Laminate and method for manufacturing the same

Abstract

To provide a laminate having an excellent bubble stability when subjected to inflation molding, and a method for producing the same.SOLUTION: Provided are a laminate comprising a layer A containing a 4-methyl-1-pentene polymer (A1) satisfying requirements (A1-1) to (A1-7) and a layer B containing a thermoplastic resin (B), and a method for manufacturing the same. Details of the requirements (A1-1) to (A1-7) are shown in the specifications.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a laminate and a method for producing the same.

Background Art

[0002] 4-Methyl-1-pentene polymers have excellent characteristics such as heat resistance, transparency, light weight, steam resistance, mold release property, stain resistance, gas permeability, and electrical properties compared to polyethylene and polypropylene. Since such excellent properties can be imparted to other materials, laminates comprising a layer of a 4-methyl-1-pentene polymer and a layer of another material are expected to be used in various fields such as food containers, auxiliary materials for electronic and information members, laboratory instruments, stationery, engineering materials for crosslinking, release films, films for electronic and information members, food packaging materials, synthetic paper, and the like.

[0003] As a film having little variation in film thickness and good film thickness accuracy (thickness accuracy) and heat resistance, for example, Patent Document 1 discloses a film characterized by containing a 4-methyl-1-pentene polymer composition (X) that satisfies specific requirements. Further, as a laminate having little variation in film thickness and good film thickness accuracy (thickness accuracy) and heat resistance, for example, Patent Document 2 discloses a laminate characterized by comprising an X layer containing a 4-methyl-1-pentene polymer composition (X) that satisfies specific requirements and a Y layer containing a thermoplastic resin (Y).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] As a method for producing a laminated film using a 4-methyl-1-pentene polymer, the cast film method is known. However, in the cast film method, only flat films or sheets can be obtained, and the thickness at the ends is likely to be non-uniform. There are problems such as poor yield due to trimming the non-uniform part (ear part). For this reason, a laminate having a layer containing a 4-methyl-1-pentene polymer and having a uniform thickness has been demanded, and in particular, a laminate obtained by inflation film forming has been demanded. However, 4-methyl-1-pentene polymers generally have poor stretchability. For example, when inflation film forming with stretching is performed using the compositions described in Patent Documents 1 and 2, further improvement is required for the bubble stability to such an extent that stable forming is possible. The problem to be solved by one embodiment of the present invention is to provide a laminate excellent in bubble stability when subjected to inflation molding and a method for producing the same.

