is not necessary to add 4-methyl-1-pentene.
[0103]
　In step (2), a slurry containing a resin (X) or particles (X) containing a polymer (x1) and a copolymer (x2) is obtained. The slurry concentration, that is, the resin (X) particle concentration or the particle (X) concentration is usually 3 to 50% by mass, preferably 5 to 40% by mass. The slurry concentration can be calculated by filtering, for example, by the method described in the Example column.
[0104]
　 << Polymerization Conditions >> The polymerization conditions in
　steps (1) and (2) are described below.
[0105]
　Examples of the polymerization solvent include hydrocarbon-based media, and specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclo. Aliphatic hydrocarbons such as pentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane; or mixtures of two or more selected from these. Further, olefins such as 4-methyl-1-pentene and other α-olefins themselves can be used as the polymerization solvent. As described above, in the present invention, olefin polymerization can be carried out in a hydrocarbon-based medium and / or using the olefin itself used for polymerization as a medium.
[0106]
　Slurry polymerization is adopted in the above-mentioned production method, but "slurry polymerization" means that the polymer produced by the polymerization is dispersed in the above-mentioned medium as fine particles, for example, without being substantially dissolved in the above-mentioned medium used at the time of polymerization. It refers to polymerization characterized by being present.
[0107]
　In steps (1) and (2), the polymerization temperature of the olefin is usually 0 to 100 ° C., preferably 20 to 70 ° C.; the polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to. The gauge pressure is 5 MPa. The polymerization reaction can be carried out by any of a batch type, a semi-continuous type and a continuous type. These conditions of steps (1) and (2) may be the same or different.
[0108]
　In particular, hydrogen can be said to be a preferable additive because it may have an effect of improving the polymerization activity of a catalyst that can be used in olefin polymerization and an effect of increasing or decreasing the molecular weight of the polymer. When hydrogen is added into the system, the amount thereof is appropriately about 0.00001 to 100 NL per mole of olefin. In addition to adjusting the amount of hydrogen supplied, the hydrogen concentration in the system includes a method of performing a reaction that produces or consumes hydrogen in the system, a method of separating hydrogen using a membrane, and some hydrogen-containing methods. It can also be adjusted by releasing the gas out of the system.
[0109]
　The molecular weight of the obtained polymer can be adjusted for each of the steps (1) and (2) by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. Further, it can be adjusted by adjusting the difference in the carrier (B) described later that can constitute the metallocene catalyst and adjusting the concentration of 4-methyl-1-pentene in the polymerization solvent.
[0110]
　In steps (1) and (2), in one embodiment, the amount of solvent-soluble portion (SP) of the polymer in the obtained slurry is adjusted to preferably 10% by mass or less, more preferably 5% by mass or less. When the amount of SP is in the above range, the solid-liquid separability is excellent. The SP amount tends to increase as the supply amount ratio of the comonomer 1 in the step (1) or the comonomer 2 in the step (2) increases, but the SP amount can be adjusted within the above range by using an appropriate metallocene catalyst. .. For example, by using a metallocene catalyst containing a preferred metallocene compound (general formula [A1], more preferably general formula [A2]) described later, the generation of the solvent-soluble portion (SP) is suppressed, and the amount of SP is preferably described above. Easy to adjust to range.
[0111]
　 << Metallocene catalyst >> In
　steps (1) and (2), it is preferable that the polymer (x1) and the copolymer (x2) are each produced using a metallocene catalyst. Compared with the case of using the Ziegler catalyst, by using the metallocene catalyst, the amount of the solvent-soluble part of the obtained polymer is reduced and the slurry properties are improved. The properties are good. Therefore, the target solvent-insoluble particles can be efficiently separated and recovered from the slurry.
[0112]
　The metallocene catalyst contains the metallocene compound (A).
[0113]
　The metallocene catalyst can further include the carrier (B).
[0114]
　The metallocene catalyst is preferably a particulate catalyst in which D50 in volume statistics is in the range of 1 to 500 μm, and D50 is more preferably in the range of 2 to 200 μm, still more preferably in the range of 5 to 50 μm. The D50 in the volume statistical value can be obtained by a laser diffraction / scattering method using, for example, MT3300EX II manufactured by Microtrac. The D50 of the metallocene catalyst is usually equivalent to the D50 of the carrier (B) described later, that is, usually in the range of 0.90 to 1.10 times the D50 of the carrier (B), preferably 0.95 to 1.05. It is in the double range, more preferably 1.0 to 1.03 times.
[0115]
　
　Examples of the metallocene compound (A) include International Publication No. 2005/121192, International Publication No. 2014/050817, International Publication No. 2014/123212, International Publication No. 2017/150265, and the like. The disclosed compounds are exemplified. The crosslinked metallocene compounds disclosed in International Publication No. 2014/050817, International Publication No. 2017/150265, etc. are preferably mentioned, but this does not limit the scope of the present invention.
[0116]
　The metallocene compound (A) is preferably a compound represented by the general formula [A1].
[0117]
[Chemical

　formula 1] In the formula [A1], R 1 is a hydrocarbon group, a silicon-containing group or a halogen-containing hydrocarbon group, and R 2 to R 10 are a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen. It may be selected from the contained hydrocarbon groups and may be the same or different, and the substituents may be bonded to each other to form a ring. M is a transition metal of Group 4 of the periodic table, and Q is a neutral conjugated or unconjugated diene having 10 or less carbon atoms, an anionic ligand, and a lone electron pair. Selected from the ligands in the same or different combinations, j is an integer from 1 to 4.
[0118]
　As a particularly preferable metallocene compound (A), the polymerization activity does not decrease much throughout the steps (1) and (2), highly stereoregular polymerization is possible, the copolymerization performance of the comonomer is excellent, and the copolymer weight of the high molecular weight is high. A complex compound that can be coalesced is preferably used. Since highly stereoregular polymerization is possible, the eluted polymer component during slurry polymerization can be suppressed, and the melting point of the polymer (x1) can be adjusted in a high range, and the heat resistance of the obtained resin can be improved. Can be adjusted high. Further, excellent comonomer copolymerization performance makes it possible to freely change the copolymerization composition of the polymer (x1) and the copolymer (x2), and it is possible to appropriately set the flexibility according to the resin application. it can. Further, it is preferable that a high molecular weight copolymer can be obtained, that is, the molecular weight of the copolymer (x2) can be adjusted to be high, and the strength and toughness of the obtained resin can be increased. ..
[0119]
　From this point of view, among the compounds represented by the general formula [A1], the compounds represented by the general formula [A2] described in International Publication No. 2014-050817 and the like are particularly preferable.
[0120]
[Chemical

　formula 2] In the formula [A2], R 1b is a hydrocarbon group, a silicon-containing group or a halogen-containing hydrocarbon group, and R 2b to R 12b are a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen. It may be selected from the contained hydrocarbon groups and may be the same or different from each other, and the respective substituents may be bonded to each other to form a ring. M is a Group 4 transition metal of the periodic table, n is an integer of 1 to 3, Q is a halogen atom, a hydrocarbon group, a neutral conjugated or unconjugated diene having 10 or less carbon atoms, an anionic ligand and Selected from the same or different combinations of neutral ligands that can be coordinated with a lone pair of electrons, j is an integer of 1 to 4.
[0121]
　 (R 1 to R 10 , R 1b to R 12b ) Examples of the hydrocarbon groups in 　R 1 to R 10 and R 1b to R 12b include linear hydrocarbon groups, branched hydrocarbon groups, and cyclic saturated hydrocarbons. Examples thereof include a group, a cyclic unsaturated hydrocarbon group, and a group formed by substituting one or more hydrogen atoms of the saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group. The hydrocarbon group usually has 1 to 20, preferably 1 to 15, and more preferably 1 to 10.
[0122]
　Examples of the linear hydrocarbon group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and n-nonyl. Examples include a linear alkyl group such as a group and an n-decanyl group; and a linear alkenyl group such as an allyl group.
[0123]
　Examples of the branched hydrocarbon group include isopropyl group, tert-butyl group, tert-amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group and 1-methyl-1. Examples thereof include branched alkyl groups such as -propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group and 1-methyl-1-isopropyl-2-methylpropyl group.
[0124]
　Examples of the cyclic saturated hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and methylcyclohexyl group; polycyclic groups such as norbornyl group, adamantyl group and methyladamantyl group. Be done.
[0125]
　Examples of the cyclic unsaturated hydrocarbon group include an aryl group such as a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a phenanthryl group and an anthrasenyl group; a cycloalkenyl group such as a cyclohexenyl group; 5-bicyclo [2.2. 1] Examples thereof include a polycyclic unsaturated alicyclic group such as a hepta-2-enyl group.
[0126]
　Examples of the group formed by substituting one or more hydrogen atoms of the saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group include a benzyl group, a cumyl group, a 1,1-diphenylethyl group and a triphenylmethyl group. Examples thereof include a group formed by substituting one or more hydrogen atoms of the alkyl group of the above with an aryl group.
[0127]
Examples of the silicon-containing group in 　R 1 to R 10 and R 1 b to R 12 b include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group and the like-SiR 3 (in the formula). , Each of the plurality of Rs is independently an alkyl group or a phenyl group having 1 to 15 carbon atoms.)
[0128]
The halogen-containing hydrocarbon groups in 　R 1 to R 10 and R 1 b to R 12 b are formed by substituting one or more hydrogen atoms of the above hydrocarbon groups, such as a trifluoromethyl group, with halogen atoms. The group is mentioned.
[0129]
Examples of the halogen atom in 　R 2 to R 10 and R 2 b to R 12 b include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
[0130]
Of the substituents 　R 2 to R 10 and R 2b to R 12b , two substituents (eg R 2b and R 3b , R 3b and R 4b , R 5b and R 6b , R 6b and R 7b , R 8b and R 9b , R 9b and R 10b , R 10b and R 11b , R 11b and R 12b ) may be bonded to each other to form a ring, and the ring formation is present at two or more positions in the molecule. You may.
[0131]
　In the present invention, examples of the ring (spiro ring, additional ring) formed by bonding two substituents to each other include an alicyclic ring and an aromatic ring. Specific examples thereof include a cyclohexane ring, a benzene ring, a hydrogenated benzene ring and a cyclopentene ring, and preferably a cyclohexane ring, a benzene ring and a hydrogenated benzene ring. Further, such a ring structure may further have a substituent such as an alkyl group on the ring.
[0132]
From the viewpoint of stereoregularity, 　R 1b is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 20 carbon atoms, further preferably not an aryl group, and a linear hydrocarbon. A group, a branched hydrocarbon group or a cyclic saturated hydrocarbon group is particularly preferable, and a carbon having a free valence (carbon bonded to a cyclopentadienyl ring) is particularly a substituent which is a tertiary carbon. preferable.
[0133]
Specific examples of 　R 1b include methyl group, ethyl group, isopropyl group, tert-butyl group, tert-pentyl group, tert-amyl group, 1-methylcyclohexyl group, and 1-adamantyl group, which are more preferable. Is a substituent in which the carbon having a free valence such as tert-butyl group, tert-pentyl group, 1-methylcyclohexyl group, 1-adamantyl group is a tertiary carbon, and particularly preferably tert-butyl group, 1- It is an adamantyl group.
[0134]
　In the general formula [A2], the fluorene ring moiety is not particularly limited as long as it has a structure obtained from a known fluorene derivative, but R 4b and R 5b are preferably hydrogen atoms from the viewpoint of stereoregularity and molecular weight.
[0135]
　R 2b , R 3b , R 6b and R 7b are preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrocarbon group, and even more preferably a hydrocarbon group having 1 to 20 carbon atoms. Further, R 2b and R 3b may be bonded to each other to form a ring, and R 6b and R 7b may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, 1,1,4,4,7,7,10,10-octamethyl-2. , 3,4,7,8,9,10,12-octahydro-1H-dibenzo [b, h] fluorenyl group, 1,1,3,3,6,6,8,8-octamethyl-2,3, 6,7,8,10-Hexahydro-1H-dicyclopenta [b, h] fluorenyl group, 1', 1', 3', 6', 8', 8'-hexamethyl-1'H, 8'H-dicyclopenta [B, h] Fluolenyl group is mentioned, and particularly preferably 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-. It is a 1H-dibenzo [b, h] fluorenyl group.
