4-methyl-1-pentene copolymer composition, molded article and film containing the 4-methyl-1-pentene copolymer composition

Abstract

To provide a molded body which, while maintaining releasability and transparency characteristic of a 4-methyl-1-pentene-based copolymer, is suppressed from deformation at the time of heating by improving high temperature rigidity (storage elastic modulus) and further is suppressed from shrinkage after molding, and to provide a copolymer composition therefor.SOLUTION: Provided is a 4-methyl-1-pentene-based copolymer composition (X) which contains 0.1 pt.mass to 10 pts.mass of a nucleating agent (B) relative to 100 pts.mass of a 4-methyl-1-pentene-based copolymer (A) and which satisfies the following requirements (a) and (b). Requirement (a): the temperature at which a loss tangent (tanδ) becomes maximum is 0°C to 60°C, as determined by a dynamic viscoelasticity measurement (frequency=10 rad / s(1.6 Hz)) of (X) at -40 to 150°C. Requirement (b): a loss tangent at 50°C is 6×106 Pa or more, as determined by a dynamic viscoelasticity measurement (frequency=10 rad / s(1.6 Hz)) of (X) at -40 to 150°C.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition comprising a 4-methyl-1-pentene copolymer, and to molded articles and films comprising the 4-methyl-1-pentene copolymer composition. [Background technology]

[0002] 4-methyl-1-pentene copolymers offer superior heat resistance, transparency, and electrical properties compared to polyethylene and polypropylene, and are widely used in various applications, particularly as industrial release films and capacitor films (Patent Document 1). Furthermore, by adjusting the molecular weight and composition of 4-methyl-1-pentene copolymers to lower the melting point, stress relaxation properties are exhibited, and industrial films capable of holding foreign matter encased have been disclosed (Patent Document 2).

[0003] On the other hand, polyolefin resins such as polyethylene and polypropylene are inexpensive and have very well-balanced performance, and are widely used in various applications. Among them, polypropylene resins have seen significant improvements in mechanical properties such as rigidity and thermal properties such as heat resistance through past improvements, and are increasingly being replaced by other materials in fields such as automotive and industrial materials. Although the mechanical properties of polypropylene resins have been greatly improved through past improvements, for example, further reductions in the amount of fillers and thinning of walls are necessary for weight reduction in automotive materials, and for that purpose, an even greater improvement in the rigidity of polypropylene resins is required.

[0004] There are two main approaches to improving the rigidity of polypropylene resins: improving the polypropylene resin itself and improving it through the addition of additives. For example, in the case of improving the polypropylene resin itself, rigidity can be improved by controlling the molecular weight, its distribution, crystallinity, and various higher-order structures (Patent Document 3). When adding additives, the simplest method is to add fillers, but this has the problem of increasing weight. In fields such as automotive materials where weight reduction is required, other methods, such as controlling the orientation of the resin by adding nucleating agents, are widely used (Patent Documents 4-6).

[0005] In 4-methyl-1-pentene copolymers, studies have been conducted to improve rigidity by incorporating nucleating agents. This is because while films made from 4-methyl-1-pentene copolymers and nucleating agents have improved rigidity, the interfacial strength between the resins decreases. Therefore, stretching the film yields a microporous film, which has led to its application as a separator for batteries (Patent Documents 7 and 8). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2014-11182 [Patent Document 2] Japanese Patent Publication No. 2013-169685 [Patent Document 3] Japanese Patent Application Publication No. 11-12322 [Patent Document 4] Japanese Patent Application Publication No. 11-293084 [Patent Document 5] Japanese Patent Publication No. 2014-95045 [Patent Document 6] Japanese Patent Publication No. 2018-168386 [Patent Document 7] Japanese Patent Publication No. 2019-73615 [Patent Document 8] International Publication No. 2010 / 013467 Pamphlet [Overview of the Initiative]

Problems to be Solved by the Invention

[0007] 4-Methyl-1-pentene copolymers excellent in stress relaxation properties have been used for industrial films due to their low dielectric properties and followability. However, due to their stress relaxation properties, the crystallization rate is slow, resulting in dimensional changes due to the occurrence of wrinkles in the film several days after molding, i.e., so-called molding shrinkage occurs. In addition, since the rigidity at high temperatures decreases due to the imparted stress relaxation properties, an improvement in rigidity at higher temperatures has been demanded.

[0008] Also, as described above, attempts have been made to improve the rigidity of polyolefin resins by various methods. However, all of them aimed to obtain a lightweight molded body by thinning due to high rigidity or to improve the porosity by reducing the elongation at break due to high rigidity. Therefore, it has become an issue to improve the rigidity (storage modulus) at high temperatures while maintaining the elongation and relaxation properties even when a nucleating agent is blended.

[0009] An object of the present invention is to provide a molded body in which deformation during heating is suppressed by improving the rigidity (storage modulus) at high temperatures while maintaining the mold release property and transparency, which are characteristics of 4-methyl-1-pentene copolymers, and further shrinkage after molding is suppressed.

Means for Solving the Problems

[0010] In view of the above situation, the present inventors have intensively studied to solve the above problems. As a result, they have found that by using a specific composition containing a 4-methyl-1-pentene copolymer (A) and a nucleating agent (B), the above problems are solved, and the present invention has been completed.

[0011] That is, the present invention includes, for example, the following [1] to [8]. [1] A 4-methyl-1-pentene copolymer composition (X) comprising 0.1 to 10 parts by mass of a crystal nucleating agent (B) per 100 parts by mass of a 4-methyl-1-pentene copolymer (A), and satisfying the following requirements (a) and (b). Requirement (a); The temperature at which the loss tangent (tanδ) value of the 4-methyl-1-pentene copolymer composition (X) is maximized by dynamic viscoelasticity measurement (frequency 10 rad / s (1.6 Hz)) in the temperature range of -40 to 150°C is between 0°C and 60°C. Requirement (b); The storage modulus at 50°C of the 4-methyl-1-pentene copolymer composition (X), determined by dynamic viscoelasticity measurement (frequency 10 rad / s (1.6 Hz)) in the temperature range of -40 to 150°C, is 6 × 10⁻¹⁰. 6 It is Pa or higher. [2] The 4-methyl-1-pentene copolymer composition (X) according to [1], wherein the 4-methyl-1-pentene copolymer (A) satisfies one or more of the following requirements (e) to (h). requirement(e); It consists of 55-97 mol% of constituent unit (i) derived from 4-methyl-1-pentene and 3-45 mol% of constituent unit (ii) derived from ethylene and one or more α-olefins having 3-20 carbon atoms (excluding 4-methyl-1-pentene) (the sum of constituent unit (i) and constituent unit (ii) is 100 mol%). requirement(f); The melting point measured by differential scanning calorimeter (DSC) is below 200°C, or no melting point is observed. requirement(g); The temperature at which the loss tangent (tanδ) value is maximized in dynamic viscoelasticity measurements (frequency 10 rad / s (1.6 Hz)) in the temperature range of -40 to 150°C is between 15°C and 45°C. requirement(h); The density is 830-870 kg / m³ 3 That is the case. [3] The 4-methyl-1-pentene copolymer composition (X) described in [1] or [2], wherein the 4-methyl-1-pentene copolymer composition (X) satisfies the following requirement (c). Requirement (c); The crystallization temperature (Tc) measured by differential scanning calorimeter (DSC) is 70°C or higher. [4] The 4-methyl-1-pentene copolymer composition (X) according to any one of [1] to [3], wherein the crystal nucleating agent (B) is a crystal nucleating agent consisting of one or more selected from sorbitol-based nucleating agents, phosphate ester salt-based nucleating agents, and amide-based nucleating agents, which are diacetal compounds. [5] A molded article comprising a 4-methyl-1-pentene copolymer composition (X) as described in any of [1] to [4]. [6] A sheet or film comprising the 4-methyl-1-pentene copolymer composition (X) described in any of [1] to [4]. A laminate comprising one or more sheets and films selected from those described in [7] and [6]. [8] A surface protective film comprising a 4-methyl-1-pentene copolymer composition (X) as described in any of [1] to [4]. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a molded article that suppresses deformation during heating and further suppresses shrinkage after molding by improving the high-temperature rigidity (storage modulus) while maintaining the release properties and transparency that are characteristic of 4-methyl-1-pentene copolymers. [Brief explanation of the drawing]

[0013] [Figure 1] Figure 1 is a graph showing the relationship between temperature and storage modulus (G') obtained from dynamic viscoelasticity measurements (frequency 10 rad / s (1.6 Hz)) of the films obtained in Example 3 and Comparative Example 1. [Modes for carrying out the invention]

[0014] The following describes specific embodiments of the present invention in detail. However, the present invention is not limited to the following embodiments and can be implemented with appropriate modifications within the scope of the object of the present invention. In this specification, unless otherwise specified, the terms "polymer" and "(co)polymer" are used to include homopolymers and copolymers.

[0015] The 4-methyl-1-pentene copolymer composition (X) of the present invention and a molded article containing the 4-methyl-1-pentene copolymer composition (X) contain a 4-methyl-1-pentene copolymer (A) and a crystal nucleating agent (B). Each of these will be described below.