Means for Solving the Problems

[0006] As a result of intensive studies in view of such a situation, the present inventor has found that the above problems can be solved in a laminate including a layer containing a 4-methyl-1-pentene polymer satisfying specific requirements and a layer containing a thermoplastic resin, and has completed the present invention. That is, the means for solving the above problems includes the following aspects. <1> An A layer containing a 4-methyl-1-pentene polymer (A1) satisfying the following requirements (A1-1) to (A1-7), a B layer containing a thermoplastic resin (B), and a laminate; Requirement (A1-1): The density measured in accordance with JIS K7112 (density gradient tube method) is 0.82 to 0.88 g / m 3 ; Requirement (A1-2): The melting point (Tm) measured by differential scanning calorimetry (DSC) is 190°C or higher and less than 220°C; Requirement (A1-3): The melting enthalpy ΔH is less than 35 J / g; Requirement (A1-4): The half-crystallization time at 215 °C measured by the following measurement method using a differential scanning calorimeter is 220 seconds or more, or not measured; Measurement method for half-crystallization time: Using DSC8500 manufactured by PerkinElmer, Inc., heat the temperature from 30 °C to 280 °C at a heating rate of 500 °C / min, hold the temperature for 10 minutes, and then measure the half-crystallization time at 215 °C when cooling to 215 °C at a cooling rate of 500 °C / min; Requirement (A1-5): The molecular weight distribution (Mw / Mn), which is the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn), is 6.0 or less; Requirement (A1-6): The content of the structural unit derived from 4-methyl-1-pentene is 90.0 mol% or more and less than 100 mol%, and the content of the structural unit derived from an α-olefin having 10 to 20 carbon atoms exceeds 0 mol% and is 10.0 mol% or less (however, the total content of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from an α-olefin having 10 to 20 carbon atoms is 100 mol%); Requirement (A1-7): The intrinsic viscosity [η] measured in decalin at 135 °C exceeds 0.6 and is 4.0 dl / g or less. <2> In the A layer, the content of the 4-methyl-1-pentene-based polymer (A1) is 60 to 100% by mass, The content of the 4-methyl-1-pentene-based polymer (A2) that satisfies the following requirements (A2-1) to (A2-7) is 0 to 40% by mass (however, the total content of the polymer (A1) and the polymer (A2) is 100% by mass), the laminate according to <1>; Requirement (A2-1): The density measured in accordance with JIS K7112 (density gradient tube method) is 0.82 to 0.88 g / m 3 ; Requirement (A2-2): The melting point (Tm) measured by differential scanning calorimetry (DSC) is 210 °C to 240 °C; Requirement (A2-3): The melting enthalpy ΔH is less than 40 J / g; Requirement (A2-4): The half-crystallization time at 215 °C measured by the following measurement method using a differential scanning calorimeter is 220 seconds or less; Method for measuring semi-crystallization time: Using DSC8500 manufactured by PerkinElmer Co., Ltd., heat the temperature from 30°C to 280°C at a heating rate of 500°C / min, hold the temperature for 10 minutes, and then measure the semi-crystallization time at 215°C when cooling to 215°C at a cooling rate of 500°C / min; Requirement (A2-5): The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 6.0 or less; Requirement (A2-6): The content of the structural unit derived from 4-methyl-1-pentene is 90.0 mol% or more and less than 100 mol%, and the content of the structural unit derived from an α-olefin having 10 to 20 carbon atoms exceeds 0 mol% and is 10.0 mol% or less (however, the total content of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from an α-olefin having 10 to 20 carbon atoms is 100 mol%); Requirement (A2-7): The intrinsic viscosity [η] measured in decalin at 135°C is 0.5 to 5.0 dl / g. <3> The laminate according to <1> or <2>, wherein the 4-methyl-1-pentene-based polymer (A1) further satisfies the following requirement (A1-8); Requirement (A1-8): The melt tension measured at 260°C is 10 mN or more. <4> The laminate according to any one of <1> to <3>, wherein the thermoplastic resin (B) is polyethylene or polypropylene. <5> The laminate according to any one of <1> to <4>, having a thickness of 1 to 70 μm. <6> The laminate according to any one of <1> to <5>, which is an inflation film. <7> The laminate according to any one of <1> to <6>, which is for packaging. <8> A resin composition (X) containing a 4-methyl-1-pentene-based polymer (A1) satisfying the following requirements (A1-1) to (A1-7) and a 4-methyl-1-pentene-based polymer (A2) satisfying the following requirements (A2-1) to (A2-7), and a thermoplastic resin (B), and a step of performing laminated inflation molding under conditions where the expansion ratio (bubble ratio) exceeds 1.0 and the molding temperature is less than 260°C, a method for manufacturing a laminate; Requirement (A1-1): The density measured in accordance with JIS K7112 (density gradient tube method) is 0.82 to 0.88 g / m 3 ; Requirement (A1-2): The melting point (Tm) measured by differential scanning calorimetry (DSC) is 190°C or higher and less than 220°C; Requirement (A1-3): The melting enthalpy ΔH is less than 35 J / g; Requirement (A1-4): The half-crystallization time at 215°C measured by the following measurement method using a differential scanning calorimeter is 220 seconds or longer, or not measured; Measurement method for half-crystallization time: Using DSC8500 manufactured by PerkinElmer, Inc., heat from 30°C to 280°C at a heating rate of 500°C / min, hold the temperature for 10 minutes, and then cool to 215°C at a cooling rate of 500°C / min, and measure the half-crystallization time at 215°C; Requirement (A1-5): The molecular weight distribution (Mw / Mn), which is the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn), is 6.0 or less; Requirement (A1-6): The content of the structural unit derived from 4-methyl-1-pentene is 90.0 mol% or more and less than 100 mol%, and the content of the structural unit derived from an α-olefin having 10 to 20 carbon atoms exceeds 0 mol% and is 10.0 mol% or less (however, the total content of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from an α-olefin having 10 to 20 carbon atoms is 100 mol%); Requirement (A1-7): The intrinsic viscosity [η] measured in decalin at 135°C exceeds 0.6 and is 4.0 dl / g or less; Requirement (A2-1): The density measured in accordance with JIS K7112 (density gradient tube method) is 0.82 to 0.88 g / m 3 ; Requirement (A2-2): The melting point (Tm) measured by differential scanning calorimetry (DSC) is 220°C to 240°C; Requirement (A2-3): The melting enthalpy ΔH is less than 40 J / g; Requirement (A2-4): The half-crystallization time at 215°C measured by the following measurement method using DSC is 220 seconds or less; Method for measuring semi-crystallization time: Using DSC8500 manufactured by PerkinElmer, Inc., heat from 30°C to 280°C at a heating rate of 500°C / min, hold the temperature for 10 minutes, and then measure the semi-crystallization time at 215°C when cooling to 215°C at a cooling rate of 500°C / min; Requirement (A2-5): The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 6.0 or less; Requirement (A2-6): The content of the structural unit derived from 4-methyl-1-pentene is 90.0 mol% or more and less than 100 mol%, and the content of the structural unit derived from an α-olefin having 10 to 20 carbon atoms exceeds 0 mol% and is 10.0 mol% or less (however, the total content of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from an α-olefin having 10 to 20 carbon atoms is 100 mol%); Requirement (A2-7): The intrinsic viscosity [η] measured in decalin at 135°C is 0.5 to 5.0 dl / g.