[0136]
　R 8b is preferably a hydrogen atom.
[0137]
　R 9b is more preferably a hydrocarbon group, and R 9b is further preferably an alkyl group having 2 or more carbon atoms such as a linear alkyl group or a branched alkyl group, a cycloalkyl group or a cycloalkenyl group. It is particularly preferable that R 9b is an alkyl group having 2 or more carbon atoms. From a synthetic point of view, it is also preferable that R 10b and R 11b are hydrogen atoms.
[0138]
　Alternatively, when n = 1, it is more preferable that R 9b and R 10b are bonded to each other to form a ring, and it is particularly preferable that the ring is a 6-membered ring such as a cyclohexane ring. In this case, R 11b is preferably a hydrogen atom.
[0139]
　R 12b is preferably a hydrocarbon group, particularly preferably an alkyl group.
[0140]
　 (Regarding M, Q, n and j)
　M is a Group 4 transition metal of the periodic table, for example Ti, Zr or Hf, preferably Zr or Hf, and particularly preferably Zr.
[0141]
　Q indicates a halogen atom, a hydrocarbon group, a neutral conjugated or unconjugated diene having 10 or less carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair.
[0142]
　Examples of the halogen atom in Q include fluorine, chlorine, bromine, and iodine.
[0143]
　As the hydrocarbon group in Q, an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms are preferable. As alkyl groups having 1 to 10 carbon atoms, methyl group, ethyl group, n-propyl group, iso-propyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1 , 1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylbutyl group, 1, Examples include 1,3-trimethylbutyl group and neopentyl group; examples of cycloalkyl group having 3 to 10 carbon atoms include cyclohexylmethyl group, cyclohexyl group and 1-methyl-1-cyclohexyl group. The number of carbon atoms of the hydrocarbon group is more preferably 5 or less.
[0144]
　The conjugated or non-conjugated diene having 10 or less of neutral atoms, s- cis - or s- trans eta 4 -1,3-butadiene, s- cis - or s- trans eta 4 -1,4- diphenyl-1,3-butadiene, s- cis - or s- trans eta 4 -3-methyl-1,3-pentadiene, s- cis - or s- trans eta 4 -1,4-dibenzyl-1, 3-butadiene, s- cis - or s- trans eta 4 -2,4-hexadiene, s- cis - or s- trans eta 4 -1,3-pentadiene, s- cis - or s- trans eta Examples thereof include 4-1 and 4 -ditril-1,3-butadiene, s-cis- or s-trans-η 4-1 and 4 -bis (trimethylsilyl) -1,3-butadiene.
[0145]
　Examples of the anion ligand include an alkoxy group such as methoxy and tert-butoxy; an aryloxy group such as phenoxy; a carboxylate group such as acetate and benzoate; and a sulfonate group such as mesylate and tosylate.
[0146]
　Organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine; as neutral ligands that can be coordinated with isolated electron pairs; tetrahydrofuran (THF), diethyl ether, dioxane, 1,2-dimethoxy Examples include ethers such as ethane.
[0147]
　A preferred embodiment of Q is a halogen atom or an alkyl group having 1 to 5 carbon atoms.
[0148]
　n is an integer of 1 to 3, preferably 1 or 2, and more preferably 1. When n is the above value, it is preferable from the viewpoint of efficiently obtaining the polymer to be produced.
[0149]
　j is an integer of 1 to 4, preferably 2.
[0150]
　In the above, preferable embodiments of the composition of the compound represented by the general formula [A1] or [A2], that is, R 1 to R 10 , R 1b to R 12b , M, n, Q and j have been described. In the present invention, any combination of the respective preferred embodiments is also a preferred embodiment. Such a crosslinked metallocene compound can be suitably used to obtain a polymer having the above physical characteristics.
[0151]
　Examples of the compound represented by the general formula [A2] include (8-octamethylfluorene-12'-yl- (2- (adamantan-1-yl) -8-methyl-3,3b, 4,5,6, 7,7a,8-octahydrocyclopenta [a] indene)) zirconium dichloride or (8- (2,3,6,7-tetramethylfluorene) -12'-yl- (2- (adamantan-1-yl)) )-8-Methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta [a] indene)) Zyroxide dichloride is particularly preferred. Here, the above-mentioned octamethylfluorene is 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo [b]. , h] Fluorene.
[0152]
　 The
　carrier (B) is preferably in the form of particles, and the metallocene catalyst is formed by immobilizing the metallocene compound (A) on the surface and inside thereof. Such a form of catalyst is generally referred to as a metallocene-supported catalyst.
[0153]
　The carrier (B) is mainly composed of an organoaluminum compound (B-1), an organoboron compound (B-2), an inorganic compound (B-3), or a complex of two or more selected from these.
[0154]
　Examples of the organoaluminum compound (B-1) include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum and trinormaloctylaluminum, dialkylaluminum hydride such as diisobutylaluminum hydride, tricycloalkylaluminum and aluminoxane. A typical organoaluminum oxy compound can be mentioned. Further, the organoaluminum compound (B-1) includes, for example, an organoaluminum oxy compound containing a boron atom and a halogen as exemplified in International Publication No. 2005/066191 and International Publication No. 2007/131010. Alminoxane, an ionic aluminoxane as exemplified in WO 2003/082879, can also be mentioned.
[0155]
　Examples of the organic boron compound (B-2) include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, and trimethylammonium tetrakis. (O-trill) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (2,) 4-Dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (4-trifluoromethylphenyl) borate, tri (n-butyl) ammonium Tetrax (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetraphenylborate, dioctadecylmethylammonium tetrakis (p-trill) borate, dioctadecyl Methylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (2,4-dimethylphenyl) borate, dioctadecil methylammonium tetrakis (3,5-dimethylphenyl) Borate, Dioctadecylmethylammonium tetrakis (4-trifluoromethylphenyl) borate, Dioctadecylmethylammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, Dioctadecylmethylammonium, N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-Ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5-ditrifluoromethylphenyl) ) Borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate.
[0156]
　Examples of the inorganic compound (B-3) include porous oxides, inorganic halides, clays, clay minerals, and ion-exchange layered compounds.
[0157]
　Examples of the porous oxide include oxides such as SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, BaO, and ThO 2 , or a composite containing these. Examples include mixtures. For example, natural or synthetic zeolite, SiO 2 -MgO, SiO 2 -Al 2 O 3 , SiO 2 -TiO 2 , SiO 2 -V 2 O 5 , SiO 2 -Cr 2 O 3 , SiO 2-TiO 2 -MgO and the like can be exemplified.
[0158]
　Examples of the inorganic halide include MgCl 2 , MgBr 2 , MnCl 2 , and MnBr 2 . The inorganic halide may be used as it is, or may be used after being crushed by a ball mill or a vibration mill. Further, it is also possible to use a product obtained by dissolving an inorganic halide in a solvent such as alcohol and then precipitating it into fine particles with a precipitant.
[0159]
　Clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak bonding force, and the contained ions can be exchanged. Most clay minerals are ion-exchange layered compounds. Further, as these clays, clay minerals, and ion-exchange layered compounds, not only naturally produced ones but also artificial synthetic compounds can be used. As the clay, clay mineral or ion-exchange layered compound, clay, clay mineral, or an ionic crystalline compound having a layered crystal structure such as hexagonal closest packing type, antimony type, CdCl 2 type and CdI 2 type can be used. It can be exemplified.
[0160]
　It is also preferable to chemically treat clay and clay minerals. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, organic substance treatment and the like.
[0161]
　As the carrier (B) used in the present invention, a carrier containing an aluminum atom is preferable from the viewpoint of high activity and further suppressing the amount of solvent-soluble parts. The content of aluminum atoms in the carrier (B) is preferably 20% by mass or more, more preferably 20 to 60% by mass, still more preferably 30 to 50% by mass, and particularly preferably 35 to 47% by mass.
[0162]
　The volume statistical value of the carrier (B) is D50, preferably 1 to 500 μm, more preferably 2 to 200 μm, and even more preferably 5 to 50 μm. The D50 in the volume statistical value can be obtained by a laser diffraction / scattering method using, for example, MT3300EX II manufactured by Microtrac.
[0163]
　As such a carrier (B), solid aluminoxane is preferably used, and is disclosed in, for example, International Publication No. 2010/055652, International Publication No. 2013/146337, or International Publication No. 2014-123212. Solid aluminoxane is particularly preferably used.
[0164]
　By "solid state" is meant that the aluminoxane remains substantially in a solid state in a reaction environment in which the solid aluminoxane is used. More specifically, for example, when each component constituting an olefin polymerization catalyst is brought into contact with each other to prepare an olefin polymerization solid catalyst component, a specific temperature and pressure are used in an inert hydrocarbon medium such as hexane or toluene used in the reaction. Indicates that the aluminoxane is in a solid state in an environment.
[0165]
　The solid aluminoxane preferably contains an aluminoxane having at least one structural unit selected from the structural unit represented by the formula (1) and the structural unit represented by the formula (2), and more preferably the structural unit represented by the formula (1). ) Is contained, and more preferably, polymethylaluminoxane composed of only the structural unit represented by the formula (1) is contained.
[0166]
[Chemical

　formula 3] In formula (1), Me is a methyl group.
[0167]
　In the formula (2), R 1 is a hydrocarbon group having 2 to 20 carbon atoms, preferably a hydrocarbon group having 2 to 15 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms. Examples of the hydrocarbon group include ethyl, propyl, n-butyl, pentyl, hexyl, octyl, decyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, 3-methylbutyl, 2-methylpentyl, 3 -Alkyl groups such as methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 2-ethylhexyl; cycloalkyl groups such as cyclohexyl and cyclooctyl; aryl groups such as phenyl and tolyl.
[0168]
　The structure of the solid aluminoxane has not always been clarified, and it is presumed that the solid aluminoxane usually has a structure in which the structural units represented by the formulas (1) and / or the formula (2) are repeated by about 2 to 50. However, the configuration is not limited to this. In addition, the binding mode of the structural unit varies from linear, cyclic or clustered, for example, and aluminoxane is usually composed of one of these or presumed to be a mixture thereof. .. Further, the aluminoxane may consist only of the structural units represented by the formula (1) or the formula (2).
[0169]
　As the solid aluminoxane, a solid polymethylaluminoxane is preferable, and a solid polymethylaluminoxane composed of only the structural unit represented by the formula (1) is more preferable.
[0170]
　The solid aluminoxane is usually in the form of particles, and D50 in the volume statistical value is preferably 1 to 500 μm, more preferably 2 to 200 μm, and further preferably 5 to 50 μm. The D50 in the volume statistical value can be obtained by a laser diffraction / scattering method using, for example, MT3300EX II manufactured by Microtrac.
[0171]
　The specific surface area of ​​the solid aluminoxane is preferably 100 to 1000 m 2 / g, more preferably 300 to 800 m 2 / g. The specific surface area can be determined by using the BET adsorption isotherm method and utilizing the gas adsorption and desorption phenomenon on the solid surface.
[0172]
　The solid aluminoxane functions as a catalyst carrier. Therefore, in addition to the solid aluminoxane, it is not necessary to use, for example, a solid inorganic carrier such as silica, alumina, silica / alumina, magnesium chloride, or a solid organic carrier such as polystyrene beads as the catalyst carrier.
[0173]
　The solid aluminoxane can be prepared, for example, by the methods described in WO 2010/055652 and WO 2014/123212.
[0174]
　 The
　metallocene catalyst may further contain the organic compound component (C) , if necessary. The organic compound component (C) is used for the purpose of improving the polymerization performance and the physical characteristics of the produced polymer, if necessary. As the organic compound component (C), the above-mentioned organic aluminum compound (B-1) can be used. Other examples include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers and sulfonates.
[0175]
　 In
　the case of olefin polymerization, the usage method and addition order of each component are arbitrarily selected, and the following methods are exemplified. Hereinafter, the metallocene compound (A), the carrier (B), and the organic compound component (C) are also referred to as “components (A) to (C)”, respectively.
(I) A method of adding the component (A) and the component (B) to the polymerizer in an arbitrary order.
(Ii) A method of adding a catalyst component in which the component (A) is supported on the component (B) to a polymerizer.
[0176]
　In each of the above methods (i) to (ii), the component (C) may be further added at any stage. Moreover, at least two of each catalyst component may be contacted in advance.