[0016] <4-methyl-1-pentene copolymer composition (X)> The 4-methyl-1-pentene copolymer composition (X) comprises a 4-methyl-1-pentene copolymer (A) and a crystal nucleating agent (B), with the crystal nucleating agent (B) being present in an amount of 0.1 to 10 parts by mass per 100 parts by mass of the 4-methyl-1-pentene copolymer (A).

[0017] In the 4-methyl-1-pentene copolymer composition (X), the amount of nucleating agent (B) per 100 parts by mass of 4-methyl-1-pentene copolymer (A) is preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass. In the 4-methyl-1-pentene copolymer composition (X), having the amount of nucleating agent (B) within the above range improves the storage modulus at high temperatures, for example, the storage modulus at 50°C obtained by the dynamic viscoelasticity measurement described later.

[0018] The 4-methyl-1-pentene copolymer composition (X) satisfies both of the following requirements (a) and (b).

[0019] [Requirement (a)] The 4-methyl-1-pentene copolymer composition (X) has a temperature (hereinafter, this temperature at which the loss tangent (tanδ) value is maximum is also referred to as the "tanδ peak temperature") at which the value of the loss tangent (tanδ) obtained by dynamic viscoelasticity measurement (frequency: 10 rad / s (1.6 Hz)) in the temperature range of -40 to 150°C is maximum, and this temperature is 0°C or higher and 60°C or lower.

[0020] Regarding the lower limit value of the tanδ peak temperature, the tanδ peak temperature is preferably 5°C or higher, more preferably 10°C or higher. Regarding the upper limit value of the tanδ peak temperature, the tanδ peak temperature is preferably 55°C or lower, more preferably 50°C or lower, and particularly preferably 45°C or lower. By adjusting the tanδ peak temperature within the above temperature range, the molded body can exhibit high stress relaxation properties while corresponding to a wide range of environmental temperatures.

[0021] [Requirement (b)] The 4-methyl-1-pentene copolymer composition (X) has a storage modulus at 50°C (hereinafter, this storage modulus at 50°C is also referred to as "G'@50°C") obtained by dynamic viscoelasticity measurement (frequency: 10 rad / s (1.6 Hz)) in the temperature range of -40 to 150°C of 6×10 6 Pa or more.

[0022] G'@50°C is preferably 6.3×10 6 Pa or more, more preferably 6.5×10 6 Pa or more, and particularly preferably 6.8×10 6 Pa or more. Although there is no particular specification for the upper limit value of G'@50°C, it is preferably 1.0×10 12 Pa or less, more preferably 1.0×1 10 Pa or less, and particularly preferably 8.0×10 9 Pa or less. By adjusting G'@50°C within the above range, the molded body can suppress dimensional changes while exhibiting high stress relaxation properties and can exhibit mold release properties at high temperatures.

[0023] In a typical embodiment of the present invention, the 4-methyl-1-pentene copolymer composition (X) of the present invention preferably satisfies requirement (c) or requirement (d) below, and more preferably satisfies both requirement (c) and requirement (d).

[0024] [Requirement (c)] The 4-methyl-1-pentene copolymer composition (X) has a crystallization temperature (Tc) of 70°C or higher, as measured by differential scanning calorimeter (DSC).

[0025] Regarding requirement (c) above, preferably the crystallization temperature (Tc) is 75°C or higher, and more preferably 85°C or higher.

[0026] By satisfying requirement (c) above, the crystallization rate of the 4-methyl-1-pentene copolymer composition (X) of the present invention is increased, and wrinkles after molding are more easily suppressed. Furthermore, there is no particular upper limit to the crystallization temperature (Tc), but the range of the 4-methyl-1-pentene copolymer composition (X) that is usually obtained is 200°C or less, preferably 150°C or less, and more preferably 130°C or less.

[0027] [Requirement (d)] The 4-methyl-1-pentene copolymer composition (X) exhibits a minimum temperature (T) at which the storage modulus G' is minimized in dynamic viscoelasticity measurements (frequency 10 rad / s (1.6 Hz)) in the temperature range of -40 to 150°C. A ) does not have.

[0028] Minimum temperature (T A ) refers to a specific temperature at which, when the storage modulus G' of a 4-methyl-1-pentene copolymer composition (X) is measured while being heated, the storage modulus G' decreases with increasing temperature, but then begins to increase.

[0029] Minimum temperature (T AThis phenomenon occurs by controlling the balance between highly crystalline and amorphous components, the comonomer species, the comonomer content, and the crystallization rate in the 4-methyl-1-pentene copolymer (A), which will be described later. It can also occur if the 4-methyl-1-pentene copolymer (A) is a polymer with a slow crystallization rate, as the crystals may not have grown completely during cooling and solidification.

[0030] <4-methyl-1-pentene copolymer (A)> The 4-methyl-1-pentene copolymer (A) contained in the 4-methyl-1-pentene copolymer composition (X) is not limited, but preferably satisfies one or more of the following requirements (e) to (h), more preferably two or more, even more preferably three or more, and particularly preferably all of them. In a typical embodiment of the present invention, the 4-methyl-1-pentene copolymer (A) satisfies at least one of the requirements (e) to (h).

[0031] [Requirement (e)] It contains 55-97 mol% of constituent units derived from 4-methyl-1-pentene (hereinafter also referred to as "constituent unit (i)") and 3-45 mol% of constituent units derived from one or more ethylene and α-olefins having 3-20 carbon atoms (excluding 4-methyl-1-pentene) (hereinafter also referred to as "constituent unit (ii)") (the sum of constituent unit (i) and constituent unit (ii) is 100 mol%).

[0032] Requirement (e) above specifies that the 4-methyl-1-pentene copolymer (A) has constituent unit (i) and constituent unit (ii) in a specific proportion.

[0033] In this specification, the structural unit derived from α-olefin refers to the structural unit corresponding to α-olefin, i.e., the structural unit represented by -CH2-CHR- (where R is a hydrogen atom or an alkyl group). Similarly, the structural unit (i) derived from 4-methyl-1-pentene refers to the structural unit corresponding to 4-methyl-1-pentene, i.e., the structural unit represented by -CH2-CH(-CH2CH(CH3)2)-.

[0034] For the 4-methyl-1-pentene copolymer (A), the lower limit of the amount of constituent unit (i) is 55 mol%, preferably 65 mol%, and more preferably 68 mol%. On the other hand, the upper limit of the amount of constituent unit (i) is 97 mol%, preferably 93 mol%, and more preferably 87 mol%.

[0035] In the 4-methyl-1-pentene copolymer (A), if the amount of constituent unit (i) is greater than or equal to the lower limit above, the tanδ peak temperature measured by dynamic viscoelasticity will be near room temperature, making it easy to adjust the tanδ peak temperature of the resin composition to within the above range. On the other hand, if the amount of constituent unit (i) is less than or equal to the upper limit above, it exhibits high stress relaxation properties near room temperature.

[0036] Therefore, in the 4-methyl-1-pentene copolymer (A), the upper limit of the amount of constituent unit (ii) is 45 mol%, preferably 35 mol%, and more preferably 32 mol%.

[0037] On the other hand, the lower limit of the amount of constituent unit (ii) is 3 mol%, preferably 7 mol%, and more preferably 13 mol%.

[0038] The content (mol%) of each constituent unit of the 4-methyl-1-pentene copolymer (A) is: 13 The measurement is performed by 13C-NMR. Details of the measurement method are described in the examples below.

[0039] Thus, the 4-methyl-1-pentene copolymer (A) used in the present invention contains, as a constituent unit other than the constituent unit derived from 4-methyl-1-pentene, a constituent unit derived from ethylene and at least one selected from α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene). A 4-methyl-1-pentene copolymer composition (X) containing such a 4-methyl-1-pentene copolymer (A) exhibits superior heat resistance and stress relaxation compared to a resin composition containing a copolymer of 4-methyl-1-pentene and an α-olefin consisting of 4-methyl-1-pentene and an α-olefin having 21 or more carbon atoms.

[0040] Specific examples of α-olefins having 3 to 20 carbon atoms other than 4-methyl-1-pentene mentioned above include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-octadecene, and 1-hexadecene, among which ethylene, propylene, and 1-butene are particularly preferred. The constituent unit (ii) may be derived from one of these compounds or from two or more compounds. By selecting propylene as ethylene and α-olefins with 3 to 20 carbon atoms (excluding 4-methyl-1-pentene), it is easier to set the tanδ peak temperature within the above range, and molded articles with high stress relaxation properties are more easily obtained.

[0041] In a typical embodiment of the present invention, the 4-methyl-1-pentene copolymer (A) constituting the 4-methyl-1-pentene copolymer composition (X) consists only of constituent unit (i) and constituent unit (ii). That is, in this embodiment, the 4-methyl-1-pentene copolymer (A) is a copolymer of 4-methyl-1-pentene and at least one monomer selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene).

[0042] [Requirement (f)] The melting point measured by differential scanning calorimeter (DSC) is below 200°C, or no melting point is observed.