Advantages of the Invention

[0007] According to one embodiment of the present invention, there are provided a laminate excellent in bubble stability when subjected to inflation molding and a method for producing the same.

Modes for Carrying Out the Invention

[0008] Hereinafter, specific embodiments of the present invention will be described in detail. The description of the contents of the constituent requirements described below may be based on representative embodiments of the present invention, but the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the present invention. In this specification, a numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. In addition, in this specification, when referring to the amount of each component in a composition, when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, it means the total amount of the plurality of substances present in the composition. In this specification, the "~" indicating a numerical range means that the unit described on either side thereof indicates the same unit unless otherwise specified. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment. In addition, various monomers in the present disclosure may be derived from fossil raw materials or may be derived from biomass. Hereinafter, the present invention will be described in more detail.

[0009] <Laminate> The laminate according to the present invention includes an A layer containing a 4-methyl-1-pentene polymer (A1) satisfying requirements (A1-1) to (A1-7), and a B layer containing a thermoplastic resin (B). By having the above configuration, the laminate has excellent bubble stability when subjected to inflation molding. Although the reason for this is not clear, the following mechanism is speculated. Since the 4-methyl-1-pentene polymer (A1) contained in the A layer satisfies requirements (A1-1) to (A1-7), it is possible to lower the crystallization rate, suppress the breakage of the film during cooling, and has a melt tension suitable for inflation molding. Therefore, when the B layer containing the thermoplastic resin (B) is subjected to inflation molding, it has excellent bubble stability. In addition, since the 4-methyl-1-pentene polymer (A1) contained in the A layer satisfies the condition that the intrinsic viscosity [η] exceeds 0.6 and is 4.0 dl / g or less, and the melting point (Tm) is 190°C or higher and less than 220°C, the A layer can be laminated with a layer made of a low-melting polyolefin such as polyethylene, for example, and it is speculated that inflation molding with good appearance of the resulting laminate is possible. Hereinafter, the A layer and the B layer included in the laminate according to the present invention will be described in detail.

[0010] <> Layer A contains a 4-methyl-1-pentene polymer (A1) (hereinafter, may also be simply referred to as "polymer (A1)") that satisfies the following requirements (A1-1) to (A1-7), and preferably contains polymer (A1) and polymer (A2) described later. Hereinafter, each component contained in each layer will be described.

[0011] <<4-methyl-1-pentene polymer (A1)>> The 4-methyl-1-pentene polymer (A1) satisfies the following requirements (A1-1) to (A1-7).

[0012] 〔Requirement (A1-1)〕 Requirement (A1-1): The density measured in accordance with JIS K7112 (density gradient tube method) is 0.82 to 0.88 g / m 3 and preferably 0.82 to 0.86 g / m 3 and more preferably 0.82 to 0.84 g / m 3 is. When the density of the 4-methyl-1-pentene polymer (A1) is within the above range, the laminate provided with the layer containing the polymer (A1) can be further lightened.

[0013] 〔Requirement (A1-2)〕 Requirement (A1-2): The melting point (Tm) measured by differential scanning calorimetry (DSC) is 190 °C or higher and less than 220 °C, preferably 190 °C to 215 °C, and more preferably 190 °C to 210 °C. While the melting point (Tm) of a general 4-methyl-1-pentene polymer is about 220 to 250 °C, the melting point (Tm) of the 4-methyl-1-pentene polymer (A1) is preferably in a range lower than this melting point range. When the melting point (Tm) of the 4-methyl-1-pentene polymer (A1) is within the above range, molding can be performed under the same conditions as the thermoplastic resin (B) described later, and laminate inflation molding with the B layer containing the thermoplastic resin (B) can be preferably performed, and a layer excellent in adhesion to the B layer containing the thermoplastic resin (B) can be formed.