[0177]
　Further, in the solid catalyst component in which the component (A) is supported on the component (B), olefins such as 4-methyl-1-pentene and 3-methyl-1-pentene may be prepolymerized, and the prepolymerization may be performed. A catalyst component may be further supported on the solid catalyst component.
[0178]
　In the present invention, it is preferable to prepare a metallocene catalyst from the metallocene compound (A), the carrier (B) and optionally other components, and to polymerize an olefin containing 4-methyl-1-pentene in the presence of this catalyst. That is, it is preferable to carry out steps (1) and (2). In "Polymerizing an olefin containing 4-methyl-1-pentene in the presence of a metallocene catalyst", as in each of the above methods, each component constituting the metallocene catalyst is added to the polymerizer to add the olefin. Includes aspects of polymerization.
[0179]
　In the steps (1) and (2), when the olefin is polymerized using the metallocene catalyst, the amount of each component that can constitute the metallocene catalyst is as follows. Further, in the metallocene catalyst, the content of each component can be adjusted as follows.
[0180]
　Component (A) per liter of the reaction volume, usually 10 -10 to 10 -2 mol, preferably 10 -8 to 10 -3 it is used in an amount such that the mole. The molar ratio [Al / M] of the aluminum atom in the component (B-1) to the total transition metal atom (M) in the component (A) of the component (B-1) is usually 10 to 10000, preferably 10,000. It can be used in an amount of 30 to 2000, particularly preferably 150 to 500. The molar ratio [(B-2) / M] of the component (B-2) to the total transition metal atoms (M) in the component (A) is usually 10 to 10000, preferably 10 to 10000. It can be used in an amount of 30 to 2000, more preferably 150 to 500. The molar ratio [(B-3) / M] of the component (B-3) to all the transition metal atoms (M) in the component (A) is usually 10 to 10000, preferably 10 to 10000. It can be used in an amount of 30 to 2000, more preferably 150 to 500.
[0181]
　When the component (C) is used, when the component (B) is the component (B-1), the molar ratio of the aluminum atom in the component (B-1) to the component (C) [Al / (C)] Is usually 0.002 to 500, preferably 0.01 to 60, and when the component (B) is the component (B-2), the component (B-2) and the component (C) In the case where the molar ratio [(B-2) / (C)] is usually 0.002 to 500, preferably 0.01 to 60, and the component (B) is the component (B-3). Is used in an amount such that the molar ratio of the component (B-3) to the component (C) [(B-3) / (C)] is usually 0.002 to 500, preferably 0.01 to 60. be able to.
[0182]
　 The
　slurry containing the resin (X) or the particles (X) containing the polymer (x1) and the copolymer (x2) obtained in the step (2) is solid-liquid separated, for example. By filtering, the resin (X) or the particles (X) can be separated and recovered. By this solid-liquid separation step, the resin (X) or the particles (X) can be efficiently recovered.
[0183]
　
　4-Methyl-1-pentene resin (X) or 4-methyl-1-pentene polymer particles (X) obtained by the above production method, for example, obtained by the above solid-liquid separation step. The resin (X) particles or particles (X) may be subjected to post-treatment steps such as a known catalyst deactivation treatment step, catalyst residue removal step, and drying step, if necessary, after being produced by the above method. ..
[0184]
　 [4-Methyl-1-pentene resin (X)]
　The 4-methyl-1-pentene resin (X) obtained by the production method of the present invention 2 will be described.
[0185]
　The resin (X) is usually 10.0 to 95.0 parts by mass, preferably 20.0 to 90.0 parts by mass, and more preferably 30.0 to 30.0 parts by mass of the 4-methyl-1-pentene polymer (x1). It contains 85.0 parts by mass and contains 4-methyl-1-pentene copolymer (x2) in an amount of usually 5.0 to 90.0 parts by mass, preferably 10.0 to 80.0 parts by mass, and more preferably 15. It contains 0.0 to 70.0 parts by mass. However, the total amount of the polymer (x1) and the copolymer (x2) is 100 parts by mass.
[0186]
　In the resin (X), the content of the structural unit derived from 4-methyl-1-pentene is preferably 30.0 to 99.7 mol%, more preferably 40.0 to 99.5 mol%, still more preferably. Is 50.0 to 99.0 mol%, particularly preferably 70.0 to 97.0 mol%, 75.0 to 96.0 mol%, or 80.0 to 95.0 mol%.
[0187]
　The content of the structural unit derived from ethylene and at least one olefin selected from α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) in the resin (X) is preferably 0. 3. 70.0 mol%, more preferably 0.5-60.0 mol%, still more preferably 1.0-50.0 mol%, particularly preferably 3.0-30.0 mol%, 4. It is 0 to 25.0 mol%, or 5.0 to 20.0 mol%.
[0188]
　The resin (X) may have the above-mentioned other structural units 1 and 2 (other structural units) as long as the effects of the present invention are not impaired. The content of the other structural units is, for example, 0 to 10.0 mol%.
[0189]
　The resin (X) has an intrinsic viscosity [η] measured in decalin at 135 ° C., preferably 0.5 to 10.0 dl / g, more preferably 0.5 to 5.0 dl / g, still more preferably 1. It is in the range of 0.0 to 5.0 dl / g.
[0190]
　The ultimate viscosity [η] of the resin (X) can be adjusted by the value of [η] of each of the polymer (x1) and the copolymer (x2), and the content ratio.
[0191]
　The mesodiad fraction (m) of the resin (X) measured by 13 C-NMR is preferably 95.0 to 100%, more preferably 96.0 to 100%, still more preferably 97.0 to 100%. It is particularly preferably in the range of 98.0 to 100%, and most preferably in the range of 98.5 to 100%. The upper limit is preferably 100%, but can also be 99.9%. The m can be adjusted to the above range by using an appropriate metallocene catalyst. For example, by using a metallocene catalyst containing the above-mentioned preferable metallocene compound (general formula [A1], more preferably general formula [A2]), the m can be easily adjusted to the above range. When the m is in the above range, the solid-liquid separability of the slurry tends to be good, which is preferable.
[0192]
　The resin (X) obtained by the production method of the present invention 2 is, for example, particles. The resin (X) is, for example, the particles (X) of the present invention 1. The particle size (D50) of the particles made of the resin (X) is usually in the range of 10 to 2000 μm, preferably 30 to 1000 μm, more preferably 50 to 500 μm, and even more preferably 70 to 300 μm. In one embodiment, the particle size (D50) of the particles made of the resin (X) is preferably in the range of 30 to 1800 μm, more preferably 50 to 1500 μm, and even more preferably 70 to 1200 μm.
[0193]
　Specifically, the particle size (D50) is a value measured using a laser diffraction / scattering device (LS13320) manufactured by Beckman Coulter, and decan can be used as the dispersion medium of the sample. Further, the particle size (D50) of the particles made of the resin (X) is usually larger than the particle size (D50) of the metallocene catalyst.
[0194]
　The bulk density of the particles made of the resin (X) is usually 0.1 to 1.0 g / cm 3 , preferably 0.2 to 0.8 g / cm 3 , and more preferably 0.3 to 0.5 g. It is in the range of / cm 3 .
[0195]
　The resin (X) obtained by the production method of the present invention may be pelletized. Examples of the pelletizing method include the following methods (1) and (2).
(1) A method in which the resin (X) and other components added if desired are mechanically blended using an extruder, a kneader or the like, and cut into a predetermined size.
(2) The resin (X) and other components added as desired are dissolved in a suitable good solvent (eg, a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene and xylene), and then the solvent is added. A method of removing and then mechanically blending using an extruder, kneader, etc., and cutting to a predetermined size.
[0196]
　In one embodiment, the resin (X) obtained by the production method of the present invention 2 is composed of 4-methyl-1-pentene polymer particles (X), for example, by melt-kneading the particles (X). The obtained resin may be used.
[0197]
　 [Resin Composition Containing 4-Methyl-1-pentene Resin (X)]
　The resin composition of the present invention contains 4-methyl-1-pentene resin (X).
[0198]
　The resin composition of the present invention may contain other components that do not correspond to the resin (X), for example, a resin other than the resin (X) and various additives.
[0199]
　Examples of the resin other than the resin (X) include a thermoplastic polyolefin resin other than the resin (X), a thermoplastic polyamide resin, a thermoplastic polyester resin, a thermoplastic resin such as a thermoplastic vinyl aromatic resin, and the like. Examples thereof include thermoplastic resins such as unsaturated polyester resin, epoxy resin, phenol resin, urea resin, melamine resin, diallyl phthalate resin, and silicone resin. Specific examples of these resins will be described later.
[0200]
　Examples of various additives include weather-resistant stabilizers, heat-resistant stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, anti-slip agents, anti-blocking agents, antifogging agents, nucleating agents, lubricants, pigments, dyes, and aging. Examples include inhibitors, hydrochloric acid absorbers, inorganic or organic fillers, organic or inorganic foaming agents, cross-linking agents, cross-linking aids, adhesives, softeners, flame retardants.
[0201]
　In the resin composition of the present invention, the content of the resin (X) is usually 30% by mass or more, preferably 40% by mass or more, and more preferably 50% by mass or more.
[0202]
　The resin composition of the present invention can be obtained, for example, by mixing two or more kinds of resins (X) or by mixing the resin (X) with other components, and the mixing method is not particularly limited, for example. , A method of compounding with a twin-screw extruder and a method of mixing by dry blending or the like.
[0203]
　 [Resin composed of 4-methyl-1-pentene polymer particles (X)]
　The resin of the present invention comprises 4-methyl-1-pentene polymer particles (X), for example, the particles (X). Obtained by melt-kneading. The melt-kneading temperature is usually in the range of 180 to 350 ° C, preferably 200 to 320 ° C, and more preferably 250 to 300 ° C. The shape is not limited, but pellets are usually preferable in terms of ease of handling. At this time, various additives described later may be blended as needed.
[0204]
　Examples of the pelletizing method include the following methods (1) and (2).
(1) A method in which particles (X) and other components added if desired are melt-kneaded using an extruder, kneader, or the like and cut into a predetermined size.
(2) The particles (X) and other components added as desired are dissolved in a suitable good solvent (eg, a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene and xylene), and then the solvent is added. A method of removing and then melting and kneading using an extruder, kneader, etc., and cutting to a predetermined size.
[0205]
　 [Characteristics of resin composed of 4-methyl-1-pentene polymer particles (X)]
　The resin of the present invention has high stereoregularity, and has both excellent heat resistance and relatively low rigidity, that is, flexibility. It has the feature of being able to do it. This is a feature brought about by the polymer particles (X) of the present invention, and high heat resistance due to a component having a peak in the amount of eluted components in the range of 100 to 140 ° C. measured by CFC (usually, the polymer (x1)). The property of flexibility is obtained by the component having the peak of the amount of the eluted component below 100 ° C. (usually, the copolymer (x2)).
[0206]
　In addition, the resin of the present invention can realize excellent stain resistance in one embodiment. The characteristic of stain resistance is obtained by the cumulative mass percentage of the components eluted at 0 ° C. or lower as measured by CFC being less than 2.0% by mass.
[0207]
　On the other hand, as compared with a resin which is a mixture of polymers obtained by individually polymerizing a polymer (x1) and a copolymer (x2), for example, a resin obtained by melt-kneading individual polymers, the present invention The resin has a feature of low haze, that is, excellent transparency. This is because the resin of the present invention is obtained from the particles (X) containing the polymer (x1) and the copolymer (x2) in each of the particles, and thus the polymer (x1) and the copolymer. It is considered that the size of the phase-separated structure with (x2) is uniform. The phase-separated structure can be confirmed by, for example, a transmission electron microscope, an X-ray scattering method, a light scattering method, or the like. If the phase-separated structure is small, or if the polymer (x1) and the copolymer (x2) are highly compatible, it may not be possible to observe the phase-separated structure by these methods. The phase-separated structure is not particularly limited, but it is presumed that it depends on the volume ratio of the polymer (x1) and the copolymer (x2), and it is considered that a co-continuous structure or a sea-island structure can be easily taken. In some cases, it is presumed that a lamellar structure (layered structure), a cylinder, or the like can be taken.
