4-Methyl-1-pentene polymer

Abstract

[Problem] To provide a 4-methyl-1-pentene polymer that has excellent preservation stability and dissolvability when being dissolved in a solvent and that is superior in heat resistance and / or coating appearance when a coating film thereof is stretched such as when said film is bent or used in applications requiring flexibility. [Solution] This 4-methyl-1-pentene polymer (A) is a copolymer of 4-methyl-1-pentene and at least one selected from linear α-olefins having 6-20 carbon atoms, and satisfies requirements (I) and (II). (I) The endothermic end temperature (TmE) is 230°C or less in a melting (endothermic) curve as measured by DSC. (II) The exothermic start temperature (TcS) is 210°C or less in a crystallization (exothermic) curve as measured by DSC.

Description

Technical Field

[0001] The present invention relates to a 4-methyl-1-pentene polymer.

Background Art

[0002] For display devices, semiconductor devices, optical members, printed circuit boards, etc., various coating agents such as those for protection, insulation, planarization, heat resistance, light resistance, and weather resistance are used. Films formed using these coating agents often undergo processes exceeding 200°C such as solder reflow and microfabrication in the manufacture of the above devices, etc., and thus high heat resistance is required. Furthermore, characteristics such as transparency and electrical insulation are required depending on the application. In particular, for a film formed by using a coating agent on the electrode surface of a capacitor, high electrical insulation is required to prevent leakage of accumulated electricity and voltage drop, along with heat resistance.

[0003] Also, in the pressing process of circuit boards such as printed wiring boards, flexible printed wiring boards, and multilayer printed wiring boards, a release film is used to prevent the circuit board from adhering to the platen. For example, in the case of a flexible printed wiring board, in order to protect the circuit portion of a base material (such as a polyimide film) having a predetermined circuit portion, the circuit portion is covered with a resin film with an adhesive, and further a release film is laminated and pressed (for example, Patent Document 1).

[0004] Against such a background, there has been a demand for a coating agent capable of forming a film having high heat resistance and electrical insulation that can be used for a release film or the like. In response to such a demand, coating agents including acrylic resins, polycarbonate resins, fluorine resins, polyacetal resins, polyester resins, silicone resins, polyethersulfone resins, polyimide resins, polyarylate resins, cyclic olefin resins, etc. have been proposed, but films having a well-balanced heat resistance and electrical insulation have not been able to be formed.

[0005] In recent years, cyclic olefin-based addition polymers containing silyl groups have been proposed as transparent resins for coatings having excellent heat resistance with a glass transition temperature of 200°C or higher (for example, Patent Documents 2 and 3). However, although cyclic olefin-based addition polymers have high heat resistance, they are rigid and lack flexibility, and are likely to crack or develop cracks when formed into films. For this reason, there is a risk that the film may be damaged during use as a release film or the like, resulting in a decrease in electrical insulation. In addition, when a large amount of silyl groups are introduced and crosslinked, there are concerns about warpage due to shrinkage, and problems such as high water absorption and high dielectric constant.

[0006] In addition, as a composition containing a 4-methyl-1-pentene copolymer and a solvent, an example is disclosed in which a composition obtained by dissolving a 4-methyl-1-pentene copolymer having a low molecular weight (or a melting point of 200°C or lower) that can be dissolved in the solvent in the solvent is used for coating (for example, Patent Documents 4 and 5).

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0008] The 4-methyl-1-pentene copolymer described in Patent Document 4 has been shown to have excellent heat resistance, and the 4-methyl-1-pentene copolymer described in Patent Document 5 has been shown to have excellent storage stability.

[0009] However, in applications where flexibility after coating is required, it has been found that the prior art lacks toughness, and when stretched, there is a risk of cracking and appearance deterioration. In particular, in the field of electrical devices and release applications, it has been found that long life is required in view of flexibility after coating, good appearance, and environmental load.

[0010] Furthermore, since 4-methyl-1-pentene copolymers are used in high-temperature processes and use environments depending on the application, it has been found that the prior art lacks heat resistance. In particular, in the field of electrical devices and release applications, it has been found that further heat resistance requirements and long life are required in view of environmental load.

[0011] In view of such problems in the prior art, a first aspect of the present invention aims to provide a 4-methyl-1-pentene polymer that is excellent in storage stability and solubility when dissolved in a solvent, and also excellent in at least one of heat resistance or the appearance of the coating film when the coating film is stretched, such as when bending the film or using it in flexible applications.

[0012] Also, a second aspect of the present invention aims to provide a 4-methyl-1-pentene polymer that is excellent in storage stability, solubility, and the appearance of the coating film when the coating film is stretched, such as when bending the film or using it in flexible applications.

[0013] Furthermore, a third aspect of the present invention aims to provide a 4-methyl-1-pentene polymer that is excellent in storage stability, heat resistance, and solubility when dissolved in a solvent.

Means for Solving the Problems

[0014] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by a specific 4-methyl-1-pentene polymer, and have completed the present invention. The first aspect of the present invention relates to the following [1].

[0015] [1] A 4-methyl-1-pentene polymer (A) which is a copolymer of 4-methyl-1-pentene and at least one selected from linear α-olefins having 6 to 20 carbon atoms and satisfies the following requirements (I) and (II). (I) The endothermic termination temperature (TmE) in the melting (endothermic) curve measured by DSC is 230°C or lower. (II) The exothermic start temperature (TcS) in the crystallization (exothermic) curve measured by DSC is 210°C or lower.

[0016] The second invention of the present invention relates to the following [2] and [3]. [2] The 4-methyl-1-pentene polymer (A) according to [1] above, wherein the melting point (Tm) measured by DSC is 170 to 242°C.

[0017] [3] The 4-methyl-1-pentene polymer (A) according to [1] or [2] above, wherein the intrinsic viscosity [η] is 1.7 to 5.5 dl / g.

[0018] The third invention of the present invention relates to the following [4]. [4] The 4-methyl-1-pentene polymer (A) according to [1] above, wherein the melting point (Tm) measured by DSC is 200 to 242°C.

[0019] The first to third inventions of the present invention further relate to, for example, the following [5] to [9]. [5] The 4-methyl-1-pentene polymer (A) according to any one of [1] to [4] above, wherein the amount (U1) of the structural unit derived from 4-methyl-1-pentene is 84.0 to 100 mol%, and the total amount (U2) of the structural units derived from at least one selected from linear α-olefins having 6 to 20 carbon atoms is 16.0 to 0 mol% (provided that the sum of U1 and U2 is 100 mol%).

[0020] [6] The 4-methyl-1-pentene polymer (A) according to any one of [1] to [5] above, which is not modified.

[0021] [7] A composition (X) comprising 0.1 to 50% by mass of any one of the 4-methyl-1-pentene polymers (A) of [1] to [6] and 50 to 99.9% by mass of a solvent (B).

[0022] [8] The composition (X) of [7], wherein the solvent (B) is an organic solvent. [9] A coating agent comprising the composition (X) of [7] or [8]. [Advantages of the Invention]

[0023] The 4-methyl-1-pentene polymer of the first aspect of the present invention is excellent in storage stability and solubility when dissolved in a solvent, and is also excellent in at least one of heat resistance and the appearance of a coating film when the coating film is stretched, such as when the film is bent or used in a flexible application.

[0024] The 4-methyl-1-pentene polymer of the second aspect of the present invention is excellent in the appearance of a coating film when the coating film is stretched, such as when the film is bent or used in a flexible application, in terms of storage stability, solubility, and the appearance of the coating film.