[0014] 〔Requirement (A1-3)〕 Requirement (A1-3): The melting enthalpy ΔH is less than 35 J / g, preferably 5 J / g or more and less than 35 J / g, more preferably 8 to 32 J / g. When the melting enthalpy ΔH of the 4-methyl-1-pentene polymer (A1) is within the above range, the moldability is improved, and the laminated inflation molding with the B layer containing the thermoplastic resin (B) described later can be preferably performed. The melting enthalpy ΔH is a value measured in accordance with JIS K7122.

[0015] 〔Requirement (A1-4)〕 The semi-crystallization time at 215°C measured by the following measurement method using a differential scanning calorimeter is 220 seconds or more, or not measured. Measurement method of semi-crystallization time: Using DSC8500 manufactured by PerkinElmer Co., Ltd., heat from 30°C to 280°C at a heating rate of 500°C / min, hold the temperature for 10 minutes, and then cool to 215°C at a cooling rate of 500°C / min, and measure the semi-crystallization time at 215°C. The semi-crystallization time is preferably 500 seconds or more, or not measured, more preferably 800 seconds or more, or not measured, even more preferably 1000 seconds or more, or not measured, particularly preferably 1500 seconds or more, or not measured, and most preferably 2000 seconds or more, or not measured. When the semi-crystallization time of the 4-methyl-1-pentene polymer (A1) is 220 seconds or more, or not measured, the crystallization rate during melt molding becomes slow, the stretchability is improved, and the effect that the laminated inflation molding involving stretching can be preferably performed is obtained. In addition, when using equipment similar to DSC8500 manufactured by PerkinElmer Co., Ltd., the same value of the semi-crystallization time can be obtained.

[0016] 〔Requirement (A1-5)〕 The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 6.0 or less, preferably from 1.0 to 6.0, more preferably from 1.5 to 5.0, still more preferably from 2.0 to 4.0, and particularly preferably from 2.3 to 3.5. When the molecular weight distribution (Mw / Mn) is 6.0 or less, the influence of low molecular weight polymers derived from the composition distribution is small, and the laminate provided with the layer containing the 4-methyl-1-pentene polymer (A1) is excellent in appearance.

[0017] The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is preferably from 500 to 10,000,000 in terms of polystyrene, more preferably from 1,000 to 5,000,000, and still more preferably from 5,000 to 2,500,000. When the weight average molecular weight (Mw) is within the above range, the laminate is likely to obtain appropriate rigidity and moldability. The above weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) are values measured by gel permeation chromatography (GPC), and specifically, they are determined by the measurement method described in the examples below.

[0018] 〔Requirement (A1-6)〕 The content of the structural unit derived from 4-methyl-1-pentene is 90.0 mol% or more and less than 100 mol%, preferably from 93.0 to 99.5 mol%, more preferably from 93.0 to 99.0 mol%, still more preferably from 94.0 to 98.0 mol%, and particularly preferably from 94 to 97.5 mol%. The content of the structural unit derived from an α-olefin having 10 to 20 carbon atoms exceeds 0 mol% and is 10.0 mol% or less. The content of the structural unit derived from an α-olefin having 10 to 20 carbon atoms exceeds 0 mol% and is 10.0 mol% or less, preferably from 0.5 to 7.0 mol%, more preferably from 1.0 to 7.0 mol%, still more preferably from 2.0 to 6.0 mol%, and particularly preferably from 2.5 to 6.0 mol%. However, the total content of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from the α-olefin having 10 to 20 carbon atoms shall be 100 mol%. When the content of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from the α-olefin having 10 to 20 carbon atoms is within the above range, inflation molding can be preferably carried out, and the resulting laminate is excellent in heat resistance, transparency and releasability.

[0019] Examples of the above α-olefin having 10 to 20 carbon atoms include 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene. Among these, from the viewpoint of obtaining a polymer with good moldability, the α-olefin having 10 to 18 carbon atoms is preferred as the α-olefin having 10 to 20 carbon atoms. Specifically, 1-decene, 1-tetradecene, 1-hexadecene and 1-octadecene are preferred. Further, for example, it is more preferable to use 1-hexadecene and 1-octadecene in combination.

[0020] The 4-methyl-1-pentene-based polymer (A1) may further have a structural unit derived from a polymerizable compound other than 4-methyl-1-pentene and the α-olefin having 10 to 20 carbon atoms (hereinafter, also simply referred to as "other polymerizable compound") as long as the object of the present invention is not impaired. Examples of other polymerizable compounds include vinyl compounds having a cyclic structure such as styrene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids such as maleic anhydride or derivatives thereof; conjugated dienes such as butadiene, isoprene, pentadiene, and 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, and 2-propenyl-2,2-norbornadiene.