[0208]
　In one embodiment, the resin made of the particles (X) of the present invention 1 or a molded product formed from a resin composition containing the resin preferably has a tensile elastic modulus satisfying the following formula 1, preferably formula 2. It is more preferable to satisfy.
[0209]
　Equation 1: Tensile elastic modulus (MPa) .
[0210]
　When the molded product satisfies the formula 1, it can be determined that the molded product has high heat resistance and excellent flexibility. The relationship of Equation 1 is represented by a solid line in FIG. When the molded product satisfies the formula 2, it can be determined that the molded product has a better balance between heat resistance and flexibility. The relationship of Equation 2 is represented by a broken line in FIG. That is, by using the resin composed of the particles (X) of the present invention 1 and the resin composition thereof, a molded product having excellent heat resistance and flexibility can be obtained.
[0211]
　A resin composed of 4-methyl-1-pentene polymer particles (X) or 4-methyl-1-pentene polymer particles (X) of the present invention 1 or 4-methyl obtained by the production method of the present invention 2. A part of the 4-methyl-1-pentene polymer constituting the -1-pentene resin (X) may be graft-modified with a polar monomer.
[0212]
　Examples of the polar monomer include a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid or a derivative thereof, and a vinyl ester compound. Examples thereof include vinyl chloride, vinyl group-containing organic silicon compounds, and carbodiimide compounds. As the polar monomer, an unsaturated carboxylic acid or a derivative thereof, and a vinyl group-containing organosilicon compound are particularly preferable.
[0213]
　Examples of the unsaturated carboxylic acid or a derivative thereof include an unsaturated compound having one or more carboxylic acid groups, an ester of a compound having a carboxylic acid group and an alkyl alcohol, and an unsaturated compound having one or more anhydrous carboxylic acid groups. Can be mentioned. Examples of the unsaturated group include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group. Conventionally known compounds can be used as these compounds, and the present invention is not particularly limited. Specific examples include (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and nadic acid [trademark] (endosis-bicyclo [2.2.1] hept. -5-En-2,3-dicarboxylic acid) and other unsaturated carboxylic acids; or derivatives thereof, such as acid halides, amides, imides, anhydrides, esters and the like. Specific examples of the derivative include methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, dimethyl fumarate, dimethyl itaconic acid, diethyl citraconic acid, dimethyl tetrahydrophthalate, and dimethyl nadicate (endosis-bicyclo [2]. .2.1] Hept-5-ene-2,3-dicarboxylic acid dimethyl), malenyl chloride, maleimide, maleic anhydride, citraconic anhydride, glycidyl maleate. These unsaturated carboxylic acids and their derivatives can be used alone or in combination of two or more. Among these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid ™ or acid anhydrides thereof are particularly preferable.
[0214]
　As the vinyl group-containing organosilicon compound, conventionally known compounds can be used and are not particularly limited. For example, vinyl triethoxysilane, vinyl trimethoxysilane, vinyltris (β-methoxy-ethoxysilane), γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, 2 -(3,4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethylethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimemethoxysilane , 3-Metachromipropylmethyldiethoxysilane, 3-Metachromipropyltriethoxysilane, 3-acroxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3) -Dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyandiapropyltriethoxysilane can be mentioned. Among these, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-acroxypropyltrimethoxysilane Is preferable, and vinyltriethoxysilane, vinyltrimethoxysilane, and 3-acroxypropyltrimethoxysilane, which have less steric damage and high graft modification efficiency, are more preferable.
[0215]
　One type of polar monomer may be used alone, or two or more types may be used in combination.
[0216]
　The polar monomer is usually 1 to 100 parts by mass, preferably 1 to 100 parts by mass, based on 100 parts by mass of the resin composed of the particles (X) and the particles (X) or the 4-methyl-1-pentene polymer constituting the resin (X). Is used in an amount of 5 to 80 parts by mass.
[0217]
　This graft polymerization is usually carried out in the presence of a radical initiator.
[0218]
　As the radical initiator, an organic peroxide, an azo compound, or the like can be used. Specifically, conventionally known substances can be used, for example, digmil peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-. Butyl cumyl peroxide, di-t-amyl peroxide, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butyl peroxy) hexin-3,2,5-dimethyl-2, 5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, etc. Dialkyl peroxides; t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxymaleic acid, t-butyl peroxyneodecanoate, t-butyl Peroxyesters such as peroxybenzoate and di-t-butylperoxyphthalate; ketone peroxides such as dicyclohexanone peroxide; and mixtures thereof.
[0219]
　The radical initiator can be used as it is by mixing it with the 4-methyl-1-pentene polymer and the polar monomer as it is, or it can be used after being dissolved in a small amount of an organic solvent. The organic solvent can be used without particular limitation as long as it is an organic solvent capable of dissolving the radical initiator.
[0220]
　Further, when the polar monomer is graft-polymerized, a reducing substance may be used. When a reducing substance is used, the amount of grafted polar monomer can be improved.
[0221]
　The graft modification can be carried out by a conventionally known method. For example, the 4-methyl-1-pentene polymer is dissolved in an organic solvent, and then a polar monomer, a radical initiator and the like are added to the solution to add 60 to 260. It can be carried out by reacting at a temperature of ° C., preferably 80 to 200 ° C., for 0.5 to 15 hours, preferably 1 to 10 hours.
[0222]
　In addition, the particles (X) of the present invention 1 or the resin composed of the particles (X), or the resin (X) obtained by the production method of the present invention 2 remains in a solid state, and a polar monomer, a radical initiator, or the like is used without solvent. It can also be added in the form of a solution and reacted at a temperature of 60 to 260 ° C., preferably 80 to 200 ° C. for 0.5 to 15 hours, preferably 1 to 10 hours.
[0223]
　It can also be produced by reacting a 4-methyl-1-pentene polymer with a polar monomer using an extruder or the like without using a solvent. This reaction is usually preferably carried out at a temperature above the melting point of the polymer, specifically 120 to 300 ° C., for usually 0.5 to 10 minutes.
[0224]
　The amount of modification of the 4-methyl-1-pentene polymer obtained by the above method (the amount of graft of the polar monomer) is 100% by mass of the 4-methyl-1-pentene polymer after graft modification. , Usually 0.1 to 50% by mass, preferably 0.2 to 30% by mass, and more preferably 0.2 to 10% by mass.
[0225]
　In the present invention, when the 4-methyl-1-pentene polymer contains a graft-modified polymer, it is excellent in adhesiveness and compatibility with other resins, and the wettability of the surface of the molded product is improved. sell. Further, the graft-modified polymer can be suitably used for a cross-linked electric wire and a cross-linked pipe by cross-linking.
[0226]
　Further, the polyolefin segment and the polar polymer segment are obtained by atom transfer radical polymerization of a radically polymerizable monomer using a halogen-modified polymer obtained by halogenating the 4-methyl-1-pentene polymer as a macro initiator. It is also possible to obtain a block-graft copolymer chemically bonded with and. The macro initiator is a polymer having an ability to initiate atom transfer radical polymerization, and represents a polymer having a site in the molecular chain that can be a starting point of atom transfer radical polymerization.
[0227]
　The halogen-modified polymer is produced by reacting the 4-methyl-1-pentene polymer with a halogenating agent. The halogenating agent is not particularly limited as long as it can halogenate the 4-methyl-1-pentene polymer to produce a halogen-modified polymer, but specifically, chlorine, bromine, iodine, and three. Phosphorus chloride, phosphorus tribromide, phosphorus triiodide, phosphorus pentachloride, phosphorus pentabromide, phosphorus pentaiodide, thionyl chloride, sulfryl chloride, thionyl bromide, N-chlorosuccinimide, N-bromosuccinimide, N-bromo Caprolactam, N-Bromophthalimide, 1,3-dibromo-5,5-dimethylhydantoin, N-chloroglutarimide, N-bromoglutarimide, N, N'-dibromoisocyanic acid, N-bromoacetamide, N-bromocarbamide Acid ester, dioxandibromid, phenyltrimethylammonium tribromid, pyridinium hydrobromid perbromid, pyrrolidone hydrotribromid, t-butyl hypochlorate, t-butyl hypobromate, copper (II) chloride, copper bromide ( II), iron (III) chloride, oxalyl chloride, IBr and the like can be mentioned. Of these, preferably chlorine, bromine, N-chlorosuccinimide, N-bromosuccinimide, N-bromocaprolactam, N-bromophthalimide, 1,3-dibromo-5,5-dimethylhydantoin, N-chloroglutalimide, N. -Bromoglutarimide, N, N'-dibromoisocyanulic acid, more preferably bromine, N-bromosuccinimide, N-bromocaprolactam, N-bromophthalimide, 1,3-dibromo-5,5-dimethylhydantin, N. -A compound having an N-Br bond such as bromoglutarimide, N, N'-dibromoisocyanulic acid.
[0228]
　The reaction between the 4-methyl-1-pentene polymer and the halogenating agent is preferably carried out in an inert gas atmosphere. Examples of the inert gas include an inert gas such as nitrogen, argon, and helium. In addition, a solvent can be used for the reaction, if necessary. Any solvent can be used as long as it does not inhibit the reaction. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, and fats such as pentane, hexane, heptane, octane, nonane and decane can be used. Alicyclic hydrocarbon solvents such as group hydrocarbon solvents, cyclohexane, methylcyclohexane and decahydronaphthalene, chlorinated carbonized such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene, tetrachloroethane. Hydrogen solvents, methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol and other alcohol solvents, acetone, methyl ethyl ketone and methyl isobutyl ketone and other ketone solvents; ethyl acetate and dimethyl Ester-based solvents such as phthalate; ether-based solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisol can be mentioned.
[0229]
　In the reaction with the halogenating agent, a radical initiator may be added as needed to accelerate the reaction. Examples of the radical initiator include the above-mentioned radical initiator.
[0230]
　As a method for reacting the 4-methyl-1-pentene polymer with a halogenating agent, various conventionally known methods can be adopted. For example, the 4-methyl-1-pentene polymer is suspended or dissolved in a solvent and halogenated at a temperature of usually -80 ° C to 250 ° C, preferably at a temperature of room temperature or higher and lower than the boiling point of the solvent. A method of adding and mixing an agent and a radical initiator as necessary to react, or the above-mentioned 4-methyl-1-pentene polymer is halogenated under melt-kneading at a temperature above its melting point, for example, 180 to 300 ° C. Examples thereof include a method of contacting the agent with a radical initiator, if necessary.
[0231]
　The polar polymer segment is a homopolymer or copolymer of one or more monomers selected from radically polymerizable monomers. Examples of the radically polymerizable monomer include (meth) acrylic acid, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, -n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and (meth). ) Acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid Cyclohexyl, (meth) acrylate-n-heptyl, (meth) acrylate-n-octyl, (meth) acrylate-2-ethylhexyl, (meth) nonyl acrylate, (meth) decyl acrylate, (meth) acrylic Dodecyl acid, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, -2-methoxyethyl (meth) acrylate, -3-methoxybutyl (meth) acrylate, (meth) acrylic 2-Hydroxyethyl acid, -2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 2-(meth) acrylate Dimethylamino) ethyl, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylic acid, 2-trifluoromethylethyl (meth) acrylic acid, ( 2-Perfluoroethyl ethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, ( Diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecyl (meth) acrylate Ethyl, (meth) acrylic acid 2-perfluorohe (Meta) acrylic acid-based monomers such as xadecylethyl, styrene-based monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof, fluorine such as perfluoroethylene, perfluoropropylene and vinylidene fluoride Silicon-containing vinyl monomers such as vinyl monomer, vinyl trimethoxysilane, vinyl triethoxysilane, maleic anhydride, maleic acid, monoalkyl ester and dialkyl ester of maleic acid, monoalkyl ester and dialkyl ester of fumaric acid, fumaric acid , Maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide and other maleimide-based monomers, acrylonitrile, methacrylonitrile and other nitrile group-containing vinyl-based monomers. Monomer, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N -Amid group-containing vinyl-based monomers such as dimethyl (meth) acrylamide, vinyl ester-based monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl laurate, vinyl chloride, vinylidene chloride, allyl chloride, allyl Examples include alcohol. These organic compounds may be used alone or in combination of two or more.