[0025] The 4-methyl-1-pentene polymer of the third aspect of the present invention is excellent in storage stability, heat resistance, and solubility when dissolved in a solvent. [Embodiments for Carrying Out the Invention]

[0026] [4-Methyl-1-pentene Polymer] The 4-methyl-1-pentene polymer (A) according to the first aspect of the present invention (hereinafter also referred to as "polymer (A)") is a copolymer of 4-methyl-1-pentene and at least one selected from linear α-olefins having 6 to 20 carbon atoms, and satisfies the following requirements (I) to (II).

[0027] In addition, as an embodiment of the polymer (A) according to the first invention, the polymer (A) according to the second invention and the polymer (A) according to the third invention described below are exemplified. The polymer (A) according to the present invention means the polymer (A) according to the first invention including the polymer (A) according to the second invention and the polymer (A) according to the third invention, unless otherwise specified.

[0028] Examples of the linear α-olefin having 6 to 20 carbon atoms include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-eicosene and the like.

[0029] Requirement (I): The endothermic termination temperature (TmE) in the melting (endothermic) curve measured by DSC is 230 °C or lower. The endothermic termination temperature means the temperature at which melting is completed. The endothermic termination temperature and the exothermic start temperature described below are different indicators from the onset and offset, which are generally the intersections of the baseline and the tangent of the steady line.

[0030] The endothermic termination temperature (TmE) is preferably less than 230 °C, more preferably 228 °C or lower, and still more preferably less than 228 °C. The polymer (A) according to the second invention in which the value of the endothermic termination temperature (TmE) is within the above range is preferable from the viewpoint of the coating film appearance.

[0031] In addition, the polymer (A) according to the third invention in which the value of the endothermic termination temperature (TmE) is within the above range is preferable from the viewpoint of heat resistance. Therefore, a coating agent obtained from a composition containing this also tends to be excellent in heat resistance and the properties of the coating agent and the like tend to be uniform.

[0032] The method for measuring the endothermic termination temperature (TmE) will be described in detail in the examples. Requirement (II): The exothermic start temperature (TcS) in the crystallization (exothermic) curve measured by DSC is 210 °C or lower. The exothermic start temperature means the temperature at which crystallization starts.

[0033] The heat generation start temperature (TcS) is preferably less than 210°C, more preferably 200°C or lower, still more preferably less than 200°C. The polymer (A) according to the second aspect of the present invention, in which the value of the heat generation start temperature (TcS) is within the above range, is preferable from the viewpoint of the coating film appearance.

[0034] In addition, the polymer (A) according to the third aspect of the present invention, in which the value of the heat generation start temperature (TcS) is within the above range, is preferable from the viewpoint of heat resistance. Therefore, a coating agent or the like obtained from a composition containing this also tends to have excellent heat resistance and the properties of the coating agent or the like tend to be uniform.

[0035] The method for measuring the heat generation start temperature (TcS) will be described in detail in the examples. The intrinsic viscosity [η] measured in decalin at 135°C of the polymer (A) according to the second aspect of the present invention is usually 0.5 to 6.0 dl / g, preferably 1.7 to 5.5 dl / g, more preferably 1.8 to 5.3 dl / g, still more preferably 2.0 to 5.3 dl / g, even more preferably 2.2 to 5.3 dl / g, and particularly preferably 2.2 to 5.2 dl / g.

[0036] The polymer (A) according to the second aspect of the present invention, in which the value of the intrinsic viscosity [η] is within the above range, is preferable from the viewpoint of the coating film appearance. When the intrinsic viscosity [η] is higher than 6.0 dl / g, the coating agent containing the polymer (A) tends to form lumps or become non-uniform during coating.

[0037] The intrinsic viscosity [η] measured in decalin at 135°C of the polymer (A) according to the third aspect of the present invention is usually 0.5 to 6.0 dl / g, preferably 1.7 to 5.3 dl / g, more preferably 1.7 to 4.5 dl / g, still more preferably 1.7 to 3.5 dl / g, and even more preferably 1.7 to 2.5 dl / g.

[0038] The polymer (A) according to the third aspect of the present invention, in which the value of the intrinsic viscosity [η] is within the above range, is preferable from the viewpoint of heat resistance. The value of the intrinsic viscosity [η] can be adjusted by the amount of hydrogen added in the polymerization step when producing the polymer (A).

[0039] The method for measuring the intrinsic viscosity [η] will be described in detail in the examples. The melting point (Tm) measured by DSC of the polymer (A) according to the second aspect of the present invention is preferably 170 to 242 °C, more preferably 170 to 232 °C, still more preferably 170 to 220 °C.

[0040] The polymer (A) according to the second aspect of the present invention having the melting point (Tm) value within the above range is preferable from the viewpoint of the coating film appearance. The melting point (Tm) measured by DSC of the polymer (A) according to the third aspect of the present invention is 200 to 242 °C, preferably 200 to 232 °C, more preferably higher than 200 °C and 232 °C or lower, still more preferably higher than 200 °C and 220 °C or lower.

[0041] The polymer (A) according to the third aspect of the present invention having the melting point (Tm) value within the above range is preferable for enhancing the heat resistance of the coating film after solvent removal. The value of the melting point (Tm) tends to depend on the stereoregularity of the polymer and the content of the α-olefin structural unit contained in the polymer. Therefore, by using the olefin polymerization catalyst described later and further controlling the content of the α-olefin structural unit, the melting point (Tm) can be adjusted.

[0042] The method for measuring the melting point (Tm) will be described in detail in the examples. Conventional 4-methyl-1-pentene polymers are difficult to dissolve in a solvent without using techniques such as lowering the melting point, reducing the molecular weight, or modifying them, and there are problems in using them as coating agents. As disclosed in Patent Document 4, there is a technique of using a 4-methyl-1-pentene polymer having a lowered melting point by limiting the comonomer species and increasing the comonomer amount as a coating agent. However, in this technique, the intrinsic viscosity [η] is low, and the stretchability and coating film appearance after coating deteriorate. Further, in this technique, the melting point is limited to the region of 200 °C or lower, and the heat resistance is insufficient depending on the application.

[0043] In the polymer (A) of the second aspect of the present invention, as described above, preferably, the melting point is maintained relatively high, the intrinsic viscosity [η] is increased, and the balance between the melting point and the intrinsic viscosity [η] is maintained, so that crystallization is slightly suppressed and a coating agent (also referred to as varnish) that can be drawn can be obtained. That is, the amount of comonomer can be adjusted so that the temperature at which crystallization starts and the temperature at which the crystals completely melt are as low as possible. As a result, a coating film appearance and solubility that meet the purpose can be realized. Within this composition range, the storage stability during solvent dissolution is also ensured.

[0044] Further, in the polymer (A) of the third aspect of the present invention, as described above, a composition that can be made into a varnish is obtained by slightly suppressing crystallization while maintaining a high melting point of 200°C or higher. That is, the melting point Tm is set to 200°C or higher, and the amount of comonomer is adjusted so that the temperature at which crystallization starts and the temperature at which the crystals completely melt are as low as possible. As a result, heat resistance and solubility that meet the purpose are realized. Within this composition range, the storage stability during solvent dissolution is also ensured.

[0045] The polymer (A) may or may not be modified. The polymer (A) can be dissolved in a solvent even if it is not modified, and the above object can be achieved. The polymer (A) may be a polymer in which all are unmodified, or a polymer in which a part is unmodified.