[0043] In requirement (f) above, the 4-methyl-1-pentene copolymer (A) has a melting point less than 200°C or no melting point observed as measured by differential scanning calorimeter (DSC), preferably 160°C or less or no melting point observed, more preferably 150°C or less or no melting point observed, and particularly preferably 150°C or less.

[0044] The 4-methyl-1-pentene copolymer (A) has a lower limit of melting point measured by differential scanning calorimeter (DSC) of 110°C or higher, or no melting point is observed, preferably with a melting point of 110°C or higher, and more preferably with a melting point of 130°C or higher.

[0045] "No melting point observed" means that when measured with a differential scanning calorimeter (DSC), no melting peak with a heat of fusion of 1 J / g or more is observed. Details of the measurement method are as described in the examples below. If two or more melting points appear, the highest temperature is considered the melting point.

[0046] By satisfying these requirements, the 4-methyl-1-pentene copolymer composition (X) can have high stress relaxation properties.

[0047] [Requirement (g)] The tanδ peak temperature, determined by dynamic viscoelasticity measurements (frequency 10 rad / s (1.6 Hz)) in the temperature range of -40 to 150°C, is between 15°C and 45°C.

[0048] Regarding requirement (f) above, the 4-methyl-1-pentene copolymer (A) has a tanδ peak temperature determined by dynamic viscoelasticity measurement (frequency 10 rad / s (1.6 Hz)) in the temperature range of -40 to 150°C, preferably between 15°C and 45°C, more preferably between 20°C and 45°C, and more preferably between 25°C and 45°C. Details of the measurement method are as described in the examples below.

[0049] By keeping the tanδ peak temperature within the above range, the stress relaxation characteristics near room temperature can be better exhibited.

[0050] [Requirement(h)] The density of the 4-methyl-1-pentene copolymer (A) is 830-870 kg / m³. 3 That is the case.

[0051] Regarding the above requirement (h), the density of the 4-methyl-1-pentene copolymer (A) is preferably 830 to 860 kg / m³. 3 Preferably 830-850 kg / m 3 The details of the measurement method are as described in the examples below.

[0052] The density of the 4-methyl-1-pentene copolymer (A) can be appropriately varied depending on the composition ratio of constituent units (i) and (ii). 4-methyl-1-pentene copolymer (A) with a density within the above range is advantageous because it exhibits good transparency and mold release properties.

[0053] The 4-methyl-1-pentene copolymer (A) preferably satisfies one or more, more preferably two or more, and most preferably all of the following requirements (i) to (k).

[0054] [Requirement (i)] The 4-methyl-1-pentene copolymer (A) has an intrinsic viscosity [η] in decalin measured at 135°C in the range of 0.1 to 5.0 dl / g.

[0055] Regarding requirement (i) above, the intrinsic viscosity [η] of the 4-methyl-1-pentene copolymer (A) is preferably 0.5 to 4.0 dl / g, more preferably 1.0 to 3.5 dl / g. As will be described later, by using hydrogen in combination during polymerization, the molecular weight can be controlled, and molecules ranging from low molecular weight to high molecular weight can be freely obtained and adjusted to the above range of intrinsic viscosity [η]. Details of the measurement method are as described in the examples below.

[0056] [Requirement(j)] The 4-methyl-1-pentene copolymer (A) has a weight-average molecular weight (Mw) of 1,000 to 1,000,000 or less in polystyrene terms, as measured by gel permeation chromatography (GPC).

[0057] Regarding the above requirement (j), the weight-average molecular weight (Mw) of the 4-methyl-1-pentene copolymer (A) is preferably 5,000 to 800,000 or less, and more preferably 10,000 to 500,000 or less. Details of the measurement method are as described in the examples below.

[0058] The 4-methyl-1-pentene copolymer (A) preferably has a molecular weight distribution (Mw / Mn), which is the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn), measured by gel permeation chromatography (GPC), in the range of 1.0 to 3.5, more preferably 1.2 to 3.0, and even more preferably 1.5 to 2.8. A molecular weight distribution (Mw / Mn) of 3.5 or less is preferable because it reduces the influence of low molecular weight and low stereoregularity polymers derived from the composition distribution, and the mechanical strength of the resulting molded article is less likely to decrease.

[0059] [Requirement(k)] The melt mass flow rate (MFR; compliant with ASTM D1238, temperature 230°C, load 2.16 kg) of the 4-methyl-1-pentene copolymer (A) is 0.1 to 100 g / 10 min.

[0060] Regarding the above requirement (j), the melt mass flow rate of the 4-methyl-1-pentene copolymer (A) is preferably 0.5 to 50 g / 10 min, and more preferably 1.0 to 30 g / 10 min.

[0061] When the melt mass flow rate (MFR) of the 4-methyl-1-pentene copolymer (A) is above the lower limit within the above range, good dispersibility with the nucleating agent (B) described later can be obtained. When it is below the upper limit within the above range, it is preferable because the molecular weight of the resin is not too low, and sufficient mechanical strength can be obtained as a molded article.

[0062] <Method for producing 4-methyl-1-pentene copolymer (A)> The method for producing the 4-methyl-1-pentene copolymer (A) is not particularly limited, but for example, the 4-methyl-1-pentene copolymer (A) can be produced by polymerizing 4-methyl-1-pentene with ethylene or a monomer of an α-olefin having 3 to 20 carbon atoms in the presence of a suitable polymerization catalyst such as a magnesium-supported titanium catalyst or a metallocene catalyst.

[0063] Suitable polymerization catalysts include conventionally known catalysts, such as magnesium-supported titanium catalysts, metallocene catalysts described in International Publication No. 01 / 53369, International Publication No. 01 / 27124, Japanese Patent Publication No. 3-193796, or Japanese Patent Publication No. 2-41303, International Publication No. 2011 / 055803, International Publication No. 2014 / 050817, etc. Polymerization can be carried out by appropriately selecting from liquid-phase polymerization methods, including dissolution polymerization and suspension polymerization, as well as gas-phase polymerization methods.

[0064] In liquid-phase polymerization, an inert hydrocarbon solvent can be used as the solvent constituting the liquid phase. Examples of the above inert hydrocarbons include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, trichloromethane, and tetrachloromethane; and mixtures thereof.

[0065] Furthermore, in liquid-phase polymerization, for example, in the case of a 4-methyl-1-pentene copolymer (A) that satisfies requirement (e) above, bulk polymerization can also be carried out using the monomer corresponding to constituent unit (i) (i.e., 4-methyl-1-pentene) and / or the monomer corresponding to constituent unit (ii) (i.e., ethylene or the aforementioned α-olefin having 3 to 20 carbon atoms) itself as the solvent.

[0066] Furthermore, when producing a methyl-1-pentene copolymer (A) that satisfies requirement (e) by the liquid-phase polymerization described above, the compositional distribution of constituent units (i) and (ii) constituting the 4-methyl-1-pentene copolymer (A) can be appropriately controlled by performing the copolymerization of 4-methyl-1-pentene with the α-olefin having 2 to 4 carbon atoms in a stepwise manner.

[0067] The polymerization temperature is preferably -50 to 200°C, more preferably 0 to 100°C, and even more preferably 20 to 100°C. The polymerization pressure is preferably atmospheric pressure to 10 MPa gauge pressure, and more preferably atmospheric pressure to 5 MPa gauge pressure.

[0068] During polymerization, hydrogen may be added to control the molecular weight and polymerization activity of the resulting polymer. The appropriate amount of hydrogen to add is approximately 0.001 to 100 NL per 1 kg of the total amount of 4-methyl-1-pentene and the α-olefin with 2 to 4 carbon atoms mentioned above.

[0069] <Crystal nucleating agent (B)> The nucleating agent (B) contained in the 4-methyl-1-pentene copolymer composition (X) of the present invention is used to increase the crystallization temperature and accelerate the crystallization rate of the resulting molded article by melting it with the 4-methyl-1-pentene copolymer (A) and molding it.

[0070] Crystal nucleating agents (B) are generally classified into soluble nucleating agents and dispersed nucleating agents, but various known nucleating agents can be used as long as the above requirements (a) and (b) are met. Specifically, examples of nucleating agents related to the present invention include diacetal compounds or sorbitol-based nucleating agents containing diacetal compounds, nonitol-based nucleating agents, amide-based nucleating agents, benzoic acid ester salt-based nucleating agents, aromatic carboxylic acid metal salts, phosphate ester salt-based nucleating agents, alicyclic carboxylic acid metal salt nucleating agents, rosin-based nucleating agents, and the like.

[0071] The nucleating agent (B) preferably satisfies one or more of the following requirements (x) and (y), more preferably all of them.

[0072] [Requirements(x)] The nucleating agent (B) has a melting point in the range of 150 to 600°C or is not observed, and its molecular weight is in the range of 200 to 1000.

[0073] Regarding requirement (x), the melting point of the nucleating agent (B) is preferably in the range of 200°C to 600°C, and more preferably in the range of 210°C to 500°C. Furthermore, the molecular weight of the nucleating agent (B) is preferably in the range of 250 to 800, and more preferably in the range of 300 to 700.