[0021] The content of the structural unit derived from other polymerizable compounds is usually 10 mol% or less, preferably 5 mol% or less, more preferably 3 mol% or less, and even more preferably substantially not contained, in 100 mol% of all the structural units constituting the polymer (A1). The 4-methyl-1-pentene polymer (A1) may be produced, for example, by the method for producing a 4-methyl-1-pentene polymer described below. Also, commercially available 4-methyl-1-pentene polymers may be used alone or in combination.

[0022] [Requirement (A1-7)] The intrinsic viscosity [η] measured in decalin at 135 °C exceeds 0.6 and is 4.0 dl / g or less, preferably 0.8 to 3.5 dl / g, more preferably 0.9 to 3.0 dl / g, even more preferably 1.0 to 3.0 dl / g, and particularly preferably 1.5 to 3.0 dl / g. The 4-methyl-1-pentene polymer (A1) has an intrinsic viscosity satisfying the above range, and thus has excellent bubble stability, resulting in good moldability, and laminated inflation molding involving stretching can be suitably performed. Further, the surface smoothness of the resulting laminate is also excellent. The intrinsic viscosity [η] can be measured by the measurement method described in the examples below.

[0023] The 4-methyl-1-pentene polymer (A1) may further satisfy the following requirement (A1-8). 〔Requirement (A1-8)〕 The melt tension measured at 260°C (i.e., melt tension: MT) is 10 mN or more, more preferably 10 to 50 mN, and even more preferably 10 to 25 mN. The melt tension can be adjusted, for example, by controlling the molecular weight of the polymer. Since the 4-methyl-1-pentene polymer (A1) has a relatively high melt tension satisfying the above range, a film can be formed by a method involving stretching, and it is particularly suitable for inflation molding. The melt tension can be adjusted, for example, by controlling the molecular weight of the polymer.

[0024] In the A layer, the content of the 4-methyl-1-pentene polymer (A1) is preferably 50 to 100% by mass, more preferably 55 to 100% by mass, and even more preferably 60 to 100% by mass. However, the total content of the polymer (A1) and the polymer (A2) described below is 100% by mass. The A layer may contain the 4-methyl-1-pentene polymer (A1) alone or in combination of two or more.

[0025] <<Polymer (A2)>> The A layer may further contain a 4-methyl-1-pentene polymer (A2) (hereinafter sometimes simply referred to as "polymer (A2)") that satisfies the following requirements (A2-1) to (A2-7).

[0026] 〔Requirement (A2-1)〕 Requirement (A2-1): The density measured in accordance with JIS K7112 (density gradient tube method) is 0.82 to 0.88 g / m 3 and preferably 0.82 to 0.86 g / m 3 and more preferably 0.82 to 0.84 g / m 3 is. When the density of the 4-methyl-1-pentene polymer (A2) is within the above range, the laminate including the layer containing the polymer (A2) can be further lightened.

[0027] 〔Requirement (A2-2)〕 Requirement (A2-2): The melting point (Tm) measured by differential scanning calorimetry (DSC) is 210°C to 240°C, and preferably 215°C to 230°C. When the melting point (Tm) of the polymer (A2) is within the above range, the laminate including the layer containing the polymer (A2) is excellent in heat resistance.

[0028] 〔Requirement (A2-3)〕 Requirement (A2-3): The melting enthalpy ΔH is less than 40 J / g, preferably 15 J / g or more and less than 40 J / g, more preferably 20 to 40 J / g, still more preferably 25 to 40 J / g, and particularly preferably 25 to 35 J / g. When the melting enthalpy ΔH of the 4-methyl-1-pentene polymer (A1) is within the above range, the moldability is improved, and the laminated inflation molding with the layer containing the thermoplastic resin (B) described later can be preferably performed. The melting enthalpy ΔH is a value measured in accordance with JIS K7122.

[0029] 〔Requirement (A2-4)〕 The semi-crystallization time at 215°C measured by the following measurement method using a differential scanning calorimeter is 220 seconds or less, preferably 500 seconds or more, more preferably 800 seconds or more, still more preferably 1000 seconds or more, particularly preferably 1500 seconds or more, and most preferably 2000 seconds or more. The measurement method of the semi-crystallization time is as follows: Using DSC8500 manufactured by PerkinElmer, Inc., the temperature is raised from 30°C to 280°C at a heating rate of 500°C / min, the temperature is maintained for 10 minutes, and then the semi-crystallization time at 215°C is measured and obtained when the temperature is lowered to 215°C at a cooling rate of 500°C / min. When the semi-crystallization time of the 4-methyl-1-pentene-based polymer (A2) is 220 seconds or more, the crystallization rate during melt molding becomes slow, the stretchability is improved, and the effect that the laminated inflation molding involving stretching can be preferably performed is obtained. In addition, when using equipment similar to DSC8500 manufactured by PerkinElmer, Inc., the same value of the above semi-crystallization time can be obtained.