[0046] The polymer (A) contains a structural unit derived from 4-methyl-1-pentene and at least one structural unit selected from linear α-olefins having 6 to 20 carbon atoms. The amount (U1) of the structural unit derived from 4-methyl-1-pentene is preferably 84.0 to 100 mol%, more preferably 90.0 to 99.0 mol%, still more preferably 94.0 to 98.5 mol%, particularly preferably 94.0 to 98.0 mol% in the second invention, and particularly preferably 94.5 to 98.0 mol% in the third invention. The total amount (U2) of the structural unit derived from at least one selected from linear α-olefins having 6 to 20 carbon atoms is preferably 16.0 to 0 mol%, more preferably 10.0 to 1.0 mol%, still more preferably 6.0 to 1.5 mol%, particularly preferably 6.0 to 2.0 mol% in the second invention, and particularly preferably 5.5 to 2.0 mol% in the third invention. In the above, the total of U1 and U2 is 100 mol%.

[0047] The polymer (A) in which U1 and U2 are within the above ranges is preferable from the viewpoint of heat resistance. As the linear α-olefin having 6 to 20 carbon atoms, a linear α-olefin having 6 to 18 carbon atoms is preferable from the viewpoint of the coating film appearance in the second invention and from the viewpoint of heat resistance in the third invention. Specifically, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene and the like are preferable, and among them, 1-decene, 1-hexadecene and 1-octadecene are preferable.

[0048] The linear α-olefin having 6 to 20 carbon atoms may be used alone or in combination of two or more. The polymer (A) may contain structural units derived from other polymerizable compounds as long as the object of the present invention is not impaired. Examples of such other polymerizable compounds include vinyl compounds having a cyclic structure such as styrene, vinylcyclopentene, vinylcyclohexane, vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids such as maleic anhydride or derivatives thereof; conjugated dienes such as butadiene, isoprene, pentadiene, 2,3-dimethylbutadiene; non-conjugated polyenes such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylenenorbornene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, etc.

[0049] The polymer (A) can contain units derived from such other polymerizable compounds in an amount of 10 mol% or less, preferably 5 mol% or less, more preferably 3 mol% or less, based on 100 mol% in total of the structural units derived from all the polymerizable compounds contained in the polymer (A).

[0050] The method for measuring the content of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from at least one selected from linear α-olefins having 6 to 20 carbon atoms in the polymer (A) will be described in detail in the examples.

[0051] The density of the polymer (A) is preferably 820 to 850 (kg / m 3 ), more preferably 825 to 850 kg / m 3 , still more preferably 825 to 845 kg / m 3 , particularly preferably 825 to 840 kg / m 3It is so. The density value of the polymer (A) can be adjusted by selecting the type and content of other olefins polymerized with 4-methyl-1-pentene. The density can be measured in accordance with JIS K6268. The polymer (A) with the density value within the above range is preferable from the viewpoint of the coating film appearance.

[0052] The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the polymer (A), is preferably 1.0 to 3.5, more preferably 1.3 to 3.0, and even more preferably 1.5 to 2.5.

[0053] The value of the molecular weight distribution (Mw / Mn) can be adjusted by the type of the olefin polymerization catalyst described later, particularly the metallocene catalyst. The molecular weight distribution (Mw / Mn) can be measured using a gel permeation chromatograph Alliance GPC-2000 type manufactured by Waters.

[0054] The polymer (A) with the value of the molecular weight distribution (Mw / Mn) within the above range is preferable from the viewpoints of transparency and mechanical properties. Further, when the molecular weight distribution of the polymer (A) is within the above range, the affinity with the solvent described later increases, and the stability of the composition is improved.

[0055] The crystallization temperature (Tc) measured by DSC of the polymer (A) is preferably 110 to 220 °C, and more preferably 120 to 205 °C. The value of the crystallization temperature (Tc) tends to depend on the stereoregularity of the polymer and the content of the linear α-olefin structural unit having 6 to 20 carbon atoms, and can be adjusted by using the olefin polymerization catalyst described later and further controlling the content of the linear α-olefin structural unit having 6 to 20 carbon atoms. The polymer (A) with the value of the crystallization temperature (Tc) within the above range is preferable from the viewpoint of moldability.

[0056] The polymer (A) can be obtained by polymerizing 4-methyl-1-pentene, the above-mentioned specific olefin, and, if necessary, the other polymerizable compound by a known method in the presence of a catalyst for olefin polymerization.

[0057] As a preferred catalyst embodiment of the above-mentioned catalyst for olefin polymerization, a metallocene catalyst can be mentioned. Preferred metallocene catalysts include those described in WO 01 / 53369 pamphlet, WO 01 / 27124 pamphlet, JP-A-3-193796, JP-A-02-41303, or WO 06 / 025540 pamphlet.

[0058] <Composition> The composition (X) of the present invention contains the 4-methyl-1-pentene polymer (A) and a solvent (B).

[0059] The content of the polymer (A) in the composition (X) is 0.1 to 50% by mass, preferably 0.5 to 30% by mass, more preferably 1.0 to 25% by mass, and still more preferably 5 to 20% by mass. The content of the solvent (B) in the composition (X) is 50 to 99.9% by mass, preferably 70 to 99.5% by mass, more preferably 75 to 99.0% by mass, and still more preferably 80 to 95% by mass.

[0060] When the contents of the polymer (A) and the solvent (B) in the composition (X) are within the above ranges, the composition (X) has a good balance between handleability and ease of removing the solvent when producing a film from the coating agent when used as a coating agent or the like.

[0061] The solvent (B) is not particularly limited as long as it can dissolve the polymer (A). Among them, organic solvents can be preferably used. Examples of the solvent (B) include aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, cyclohexane, methylcyclohexane, and ethylcyclohexane; aromatic hydrocarbons such as toluene and xylene. Among these, toluene, cyclohexane, methylcyclohexane, etc. can be preferably used.

[0062] The composition (X) may further contain, as necessary, antioxidants, heat stabilizers, weather stabilizers, antistatic agents, slip agents, leveling agents, reinforcing agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, fillers, etc., as long as the object of the present invention is not impaired.

[0063] As the antioxidant, known antioxidants can be used. Specifically, hindered phenol compounds, sulfur-based antioxidants, lactone-based antioxidants, organic phosphite compounds, organic phosphonite compounds, or a combination of several of these can be used.

[0064] Examples of the lubricant include sodium, calcium, and magnesium salts of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid, and stearic acid. These can be used alone or in combination of two or more. The blending amount of such a lubricant is usually 0.1 to 3 parts by mass, preferably about 0.1 to 2 parts by mass, based on 100 parts by mass of the composition.

[0065] As the slip agent, amides of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid, stearic acid, erucic acid, and behenic acid, or bisamides of these saturated or unsaturated fatty acids are preferably used. Among these, erucic acid amide and ethylene bisstearamide are particularly preferred. These fatty acid amides are preferably blended in the range of 0.01 to 5 parts by mass based on 100 parts by mass of the polymer (A).

[0066] Examples of the antiblocking agent include fine powder silica, fine powder aluminum oxide, fine powder clay, powdery or liquid silicone resin, tetrafluoroethylene resin, fine powder crosslinked resin such as crosslinked acrylic and methacrylic resin powder. Among these, fine powder silica and crosslinked acrylic and methacrylic resin powder are preferred.

[0067] Also, when using the composition (X) as a coating agent as described later, it is also a preferred embodiment to add a leveling agent to the composition (X). As the leveling agent for reducing the surface roughness of the film made of the composition (X), a fluorine-based nonionic surfactant, a special acrylic resin-based leveling agent, a silicone-based leveling agent, etc. can be used, and those having good compatibility with the solvent are preferred. The addition amount is used in the range of 1 to 50,000 ppm with respect to the polymer (A) in the composition (X).