[0074] [Requirement (y)] The crystal nucleating agent (B) consists of an organic compound and is one of the following: a sorbitol-based nucleating agent, a phosphate ester-based nucleating agent, or an amide-based nucleating agent.

[0075] Regarding requirement (y), the nucleating agent (B) is particularly preferably a phosphate ester salt or a diacetal compound. The phosphate ester salt and diacetal compound will be described below.

[0076] (1) Phosphate ester salt As the phosphate ester salt, any known one used as a nucleating agent can be used, but preferably it is a compound represented by the following general formula (1).

[0077] [ka]

[0078] In general formula (1), R 1 ~R 4 R represents an alkyl group with 1 to 6 carbon atoms. 5 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, n represents 1 or 2, if n is 1, M represents lithium or dihydroxyaluminum, if n is 2, M represents hydroxyaluminum.

[0079] R in general formula (1) 1 ~R 4 Examples of alkyl groups having 1 to 6 carbon atoms represented by include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, 2-hexyl, and 3-hexyl. Among these, tert-butyl is preferred because it exhibits excellent nucleating agent effects. Also, R in general formula (1) 5 Examples of alkyl groups with 1 to 3 carbon atoms represented by include methyl, ethyl, propyl, and isopropyl.

[0080] The phosphate ester salts mentioned above may be those currently available on the market as crystal nucleating agents for polyolefins, such as NA-11, NA-21, NA-27, and NA-71 from ADEKA Corporation, and can be used as is.

[0081] (2) Diacetal compounds As the diacetal compound, known compounds disclosed in Japanese Patent Publication No. 2012-233149 and others can be used, but preferably a diacetal compound represented by the following general formula (2).

[0082] [ka]

[0083] In formula (2), R 1 and R 2These represent, either the same or different, a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, an alkoxycarbonyl group with 1 to 4 carbon atoms, or a halogen atom, respectively. a and b each represent integers from 1 to 5. c represents 0 or 1. If a is 2, then two R 1 The groups may be bonded to each other to form a tetraline ring with the benzene ring to which they are bonded, and if b is 2, the two R2 groups may be bonded to each other to form a tetraline ring with the benzene ring to which they are bonded. R3 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms, or an alkyl halogenated group having 1 to 4 carbon atoms.

[0084] Among the above diacetal compounds, 1,3:2,4-bis-O-(p-methylbenzylidene)-D-sorbitol, 1,3:2,4-bis-O-(p-ethylbenzylidene)-D-sorbitol, 1,3:2,4-bis-O-(3',4'-dimethylbenzylidene)-D-sorbitol, and 1,3:2,4-bis-O-(pn-propylbenzylidene)-1-propylsorbitol are particularly preferred from the viewpoint of improving rigidity.

[0085] Furthermore, while the diacetal compounds described in the specific embodiments above may be used alone, they may also be used in combination with two or more diacetal compounds, or as a pre-mixed mixture, from the viewpoint of other properties, such as low-temperature processability.

[0086] Alternatively, commercially available nucleating agents for polyolefins, such as Gelol D, Gelol MD, and Gelol DXR from Shin Nippon Rika Co., Ltd., Mirad 3988 and Mirad NX8000 from Milliken Corporation (USA), and Clearmaster from Dainichi Seika Kogyo Co., Ltd., may be used as is.

[0087] (3) Amide-based nucleating agents The amide-based nucleating agent of the present invention can be one of the known ones disclosed in International Publication No. 2010 / 035912, etc., but preferably it is an amide-based compound represented by the following general formula (3).

[0088] [ka]

[0089] In formula (3), R 4 , R 5 , R 6 and R 7 Each of these, either identical or different, represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group which may have substituents having 5 to 20 carbon atoms, or an aryl group which may have substituents having 6 to 20 carbon atoms. 4 and R 5 or R 6 and R 7 These two components may bond to each other to form an alkylene group.

[0090] Examples of amide-based nucleating agents of the present invention include, for example, 1,2,3-propanetricarboxylic acid tricyclohexylamide, 1,2,3-propanetricarboxylic acid tri(2-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri(3-methylcyclohexylamide), and 1,2,3-propanetricarboxylic acid tri(4-methylcyclohexylamide).

[0091] The above-mentioned amide-based nucleating agents may be commercially available products such as Shin Nippon Rika Co., Ltd.'s Rikaclear PC-1 or NJester NU-100, which can be used as is.

[0092] The nucleating agent (B) of the present invention may contain an auxiliary agent. The auxiliary agent is at least one selected from the group consisting of water and polyol compounds.

[0093] Examples of water include tap water, industrial water, and purified water. Examples of purified water include ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water.

[0094] Polyol compounds are compounds that have two or more hydroxyl groups. Specific examples of polyol compounds include, for example, 1,2-ethanediol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, tricyclohexanedimethanol, tricyclodecanedimethanol, hydroxypropylcyclohexanol, tricyclo[5,2,1,0,2,6]decanedimethanol, bicyclo[4,3,0]nonanediol, dicyclohexanediol, tricyclo[5,3,1,1]dodecanediol, bicyclo[4,3,0]nonanedimethanol, tricyclo[5,3,1,1]dodecanediethanol, hydroxypropylcyclohexanol, tricyclo[5,2,1,0,2,6]decanedimethanol, bicyclo[4,3,0]nonanedimethanol, tricyclo[5,3,1,1]dodecanediethanol, hydroxypropylcyclohexanol Glycols such as roxypropyltricyclo[5,3,1,1]dodecanol, spiro[3,4]octanediol, butylcyclohexanediol, 1,1'-bicyclohexylidenediol, 4,4'-isopropylpyridene-biscyclohexanol, 4,4'-oxybiscyclohexanol, and bis(4-hydroxycyclohexanol)methane; sugar alcohols such as glycerol, erythritol, pentaerythritol, dipentaerythritol, sorbitol, xylitol, maltitol, lactitol, mannitol, and isomalt; monofatty acid esters consisting of these sugar alcohols and fatty acids such as myristic acid, palmitic acid, stearic acid, oleic acid, and 12-hydroxystearic acid; linear, branched, or cyclic aliphatic polyols having three or more hydroxyl groups, such as polyvinyl alcohol, polycaprolactone triol, cyclohexanetriol, trimethylolethane, trimethylolpropane, and ditrimethylolpropane;Aromatic polyols such as cyclohexanediethanoldihydroxybenzene, benzenetriol, hydroxybenzyl alcohol, dihydroxytoluene, 4,4'-oxybisphenol, 4,4'-dihydroxybenzophenone, 4,4'-thiobisphenol, phenolphthalein, bis(4-hydroxyphenyl)methane, 4,4'-(1,2-ethendiyl)bisphenol, 4,4'-sulfonylbisphenol, 4,4'-isopropylidenebis(2,6-dibromophenol), 4,4'-isopropylidenebis(2,6-dichlorophenol), and 4,4'-isopropylidenebis(2,3,5,6-tetrachlorophenol); and 4,4'-thiobiscyclohexanol, etc.

[0095] Among these, glycols, sugar alcohols, monofatty acid esters consisting of sugar alcohols and fatty acids, and polyvinyl alcohol are preferred from the viewpoint of further improving the mechanical properties and transparency of the molded article. Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, erythritol, pentaerythritol, dipentaerythritol, xylitol, sorbitol, maltitol, lactitol, glycerol monostearate, glycerol monooleate, glycerol mono-12-hydroxystearate, and polyvinyl alcohol are even more preferred, and ethylene glycol, glycerol, pentaerythritol, xylitol, glycerol monostearate, and polyvinyl alcohol are particularly preferred.

[0096] <Other ingredients> The 4-methyl-1-pentene copolymer composition (X) of the present invention may further contain other components (hereinafter also referred to as "other components") that are neither the 4-methyl-1-pentene copolymer (A) nor the crystal nucleating agent (B), as necessary, to the extent that they do not impair the properties of the present invention. Examples of other components include known thermoplastic resins or additives.