[0030] [Requirement (A2-5)] The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 6.0 or less, preferably 1.0 to 6.0, more preferably 1.5 to 5.0, still more preferably 2.0 to 4.0, and particularly preferably 2.3 to 3.5. When the molecular weight distribution (Mw / Mn) is 6.0 or less, the influence of the high molecular weight polymer derived from the composition distribution is small, and the laminate including the layer containing the 4-methyl-1-pentene-based polymer (A2) has a more excellent appearance.

[0031] In addition, the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is preferably 500 to 10,000,000 in terms of polystyrene conversion, more preferably 1,000 to 5,000,000, and still more preferably 5,000 to 2,500,000. When the weight average molecular weight (Mw) is within the above range, the laminate is likely to obtain appropriate rigidity. The above weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) are values measured by gel permeation chromatography (GPC), and specifically, they are obtained by the measurement method described in the examples below.

[0032] [Requirement (A2-6)] The content of the structural unit derived from 4-methyl-1-pentene is 90.0 mol% or more and less than 100 mol%, preferably 95.0 to 99.5 mol%, more preferably 96.0 to 99.0 mol%, still more preferably 96.5 to 98.0 mol%, and particularly preferably 97.0 to 98.0 mol%. The content of the structural unit derived from an α-olefin having 10 to 20 carbon atoms is more than 0 mol% and 10.0 mol% or less, preferably 0.5 to 5.0 mol%, more preferably 1.0 to 4.0 mol%, still more preferably 1.5 to 3.5 mol%, and particularly preferably 1.5 to 3.0 mol%. However, the total content of the structural unit derived from the 4-methyl-1-pentene and the structural unit derived from the α-olefin having 10 to 20 carbon atoms is 100 mol%. When the content of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from an α-olefin having 10 to 20 carbon atoms is within the above range, inflation molding can be preferably performed, and the resulting laminate is excellent in heat resistance, transparency, and releasability.

[0033] Examples of the α-olefin having 10 to 20 carbon atoms include 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene. Among these, from the viewpoint of obtaining a polymer with good moldability, α-olefins having 10 to 18 carbon atoms are preferred as the α-olefin having 10 to 20 carbon atoms. Specifically, 1-decene, 1-tetradecene, 1-hexadecene, and 1-octadecene are preferred. Further, for example, it is more preferable to use 1-hexadecene and 1-octadecene in combination.

[0034] The 4-methyl-1-pentene-based polymer (A2) may further have a structural unit derived from a polymerizable compound other than 4-methyl-1-pentene and an α-olefin having 10 to 20 carbon atoms (hereinafter, also simply referred to as "other polymerizable compound") as long as the object of the present invention is not impaired. Examples of other polymerizable compounds include the other polymerizable compounds in the above-described 4-methyl-1-pentene polymer (A1), and preferred embodiments are the same.

[0035] 〔Requirement (A2-7)〕 The intrinsic viscosity [η] measured in decalin at 135°C is 0.5 to 5.0 dl / g, preferably 1.0 to 3.5 dl / g, more preferably 1.5 to 3.0 dl / g, still more preferably 2.0 to 3.0 dl / g, and particularly preferably 2.0 to 2.8 dl / g. By having an intrinsic viscosity within the above range, the 4-methyl-1-pentene polymer (A2) is excellent in bubble stability, so that the moldability is good, and laminated inflation molding involving stretching can be suitably performed. Further, the surface smoothness of the obtained laminate is also excellent. The intrinsic viscosity [η] can be measured by the measuring method described in the examples below.

[0036] The 4-methyl-1-pentene polymer (A2) may further satisfy the following requirement (A2-8). 〔Requirement (A2-8)〕 The melt tension (i.e., melt tension: MT) measured at 260°C is 10 mN or more, preferably 15 to 100 mN, more preferably 15 to 60 mN. The melt tension can be adjusted, for example, by controlling the molecular weight of the polymer. By having a relatively high melt tension within the above range, the 4-methyl-1-pentene polymer (A2) can form a film by a method involving stretching, and is particularly suitable for inflation molding. The melt tension can be adjusted, for example, by controlling the molecular weight of the polymer.