[0068] Examples of the reinforcing agent include metal oxides such as silicon, titanium, aluminum, and zirconium, polyfunctional alkoxy compounds or their oligomers, and clay minerals. 5 to 50 parts by mass can be blended with respect to 100 parts by mass of the polymer (A) in the composition (X), and the hardness and elastic modulus of the film (also referred to as the coat layer in this case) made by using the composition (X) as a coating agent can be increased. If the addition amount is less than 5 parts by mass, the effect is too low, and if it exceeds 50 parts by mass, the transparency and mechanical strength of the coat layer may be impaired.

[0069] The production method of the composition (X) is not particularly limited and can be produced by a commonly used method. For example, it can be produced by adding the polymer (A) to the solvent (B) and stirring at a temperature below the boiling point of the solvent (B) for a predetermined time.

[0070] The polymer (A) according to the first invention is excellent in storage stability and solubility when dissolved in a solvent. The polymer (A) according to the second invention is excellent in the appearance of the coating film when the coating film is stretched, such as when bending the film or using it for flexible applications, as well as in storage stability and solubility when dissolved in a solvent. The polymer (A) according to the third invention is excellent in storage stability, heat resistance, and solubility when dissolved in a solvent. Furthermore, any of the polymers (A) has properties such as mold release property, stretchability, electrical insulation property, and chemical resistance, which are generally peculiar to 4-methyl-1-pentene polymers. Therefore, the composition (X) containing the polymer (A) can be applied to various uses.

[0071] Since the composition (X) can produce a film with high heat resistance, it can be suitably used as various coating agents for surface protection, insulation, planarization, heat resistance, light resistance, weather resistance, etc. for coating agents, particularly various display devices such as liquid crystal display elements and electroluminescence display elements; semiconductor devices; optical members such as light guide plates, polarizing films, light diffusing films, retardation films, and antireflection films; printed circuit boards, etc.

[0072] A thin film can be obtained by applying the composition (X) to an object to be coated and drying it. In particular, since the composition (X) can form a protective layer on a substrate having a complex shape, it can be suitably used as a coating agent for forming a protective layer on the electrode surface of a printed wiring board or a capacitor. Also, by applying the composition (X) on another film and removing the solvent, the other film can be made into a release film.

Examples

[0073] Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited to these examples. [Measurement methods for various physical properties] [Content of constitutional units in 4-methyl-1-pentene polymer] The amount of structural units derived from 4-methyl-1-pentene (4-methyl-1-pentene content) and the amount of structural units derived from α-olefins other than 4-methyl-1-pentene (α-olefin content) were determined by the following apparatus and conditions: 13 Calculated from the C-NMR spectrum.

[0074] Using a JEOL Ltd. ECP500 nuclear magnetic resonance apparatus, with an o-dichlorobenzene / heavy benzene (80 / 20 vol%) mixed solvent as the solvent, a sample concentration of 55 mg / 0.6 mL, a measurement temperature of 120 °C, the observed nucleus being 13C (125 MHz), the sequence being single-pulse proton decoupling, the pulse width being 4.7 μs (45° pulse), the repetition time being 5.5 s, the number of accumulations being 10,000 or more, and 27.50 ppm being used as the reference value for chemical shift measurement. The obtained 13 The composition of 4-methyl-1-pentene and α-olefin was quantified from the C-NMR spectrum.

[0075] [Intrinsic viscosity [η]] The intrinsic viscosity [η] was measured at 135 °C using a decalin solvent. That is, approximately 20 mg of polymerization powder, pellets or resin mass was dissolved in 15 mL of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 °C. After adding 5 mL of decalin solvent to this decalin solution for dilution, the specific viscosity ηsp was measured in the same manner. This dilution operation was repeated two more times, and the value of ηsp / C when extrapolating the concentration (C) to 0 was determined as the intrinsic viscosity (see the following formula).

[0076] [η]=lim(ηsp / C) (C→0) [Melting point (Tm), crystallization temperature (Tc), endothermic termination temperature (TmE), exothermic start temperature (TcS)] Using a DSC measuring apparatus (DSC220C) manufactured by Seiko Instruments Inc., an exothermic / endothermic curve was obtained in accordance with ASTM D3418, and the melting point (Tm) and crystallization temperature (Tc) were determined as follows.

[0077] Approximately 5 mg of the sample was placed in an aluminum pan for measurement, heated from 20°C to 280°C at a heating rate of 10°C / min, held at 280°C for 5 minutes, then cooled to 20°C at a cooling rate of 10°C / min, held at 20°C for 5 minutes, and then heated from 20°C to 280°C again at a heating rate of 10°C / min. The crystallization peak that appeared during the first cooling was defined as the crystallization temperature (Tc). When multiple peaks were detected, the one with the highest temperature was taken as the crystallization temperature (Tc). The melting peak that appeared during the second heating was defined as the melting point (Tm). When multiple peaks were detected, the one with the highest temperature was taken as the melting point (Tm).

[0078] The temperature at which the endotherm of the above melting (endothermic) curve ended was defined as the endotherm end temperature (TmE). Also, the temperature at which the exotherm of the above crystallization (exothermic) curve started was defined as the exotherm start temperature (TcS).

[0079] The above start and end points are the points at which it can be confirmed that the curve deviates from the baseline where the heat quantity becomes constant at the start or end of the endotherm or exotherm, and a difference in heat quantity begins to occur.

[0080] [Storage Stability] In the production of the composition described below, the polymer and the solvent were placed in a container equipped with a stirrer, stirred at 90°C for 1 hour at 200 rpm to dissolve the polymer, and then stored at room temperature for 24 hours. Thereafter, the composition was visually evaluated under visible light. If it was transparent, it was designated as A; if it appeared turbid but fluidity was observed, it was designated as B; if it appeared turbid and no fluidity was observed, it was designated as C, as shown in Table 1.

[0081] [Measurement of Water Contact Angle] Using a DropMaster500 image processing type, solid-liquid interface analysis system, the contact angle values when water droplets were dropped on the films obtained in the examples and comparative examples were measured. The larger the contact angle value, the higher the degree of hydrophobicity, which means higher mold release properties for materials with high polarity.

[0082] [Normalized Dielectric Breakdown Voltage] In accordance with ASTM-D149, an insulation breakdown tester manufactured by Yamayo Testing Machine Co., Ltd. was used. The films obtained in the examples and comparative examples were subjected to voltage application at a voltage increase rate of 500 V / sec to measure the insulation breakdown voltage (BVD), and the withstand voltage characteristics were determined. Further, the thickness of the vicinity of the insulation breakdown point of the film for which the insulation breakdown voltage was measured was measured, and the value obtained by dividing the insulation breakdown voltage by the thickness was defined as the normalized insulation breakdown voltage (kV / μm). The larger this normalized insulation breakdown voltage, the higher the electrical insulation property.

[0083] [Appearance of coating film] The films obtained by applying the compositions obtained in the examples and comparative examples onto a PET substrate were cut into 5 mm × 1 mm pieces, and using a tensile test (INSTRON 5982) at room temperature, they were stretched by 50% at a rate of 10 mm / min, and the coating films of the compositions were observed with a microscope (Keyence VK-X100). The presence or absence of cracks was evaluated, and in Table 1, the case where there were no cracks was designated as A, and the case where there were cracks was designated as B.