[0097] Thermoplastic resins include olefin polymers; for example, low-density, medium-density, and high-density polyethylene, ultra-high molecular weight polyethylene, high-pressure low-density polyethylene, isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene, poly-1-butene, poly-4-methyl-1-pentene, poly-3-methyl-1-butene, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, 1-butene-α-olefin copolymer, cyclic olefin copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, ethylene-unsaturated carboxylic acid copolymer; for example, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, etc. Teylene-unsaturated carboxylic acid copolymers; for example, ethylene-(meth)acrylic acid copolymers, ethylene-crotonic acid copolymers, ethylene-methyl (meth)acrylate, ethylene-ethyl (meth)acrylate, ethylene-n-butyl (meth)acrylate, ethylene-isobutyl (meth)acrylate, ethylene-cyclohexyl (meth)acrylate copolymers, ethylene-glycidyl (meth)acrylate copolymers, ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid copolymers; for example, ethylene-vinyl acetate-glycidyl (meth)acrylate copolymers, ethylene-(meth)acrylic acid-glycidyl (meth)acrylate copolymers, ionomers, styrene resins;For example, polystyrene, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, styrene-butadiene copolymer and its hydrogenated products, styrene-isoprene copolymer and its hydrogenated products, styrene-isobutylene copolymer, styrene-isobutylene-styrene block copolymer, styrene-acrylonitrile copolymer, ABS resin, ACS resin, AES resin, ASA resin, fluororesin resin, rosin resin, terpene resin and petroleum resin, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, polyacrylonitrile, polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polylactic acid, polycaprolact The materials include polybutylene succinate, polyamino acids, polydimethylsiloxane, polytetramethylene glycol, polyhydroxyethyl methacrylate, polyphenylene terephthalamide, polyacrylamide, polyurethane, polyamide, polyoxymethylene, polycarbonate, polyphenylene ether, polyphenylene sulfide, polysulfone, polyether ether ketone, polyether ketone, polyethylene oxide, polymethyl methacrylate, polyimide, liquid crystal polymer, polyamide-imide, polyaminobismaleimide, polyarylate, polyetherimide, polyketone, polybenzimidazole, silicone resin, polybutadiene, cellulose resin, and mixtures thereof, among which olefin-based polymers (olefin-based resins) are preferred.

[0098] Examples of additives include, but are not limited to, softeners, mold release agents, antioxidants, flame retardants, UV absorbers, surfactants, antistatic agents, pigments, dyes, slip agents, weather stabilizers, heat stabilizers, infrared absorbers, antiblocking agents, antifogging agents, lubricants, plasticizers, anti-aging agents, hydrochloric acid absorbers, crystal nucleating agents, antifungal agents, antibacterial agents, and organic fillers. These additives may be used individually or in combination of two or more.

[0099] Examples of softeners include petroleum-based substances such as process oils, lubricating oils, paraffin, liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt, and petrolatum; coal tars such as coal tar and coal tar pitch; fatty oils such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; waxes such as tall oil, beeswax, carnauba wax, and lanolin; fatty acids or their metal salts such as ricinoleic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, montanic acid, oleic acid, and erucic acid; synthetic polymers such as petroleum resins, coumarone indene resin, and atactic polypropylene; ester-based plasticizers such as dioctyl phthalate, dioctyl adipate, and dioctyl sebacate; microcrystalline wax, liquid polybutadiene or modified or hydrogenated products thereof; and known softeners such as liquid thiocol.

[0100] Furthermore, examples of softening agents include aromatic carboxylic acid esters (such as dibutyl phthalate), aliphatic carboxylic acid esters (such as methylacetyl ricinolate), aliphatic dialbonate esters (such as adipic acid-propylene glycol polyesters), aliphatic tricarboxylic acid esters (such as triethyl citrate), phosphate triesters (such as triphenyl phosphate), epoxy fatty acid esters (such as epoxybutyl stearate), and petroleum resins.

[0101] Examples of release agents include lower (1-4 carbon atoms) alcohol esters of higher fatty acids (such as butyl stearate), polyhydric alcohol esters of fatty acids (4-30 carbon atoms) (such as hydrogenated castor oil), glycol esters of fatty acids, and liquid paraffin.

[0102] Examples of antioxidants include phenolic compounds (such as 2,6-di-t-butyl-4-methylphenol), polycyclic phenolic compounds (such as 2,2'-methylenebis(4-methyl-6-t-butylphenol) and other methylene-crosslinked polycyclic phenols), phosphorus compounds (such as tetrakis(2,4-di-t-butylphenyl)-4,4-biphenylenediphosphonate), and amine compounds (such as N,N-diisopropyl-p-phenylenediamine).

[0103] Examples of flame retardants include phosphate esters such as ammonium polyphosphate, ethylenebistris(2-cyanoethyl)phosphonium chloride, tris(tribromophenyl)phosphate, tris(tribromophenyl)phosphate, and tris(3-hydroxypropyl)phosphine oxide, as well as other phosphorus compounds, chlorinated flame retardants such as chlorinated paraffin, chlorinated polyolefin, and perchlorocyclopentadecane, brominated flame retardants such as hexabromobenzene, ethylenebisdibromonolbornanedicarboxyimide, ethylenebistetrabromophthalimide, tetrabromobisphenol A derivatives, tetrabromobisphenol S, and tetrabromodipentaerythritol, and mixtures thereof.

[0104] Examples of UV absorbers include benzotriazole-based, benzophenone-based, salicylic acid-based, and acrylate-based agents.

[0105] Examples of antibacterial agents include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, and organic iodine.

[0106] Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, or amphoteric surfactants.

[0107] Examples of nonionic surfactants include polyethylene glycol-type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts; and polyhydric alcohol-type nonionic surfactants such as fatty acid esters of polyethylene oxide and glycerin, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol or sorbitan, alkyl ethers of polyhydric alcohols, and aliphatic amides of alkanolamines.

[0108] Examples of anionic surfactants include sulfate esters of alkali metal salts of higher fatty acids, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates, and phosphate esters such as higher alcohol phosphate esters. Examples of cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium salts.

[0109] Examples of amphoteric surfactants include amino acid-type amphoteric surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyldimethyl betaine and higher alkyldihydroxyethyl betaine.

[0110] Examples of antistatic agents include the aforementioned surfactants, fatty acid esters, and polymeric antistatic agents. Examples of fatty acid esters include esters of stearic acid and oleic acid, and examples of polymeric antistatic agents include polyether ester amides.

[0111] Examples of pigments include inorganic pigments (titanium dioxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (azo lakes, thioindigos, phthalocyanines, anthraquinones). Examples of dyes include azo dyes, anthraquinone dyes, and triphenylmethane dyes.

[0112] Examples of slip agents include waxes (such as carnauba wax), higher fatty acids (such as stearic acid), higher fatty acid salts (such as calcium stearate), higher alcohols (such as stearyl alcohol), and higher fatty acid amides (such as stearic acid amide and erucic acid amide).

[0113] The amount of the above-mentioned other components added is not particularly limited, depending on the application, as long as it does not impair the purpose of the present invention, but is preferably 0.01 to 100 parts by mass, more preferably 0.01 to 30 parts by mass, and particularly preferably 0.05 to 20 parts by mass, per 100 parts by mass of the 4-methyl-1-pentene copolymer composition (X).

[0114] <Method for producing 4-methyl-1-pentene copolymer composition (X)> The method for producing the 4-methyl-1-pentene copolymer composition (X) of the present invention is not particularly limited, and conventionally known production methods can be used, for example. For example, methods include dry blending the 4-methyl-1-pentene copolymer (A) constituting the 4-methyl-1-pentene copolymer composition (X), a crystal nucleating agent (B), and optionally other components using a known mixer, and a solution mixing method by dissolving them in a solvent. Examples of the above-mentioned mixer include a Henschel mixer, a tumbler blender, a V-blender, and the like.

[0115] After dry blending in the above mixer, a method of melt-kneading using a single-screw extruder, twin-screw extruder, Banbury mixer, kneader, roll mill, etc., at a temperature setting of 100 to 270°C, followed by granulation or grinding, can be employed. Among these, melt-kneading using a twin-screw extruder or Banbury mixer is preferred from the viewpoint of the miscibility of each component and productivity. By these methods, high-quality pellets of 4-methyl-1-pentene copolymer composition (X) in which each component is uniformly mixed and dispersed can be obtained.

[0116] A particularly preferred method for producing the 4-methyl-1-pentene copolymer composition (X) is to melt and mix the nucleating agent (B) with the molten 4-methyl-1-pentene copolymer (A) at a temperature above which it dissolves, and then cool and solidify the mixture. This method allows for obtaining solid materials such as pellets.

[0117] The temperature at which the nucleating agent (B) dissolves in the molten 4-methyl-1-pentene copolymer (A) is any temperature at which the effects of the present invention are achieved, and it is not necessarily the temperature at which 100% by weight of the nucleating agent (B) dissolves. For example, it means the temperature at which 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more, and particularly preferably 95% by weight or more of the contained nucleating agent (B) dissolves.

[0118] Furthermore, from the standpoint of deterioration such as discoloration of the resin, it is undesirable for the temperature (T1) during melting and mixing to be too high. For example, a temperature within the range of formula (a) below is particularly recommended.

[0119] T≦T1 <T+15···(a) (T indicates the temperature at which the compounded nucleating agent (B) dissolves in the molten 4-methyl-1-pentene copolymer (A) at a maximum of 1% by weight.)

[0120] <Molded article containing a 4-methyl-1-pentene copolymer composition (X)> A molded article comprising the 4-methyl-1-pentene copolymer composition (X) of the present invention can be produced by molding the 4-methyl-1-pentene copolymer composition (X) obtained as described above. Examples of molded articles containing the 4-methyl-1-pentene copolymer composition (X) include sheets, films, and injection-molded articles.

[0121] The method for manufacturing the molded article of the present invention is not particularly limited, and conventionally known manufacturing methods can be used, such as extrusion molding, compression molding, injection molding, 3D printing, and microwave heat molding. Among such molding methods, extrusion molding is preferable for manufacturing the molded article.