[0232]
　The atomic transfer radical polymerization can be carried out by a conventionally known method, and the polymerization method is not particularly limited, and bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, bulk / suspension polymerization and the like can be applied. The reaction temperature may be any temperature as long as the radical polymerization reaction proceeds, and is not uniform depending on the desired degree of polymerization of the polymer, the type and amount of the radical initiator and solvent used, but is usually from -100 ° C. to It is 250 ° C.
[0233]
　 [Resin Composition Containing Resin Consisting of 4-Methyl-1-pentene Polymer Particles (X)]
　The resin composition of the present invention is a resin composed of 4-methyl-1-pentene polymer particles (X). Contains.
[0234]
　The resin composition of the present invention may contain other components that do not correspond to the resin composed of particles (X), for example, a resin other than the resin composed of particles (X), and various additives.
[0235]
　Examples of the resin other than the resin include thermoplastic polyolefin resins other than the resin composed of particles (X), such as polyethylene, polypropylene, polybutene-1, ethylene / propylene copolymer, ethylene / butene copolymer, and propylene. Butene copolymer, ethylene / propylene / butene-1 copolymer, ethylene / propylene / hexene-1 copolymer, ethylene / propylene / octene-1 copolymer, ethylene / butene-1 / hexene-1 copolymer , Ethylene-butene-1, octene-1 copolymer, ethylene-α-olefin-non-conjugated diene copolymer, chlorinated polyethylene, polyvinyl chloride, polyvinylidene chloride, acrylonitrile-butadiene-styrene copolymer, polyvinyl alcohol , Acrylic resin, acrylonitrile / styrene copolymer, polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, polyamide 6T / 66 copolymer, polyamide 6T / 6I copolymer, polyamide 9T, polyamide 10T Thermoplastic polyamide-based resin such as, polyethylene terephthalate, polybutylene terephthalate, thermoplastic polyester-based resin such as polyarylate, thermoplastic vinyl aromatic resin such as polystyrene, thermoplastic polyurethane, polycarbonate resin, polyphenylene ether, polyphenylene sulfide, polyimide , Polysulfone, polyether sulfone and other thermoplastic resins, and thermocurable resins such as unsaturated polyester resin, epoxy resin, phenol resin, urea resin, melamine resin, diallyl phthalate resin and silicone resin.
[0236]
　Examples of various additives include weather stabilizers, heat stabilizers, antioxidants, UV absorbers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, nucleating agents, lubricants, pigments, dyes, and aging. Examples thereof include inhibitors, hydrochloric acid absorbers, inorganic or organic fillers, organic or inorganic foaming agents, cross-linking agents, cross-linking aids, pressure-sensitive adhesives, softeners, flame retardants and the like.
[0237]
　In the resin composition of the present invention, the content of the resin composed of the particles (X) is usually 30% by mass or more, preferably 40% by mass or more, and more preferably 50% by mass or more.
[0238]
　The resin composition of the present invention contains the resin composed of the particles (X) of the present invention 1, but may further contain other components as described above, in which case, for example, the resin and other components. And are obtained by mixing, and the mixing method is not particularly limited, and examples thereof include a method of compounding with a twin-screw extruder and a method of mixing by dry blending and the like.
[0239]
　 [Molded article]
　The molded article of the present invention is the resin composed of the 4-methyl-1-pentene polymer particles (X) and the particles (X) of the present invention 1, or the resin composition containing the resin. Obtained by molding. Further, the molded product of the present invention can be obtained by molding the 4-methyl-1-pentene resin (X) obtained by the production method of the present invention 2 or the resin composition containing the resin (X). ..
[0240]
　(1) Molding method As the
　molding method, various known molding methods can be applied, for example, injection molding, extrusion molding, injection stretch blow molding, blow molding, cast molding, calendar molding, press molding, stamping molding, inflation. Various molding methods such as molding and roll molding can be mentioned. By these molding methods, it is possible to process a target molded product, for example, a single-layer or laminated film, sheet, membrane, tape, hollow molded product, injection molded product, fiber, foam or the like.
[0241]
　(2) Shape There
　are no particular restrictions on the shape of the molded product. Examples thereof include tube shape, film shape, sheet shape, membrane shape, tape shape, plate shape, rod shape, fibrous shape, and non-woven fabric shape.
[0242]
　In the following description, film is a general term for flat molded bodies, and is a concept including sheets, tapes, and the like.
[0243]
　(3) Applications Since
　the molded product of the present invention is excellent in high heat resistance, high toughness, light weight, water resistance, low dielectric constant, low bending whitening property, etc., food containers, medical containers, household goods, electric / electronic materials, etc. It can be used in a wide range of fields such as automobile parts without any restrictions.
[0244]
　In the fields of food, medical care, and daily necessities, for example,
　commercial wrapping film, household wrapping film, processed fish wrapping material, vegetable wrapping material, fruit wrapping material, fermented food wrapping material, confectionery wrapping material, oxygen absorber packaging material, retort pouch Food packaging materials such as food packaging materials, freshness-preserving films, bulb packaging materials, seed packaging materials, vegetables / mushroom cultivation films; retort food containers, heat-resistant vacuum-molded containers, side dish containers, side dish lids, baking cartons, tableware , Food containers such as tampering containers, kitchen utensils, retort pouches, frozen storage containers, retort pouches, microwave heat-resistant containers, frozen food containers, chilled confectionery cups, cups, baby bottles, beverage bottles;
　Blood transfer set, medical bottle, medical container, medical tube, infusion tube, connector and packing, medical hollow bottle, medical bag, infusion bag, blood storage bag, infusion bottle, drug container, detergent container, softener container , Bleaching agent container, vial, plastic syringe, prefilled syringe, pharmaceutical packaging material, cell culture bag, cell culture container, cell test film, medical gasket, medical cap, drug stopper, gasket, boiling treatment, high-pressure steam sterilization, etc. Medical equipment such as packing materials for high temperature treatment; physics and chemistry laboratory equipment such as beakers, chalets, flasks, animal gauges, storage containers; PCR plates, PCR tubes, foil seals for PCR plates, buffer containers, marker containers, etc. Various medical inspection kits; Lens applications such as contact lenses and spectacle lenses; Protective glasses for work / experiments or eyeglass applications such as goggles and sunglasses; Head-up displays, head mount displays and their in-vehicle applications; Product displays, household use Ornamental containers such as viewing tanks and large commercial tanks; other containers such as shoe soles, automobile parts, writing tools, sporting goods, laminated resins, asphalt blend resins, electron beam bridging materials, shampoo containers, rinse containers, cosmetic containers , Perfume container, container container, powder container, adhesive container, gasoline tank container, kerosene container, heat-resistant container and the like.
[0245]
　In the field of electronic materials, for electronic displays such as electronic paper, organic EL display devices, LED (light emitting diode) lighting devices, CMOS (complementary metal oxide film semiconductor) sensors, etc., which utilize transparent and flexible performance. Transparent flexible film; film for various electronic devices and optical waveguides such as interlayer insulating film for semiconductors, buffer coat, substrate for flexible printed wiring circuit, liquid crystal alignment film; flexible for liquid crystal display device, organic EL display device, organic TFT, etc. Substrate: Films for electronic materials that take advantage of releasability, heat resistance and low dielectric properties, such as release films for flexible printed substrates, release films for ACM substrates, release films for rigid substrates, and release films for rigid flexible substrates. Film, release film for advanced composite material, release film for curing carbon fiber composite material, release film for curing glass fiber composite material, release film for curing aramid fiber composite material, release film for curing nano composite material, filler Release film for curing filler, release film for semiconductor encapsulation, release film for polarizing plate, release film for diffusion sheet, release film for prism sheet, release film for reflection sheet, cushion film for release film , Release film for fuel cell, release film for various rubber sheets, release film for urethane curing, release film for epoxy curing, solar cell sealing sheet, solar cell back sheet, solar cell Plastic film for, battery separator, separator for lithium ion battery, electrolyte film for fuel cell, adhesive / adhesive separator, light guide plate, optical disk, dicing tape / back grind tape / dibonding film, double layer FCCL, film for film condenser, etc. Substrate / adhesive / separator, adhesive film, stress relief film, pellicle film, polarizing plate film, protective film for polarizing plate, protective film for liquid panel, protective film for optical parts, lens Protective film for electrical parts / electrical products, protective film for mobile phones, protective film for personal computersLM, protective film for touch panel, protective film for window glass, film for baking finish, masking film, film for condenser, capacitor film, tab lead film, capacitor film for fuel cell, reflective film, diffusion film, laminate (including glass), Radiation-resistant film, γ-ray resistant film, protective film such as porous film, heat-dissipating film / sheet, mold for manufacturing electronic component encapsulants, LED molds, laminates for high-frequency circuits, coating materials for high-frequency cables, optical waveguide substrates, Glass fiber composite, carbon fiber composite, glass interlayer film, laminated glass film, window film for building materials, arcade dome, gymnasium window glass substitute, LCD substrate film, bulletproof material, bulletproof glass film, heat shield sheet, shield Thermal film, release paper for synthetic leather, release paper for advanced composite material, release paper for curing carbon fiber composite material, release paper for curing glass fiber composite material, release paper for curing aramid fiber composite material, release paper for curing nano composite material , Release paper such as release paper for curing filler filler, heat and water resistant printing paper, packaging film, release film, breathable film, reflective film, synthetic paper, display film, display conductive film, display barrier film, etc. Be done.