[0084] [Heat resistance of coating film] The films obtained in the examples and comparative examples were cut into 50 mm square pieces, placed on a hot plate heated to 200°C, and the change in shape was observed. In Table 1, the case where the change rate of the length of the side with the largest change in length was 10% or less within 10 seconds was designated as A, the case where it was 10 - 20% was designated as B, and the case where it was 20% or more, or the case where obvious melting was observed in the film was designated as C.

[0085] [Synthesis Example 1] (8-Octamethylfluorene-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride was synthesized according to the method described in Preliminary Experiment 5 of International Publication No. WO2014 / 123212.

[0086] [Synthesis Example 2] Production of olefin polymerization catalyst In a 200 mL three-necked flask equipped with a stirrer and sufficiently purged with nitrogen at 30 °C, 30 mL of purified decane and 14.65 mmol of solid polymethylaluminoxane in particulate form with a D50 of 28 μm and an aluminum atom content of 43% by mass (synthesized using the method described in International Publication No. 2014 / 123212, hereinafter also referred to as "solid MAO") were charged in terms of aluminum atoms and made into a suspension. To this suspension, 50.0 mg (0.0586 mmol) of the transition metal compound (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)) zirconium dichloride described in Synthesis Example 1 was added as a 4.58 mmol / L toluene solution while stirring. After stirring was stopped after 1 hour, the resulting mixture was washed with 100 mL of decane by the decantation method and then decane was added to make a 50 mL slurry (Zr loading rate 98%).

[0087] [Synthesis Example 3] Preparation of prepolymerization catalyst component To the slurry prepared in Synthesis Example 2, 1.0 mL of a decane solution of triisobutylaluminum (0.5 mmol / mL in terms of aluminum atoms) was charged at 25 °C under a nitrogen stream. After cooling to 15 °C, 10 mL of 4-methyl-1-pentene was charged into the reactor over 60 minutes. The start point of charging was taken as the start of prepolymerization. Stirring was stopped 2.0 hours after the start of polymerization, and the resulting mixture was washed 3 times with 100 mL of decane by the decantation method. The prepolymerization catalyst component was obtained as a decane slurry (9.5 g / L, 0.56 mmol-Zr / L).

[0088] [Example 1] (Production of Polymer 1) Under room temperature and a nitrogen stream, 425 mL of purified decane was inserted into a SUS polymerization reactor equipped with a stirrer having an internal volume of 1 L, and the temperature was raised to 40°C. After reaching 40°C, 0.8 mL (0.4 mmol in terms of aluminum atoms) of a decane solution of triisobutylaluminum (0.5 mmol / mL in terms of aluminum atoms) was charged, and then 0.002 mmol in terms of zirconium atoms of the decane slurry of the prepolymerization catalyst component of Synthesis Example 3 prepared previously was charged. 16.25 NmL of hydrogen was charged, and then a mixed solution of 234 mL of 4-methyl-1-pentene and 18.5 mL of an α-olefin mixture of carbon number 16 / carbon number 18 (trade name; Linen 168, manufactured by Idemitsu Kosan Co., Ltd.) was continuously charged into the polymerization reactor at a constant rate over 2 hours. The start point of this charging was defined as the start of polymerization, and it was held at 45°C for 4.5 hours. 16.25 NmL of hydrogen was charged 1 hour and 2 hours after the start of polymerization, respectively. After 4.5 hours had elapsed since the start of polymerization, the temperature was lowered to room temperature, and after depressurization, the polymerization solution containing a white solid was immediately filtered to obtain a solid substance. This solid substance was dried at 80°C under reduced pressure for 8 hours to obtain Polymer 1. The yield was 124 g. The content of 4-methyl-1-pentene in Polymer 1 was 97.5 mol%, and the content of α-olefins (1-hexadecene, 1-octadecene) was 2.5 mol%. The melting point (Tm) of Polymer 1 was 205°C, and the intrinsic viscosity [η] was 5.1 dl / g.

[0089] [Example 2] (Production of Polymer 2) Under a nitrogen stream at room temperature, 425 mL of purified decane was inserted into a SUS polymerization vessel equipped with a stirrer having an internal volume of 1 L and cooled to 10°C. After reaching 10°C, 0.8 mL (0.4 mmol in terms of aluminum atoms) of a decane solution of triisobutylaluminum (0.5 mmol / mL in terms of aluminum atoms) was charged, and then 0.006 mmol in terms of zirconium atoms of the prepolymerization catalyst component decane slurry prepared in Synthesis Example 3 above was charged. 22.5 NmL of hydrogen was charged, and then a mixed solution of 219 mL of 4-methyl-1-pentene and 33.0 mL of an α-olefin mixture having 16 or 18 carbon atoms (trade name; Linearene 168, manufactured by Idemitsu Kosan Co., Ltd.) was continuously charged into the polymerization vessel at a constant rate over 2 hours. The start point of this charging was defined as the start of polymerization, and the mixture was held at 10°C for 4.5 hours. 22.5 NmL of hydrogen was charged 1 hour and 2 hours after the start of polymerization, respectively. After 4.5 hours from the start of polymerization, the pressure was released, and immediately thereafter, the polymerization solution containing a white solid was filtered to obtain a solid substance. This solid substance was dried at 80°C under reduced pressure for 8 hours to obtain Polymer 2. The yield was 162 g. The 4-methyl-1-pentene content in Polymer 2 was 94.3 mol%, and the α-olefin (1-hexadecene, 1-octadecene) content was 5.7 mol%. The melting point (Tm) of Polymer 2 was 184°C, and the intrinsic viscosity [η] was 4.4 dl / g.

[0090] [Example 3] (Production of Polymer 3) Under a nitrogen stream at room temperature, 425 mL of purified heptane, 69 mL of 4-methyl-1-pentene, and 5.1 mL of Linearene 168 (manufactured by Idemitsu Kosan) were inserted into a SUS polymerization vessel equipped with a stirrer having an internal volume of 1 L, and the temperature was raised to 40°C. 0.43 mL (0.43 mmol in terms of aluminum atoms) of a toluene solution of triisobutylaluminum (1.0 mmol / mL in terms of aluminum atoms) was charged. Next, 0.189 mmol of methylaluminoxane prepared in advance and (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta [a] A toluene solution (2.67 mL) containing 0.00063 mmol of indenyl zirconium dichloride was inserted. Then, 31.25 NmL of hydrogen was charged and polymerization was initiated. Starting from the time of charging initiation as the polymerization start, it was maintained at 45 °C for 90 minutes. After 90 minutes from the start of polymerization, the pressure was released, and then it was exposed to air to stop the polymerization. The reaction solution was poured into acetone with hydrochloric acid added to precipitate the entire amount of the polymer. After stirring, it was filtered through filter paper to obtain a solid substance. This solid substance was dried at 80 °C for 8 hours under reduced pressure to obtain Polymer 3. The yield was 35 g. The 4-methyl-1-pentene content in Polymer 3 was 96.7 mol%, and the α-olefin (1-hexadecene, 1-octadecene) content was 3.3 mol%. The melting point (Tm) of Polymer 3 was 199 °C, and the intrinsic viscosity [η] was 3.4 dl / g.