[0122] Furthermore, when obtaining sheet-like or film-like molded articles, extrusion molding with a general-purpose T-die is preferred. Sheets can be manufactured by forming a film using a single-screw or twin-screw extruder equipped with a T-die, at a cylinder temperature of 180-250°C and a casting roll temperature of 20-80°C. The thickness of the sheet depends on its application, but it is usually 10-1000 μm, preferably 20-500 μm, which prevents pinholes from forming during extrusion molding, provides sufficient mechanical strength, and is advantageous for mass production of sheets.

[0123] The surface of the sheet or film may be embossed, and may be stretched during extrusion molding or after sheet molding. Furthermore, annealing may be performed at a temperature below the melting point of the resin in order to remove residual stress from the sheet.

[0124] Furthermore, the molded article containing the 4-methyl-1-pentene copolymer composition (X) may be molded by an orientation gel molding method at a temperature below the temperature at which the crystal nucleating agent (B) dissolves in the molten 4-methyl-1-pentene copolymer (A). The temperature below the temperature at which the crystal nucleating agent (B) dissolves in the molten 4-methyl-1-pentene copolymer (A) is sufficient to achieve the effects of the present invention, and does not necessarily mean that 100% by weight of the crystal nucleating agent (B) is not dissolved. For example, it means a temperature at which 70% or more by weight, preferably 80% or more by weight, more preferably 90% or more by weight, and particularly preferably 95% or more of the contained crystal nucleating agent (B) is not dissolved.

[0125] Furthermore, from the standpoint of moldability, a molding temperature (T2) that is too low is undesirable, and a temperature within the range of formula (b) below is particularly recommended.

[0126] T-15 ≤ T2 <T···(b) (T indicates the temperature at which the compounded nucleating agent (B) dissolves in the molten 4-methyl-1-pentene copolymer (A) at a maximum of 1% by weight.)

[0127] A molded article containing a 4-methyl-1-pentene copolymer composition (X) is a laminate containing a sheet or film containing the 4-methyl-1-pentene copolymer composition (X), and is typically a multilayer sheet or multilayer film. When the laminate is a multilayer sheet or multilayer film, the 4-methyl-1-pentene copolymer composition (X) may be contained in one of the layers constituting the multilayer sheet or multilayer film, but is preferably contained in the base layer (L2) or surface layer (L3) of the multilayer sheet or multilayer film.

[0128] The method for manufacturing the laminate is not particularly limited, and any known method for forming multilayer sheets or multilayer films may be used. Examples of preferred methods include co-extruding a substrate layer (L2) containing a separately prepared adhesive layer (L1) and a 4-methyl-1-pentene copolymer composition (X) using a T-die film molding method or an inflation film molding method, or extruding and coating a pre-formed substrate layer (L2) with the adhesive layer (L1). Another method involves applying a solution of the 4-methyl-1-pentene copolymer composition (X) onto the substrate layer (L2) to form the adhesive layer (L1). Among these, the method of co-extruding the adhesive layer (L1) and the substrate layer (L2) is preferred, and the T-die film molding method is more preferred as the co-extrusion method.

[0129] The method for producing a laminate comprising a base layer (L2), an adhesive layer (L1), and a surface layer (L3) containing a 4-methyl-1-pentene copolymer composition (X), which may be provided as needed, is not particularly limited. Examples include forming the surface layer (L3) in advance by T-die film molding or inflation film molding, and then laminating the base layer (L2) and adhesive layer (L1) on the surface layer (L3) by known lamination methods such as extrusion lamination or extrusion coating, or forming the surface layer (L3), base layer (L2), and adhesive layer (L1) as separate films and then laminating each film by dry lamination. However, from the viewpoint of productivity, co-extrusion molding, in which the raw materials for forming each of the layers of the surface layer (L3), base layer (L2), and adhesive layer (L1) are fed into a multi-layer extruder for molding, is preferred, and the T-die film molding method is more preferred as the co-extrusion method. This also applies when producing a laminate having other layers such as an intermediate layer (L4).

[0130] The laminate described above may be stretched in a uniaxial or biaxial direction. A preferred method for uniaxial stretching is the commonly used roll stretching method. Examples of biaxial stretching methods include sequential stretching, in which biaxial stretching is performed after uniaxial stretching, and simultaneous biaxial stretching methods such as tubular stretching.

[0131] <Application> The uses of the 4-methyl-1-pentene copolymer composition (X) and molded articles made from the present invention are not particularly limited, but can be used in a wide range of applications, such as in the automotive, electrical and electronic, civil engineering and construction, biomass and energy-related fields, optics, food, and medical fields. In particular, it is useful not only for adhesives, adhesive films and daily necessities, and sheets, but also for conventionally known materials for automobiles, clothing, hygiene, construction, sports, daily life, leisure, industrial, and electronic materials.

[0132] Applications of laminates include industrial release films, semiconductor process films, and surface protection films.

[0133] Furthermore, it can be suitably used in films or tapes used in the electronics field, such as adhesive films, protective films, semiconductor process protection films, lens protection films, semiconductor wafer backgrind tapes, dicing tapes, and substrate protection tapes (e.g., protective tapes for plating masks used during the plating process of flexible printed circuit boards), as well as window glass protection films and baking paint films.

[0134] Furthermore, because the adhesive layer (L1) has the ability to conform to uneven surfaces, it is also suitable for use in prism sheets, reflective sheets, and protective sheets for textured surfaces, as well as for applications with many uneven surfaces.

[0135] Specifically, it can be suitably used as a surface protective film to protect adherends such as metal components made of aluminum, steel, stainless steel, etc., components coated with paint on these metal components, glass components, synthetic resin components, and even home appliances, automobile parts, and electronic components that use these components. [Examples]

[0136] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. The measurement methods, compounds used, methods for preparing test specimens, and evaluation methods for each synthesis example, example, and comparative example are as follows.

[0137] [Methods for measuring the physical properties of resins] <Content of constituent units> The quantification of the content of 4-methyl-1-pentene and α-olefins in the 4-methyl-1-pentene copolymer (A) is performed using the following apparatus and conditions. 13 The results are based on measurements using 1C-NMR. However, the α-olefin content in these measurements does not include the content of 4-methyl-1-pentene.

[0138] Using a JEOL Ltd. ECP500 nuclear magnetic resonance spectrometer, the following measurements were taken: orthodichlorobenzene / deuterated benzene (80 / 20 vol%) mixed solvent, sample concentration 55 mg / 0.6 mL, measurement temperature 120°C, and observed nuclei. 13 The measurement was performed using C (125 MHz), a single-pulse proton decoupling sequence, a pulse width of 4.7 μs (45° pulse), a repetition time of 5.5 seconds, and an accumulation count of over 10,000 times, with 27.50 ppm as the reference value for chemical shift. 13 The composition of the 4-methyl-1-pentene copolymer (A) was quantified by 13C-NMR spectroscopy.

[0139] <Intrinsic viscosity> The intrinsic viscosity was measured using an Ubbelohde viscometer at 135°C in decalin. Specifically, approximately 20 mg of the powdered and lumpy polymers obtained in the synthesis example were taken and dissolved in 15 mL of decalin. The specific viscosity ηsp of the resulting decalin solution was measured in an oil bath heated to 135°C. After diluting this decalin solution by adding 5 mL of decalin solvent, the specific viscosity ηsp was measured again in the same manner. This dilution procedure and measurement were repeated two more times, and the intrinsic viscosity [η] was calculated using the following formula, with the value of ηsp / C extrapolated to concentration (C) being zero. [η] = lim(ηsp / C) (C→0)

[0140] <Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn)> Molecular weight was measured by gel permeation chromatography (GPC). Specifically, a Waters ALC / GPC150-Cplus liquid chromatograph (integrated differential refractometer detector) was used, with two GMH6-HT columns and two GMH6-HTL columns connected in series from Tosoh Corporation as the separation columns. o-dichlorobenzene was used as the mobile phase medium, and 0.025% by mass of dibutylhydroxytoluene (Takeda Pharmaceutical Company Limited) was used as the antioxidant. The mobile phase medium was moved at 1.0 mL / min, the sample concentration was 15 mg / 10 mL, the sample injection volume was 500 μL, and a differential refractometer was used as the detector. Standard polystyrene used was manufactured by Tosoh Corporation, with a weight-average molecular weight (Mw) between 1,000 and 4,000,000.

[0141] The obtained chromatograms were analyzed by creating calibration curves using standard polystyrene samples using known methods to calculate the weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn value). The measurement time per sample was 60 minutes.

[0142] <Melting point (Tm), crystallization temperature (Tc)> The melting point (Tm) and crystallization temperature (Tc) were measured using a differential scanning calorimeter (DSC) (DSC220C instrument manufactured by Seiko Instruments Inc.). When two or more peaks appeared, the higher temperature was recorded, and this fact was noted.