[0246]
　Other applications include, for example, rubber hose manufacturing mandrel, sheath, rubber hose manufacturing sheath, hose, tube, synthetic leather release paper, industrial tube, cooling water pipe, hot water pipe, electric wire coating material, millimeter wave signal cable coating. Materials, high-frequency signal cable coating materials, eco-electric wire coating materials, in-vehicle cable coating materials, signal cable coating materials, high-voltage wire bumpers, wiring ducts, cosmetic / perfume spray tubes, piffs, wire harnesses, automobiles / motorcycles / railways Interior / exterior materials for vehicles / aircraft / ships, wear-resistant automobile interior / exterior materials, instrument panel skins, door trim skins, rear package trim skins, ceiling skins, rear pillar skins, seat back garnishes, console boxes, armrests, airbag cases Lid, shift knob, assist grip, side step mat, meter cover, battery cap, fuse, automatic water wash sensor parts, ignition, coil bobbin, bushing, bumper, car heater fan, radiator grill, wheel cap, EV power connector, in-vehicle display Plate plate, louver, armrest, rail insulation plate, two-wheeled vehicle windproof, reclining cover, trunk seat, seat belt buckle, inner / outer molding, bumper molding, side molding, roof molding, belt molding and other molding materials, air spoiler, door seal , Body seals and other automotive sealants, glass run channels, mudguards, kicking plates, step mats, number plate housings, automotive hose components, air duct hoses, air duct covers, air intake pipes, air dam skirts, timing belt cover seals, Bumper cushion, door cushion, cup holder, side brake grip, shift knob cover, seat adjustment knob, wire harness grommet, suspension cover boots, glass guide, inner belt line seal, roof guide, trunk lid seal, molded quarter wind gasket, corner Molding, Grass EncapAutomotive interior / exterior materials such as oscillations, hood seals, glass run channels, secondary seals, bumper parts, body panels, side shields, door skins, weather strip materials, hoses, steering wheels, wire harness covers, seat adjuster covers, vibration damping tires. , Static tires, car race tires, special tires such as radio control tires, packing, automobile dust cover, lamp seal, automobile boot material, rack and pinion boot, timing belt, wire harness, grommet, emprem, air filter packing, automobile For connection, ignition coil, switch, lamp reflector, relay, electric control unit case, sensor housing, headlamp, meter plate, insulator, bearing retainer, thrust washer, lamp reflector, door handle, glazing, panoramic roof, solenoy valve, ECU Cases, unit connection connectors, alternators, HEV terminal blocks, electromagnetic valves, coil sealing parts, skin materials for furniture, footwear, clothing, bags, building materials, etc., building sealants, waterproof sheets, building material sheets, pipe joints, etc. Dressing table, bathroom ceiling, impeller, building material gasket, window film for building material, iron core protective member, ground improvement sheet, water blocking material, joint material, gasket, door, door frame, window frame, peripheral edge, skirt, opening Frames, floor materials, ceiling materials, wallpaper, health products (eg non-slip mats / sheets, fall prevention films / mats / sheets), health equipment parts, shock absorbing pads, protectors / protective equipment (eg helmets, guards) , Sporting goods (eg sports grips, protectors), sports gear, rackets, mouth guards, balls, golf balls, carrying equipment (eg)Shock absorbing glyphs for transportation, shock absorbing sheets), vibration damping pallets, shock absorbing dampers, insulators, shock absorbing materials for footwear, shock absorbing foams, shock absorbing materials such as shock absorbing films and sheets, grip materials (writing tools, tools, etc. Exercise equipment, vehicle handles, daily necessities, electrical appliances, furniture, etc.), camera bodies and parts, OA equipment parts, copying machine structural parts, printer structural parts, aircraft parts, in-flight meal trays, facsimile structural parts, pump parts, electric Tool parts, drying washing machine parts, heater pump spout / outlet, IH rice cooker, rice cooker inner lid, range roller staying, vacuum cleaner fan guide, electronic jar pump / filter case, food waste disposer parts / processing Tank / heating / drying parts, milk meter, filter bowl, escalator parts, ultrasonic motor housing, absolute encoder, small pump housing, TV parts, hair dryer housing, lighting cover, miscellaneous goods, coffee dripper, humidifier parts, iron parts, water supply Equipment parts, water cylinders, combs, pencil cases, pencil cases, pencil cases, sports and leisure goods, ski goggles, karate / kendo armor, surfing fins, musical instruments, fish tanks, sandals, snow scraping scoops, fishing rod cases, toys, shoe soles, shoe soles. Sole, midsole / inner sole of shoes, sole, sandals, chair skin, bag, school cell, jumper coat and other clothing, band, stick, ribbon, notebook cover, book cover, key holder, pencil case, wallet, chopsticks, ranger , Microwave cooking pan, business card holder, regular holder, sucker, toothbrush, floor material, gym mat, power tool member, farm equipment member, heat dissipation material, transparent substrate, soundproofing material, sound absorbing material, cushioning material, electric wire cable, shape memory Materials, connectors, switches, plugs, home appliances parts (motor parts, housings, etc.), industrial sealing materials, industrial sewing tables, number plate housings, cap liners such as PET bottle cap liners, protective film adhesive layers, hot melt adhesive materials Adhesive materials such as stationery, office supplies, OA printer legs, fax legs, sewing machine legs, motor support mats,As precision equipment such as audio vibration isolator, OA equipment support member, heat resistant packing for OA, optical media such as CD / DVD / Blu-ray, cell for optical measurement, costume case, clear case, clear file, clear sheet, desk mat, fiber Applications include, for example, monofilaments, multifilaments, cut fibers, hollow fibers, non-woven fibers, elastic non-woven fabrics, fibers, waterproof cloths, breathable fabrics and cloths, paper diapers, sanitary goods, sanitary goods, filters, bag filters, dust collection Filter, air cleaner, hollow fiber filter, water purification filter, care, paper, gas separation membrane, artificial liver (case, hollow fiber), filter reverse osmotic membrane, artificial cardiopulmonary, syringe syringe, three-way activation plug, infusion set, Examples include surgeon's instruments, flow meters, dental instruments, contact lens sterilization instruments, inhalation masks, analytical cells, milking machines, fire alarms, fire extinguishers, helmets, burn-in sockets and the like.
[0247]
　In addition, coating materials, films obtained by coating, sheets, mold release materials, water-shooting materials, insulating films, adhesives, adhesives, coated paper, transparent sealants, sealants, hot melt type adhesives, solvent type adhesives It is also suitably used for agents, film-like adhesives, cloth tapes, kraft tapes, elastic adhesives and the like.
[0248]
　Further, the 4-methyl-1-pentene polymer particles (X), the resin and the resin composition, and the 4-methyl-1-pentene resin (X) and the resin composition containing the same are pulverized. It can also be processed into a fine powder. The obtained fine powder can be used as, for example, as an additive for an ink composition or a coating composition, as an additive for a metallurgical powder composition, as an additive for a ceramic sintering powder composition, or as an additive for a pressure-sensitive adhesive. It can be used as an additive for rubber, as a mold release agent for toner, and as a mold release agent. Furthermore, the obtained fine powder can be used as a resin additive for shafts, gears, cams, electrical parts, camera parts, automobile parts, household parts, wax, grease, engine oil, fine ceramics, plating, etc. It can also be used as a resin additive for.
Example
[0249]
　Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited to these examples.
[0250]
　 [Measurement method of various physical properties]
　 D50 in the
　volume statistical value was determined by a laser diffraction / scattering method using MT3300EX II manufactured by Microtrac.
[0251]
　
　Measurement was performed using an ICP (inductively coupled plasma) emission spectrometer manufactured by Shimadzu Corporation: ICPS-8100. For the quantitative and qualitative analysis of aluminum and zirconium, the sample was wet-decomposed with sulfuric acid and nitric acid, and then subjected to constant volume (including filtration and dilution as necessary) as a test solution.
[0252]
　 The
　polymer slurry obtained in step (2) was separated into a solid substance (white solid) and a filtrate by filtration. Then, the solvent was removed from the filtrate by an evaporation method to obtain a polymer dissolved in the filtrate. Then, the amount of the polymer in the filtrate was calculated based on the following formula.
[0253]
　Amount of polymer in filtrate (% by mass) = W2 / (W1 + W2) × 100
　　W1: Mass of filtered solid substance (white solid) (g)
　　W2: of polymer dissolved in the filtrate of slurry Mass (g)
　 The
　polymer slurry obtained in step (2) was filtered to separate a solid substance (white solid) and a filtrate. The bulk density of the obtained particulate solid was determined by the mass of the sample in a container having an internal volume of 100 mL according to JIS K-6721.
[0254]
　
　Regarding the obtained polymerization liquid, if it is a slurry with good solid-liquid separability in the filtration process, it is "good", and although it is a slurry, it is porridge-like and solid in the filtration process. The case where the liquid separability was poor was described as "poor", and the case where the liquid was not a slurry but was a solution was described as "solution".
[0255]
　 [Measuring method for polymer physical characteristics, etc.]
　
　At the end of polymerization in step (1), the polymer slurry is extracted and the slurry concentration is measured. The amount of the polymer produced in (1) was calculated. Along with this amount, the mass ratio of the polymer produced in each step was determined from the amount of the polymer finally obtained. The temperature at the time of filtration: room temperature (25 ° C.), filtration method: filtration was performed while washing with hexane using Kiriyama filter paper (opening 1 μm), and the slurry concentration was calculated. Filtration was performed under these conditions in the following examples. The solvent-soluble portion is not included in the calculation of the polymer ratio or the measurement of the following physical properties (excluding Reference Example 2A).
[0256]
　
　The content (comonomer content) of the structural unit derived from the comonomer was calculated from the 13 C-NMR spectrum by the following equipment and conditions .
[0257]
　Using AVANCE III cryo-500 nuclear magnetic resonance system manufactured by Bruker Biospin, the solvent is o-dichlorobenzene / benzene-d 6 (4/1 v / v) mixed solvent, the sample concentration is 55 mg / 0.6 mL, and the measurement temperature. Is 120 ° C, the observation nucleus is 13 C (125 MHz), the sequence is single-pulse Freton broadband decoupling, the pulse width is 5.0 μsec (45 ° pulse), the repetition time is 5.5 seconds, and the number of integrations is 64 times. , 128 ppm of benzene-d 6 was measured as a reference value for chemical shift. The comonomer content was calculated by the following formula using the integrated value of the main chain methine signal.
[0258]
　Comonomer content (%) = [P / (P + M)] × 100
　where P indicates the total peak area of ​​the comonomer backbone methine signal and
　M indicates the total peak area of the 4-methyl-1-pentene backbone methine signal. ..
[0259]
　The comonomer content in the polymer produced in step (1) was determined using a polymer obtained from the polymer slurry extracted at the end of polymerization in step (1), and was found in the polymer produced in step (2). The comonomer content in is the comonomer content in the polymer obtained in step (1), the comonomer content in the final polymer (step (1) + step (2)), and the ratio of the polymer produced in each step. Was obtained using. Specifically, the comonomer contents in the polymers and final polymers produced in steps (1) and (2) were set to m 1 , m 2 and m f , respectively , and the weights produced in steps (1) and (2) were set. Assuming that the coalescence ratios are w 1 and w 2 , respectively , m 2 = (m f − w 1 · m 1 ) / w 2 .
[0260]
　 The mesodiad
　isotacticity (mesodiad fraction) (m) of 4-methyl-1-pentene polymer is 4-methyl-1-linked by any two heads and tails in the polymer chain. When the penten unit chain was expressed in a planar zigzag structure, it was defined as the ratio in which the directions of the isobutyl branches were the same, and it was calculated from the 13 C-NMR spectrum by the following formula.
[0261]
　Mesodiad isotacticity (m) (%) = [m / (m + r)] × 100
[In the formula, m and r are 4-methyl-1-bonded by the head-tail represented by the following formula. It shows the absorption intensity derived from the main chain methylene in pentene units. ]
[0262]
[Chemical formula 4]

　 13 The C-NMR spectrum uses an AVANCE III cryo-500 type nuclear magnetic resonance apparatus manufactured by Bruker Biospin, and the solvent is an o-dichlorobenzene / benzene-d6 (4/1 v / v) mixed solvent and a sample. The concentration is 60 mg / 0.6 mL, the measurement temperature is 120 ° C, the observation nucleus is 13 C (125 MHz), the sequence is single pulse proton broadband decoupling, the pulse width is 5.0 μsec (45 ° pulse), and the repetition time is 5. For 5 seconds, 128 ppm of benzene-d6 was measured as a reference value for chemical shift.
[0263]
　In the peak region, the region of 41.5 to 43.3 ppm was divided by the minimum point of the peak profile, and the high magnetic field side was classified into the first region and the low magnetic field side was classified into the second region.
[0264]
　In the first region, the main chain methylene in the 4-methyl-1-pentene unit 2 chain represented by (m) resonates, but the integrated value regarded as a 4-methyl-1-pentene homopolymer is "m". And said. In the second region, the main chain methylene in the 4-methyl-1-pentene unit 2 chain represented by (r) resonated, and the integrated value was defined as “r”. In addition, less than 0.01% was set to be below the detection limit.
[0265]
　 Using the
　automatic kinematic viscosity measuring device VMR-053PC manufactured by Rigosha and the improved Ubbelohde type capillary viscometer, the specific viscosity ηsp at 135 ° C was obtained with decalin, and the ultimate viscosity ([η]) was obtained from the following formula. Was calculated.
[0266]
　[Η] = ηsp / {c (1 + K · ηsp)}
　(c: Solution concentration [g / dl], K: constant)
　Note that the ultimate viscosity [η] of the polymer produced in step (1) is the step ( The ultimate viscosity [η] of the polymer obtained in step (2) obtained by using the polymer obtained from the polymer slurry extracted at the end of the polymerization of 1) is the limit of the polymer obtained in step (1). It was determined using the viscosity [η], the ultimate viscosity [η] of the final polymer (step (1) + step (2)), and the ratio of the polymer produced in each step. Specifically, the [η] of the polymers and final polymers produced in steps (1) and (2) are set to [η] 1 , [η] 2 and [η] f , respectively, and steps (1) and ( Assuming that the proportions of the polymers produced in 2) are w 1 and w 2 , respectively , [η] 2 = ([η] f −w 1 · [η] 1 ) / w 2 .
[0267]
　
　Using EXSTAR DSC6220 manufactured by SI Nanotechnology, a sample of about 4 mg was heated from 30 ° C. to 280 ° C. under a nitrogen atmosphere (30 ml / min). After holding at 280 ° C. for 5 minutes, the mixture was cooled to −50 ° C. at 10 ° C./min. After holding at −50 ° C. for 5 minutes, the temperature was raised to 280 ° C. at 10 ° C./min. The apex of the crystal melting peak observed at the time of the second temperature rise was defined as the melting point (Tm). The amount of heat of fusion associated with melting was defined as ΔH. When a plurality of peaks were detected in the polymer produced in each step, the one having the highest temperature was defined as the melting point (Tm). The melting point (Tm) of the polymer produced in the step (2) was determined by analyzing the polymer produced in the step (1) and the final polymer.
[0268]
　
　CFC measurement was performed under the following conditions.