[0091] [Example 4] (Production of Polymer 4) A 1.5 L stirred SUS polymerizer with a stirring blade, fully purged with nitrogen, was charged with 500 mL of 4-methyl-1-pentene and 230 mL of heptane at 23 °C. To this autoclave, 20 mL of Linearene 168 (manufactured by Idemitsu Kosan Co., Ltd.) and 0.3 mL of a 1.0 mmol / mL toluene solution of triisobutylaluminum (TIBAL) were successively charged and stirring was started. Next, 140 mL of hydrogen was inserted and the autoclave was heated to an internal temperature of 60 °C. 2 mL of a toluene solution containing 0.033 mmol of methylaluminoxane in terms of Al and 0.00011 mmol of (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)) zirconium dichloride was pressured into the autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave reached 60 °C. 13 minutes after the start of polymerization, 5 mL of methanol was pressured into the autoclave with nitrogen to terminate the polymerization, and the autoclave was depressurized to atmospheric pressure. The reaction solution was poured into acetone while stirring to precipitate the polymer. The obtained polymer containing the solvent was dried at 130 °C under reduced pressure for 10 hours. The obtained Polymer 4 was 68.4 g, the 4-methyl-1-pentene content in Polymer 4 was 97.6 mol%, and the α-olefin (1-hexadecene, 1-octadecene) content was 2.4 mol%. The melting point (Tm) of Polymer 4 was 207 °C, and the intrinsic viscosity [η] was 2.4 dl / g.

[0092] [Example 5] (Production of Polymer 5) A 1.5 L stirred SUS polymerization reactor with sufficient nitrogen replacement was charged with 500 mL of 4-methyl-1-pentene and 210 mL of heptane at 23°C. To this autoclave, 45 mL of linearene 168 (manufactured by Idemitsu Kosan Co., Ltd.) and 0.3 mL of a 1.0 mmol / mL toluene solution of triisobutylaluminum (TIBAL) were successively charged and stirring was started. Next, 140 mL of hydrogen was inserted and the autoclave was heated to an internal temperature of 60°C. A toluene solution containing 0.033 mmol of methylaluminoxane in terms of Al and 0.00011 mmol of (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)) zirconium dichloride in 2 mL was pressured into the autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave reached 60°C. 13 minutes after the start of polymerization, 5 mL of methanol was pressured into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. The reaction solution was poured into acetone while stirring to precipitate the polymer.

[0093] The obtained polymer containing the solvent was dried at 130°C under reduced pressure for 10 hours. The obtained polymer 5 was 68.6 g, the 4-methyl-1-pentene content in polymer 5 was 94.6 mol%, and the α-olefin (1-hexadecene, 1-octadecene) content was 5.4 mol%. The melting point (Tm) of polymer 5 was 173°C, and the intrinsic viscosity [η] was 2.4 dl / g.

[0094] [Example 6] (Production of Polymer 6) A 1.5 L SUS polymerization reactor with a stirrer blade, fully purged with nitrogen, was charged with 500 mL of 4-methyl-1-pentene and 220 mL of heptane at 23 °C. To this autoclave, 30 mL of 1-decene and 0.3 mL of a 1.0 mmol / mL toluene solution of triisobutylaluminum (TIBAL) were successively charged and stirring was started. Next, 140 mL of hydrogen was inserted and the autoclave was heated to an internal temperature of 60 °C. A toluene solution containing 0.039 mmol of methylaluminoxane in terms of Al and 0.00013 mmol of (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]inden)) zirconium dichloride in 2 mL was pressured into the autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave reached 60 °C. Ten minutes after the start of polymerization, 5 mL of methanol was pressured into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. The reaction solution was poured into acetone while stirring to precipitate the polymer. The obtained polymer containing the solvent was dried at 130 °C under reduced pressure for 10 hours. The obtained Polymer 6 was 66.5 g, the 4-methyl-1-pentene content in Polymer 6 was 94.1 mol%, and the α-olefin (1-decene content) was 5.9 mol%. The melting point (Tm) of Polymer 6 was 190 °C, and the intrinsic viscosity [η] was 2.3 dl / g.

[0095] [Example 7] (Production of Polymer 7) A 1.5 L stirred SUS polymerizer with sufficient nitrogen replacement was charged with 500 mL of 4-methyl-1-pentene and 230 mL of heptane at 23°C. To this autoclave, 15 mL of 1-decene and 0.3 mL of a 1.0 mmol / mL toluene solution of triisobutylaluminum (TIBAL) were successively charged and stirring was started. Next, 140 mL of hydrogen was inserted and the autoclave was heated to an internal temperature of 60°C. 2 mL of a toluene solution containing 0.06 mmol of methylaluminoxane in terms of Al and 0.0002 mmol of (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]inden))zirconium dichloride was pressured into the autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave reached 60°C. 30 minutes after the start of polymerization, 5 mL of methanol was pressured into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. The reaction solution was poured into acetone while stirring to precipitate the polymer. The obtained polymer containing the solvent was dried at 130°C under reduced pressure for 10 hours. The obtained polymer 7 was 35.6 g, the 4-methyl-1-pentene content in polymer 7 was 96.7 mol%, and the α-olefin (1-decene content) was 3.3 mol%. The melting point (Tm) of polymer 7 was 212°C, and the intrinsic viscosity [η] was 2.3 dl / g.

[0096] [Example 8] (Production of Polymer 8) At room temperature and under a nitrogen stream, 425 mL of purified decane was inserted into a SUS polymerization vessel equipped with a stirrer having an internal volume of 1 L, and the temperature was raised to 40°C. After reaching 40°C, 0.8 mL (0.4 mmol in terms of aluminum atoms) of a decane solution of triisobutylaluminum (0.5 mmol / mL in terms of aluminum atoms) was charged, and then 0.00075 mmol in terms of zirconium atoms of the decane slurry of the prepolymerization catalyst component of Synthesis Example 3 prepared previously was charged. 35 NmL of hydrogen was charged, and then a mixed solution of 238 mL of 4-methyl-1-pentene and 13.6 mL of 1-decene was continuously charged into the polymerization vessel at a constant rate over 2 hours. The start point of this charging was defined as the start of polymerization, and it was held at 45°C for 4.5 hours. 35 NmL of hydrogen was charged 1 hour and 2 hours after the start of polymerization, respectively. After 4.5 hours from the start of polymerization, the temperature was lowered to room temperature, the pressure was released, and immediately after that, the polymerization solution containing a white solid was filtered to obtain a solid substance. This solid substance was dried at 80°C for 8 hours under reduced pressure to obtain Polymer 8. The yield was 154 g. The 4-methyl-1-pentene content in Polymer 8 was 96.2 mol%, and the α-olefin (1-decene content) was 3.8 mol%. The melting point (Tm) of Polymer 8 was 207°C, and the intrinsic viscosity [η] was 2.2 dl / g.

[0097] [Example 9] (Production of Polymer 9) At room temperature and under a nitrogen stream, 425 mL of purified decane was inserted into a SUS polymerization vessel equipped with a stirrer having an internal volume of 1 L, and the temperature was raised to 40°C. After reaching 40°C, 0.8 mL (0.4 mmol in terms of aluminum atoms) of a decane solution of triisobutylaluminum (TIBAL) (0.5 mmol / mL in terms of aluminum atoms) was charged, and then 0.0020 mmol in terms of zirconium atoms of the decane slurry of the prepolymerization catalyst component of Synthesis Example 3 was charged. 16.25 NmL of hydrogen was charged, and then a mixed solution of 231 mL of 4-methyl-1-pentene and 20.6 mL of linearene 168 (manufactured by Idemitsu Kosan Co., Ltd., a mixture of 1-hexadecene and 1-octadecene) was continuously charged into the polymerization vessel at a constant rate over 2 hours. The start point of charging the mixed solution was taken as the start of polymerization, and it was held at 45°C for 4.5 hours. 16.25 NmL of hydrogen was charged 1 hour and 2 hours after the start of polymerization, respectively. After 4.5 hours had elapsed since the start of polymerization, the temperature was lowered to room temperature, the pressure was released, and immediately thereafter, the polymerization solution containing a white solid was filtered to obtain a solid substance. This solid substance was dried at 80°C under reduced pressure for 8 hours to obtain Polymer 9. The yield was 128 g. The 4-methyl-1-pentene content in Polymer 9 was 97.0 mol%, and the α-olefin (1-hexadecene, 1-octadecene) content was 3.0 mol%. The melting point (Tm) of Polymer 9 was 203°C, and the intrinsic viscosity [η] was 5.3 dl / g.