[0037] In the A layer, the content of the 4-methyl-1-pentene polymer (A2) is preferably 0 to 40% by mass, more preferably 5 to 45% by mass, still more preferably 10 to 40% by mass, and the content of the above-mentioned 4-methyl-1-pentene polymer (A1) is preferably 60 to 100% by mass, more preferably 55 to 95% by mass, still more preferably 60 to 90% by mass. However, the total content of the polymer (A1) and the polymer (A2) is 100% by mass. The A layer may contain the 4-methyl-1-pentene polymer (A2) alone or in combination of two or more.

[0038] <Method for Producing 4-Methyl-1-Pentene Polymers (A1) and (A2)> For the 4-methyl-1-pentene polymers (A1) and (A2), known production methods can be used. For example, they can be obtained by polymerizing 4-methyl-1-pentene, an α-olefin having 10 to 20 carbon atoms as required, and further, if necessary, the other polymerizable compound. The 4-methyl-1-pentene polymers (A1) and (A2) can be preferably produced by carrying out the polymerization in the presence of a metallocene catalyst.

[0039] Examples of the metallocene catalyst include the metallocene catalysts described in International Publication No. 01 / 53369, International Publication No. 01 / 27124, Japanese Patent Application Laid-Open No. 3-193796, Japanese Patent Application Laid-Open No. 02-41303, International Publication No. 06 / 025540, or International Publication No. 2013 / 099876.

[0040] Examples of the metallocene catalyst include a catalyst composed of at least a metallocene compound (a) and a carrier (b).

[0041] <<Metallocene Compound (a)>> The metallocene compound (a) is represented by, for example, General Formula (1) or (2).

[0042]

Chemical Formula

[0043] The meanings of the symbols in general formula (1) or (2) are as follows. R 1 ~R 14 are each independently a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, or a silicon-containing group. R 1 from R 4 to R 5 to R 12 adjacent substituents may be bonded to each other to form a ring.

[0044] Y is a carbon atom or a silicon atom. A is a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain an unsaturated bond and / or an aromatic ring. A may contain two or more ring structures including the ring formed with Y.

[0045] M is a metal (transition metal) selected from Group 4 of the periodic table, and examples thereof include titanium, zirconium, and hafnium. Q is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with an unshared electron pair. When j is 2 or more, each Q may be the same or different. j is an integer of 1 to 4, and preferably 2.

[0046] R 1 ~R 14 Examples of the hydrocarbon group in R

[0047] R 1 ~R 14The substituted hydrocarbon group (excluding the silicon-containing group) herein is a group in which some or all of the hydrogen atoms contained in the hydrocarbon group are substituted with functional groups such as halogen atoms (fluorine, chlorine, bromine, iodine), hydroxyl groups, and amino groups.

[0048] R 1 ~R 14 Examples of the silicon-containing group in R

[0049] ~R 5 include, for example, an alkylsilyl group or an arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms, and specific examples thereof include trimethylsilyl, tert-butyldimethylsilyl, and triphenylsilyl. 12 The adjacent substituents from R

[0050] to R 5 on the fluorene ring may be bonded to each other to form a ring. Examples of such a substituted fluorenyl group include benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, and octamethyloctahydrodibenzofluorenyl. 12 The substituents of R 5 to R 12 on the fluorene ring are preferably symmetric with respect to the ease of synthesis, that is, R 6 =R 11 , R 7 =R 10 , R 8 =R 9 . The fluorene ring moiety is preferably unsubstituted fluorene, 3,6-disubstituted fluorene, 2,7-disubstituted fluorene, or 2,3,6,7-tetrasubstituted fluorene. The 3-position, 6-position, 2-position, and 7-position on the fluorene ring correspond to R 7 , R 10 , R 6 , R 11 respectively. R 13 and R 14 are each preferably independently a hydrogen atom, a hydrocarbon group, or a substituted hydrocarbon group.

[0051] In the case of the general formula (1), R 13 and R 14 are bonded to Y to form a substituted methylene group or a substituted silylene group as a crosslinked portion. Specific examples of the substituted methylene group and the substituted silylene group include, for example, dialkylmethylene, dicycloalkylmethylene, alkylcycloalkylmethylene, alkylarylmethylene, diarylmethylene, dialkylsilylene, dicycloalkylsilylene, alkylcycloalkylsilylene, alkylarylsilylene, diarylsilylene, and groups in which these are halogenated.

[0052] In the case of the general formula (2), Y is bonded to the divalent hydrocarbon group A to form a cycloalkylidene group, a cyclomethylenesilylene group, or the like. Specific examples of the cycloalkylidene group and the cyclomethylenesilylene group include, for example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo[3.3.1]nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroindenylidene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, cycloheptamethylenesilylene.