Equipment: CFC2 type cross fractionation chromatograph (Polymer Char)
detector (built-in): IR4 type infrared spectrophotometer (Polymer Char)
Detection wavelength: 3.42 μm (2,920 cm -1 ); Fixed
sample concentration: Sample: 30 mg / 30 mL (diluted with o-dichlorobenzene (ODCB))
Injection volume: 0.5 mL
Temperature condition: Increase to 145 ° C at 40 ° C / min and hold for 30 minutes. After cooling to 0 ° C. at 1 ° C./min and holding for 60 minutes, the elution amount for each of the following elution categories was evaluated. The temperature change between the divisions was 40 ° C / min.
Elution classification: 0, 5, 10, 15, 20, 25, 30, 35, 50, 70, 90, 95, 100, 102, 104, 106 ° C, and from 108 ° C to 135 ° C in 1 ° C increments. Evaluate the amount of elution at 140,145 ° C.
GPC column: Shodex HT-806M x 3 (Showa Denko)
GPC column temperature: 145 ° C
GPC column calibration: Monodisperse polystyrene (Tosoh)
Molecular weight calibration method: Standard calibration method (polystyrene conversion)
Mobile phase: o-dichlorobenzene ( ODCB), BHT addition
flow rate: 1.0 mL / min
　 [Synthesis Example 1]
　 [Synthesis of Transition Metal Complex (Metallocene Compound (A))] According
　to Synthesis Example 4 of International Publication No. 2014/050817, (8-octamethylfluorene-12'-yl- (2- (adamantane-1-yl)-)- 8-Methyl-3,3b, 4,5,6,7,7a,8-octahydrocyclopenta [a] indene)) zirconium dichloride (metallocene compound (a1)) was synthesized.
[0269]
　 [Preparation of Solid Catalyst Component (Metallocene Catalyst)] As the
　carrier (B), solid polymethylaluminoxane (manufactured by Toso Finechem) having a particulate D50 of 8 μm and an aluminum atom content of 42% by mass was used. In a 100 mL three-necked flask equipped with a stirrer, which was sufficiently nitrogen-substituted at 30 ° C., 29.9 mL of purified decane and 7.26 mL of a hexane / decane solution of the solid polymethylaluminoxane (aluminum atom) were placed in a nitrogen stream. It was charged with 14.3 mmol) to prepare a suspension. To the suspension, 50 mg (0.0586 mmol in terms of zirconium atom) of the previously synthesized metallocene compound (a1) was added as a 4.59 mmol / L toluene solution with stirring 12.8 mL. After 1.5 hours, stirring was stopped and decantation washing with decan was performed (cleaning efficiency 98%) to prepare 50 mL of slurry liquid (Zr carrying rate 96%). The obtained solid catalyst component (metallocene catalyst) was in the form of particles, and its D50 was 8 μm.
[0270]
　 [Preparation of Prepolymerization Catalyst Component]
　4.0 mL of decane solution of diisobutylaluminum hydride (1 mol / L in terms of aluminum atom) and 15 mL of 3-methyl-1-pentene were added to the slurry liquid prepared as described above under a nitrogen stream. (10.0 g) was charged. After 1.5 hours, stirring was stopped and decantation washing with decan was performed (cleaning efficiency 95%) to make 100 mL of decan slurry (Zr recovery rate 93%, 0.548 mmol / L in terms of zirconium atom).
[0271]
　 [Synthesis Example 2] As
　the carrier (B) in [Preparation of solid catalyst component (metallocene catalyst) ] of Synthesis Example 1, a solid polyaluminoxane (B) in the form of particles having a D50 of 32 μm and an aluminum atom content of 44% by mass ( A solid catalyst component (metallocene catalyst) was obtained in the same manner as in Synthesis Example 1 except that (synthesized using the method described in International Publication No. 2014/123212) was used. The obtained solid catalyst component (metallocene catalyst) was in the form of particles, and D50 was 32 μm. Further, a prepolymerization catalyst component was prepared in the same manner as in Synthesis Example 1 to prepare 100 mL of decan slurry (Zr recovery rate 82%, 0.482 mmol / L in terms of zirconium atom).
[0272]
　 [Example 1A] Particles (X1-1)
　at room temperature (25 ° C.) under a nitrogen stream, in a SUS polymerizer equipped with a stirrer having an internal volume of 1 L, 425 mL of purified decan and a triethylaluminum solution (1 in terms of aluminum atoms). .0 mmol / mL) was charged in 0.4 mL (0.4 mmol in terms of aluminum atom). Next, 0.0014 mmol of the previously prepared decan slurry of the prepolymerization catalyst component of Synthesis Example 1 was added in terms of zirconium atoms, and the temperature was raised to 40 ° C. After reaching 40 ° C., 30 NmL of hydrogen was charged, and then 106 mL of 4-methyl-1-pentene (4MP-1) was continuously charged into the polymer over 30 minutes at a constant rate. The time at which the charge was started was defined as the start of polymerization, and the mixture was held at 45 ° C. for 3 hours (step (1)). After 3 hours had passed, pressurization and decompression with nitrogen (0.6 MPa) were performed three times in order to depressurize the inside of the system at 45 ° C. and discharge residual hydrogen to the outside of the system. Then, 30 NmL of hydrogen was charged under a nitrogen stream at 45 ° C., and then a mixed solution of 79.4 mL of 4-methyl-1-pentene and 7.4 mL of 1-decene was continuously introduced into the polymer over 30 minutes. It was charged at a constant speed. The time at which the charge was started was defined as the start of polymerization, and the mixture was held at 45 ° C. for 3 hours (step (2)). After 3 hours from the start of the polymerization, the temperature was lowered to room temperature, the pressure was depressurized, and then the polymerization solution (slurry) containing the white solid was immediately filtered to obtain a solid substance. This solid substance was dried under reduced pressure at 80 ° C. for 8 hours to obtain 105.4 g of particles (X1-1). The various results are shown in Tables 1A and 2A.
[0273]
　 [Examples 2A to 8A]
　Polymer particles were obtained in the same manner as in Example 1A except that the polymerization conditions were changed as shown in Table 1A. The various results are shown in Tables 1A and 2A.
[0274]
　 [Comparative Example 1A]
　Polymerization was carried out only by the operation of step (1) at the catalyst amount, 4MP-1 feed amount, hydrogen amount, 1-decene feed amount, and polymerization time shown in Table 1A. The various results are shown in Tables 1A and 2A.
[0275]
　 [Comparative Examples 2A to 6A] With
　4-methyl-1-pentene and other α-olefins (1-decene or 1-hexadecene) according to the polymerization method described in Comparative Example 9 of International Publication No. 2006/054613. 4-Methyl-1-pentene polymer particles were obtained by changing the ratio of 1-octadecene) and hydrogen. That is, all of these 4-methyl-1-pentene polymer particles are reacted with anhydrous magnesium chloride, 2-ethylhexyl alcohol, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane and titanium tetrachloride. This means that it was obtained by single-stage polymerization using the solid titanium catalyst thus obtained as a polymerization catalyst. The various results are shown in Tables 1A and 2A.
[0276]
　 [Comparative Example 7A] The
　catalyst component was changed to the solid titanium catalyst component (0.042 mmol in terms of Ti atom) described in [Preparation Example 1] and [Preparation Example 2] of International Publication No. 2009/008409, and Table 1A. The polymerization operation was carried out under the conditions described in 1 to obtain polymer particles. The various results are shown in Tables 1A and 2A.
[0277]
　In Table 2A, "step (1)" is the polymer produced in step (1), "step (2)" is the polymer produced in step (2), and "total" is the final polymer (in the case of Examples). Corresponds to the particle (X)).
[0278]
　
　Polymerization was carried out using only the operation of step (1) at the catalyst amount, 4MP-1 feed amount, hydrogen amount, and polymerization time shown in Table 1A to obtain polymer particles. The various results are shown in Tables 1A and 2A.
[0279]
　
　Polymerization was carried out only by the operation of step (2) at the catalyst amount, 4MP-1 feed amount, hydrogen amount, 1-decene feed amount, and polymerization time shown in Table 1A. Since the polymer was dissolved in a solvent, it was dried at 120 ° C. for 8 hours using a vacuum dryer to obtain a polymer. The various results are shown in Tables 1A and 2A.
[0280]
　 [Comparative Example 8A]
　A resin obtained by blending the polymer particles obtained in Reference Example 1A and the polymer obtained in Reference Example 2A at a mass ratio of 42:58 and granulating by the following method. The composition was evaluated. The various results are shown in Tables 1A and 2A.
[0281]
　 [Measuring method of
　resin physical characteristics ] The resin physical properties were evaluated by the following methods. The results are shown in Table 3A.
[0282]
　 In
　the polymer particles of Examples 1A to 8A, the polymer particles of Comparative Examples 1A to 7A, or the polymer for evaluation of Comparative Example 8A (the polymer particles obtained in Reference Example 1A and the polymer particles of Reference Example 2A). The obtained polymer was blended so as to have a mass ratio of 42:58), and tri (2,4-di-t-butylphenyl) phosphate was added as a secondary antioxidant to 100 parts by mass. 1 part by mass and 0.1 part by mass of n-octadecyl-3- (4'-hydroxy-3', 5'-di-t-butylphenyl) propine as a heat-resistant stabilizer were blended. After that, using a twin-screw extruder BT-30 (screw system 30 mmφ, L / D 46) manufactured by Plastic Engineering Laboratory Co., Ltd., the conditions are a set temperature of 260 ° C., a resin extrusion rate of 60 g / min, and a rotation speed of 200 rpm. A resin composition was obtained by granulating with.
[0283]
　A 1 mm-thick iron plate hollowed out in an 8 cm square was placed between the two iron plates, and 5.2 g of the above resin composition was charged in the hollowed out portion. A compression molding machine (mold clamping 50 tons) manufactured by Shinto Metal Industry Co., Ltd. was heated to 270 ° C., and the above iron plate was inserted. After allowing to stand for 7 minutes to melt the resin composition, the iron plate is compressed at a pressure of 10 MPa, held for 3 minutes, then taken out, and the iron plate is inserted into the compressor set at 23 ° C. for 3 minutes at a pressure of 10 MPa. It was cooled over. A 1 mm thick molded body was taken out from the hollowed out portion and used as a press plate for evaluation.
[0284]
　 The elastic modulus,
　which is a tensile characteristic, is based on ASTM D638, using a test piece shot from the above-mentioned 1 mm thick press plate, and using a universal tensile tester 3380 manufactured by Instron, between chucks. A tensile test was performed at 65 mm and a tensile speed of 50 mm / min for evaluation.
[0285]
　 As an index of high heat resistance and low rigidity (flexibility), at least one of the melting point peaks is 220 ° C. or higher, and the tensile elastic modulus (MPa) is Tm (° C.). The case where it was smaller than × 49.6-10400 was evaluated as ◯, and the case where the tensile elastic modulus (MPa) was smaller than Tm (° C.) × 49.6-10800 was evaluated as ⊚.
[0286]
　 For
　Examples 1A to 3A and Comparative Example 8A, the cross section of the press plate was sliced ​​in the side view (side view), and a transmission electron microscope JEM-2100Plus manufactured by JEOL Ltd. was used. The phase separation structure was observed. Images at an observation magnification of 10,000 times are shown in FIGS. 2 to 5.
[0287]
　
　Using a haze meter NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd., the haze value (total haze) of the press plate in air was evaluated in accordance with JIS-K-7136.
[0288]
　
　 Using a single-screw sheet molding machine manufactured by Tanaka Iron Works Co., Ltd., the resin composition granulated by the method described is used to form a cylinder temperature of 270 ° C, a die temperature of 270 ° C, and a roll temperature of 80 ° C. A film having a thickness of 50 μm was obtained by melt casting molding under the conditions of a take-up speed of 5 m / min. It was investigated how often the eye tars accumulated on the lip were dropped onto the film when the film was continuously formed at 1000 m, and the appearance of the film was deteriorated and defects occurred. For a 1000 m film, the case where the number of defects of contamination by the eye tar was 5 or less was evaluated as 0, and the case where the number was 6 or more was evaluated as ×. The lip of the molding machine was cleaned and compared after each level.
[0289]
　In addition, regarding the above level of 〇, those in which no appearance defects due to cracks or cracks at the edges occurred during mold release from the surface of the cooling roll during 1000 m film formation were judged to be in a particularly good condition. did.