[0098] [Example 10] (Production of Polymer 10) Under room temperature and a nitrogen stream, 425 mL of purified decane was inserted into a SUS polymerization vessel equipped with a stirrer having an internal volume of 1 L, and the temperature was raised to 40°C. After reaching 40°C, 0.8 mL (0.4 mmol in terms of aluminum atoms) of a decane solution of triisobutylaluminum (TIBAL) (0.5 mmol / mL in terms of aluminum atoms) was charged, and then 0.00175 mmol in terms of zirconium atoms of the decane slurry of the prepolymerization catalyst component of Synthesis Example 3 was charged. 23.75 NmL of hydrogen was charged, and then a mixed solution of 232 mL of 4-methyl-1-pentene and 19.6 mL of linearene 168 (manufactured by Idemitsu Kosan Co., Ltd., a mixture of 1-hexadecene and 1-octadecene) was continuously charged into the polymerization vessel at a constant rate over 2 hours. The start point of charging the mixed solution was defined as the start of polymerization, and it was held at 45°C for 4.5 hours. 23.75 NmL of hydrogen was charged 1 hour and 2 hours after the start of polymerization, respectively. After 4.5 hours from the start of polymerization, the temperature was lowered to room temperature, the pressure was released, and immediately after that, the polymerization solution containing a white solid was filtered to obtain a solid substance. This solid substance was dried at 80°C under reduced pressure for 8 hours to obtain Polymer 10. The yield was 146 g. The 4-methyl-1-pentene content in Polymer 10 was 96.7 mol%, and the α-olefin (1-hexadecene, 1-octadecene) content was 3.3 mol%. The melting point (Tm) of Polymer 10 was 203°C, and the intrinsic viscosity [η] was 4.0 dl / g.

[0099] [Example 11] (Production of Polymer 11) Under a nitrogen stream at room temperature, 425 mL of purified decane was inserted into a SUS polymerization vessel equipped with a stirrer having an internal volume of 1 L, and the temperature was raised to 40°C. After reaching 40°C, 0.8 mL (0.4 mmol in terms of aluminum atoms) of a decane solution of triisobutylaluminum (TIBAL) (0.5 mmol / mL in terms of aluminum atoms) was charged, and then 0.00175 mmol in terms of zirconium atoms of the decane slurry of the prepolymerization catalyst component of Synthesis Example 3 was charged. 23.75 NmL of hydrogen was charged, and then a mixture of 230 mL of 4-methyl-1-pentene and 22.4 mL of linearene 168 (manufactured by Idemitsu Kosan Co., Ltd., a mixture of 1-hexadecene and 1-octadecene) was continuously charged into the polymerization vessel at a constant rate over 2 hours. The start point of charging the above mixture was taken as the start of polymerization, and it was maintained at 45°C for 4.5 hours. 23.75 NmL of hydrogen was charged 1 hour and 2 hours after the start of polymerization, respectively. After 4.5 hours from the start of polymerization, the temperature was lowered to room temperature, the pressure was released, and immediately after that, the polymerization solution containing a white solid was filtered to obtain a solid substance. This solid substance was dried at 80°C under reduced pressure for 8 hours to obtain Polymer 11. The yield was 142 g. The 4-methyl-1-pentene content in Polymer 11 was 96.5 mol%, and the α-olefin (1-hexadecene, 1-octadecene) content was 3.5 mol%. The melting point (Tm) of Polymer 11 was 201°C, and the intrinsic viscosity [η] was 4.2 dl / g.

[0100] [Example 12] (Production of Polymer 12) 9 (100 parts by mass) of the polymer obtained in Example 9, 2 parts by mass of maleic anhydride, and 0.02 part by mass of 2,5-dimethyl-2,5-bis(t-butylperoxy)hexine-3 (Perhexyne 25B, manufactured by NOF Corporation) as an organic peroxide were blended, and kneaded at a resin temperature of 280°C and a screw rotation speed of 150 rpm using a mixer of a Laboplastomill manufactured by Toyo Seiki Seisakusho Co., Ltd. to obtain Polymer 12. The amount of the constitutional unit in Polymer 12 was assumed to be the same as that of Polymer 9. The melting point (Tm) of Polymer 12 was 203°C, the intrinsic viscosity [η] was 0.8 dl / g, and the graft amount was 1.5% by mass.

[0101] [Example 13] (Production of Polymer 13) Polymer 13 was obtained by conducting the production in the same manner as Polymer 12, except that Polymer 10 was used instead of Polymer 9.

[0102] The amount of the structural unit in Polymer 13 was assumed to be the same as that in Polymer 10. The melting point (Tm) of Polymer 13 was 203 °C, the intrinsic viscosity [η] was 0.9 dl / g, and the graft amount was 1.6 mass%.

[0103] [Example 14] (Production of Polymer 14) Polymer 14 was obtained by conducting the production in the same manner as Polymer 12, except that Polymer 11 was used instead of Polymer 9.

[0104] The amount of the structural unit in Polymer 14 was assumed to be the same as that in Polymer 11. The melting point (Tm) of Polymer 14 was 201 °C, the intrinsic viscosity [η] was 0.9 dl / g, and the graft amount was 1.5 mass%.

[0105] [Example 15] (Production of Polymer 15) 100 parts by mass of Polymer 9 obtained in Example 9, 1 part by mass of maleic anhydride, and 0.01 part by mass of 2,5 - dimethyl - 2,5 - bis(t - butylperoxy)hexane - 3 (Perhexyne 25B, manufactured by NOF Corporation) as an organic peroxide were blended, and kneaded at a resin temperature of 230 °C and a screw rotation speed of 130 rpm using a mixer of a Laboplastomill manufactured by Toyo Seiki Seisaku - sho, Ltd., to obtain Polymer 15. The amount of the structural unit in Polymer 15 was assumed to be the same as that in Polymer 9. The melting point (Tm) of Polymer 15 was 203 °C, the intrinsic viscosity [η] was 2.4 dl / g, and the graft amount was 0.6 mass%.

[0106] [Comparative Example 1] (Production of Polymer 16) 750 ml of 4-methyl-1-pentene was charged into a 1.5-liter SUS polymerization vessel with a stirrer blade that had been fully purged with nitrogen at 23°C. 0.75 ml of a toluene solution of triisobutylaluminum (TIBAL) at 1.0 mmol / ml was charged into this autoclave, and the stirrer was rotated.

[0107] Next, the autoclave was heated to an internal temperature of 60°C and pressurized with propylene so that the total pressure became 0.15 MPa (gauge pressure). Subsequently, 0.34 ml of a toluene solution containing 1 mmol of methylaluminoxane in terms of Al and 0.003 mmol of diphenylmethylene(1-ethyl-3-t-butyl-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride, which had been prepared in advance, was pressured into the autoclave with nitrogen, and polymerization was initiated. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave became 60°C. Five minutes after the start of polymerization, 5 ml of methanol was pressured into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution while stirring. The obtained powdery polymer containing the solvent was dried at 130°C under reduced pressure for 12 hours. The obtained polymer 16 was 19.9 g, the 4-methyl-1-pentene content in polymer 16 was 92.0 mol%, and the propylene content was 8.0 mol%. The melting point Tm of polymer 16 was 180°C, and the intrinsic viscosity [η] was 1.6 dl / g.