[0143] Specifically, 7 to 12 mg each of copolymers (A-1) to (A-4) obtained in the synthesis example below were sealed in an aluminum pan and heated from room temperature to 200°C at a rate of 10°C / min. Then, each copolymer was held at 250°C for 5 minutes to completely melt, and subsequently cooled to -50°C at a rate of 10°C / min. After being left at -50°C for 5 minutes, the sample was heated again to 250°C at a rate of 10°C / min. The peak temperature obtained during this second heating was adopted as the melting point (Tm). The peak temperature obtained during the cooling process was adopted as the crystallization temperature (Tc).

[0144] <density> The density was measured using a density gradient tube in accordance with JIS K7112.

[0145] <Meltmass Flow Rate (MFR)> In accordance with ASTM D1238, the melt mass flow rate (MFR) of copolymers (A-1) to (A-4) was measured at a temperature of 230°C and a load of 2.16 kgf.

[0146] <Method for fabricating molded bodies for dynamic viscoelasticity measurement> Sheets were formed using a Shinto Metal Industries hydraulic hot press (NS-50) set to 200-260°C and a gauge pressure of 10 MPa. For sheets with a thickness of 1-3 mm (spacer shape; 200 x 200 x 1-3 mm on a 240 x 240 mm plate), preheating was performed for 5-7 minutes, followed by pressurization at a gauge pressure of 10 MPa for 1-2 minutes. Then, using another Shinto Metal Industries hydraulic hot press set to 20°C, the sheets were compressed at a gauge pressure of 10 MPa and cooled for about 5 minutes to create molded bodies for measurement. A 5 mm thick brass plate was used as the heating plate. The molded bodies prepared by the above method were used as samples for dynamic viscoelasticity measurement.

[0147] <Dynamic viscoelasticity> From the 3.0 mm thick molded body obtained above, test specimens measuring 35 mm in length and 10 mm in width were prepared by punching them out. Using a rheometer (Anton Paar MCR301), the tanδ peak temperature and tanδ peak value were observed in a temperature dispersion of -40 to 150°C under the conditions of torsion mode, frequency 10 rad / s (1.6 Hz), strain setting 0.1%, and heating rate 2°C / min. In addition, the values ​​for 50°C and 100°C were read from the obtained storage modulus (G') and defined as G'@50°C and G'@100°C, respectively.

[0148] [Method for measuring the physical properties of film] The film properties were measured using the following method. <Molding shrinkage / wrinkling> A T-die molding machine with a die width of 250 mm and a 30 mm diameter single-screw extruder was used. Resin pellets were fed from a resin supply hopper, melted through a cylinder in the single-screw extruder set to 200-240°C, and then extruded through the T-die at a die temperature of 240°C to obtain a 50 μm thick film. The obtained film was left to stand at room temperature for one day, and the presence or absence of wrinkles on the film surface was visually checked. Wrinkles occurred because the crystallization rate of the 4-methyl-1-pentene copolymer composition is slow, resulting in unstable dimensions after molding, and were therefore used as an indicator of molding shrinkage.

[0149] <Tensile Test> For test specimens cut from laminated film into strips measuring 15 mm wide x 100 mm long, the tensile breaking strength (TS) (unit: MPa) and tensile breaking elongation (EL) (unit: %) were measured in the MD and TD directions of the test specimens under the following conditions: chuck distance of 50 mm, tensile speed of 200 mm / min, and temperature of 23°C, using a tensile testing machine (universal tensile testing machine 3380, manufactured by Instron), in accordance with JIS K7127 (1999).

[0150] <Tensile stress relaxation test> From the obtained surface protection film, a 15mm wide x 100mm test specimen was taken and stretched and stopped using a Shimadzu Autograph precision universal testing machine AG-XP under the following conditions: test temperature 23°C and 120°C, test speed 200mm / min, chuck distance 70.0mm, and tensile load 10%. The stress change profile over time was measured. The initial tensile force after stretching, the maximum stress (initial value of 10% stress), and the stress after 60 seconds were determined. The stress relaxation rate was also calculated based on the following formula. Stress relaxation rate = (Initial stress value at 10% - Stress value after holding for 60 seconds) / (Initial stress value at 10%) × 100

[0151] <Elmendref tear strength> The laminated film was measured for Elmendorf tear strength in both the MD direction and the TD direction at 23°C and 55% RH using a light-load tearing device manufactured by Toyo Seiki Co., Ltd. in accordance with JIS K7128-1991 to measure the Elmendorf tear load by the Elmendorf method.

[0152] <HAZE, total light transmittance> The internal haze and total light transmittance were measured using a digital turbidimeter (NDH-20D) manufactured by Nippon Denshoku Industries Co., Ltd. in benzyl alcohol with the 0.05 mm thick film obtained by the above method as a test piece.

[0153] [Synthesis example of 4-methyl-1-pentene-based copolymer (A)] <Synthesis of 4-methyl-1-pentene-based copolymer (A-1)> 300 ml of normal hexane (in a dry nitrogen atmosphere, dried with activated alumina) and 450 ml of 4-methyl-1-pentene were charged into a 1.5-liter SUS autoclave with a stirrer fully purged with nitrogen at 23°C. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was charged into this autoclave and the stirrer was rotated.

[0154] Next, the autoclave was heated to an internal temperature of 60°C and pressurized with propylene so that the total pressure became 0.19 MPa (gauge pressure). Subsequently, 0.34 ml of a toluene solution containing 1 mmol of methylaluminoxane in terms of Al and 0.01 mmol of diphenylmethylene(1-ethyl-3-t-butyl-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)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 became 60°C. 60 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. Thereafter, acetone was poured into the reaction solution while stirring.

[0155] The resulting bulk polymer containing the solvent was dried at 100°C under reduced pressure for 12 hours to obtain 4-methyl-1-pentene copolymer (A-1). The amount of 4-methyl-1-pentene copolymer (A-1) obtained was 44.0 g, with a content of constituent unit (i) of 84.1 mol% and a content of constituent unit (ii) of 15.9 mol%. The various physical properties of the obtained 4-methyl-1-pentene copolymer (A-1) are shown in Table 1.

[0156] <Synthesis of 4-methyl-1-pentene copolymer (A-2)> A 1.5-liter stainless steel autoclave with stirring blades, thoroughly purged with nitrogen, was charged with 300 ml of n-hexane (dried on activated alumina under a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene at 23°C. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was then added to the autoclave and the mixture was stirred.

[0157] Next, the autoclave was heated to an internal temperature of 60°C and pressurized with propylene to a total pressure of 0.16 MPa (gauge pressure). Subsequently, 0.34 ml of a toluene solution containing 1 mmol of methyl aluminoxane (in terms of Al) and 0.01 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl) zirconium dichloride, which had been prepared in advance, was injected into the autoclave under nitrogen pressure to start polymerization. During the polymerization reaction, the temperature inside the autoclave was adjusted to 60°C. 60 minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave under nitrogen pressure to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution while stirring.

[0158] The resulting bulk polymer containing the solvent was dried at 100°C under reduced pressure for 12 hours to obtain 4-methyl-1-pentene copolymer (A-2). The amount of 4-methyl-1-pentene copolymer (A-2) obtained was 36.3 g, with a content of constituent unit (i) of 86.2 mol% and a content of constituent unit (ii) of 13.8 mol%. The various physical properties of 4-methyl-1-pentene copolymer (A-2) are shown in Table 1.

[0159] <Synthesis of 4-methyl-1-pentene copolymer (A-3)> 750 ml of 4-methyl-1-pentene was charged into a 1.5-liter stainless steel autoclave with stirring blades, which had been thoroughly purged with nitrogen, at 23°C. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was then charged into the autoclave, and the mixture was stirred.

[0160] Next, the autoclave was heated to an internal temperature of 60°C and pressurized with propylene to a total pressure of 0.13 MPa (gauge pressure). Subsequently, 0.34 ml of a toluene solution containing 1 mmol of pre-prepared methylaluminoxane (in terms of Al) and 0.01 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride was injected into the autoclave under nitrogen pressure to start polymerization. During the polymerization reaction, the temperature inside the autoclave was adjusted to 60°C. 60 minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave under nitrogen pressure to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Then, acetone was added to the reaction solution while stirring.

[0161] The resulting bulk polymer containing the solvent was dried at 100°C under reduced pressure for 12 hours to obtain 4-methyl-1-pentene copolymer (A-3). The amount of 4-methyl-1-pentene copolymer (A-3) obtained was 36.9 g, with a content of constituent unit (i) of 72.5 mol% and a content of constituent unit (ii) of 27.5 mol%. The various physical properties of the obtained 4-methyl-1-pentene copolymer (A-3) are shown in Table 1.

[0162] <Synthesis of 4-methyl-1-pentene copolymer (A-4)> 750 ml of 4-methyl-1-pentene was charged into a 1.5-liter stainless steel autoclave with stirring blades, which had been thoroughly purged with nitrogen, at 23°C. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was then added to the autoclave and stirring was started.

[0163] Next, the autoclave was heated to an internal temperature of 60°C and pressurized with propylene to a total pressure of 0.17 MPa (gauge pressure). Subsequently, 0.34 ml of a toluene solution containing 1 mmol of methylaluminoxane (in terms of Al) and 0.005 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride, which had been prepared in advance, was injected into the autoclave under nitrogen pressure to start polymerization. During the polymerization reaction, the temperature inside the autoclave was adjusted to 60°C. 60 minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave under nitrogen pressure to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution while stirring.