[0290]
　
　Examples 1A to 8A have high stereoregularity due to the high mesodiad fraction, excellent heat resistance due to the high melting point (Tm), and the melting point (Tm) and tensile elastic modulus. From the relationship, it can be seen that the balance between heat resistance and flexibility is excellent. Examples 2A and 3A have a particularly excellent balance between heat resistance and flexibility.
[0291]
　It can be seen that Comparative Examples 1A to 6A do not satisfy the requirement (Xb), and the balance between heat resistance and flexibility is not sufficient as compared with Examples.
[0292]
　Comparative Example 7A has insufficient stereoregularity and does not satisfy the requirement (Xc).
[0293]
　Comparative Example 8A is an example in which the polymer (x1) and the polymer corresponding to the copolymer (x2) are individually produced and then produced by melt blending, and does not correspond to the polymer particles of the present invention. It can be seen that although it has an excellent balance of stereoregularity, heat resistance, heat resistance and flexibility, it is inferior in transparency. From the transmission electron microscope (TEM) image, it can be seen that the uniformity of the phase-separated structure is lower than that of Examples 1A to 3A.
[0294]
[Table 1A]

[0295]
[Table 2A]

[0296]
[Table 3A]

　 [Example 1B] 425
　mL of purified decan and a triethylaluminum solution (aluminum) were placed in a SUS polymerizer equipped with a stirrer having an internal volume of 1 L under a resin (X1-1) room temperature (25 ° C.) and a nitrogen stream. 0.4 mL (0.4 mmol in terms of aluminum atom) was charged (1.0 mmol / mL in terms of atom). Next, 0.0014 mmol of the previously prepared decan slurry of the prepolymerization catalyst component of Synthesis Example 1 was added in terms of zirconium atoms, and the temperature was raised to 40 ° C. After reaching 40 ° C., 30 NmL of hydrogen was charged, and then 106 mL of 4-methyl-1-pentene (4MP-1) was continuously charged into the polymer over 30 minutes at a constant rate. The time at which the charge was started was defined as the start of polymerization, and the mixture was held at 45 ° C. for 3 hours (step (1)). After 3 hours had passed, pressurization and decompression with nitrogen (0.6 MPa) were performed three times in order to depressurize the inside of the system at 45 ° C. and discharge residual hydrogen to the outside of the system. Then, 30 NmL of hydrogen was charged under a nitrogen stream at 45 ° C., and then a mixed solution of 79.4 mL of 4-methyl-1-pentene and 7.4 mL of 1-decene was continuously introduced into the polymer over 30 minutes. It was charged at a constant speed. The time at which the charge was started was defined as the start of polymerization, and the mixture was held at 45 ° C. for 3 hours (step (2)). After 3 hours from the start of the polymerization, the temperature was lowered to room temperature, the pressure was depressurized, and then the polymerization solution (slurry) containing the white solid was immediately filtered to obtain a solid substance. This solid substance was dried under reduced pressure at 80 ° C. for 8 hours to obtain 105.4 g of a resin (X1-1). The filtrate was dried under reduced pressure at 120 ° C. to obtain a solvent-soluble portion (SP). The various results are shown in Tables 2B to 3B.
[0297]
　 [Examples 2B to 19B]
　The same operation as in Example 1B was carried out except that the polymerization conditions were changed as shown in Table 1B to obtain a polymer. The various results are shown in Tables 2B to 3B. In the table, L168 is a mixture of a linear α-olefin having 16 carbon atoms and a linear α-olefin having 18 carbon atoms (mixed molar ratio: α-olefin having 16 carbon atoms: α-olefin having 18 carbon atoms = It means 60:40).
[0298]
　 [Examples 20B to 24B] The
　polymer was prepared by using the prepolymerization catalyst component obtained in Synthesis Example 2 and performing the same operation as in Example 1B except that the polymerization conditions were changed as shown in Table 1B. Obtained. The various results are shown in Tables 2B to 3B.
[0299]
　 [Comparative Example 1B]
　Same as Example 1B except that the 4MP-1 feed amount and 1-decene feed amount in step (1) and the 1-decene feed amount in step (2) were changed as shown in Table 1B. The same operation was performed, but the polymer produced in step (1) was dissolved in a solvent, so that slurry polymerization could not be performed and the polymer could not be recovered.
[0300]
　 [Comparative Examples 2B and 3B] The
　catalyst component was changed to the solid titanium catalyst component (0.042 mmol in terms of Ti atom) described in [Preparation Example 1] and [Preparation Example 2] of International Publication No. 2009/008409. A polymerization operation was carried out under the conditions shown in Table 1B to obtain a polymer. The various results are shown in Tables 2B to 3B. The slurry properties were good for Comparative Example 2B, but poor (porridge) for Comparative Example 3B.
[0301]
　 In
　Examples 1B to 24B, the properties of the polymerization solution were good, that is, the solid-liquid separability of the slurry was good. It shows that polymerization is possible in a wide range of the total comonomer content or the comonomer content in the polymer of step (2).
[0302]
　Comparative Example 1B is an example in which more comonomer was copolymerized in step (1) than in step (2), but slurry polymerization was not possible.
[0303]
　Comparative Examples 2B and 3B are examples in which a so-called Ziegler catalyst is used, but it shows that the properties of the polymer solution become poor in a region where the amount of comonomer feed is large. Further, although Comparative Example 2B has good polymer liquid properties, the amount of the solvent-soluble part is larger than that of Examples having the same amount of comonomer feed.
[0304]
[Table 1B]

[0305]
[Table 2B]

[0306]
[Table 3B]

The scope of the claims
[Claim 1]
　4-Methyl-1-pentene polymer particles (X) satisfying the following requirements (Xa), (Xb) and (Xc).
　(X-a) The content of the structural unit derived from 4-methyl-1-pentene of the 4-methyl-1-pentene polymer constituting the particle (X) is 30.0 to 99.7 mol%. Yes, the content of the structural unit derived from ethylene and at least one olefin selected from α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 0.3 to 70.0 mol%. Is.
　(Xb) When measured by a cross fractionation chromatograph (CFC) using an infrared spectrophotometer in the detection unit, at least one peak A of the amount of eluted components is present in the range of 100 to 140 ° C. In addition, at least one peak B of the amount of eluted components is present below 100 ° C.
　(Xc) 13 The mesodiad fraction (m) measured by C-NMR is in the range of 95.0 to 100%.
[Claim 2]
　10.0 to 95.0 parts by mass of 4-methyl-1-pentene polymer (x1) satisfying the following requirement (x1-a) and 4-methyl-1-pentene copolymer satisfying the following requirement (x2-a) The first aspect of the present invention, which contains 5.0 to 90.0 parts by mass of the coalescence (x2) (provided that the total amount of the polymer (x1) and the copolymer (x2) is 100 parts by mass). 4-Methyl-1-pentene polymer particles (X).
　The content of the structural unit derived from (X1-a) 4-methyl-1-pentene is 80.0 to 100 mol%, and ethylene and α-olefin having 3 to 20 carbon atoms (4-methyl-1-pentene). The content of the structural unit derived from at least one olefin selected from (excluding) is 0 to 20.0 mol%.
　The content of the structural unit derived from (x2-a) 4-methyl-1-pentene is 20.0 to 98.0 mol%, and ethylene and α-olefin having 3 to 20 carbon atoms (4-methyl-1). -The content of the structural unit derived from at least one olefin selected from (excluding pentene) is 2.0 to 80.0 mol%, but ethylene and 3 to 3 carbon atoms in the polymer (x1). It is greater than the content of the building blocks derived from at least one olefin selected from 20 α-olefins (excluding 4-methyl-1-pentene).
[Claim 3]
　The ultimate viscosity [η] of the polymer (x1) measured in decalin at 135 ° C. is in the range of 0.5 to 20 dl / g, and the melting point (Tm) measured by DSC is in the range of 210 to 260 ° C. There,
　the copolymer (x2), is in the range of 135 ° C. intrinsic viscosity measured in decalin at [eta] is 0.5 ~ 20 dl / g, melting point measured by DSC (Tm) is lower than 220 ° C.
The 4-methyl-1-pentene polymer particle (X) according to claim 2 , wherein the peak indicating the melting point does not appear in the range or in the DSC measurement .
[Claim 4]
　The 4-methyl-1-pentene-based weight according to any one of claims 1 to 3, wherein the ultimate viscosity [η] measured in decalin at 135 ° C. is in the range of 0.5 to 10.0 dl / g. Combined particles (X).
[Claim 5]
　The 4-methyl-1-pentene polymer according to any one of claims 1 to 4, wherein the mesodiad fraction (m) is in the range of 98.0 to 100% in the requirement (Xc). Particle (X).
[Claim 6]
　A resin comprising the 4-methyl-1-pentene polymer particles (X) according to any one of claims 1 to 5.
[Claim 7]
　A resin composition containing the resin according to claim 6.
[Claim 8]
　Molded from the 4-methyl-1-pentene polymer particles (X) according to any one of claims 1 to 5, the resin according to claim 6, or the resin composition according to claim 7. Molded body.
[Claim 9]
　A step (1) of producing a 4-methyl-1-pentene polymer (x1) satisfying the following requirement (x1-a) by slurry polymerization using a metallocene catalyst, and
　a polymer obtained in the above step (1). In the presence of (x1), a 4-methyl-1-pentene copolymer (x2) satisfying the following requirement (x2-a), and the total amount of the polymer (x1) and the copolymer (x2) to the extent that the amount of the copolymer is 100 parts by weight (x2) is 5.0 to 90.0 parts by weight, and step (2) be prepared by slurry polymerization using a metallocene catalyst
having a 4 -A method for producing a methyl-1-pentene resin (X).
　The content of the structural unit derived from (x1-a) 4-methyl-1-pentene is 80.0 to 100 mol%, and ethylene and α-olefin having 3 to 20 carbon atoms (4-methyl-1-pentene). The content of the structural unit derived from at least one olefin selected from (excluding) is 0 to 20.0 mol%.
　The content of the structural unit derived from (x2-a) 4-methyl-1-pentene is 20.0 to 98.0 mol%, and ethylene and α-olefin having 3 to 20 carbon atoms (4-methyl-1). -The content of the structural unit derived from at least one olefin selected from (excluding pentene) is 2.0 to 80.0 mol%, but ethylene and 3 to 3 carbon atoms in the polymer (x1). It is greater than the content of the building blocks derived from at least one olefin selected from 20 α-olefins (excluding 4-methyl-1-pentene).
[Claim 10]
　The ultimate viscosity [η] of the polymer (x1) measured in decalin at 135 ° C. is in the range of 0.5 to 20 dl / g, and the melting point (Tm) measured by DSC is in the range of 210 to 260 ° C. There,
　the copolymer (x2), is in the range of 135 ° C. intrinsic viscosity measured in decalin at [eta] is 0.5 ~ 20 dl / g, melting point measured by DSC (Tm) is lower than 220 ° C. The
method for producing a 4-methyl-1-pentene resin (X) according to claim 9 , wherein the peak indicating the melting point does not appear in the range or in the DSC measurement .
[Claim 11]
　The method for producing a 4-methyl-1-pentene resin (X) according to claim 9 or 10, wherein the polymerization temperatures in the step (1) and the step (2) are independently in the range of 0 to 100 ° C. ..
[Claim 12]
　4. Methyl- according to any one of claims 9 to 11, wherein the metallocene catalyst is a particulate catalyst containing the metallocene compound (A) and having a D50 in the volume statistical value in the range of 1 to 500 μm. 1-Method for producing penten-based resin (X).
[Claim 13]
　The metallocene catalyst contains a metallocene compound (A) and a carrier (B), the carrier (B) contains 20% by mass or more of aluminum atoms, and D50 in the volume statistical value is in the range of 1 to 500 μm. The method for producing a 4-methyl-1-pentene resin (X), which is a carrier, according to any one of claims 9 to 12.
[Claim 14]
　The 4-methyl-1-pentene resin (X) obtained by the method for producing a 4-methyl-1-pentene resin (X) according to any one of claims 9 to 13.
[Claim 15]
　A resin composition containing the 4-methyl-1-pentene resin (X) according to claim 14.
[Claim 16]
　A molded product molded from the 4-methyl-1-pentene resin (X) according to claim 14 or the resin composition according to claim 7.