[0108] [Comparative Example 2] (Production of Polymer 17) According to the polymerization method described in Comparative Example 9 of International Publication No. 2006 / 054613, by changing the ratios of 4-methyl-1-pentene, other α-olefins (a mass mixture such as 1-hexadecene and 1-octadecene), and hydrogen, the 4-methyl-1-pentene-based polymer (polymer 17) described in Table 1 was obtained.

[0109] [Example 16] To 10 g of Polymer 1, 0.1 wt% of tris(2,4-di-t-butylphenyl) phosphate as an antioxidant and 0.1 wt% of n-octadecyl 3-(4'-hydroxy-3',5'-di-t-butylphenyl) propionate as a heat stabilizer were added, and methylcyclohexane (manufactured by Wako Pure Chemical Industries, Ltd.) was added so that the solid content concentration became 5 wt%. The mixture was stirred at 90 °C for 1 hour at 200 rpm to produce a composition containing Polymer 1. This composition was applied onto a glass substrate at 25 °C and uniformly spread with an applicator, and then dried at 25 °C for 30 minutes and further at 80 °C for 10 minutes to obtain a film.

[0110] Also, for the evaluation of the coating film appearance, the composition was applied onto a PET ("Lumirror" manufactured by Toray Industries, Inc.) substrate at 25 °C and uniformly spread with an applicator, and then dried at 25 °C for 30 minutes and further at 80 °C for 10 minutes to obtain a coating film.

[0111] [Example 17] The same operations as in Example 16 were performed except that Polymer 2 was used instead of Polymer 1 to obtain a composition, a film, and a coating film.

[0112] [Example 18] The same operations as in Example 16 were performed except that Polymer 3 was used instead of Polymer 1 to obtain a composition, a film, and a coating film.

[0113] [Example 19] The same operations as in Example 16 were performed except that Polymer 4 was used instead of Polymer 1 to obtain a composition, a film, and a coating film.

[0114] [Example 20] The same operations as in Example 16 were performed except that Polymer 5 was used instead of Polymer 1 to obtain a composition, a film, and a coating film.

[0115] [Example 21] The same operations as in Example 16 were carried out except that polymer 6 was used instead of polymer 1, and a composition, a film, and a coating film were obtained.

[0116] [Example 22] The same operations as in Example 16 were carried out except that polymer 7 was used instead of polymer 1, and a composition, a film, and a coating film were obtained.

[0117] [Example 23] The same operations as in Example 16 were carried out except that polymer 8 was used instead of polymer 1, and a composition, a film, and a coating film were obtained.

[0118] [Example 24] The same operations as in Example 16 were carried out except that polymer 9 was used instead of polymer 1, and a composition, a film, and a coating film were obtained.

[0119] [Example 25] The same operations as in Example 16 were carried out except that polymer 10 was used instead of polymer 1, and a composition, a film, and a coating film were obtained.

[0120] [Example 26] The same operations as in Example 16 were carried out except that polymer 11 was used instead of polymer 1, and a composition, a film, and a coating film were obtained.

[0121] [Example 27] The same operations as in Example 16 were carried out except that polymer 12 was used instead of polymer 1, and a composition, a film, and a coating film were obtained.

[0122] [Example 28] The same operations as in Example 16 were carried out except that polymer 13 was used instead of polymer 1, and a composition, a film, and a coating film were obtained.

[0123] [Example 29] The same operations as in Example 16 were carried out except that polymer 14 was used instead of polymer 1, and a composition, a film, and a coating film were obtained.

[0124] [Example 30] The same operations as in Example 16 were carried out except that polymer 15 was used instead of polymer 1, and a composition, a film, and a coating film were obtained.

[0125] [Comparative Example 3] The same operations as in Example 16 were carried out except that polymer 16 was used instead of polymer 1, and a composition, a film, and a coating film were obtained.

[0126] [Comparative Example 4] Polymer 17 was used instead of polymer 1, and the mixture was stirred at 90 °C for 1 hour at 200 rpm in the same manner as in Example 16. However, most of polymer 17 did not dissolve and remained undissolved. Thus, since a solution having a concentration sufficient for forming a coating film could not be obtained, a composition, a film, and a coating film could not be obtained.

[0127] Table 1 shows the compositions and physical properties of the polymers of Examples 1 to 30 and Comparative Examples 1 to 4, and the physical properties of the compositions, films, and coating films. In Comparative Example 4, since a composition, a film, and a coating film could not be obtained, evaluation of storage stability, water contact angle, normalized dielectric breakdown voltage, and coating film appearance could not be performed.

[0128]

Table 1-1

[0129]

Table 1-2

Claims

1. A copolymer of 4-methyl-1-pentene and at least one selected from linear α-olefins having 6 to 20 carbon atoms, which is a 4-methyl-1-pentene polymer (A) satisfying the following requirements (I) and (II) and satisfying the following requirements (III), (IV) and (V). (I) The endothermic termination temperature (TmE) in the melting (endothermic) curve measured by DSC is 230 °C or lower. (II) The exothermic start temperature (TcS) in the crystallization (exothermic) curve measured by DSC is 210 °C or lower. (III) The melting point (Tm) measured by DSC is 170 to 220 °C. (IV) The intrinsic viscosity [η] is 1.7 to 5.5 dl / g. (V) The crystallization temperature (Tc) measured by DSC is 110 to 186 °C.

2. A copolymer of 4-methyl-1-pentene and at least one selected from linear α-olefins having 6 to 20 carbon atoms, which is a 4-methyl-1-pentene polymer (A) satisfying the following requirements (I) and (II) and satisfying the following requirements (III'), (IV') and (V). (I) The endothermic termination temperature (TmE) in the melting (endothermic) curve measured by DSC is 230 °C or lower. (II) The exothermic start temperature (TcS) in the crystallization (exothermic) curve measured by DSC is 210 °C or lower. (III') The melting point (Tm) measured by DSC is higher than 200 °C and 220 °C or lower. (IV') The intrinsic viscosity [η] is 1.7 to 5.3 dl / g. (V) The crystallization temperature (Tc) measured by DSC is 110 to 186 °C.

3. The 4-methyl-1-pentene polymer (A) according to claim 1 or 2, wherein the amount (U1) of the structural unit derived from 4-methyl-1-pentene is 84.0 to 99.0 mol%, and the total amount (U2) of the structural units derived from at least one selected from linear α-olefins having 6 to 20 carbon atoms is 16.0 to 1.0 mol% (however, the total of the U1 and the U2 is 100 mol%).

4. The unmodified 4-methyl-1-pentene polymer (A) according to any one of claims 1 to 3.

5. The 4-methyl-1-pentene polymer (A) according to any one of claims 1 to 4, wherein the linear α-olefin having 6 to 20 carbon atoms is selected from 1-decene, 1-hexadecene and 1-octadecene.

6. A composition (X) comprising 0.1 to 50% by mass of a 4-methyl-1-pentene polymer (A) according to any one of claims 1 to 5 and 50 to 99.9% by mass of a solvent (B).

7. The composition (X) according to claim 6, wherein the solvent (B) is an organic solvent.

8. A coating agent comprising the composition (X) according to claim 6 or 7.

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