[0164] The resulting powdered polymer containing the solvent was dried at 130°C under reduced pressure for 12 hours to obtain 4-methyl-1-pentene copolymer (A-4). The weight of the obtained 4-methyl-1-pentene copolymer (A-4) was 35.2 g, and the content of constituent unit (i) in 4-methyl-1-pentene copolymer (A-4) was 93.0 mol%, and the content of constituent unit (ii) was 7.0 mol%.

[0165] [Table 1]

[0166] [Crystal Nucleating Agent (B)] The following was used as the nucleating agent (B). <Crystal nucleating agent (B-1)> ADEKA Corporation: ADEKA Stab NA-11 (Molecular weight: 508, Melting point: ≥400℃) <Crystal nucleating agent (B-2)> Manufactured by ADEKA Corporation: ADEKA Stab NA-21 (Molecular weight: 562, Melting point: ≥210℃) <Crystal nucleating agent (B-3)> Shin-Nippon Rika Co., Ltd.: Sorbitol-based compound Gelol MD (Molecular weight: 386, Melting point: 260℃) <Crystal nucleating agent (B-4)> Shin-Nippon Rika Co., Ltd.: Sorbitol-based compound Gelol D (Molecular weight: 358, Melting point: 220℃) <Crystal nucleating agent (B-5)> Shin-Nippon Rika Co., Ltd.: Amide compound NJester NU-100 (Molecular weight: 378, Melting point: 380℃)

[0167] [Example 1] Pellet pellets consisting of the composition of Example 1 were prepared by blending 100 parts by mass of a 4-methyl-1-pentene copolymer (A-1), 0.3 parts by mass of a crystal nucleating agent (B-1), and 0.2 parts by mass of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a heat-resistant stabilizer, and kneading the mixture at 200°C using a twin-screw extruder.

[0168] Using a T-die molding machine with a die width of 250 mm and a 30 mm diameter single-screw extruder, resin pellets were fed from a resin supply hopper, melted through a cylinder in the single-screw extruder set to 200-240°C, and then extruded through the T-die at a die temperature of 240°C to obtain a film with a thickness of 50 μm. The various physical properties of the obtained film are shown in Table 2.

[0169] [Example 2] A film was obtained in the same manner as in Example 1, except that 100 parts by mass of a 4-methyl-1-pentene copolymer (A-1), 0.3 parts by mass of a crystal nucleating agent (B-2), and 0.2 parts by mass of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a heat-resistant stabilizer were added. The various physical properties of the obtained film are shown in Table 2.

[0170] [Example 3] A film was obtained in the same manner as in Example 1, except that 100 parts by mass of a 4-methyl-1-pentene copolymer (A-1), 0.3 parts by mass of a crystal nucleating agent (B-3), and 0.2 parts by mass of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a heat-resistant stabilizer were added. The various physical properties of the obtained film are shown in Table 2. The results of the dynamic viscoelasticity measurement are shown in Figure 1.

[0171] [Example 4] A film was obtained in the same manner as in Example 1, except that 100 parts by mass of a 4-methyl-1-pentene copolymer (A-1), 0.3 parts by mass of a crystal nucleating agent (B-5), and 0.2 parts by mass of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a heat-resistant stabilizer were added. The various physical properties of the obtained film are shown in Table 2.

[0172] [Example 5] A film was obtained in the same manner as in Example 1, except that 100 parts by mass of 4-methyl-1-pentene copolymer (A-2), 0.3 parts by mass of crystal nucleating agent (B-2), and 0.2 parts by mass of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a heat-resistant stabilizer were added. The various physical properties of the obtained film are shown in Table 2.

[0173] [Example 6] A film was obtained in the same manner as in Example 1, except that 100 parts by mass of a 4-methyl-1-pentene copolymer (A-2), 0.3 parts by mass of a crystal nucleating agent (B-3), and 0.2 parts by mass of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a heat-resistant stabilizer were added. The various physical properties of the obtained film are shown in Table 2.

[0174] [Example 7] A film was obtained in the same manner as in Example 1, except that 100 parts by mass of a 4-methyl-1-pentene copolymer (A-4), 0.3 parts by mass of a crystal nucleating agent (B-3), and 0.2 parts by mass of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a heat-resistant stabilizer were added. The various physical properties of the obtained film are shown in Table 2.

[0175] [Comparative Example 1] A film was obtained in the same manner as in Example 1, except that 100 parts by mass of 4-methyl-1-pentene copolymer (A-1) and 0.2 parts by mass of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate were added as a heat-resistant stabilizer. The various physical properties of the obtained film are shown in Table 2. The results of the dynamic viscoelasticity measurement are shown in Figure 1.

[0176] [Comparative Example 2] A film was obtained in the same manner as in Example 1, except that 100 parts by mass of 4-methyl-1-pentene copolymer (A-2), 0.2 parts by mass of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a heat-resistant stabilizer, and 1 part by mass of polypropylene (manufactured by Prime Polymer Co., Ltd., brand name: F107BV, molecular weight: 350,000, melting point: 160°C) was added instead of the crystal nucleating agent (B-2). The various physical properties of the obtained film are shown in Table 2.

[0177] [Comparative Example 3] A film was obtained in the same manner as in Example 1, except that 100 parts by mass of a 4-methyl-1-pentene copolymer (A-1), 0.3 parts by mass of a crystal nucleating agent (B-4), and 0.2 parts by mass of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a heat-resistant stabilizer were added. The various physical properties of the obtained film are shown in Table 2.

[0178] [Table 2] [Industrial applicability]

[0179] The 4-methyl-1-pentene copolymer composition (X) and the 4-methyl-1-pentene copolymer composition (X) of the present invention, which contain the 4-methyl-1-pentene copolymer (A) and a crystal nucleating agent (B), and the molded articles containing the 4-methyl-1-pentene copolymer composition (X) have stress relaxation properties, transparency and release properties, and are less susceptible to temperature changes due to their high elastic modulus at high temperatures. Furthermore, shrinkage after molding is suppressed, making them less prone to wrinkling. For these reasons, they can be used in various molded articles, industrial films, surface protective films, and the like.

Claims

1. A 4-methyl-1-pentene copolymer composition (X) comprising 0.1 to 10 parts by mass of a crystal nucleating agent (B) per 100 parts by mass of a 4-methyl-1-pentene copolymer (A), and satisfying the following requirements (a), (b), and (f). Requirement (a); The temperature at which the loss tangent (tanδ) value of the 4-methyl-1-pentene copolymer composition (X) is maximized by dynamic viscoelasticity measurement (frequency 10 rad / s (1.6 Hz)) in the temperature range of -40 to 150°C is between 0°C and 60°C. Requirement (b); The storage modulus at 50°C of the 4-methyl-1-pentene copolymer composition (X), determined by dynamic viscoelasticity measurement (frequency 10 rad / s (1.6 Hz)) in the temperature range of -40 to 150°C, is 6 × 10⁻¹⁶. 6 It is Pa or higher. Requirement (f); The melting point of the 4-methyl-1-pentene copolymer (A), as measured by differential scanning calorimeter (DSC), is less than 200°C, or no melting point is observed.

2. The 4-methyl-1-pentene copolymer composition (X) according to claim 1, wherein the 4-methyl-1-pentene copolymer (A) satisfies one or more of the following requirements (e), (g), and (h). Requirement (e); It consists of 55 to 97 mol% of constituent unit (i) derived from 4-methyl-1-pentene and 3 to 45 mol% of constituent unit (ii) derived from one or more ethylenes and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) (the sum of constituent unit (i) and constituent unit (ii) is 100 mol%). Requirement (g); The temperature at which the loss tangent (tanδ) value is maximized, as determined by dynamic viscoelasticity measurement (frequency 10 rad / s (1.6 Hz)) in the temperature range of -40 to 150°C, is between 15°C and 45°C. Requirement (h); The density is 830-870 kg / m³. 3 That is the case.

3. The 4-methyl-1-pentene copolymer composition (X) according to claim 1 or 2, wherein the 4-methyl-1-pentene copolymer composition (X) satisfies the following requirement (c). Requirement (c); The crystallization temperature (Tc) measured by differential scanning calorimeter (DSC) is 70°C or higher.

4. The 4-methyl-1-pentene copolymer composition (X) according to any one of claims 1 to 3, wherein the nucleating agent (B) is a nucleating agent consisting of one or more selected from sorbitol-based nucleating agents, phosphate ester salt-based nucleating agents, and amide-based nucleating agents, all of which are diacetal compounds.

5. A molded article comprising the 4-methyl-1-pentene copolymer composition (X) according to any one of claims 1 to 4.

6. A sheet or film comprising the 4-methyl-1-pentene copolymer composition (X) according to any one of claims 1 to 4.

7. A laminate comprising one or more selected from the sheets and films described in claim 6.

8. A surface protective film comprising the 4-methyl-1-pentene copolymer composition (X) according to any one of claims 1 to 4.

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