[0053] In Q, examples of the halogen atom include fluorine, chlorine, bromine, and iodine; examples of the hydrocarbon group having 1 to 20 carbon atoms include the same groups as the hydrocarbon groups of R 1 to R 14 ; examples of the anionic ligand include an alkoxy group, an aryloxy group, a carboxylate group, a sulfonate group, and the like; examples of the neutral ligand capable of coordinating with an unshared electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, and ethers such as tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxyethane. At least one of Q is preferably a halogen atom or an alkyl group having 1 to 20 carbon atoms.

[0054] Specific examples of the metallocene compound (a) include, for example, the compounds exemplified in International Publication No. 01 / 27124, International Publication No. 2006 / 025540, or International Publication No. 2007 / 308607.

[0055] As the metallocene compound (a), the compound represented by the following general formula (3) described in International Publication No. 2014 / 050817 and the like is particularly preferable.

[0056]

Chemical formula

[0057] In the general formula (3), R 1b is a hydrocarbon group, a silicon-containing group, or a halogen-containing hydrocarbon group, and R 2b ~R 12b are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom, and a halogen-containing hydrocarbon group, and may be the same or different from each other, and each substituent may be bonded to each other to form a ring. M is a Group 4 transition metal in the periodic table, n is an integer of 1 to 3, Q is synonymous with Q in the general formula (1) or (2) above, and j is an integer of 1 to 4.

[0058] R 1b to R 12b Examples of the hydrocarbon group in include linear hydrocarbon groups such as linear alkyl groups and linear alkenyl groups; branched hydrocarbon groups such as branched alkyl groups; cyclic saturated hydrocarbon groups such as cycloalkyl groups, norbornyl groups, and adamantyl groups; cyclic unsaturated hydrocarbon groups such as aryl groups and cycloalkenyl groups; and groups in which one or more hydrogen atoms of the saturated hydrocarbon group are substituted with a cyclic unsaturated hydrocarbon group, such as aralkyl groups. The number of carbon atoms of the hydrocarbon group is usually 1 to 20, preferably 1 to 15, more preferably 1 to 10.

[0059] R 1b to R 12bExamples of the silicon-containing group in [compound name] include a group represented by the formula -SiR3 (wherein a plurality of Rs are each independently an alkyl group having 1 to 15 carbon atoms or a phenyl group).

[0060] R 1b from R 12b Examples of the halogen-containing hydrocarbon group in [compound name] include a group formed by substituting one or more hydrogen atoms of the above hydrocarbon group with a halogen atom, such as a trifluoromethyl group. R 2b from R 12b Examples of the halogen atom in [compound name] include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0061] Examples of the ring (spiro ring, additional ring) formed by bonding two substituents to each other in the general formula (3) include an alicyclic ring and an aromatic ring. Specifically, a cyclohexane ring, a benzene ring, a hydrogenated benzene ring, and a cyclopentene ring can be mentioned, and a cyclohexane ring, a benzene ring, and a hydrogenated benzene ring are preferred. Further, such a ring structure may further have a substituent such as an alkyl group on the ring.

[0062] R 1b It is particularly preferable that R is a substituent in which the carbon atom having a free valence (the carbon atom bonded to the cyclopentadienyl ring) is a tertiary carbon atom. R 1b Specific examples of R include a tert-butyl group, a tert-pentyl group, a 1-methylcyclohexyl group, and a 1-adamantyl group. The fluorene ring moiety is not particularly limited as long as it is a structure obtained from a known fluorene derivative, but R 4b and R 5b are preferably hydrogen atoms from the viewpoint of molecular weight.

[0063] R 2b 、R 3b 、R 6b and R 7b are preferably hydrocarbon groups having 1 to 20 carbon atoms. Also, R 2b and R 3bare bonded to each other to form a ring, and R 6b and R 7b may be bonded to each other to form a ring. Examples of such a substituted fluorenyl group include a benzofluorenyl group, a dibenzofluorenyl group, an octahydrodibenzofluorenyl group, a 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorenyl group, a 1,1,3,3,6,6,8,8-octamethyl-2,3,6,7,8,10-hexahydro-1H-dicyclopenta[b,h]fluorenyl group, and a 1’,1’,3’,6’,8’,8’-hexamethyl-1’H,8’H-dicyclopenta[b,h]fluorenyl group.

[0064] R 8b is preferably a hydrogen atom. R 9b is preferably an alkyl group having 2 or more carbon atoms. From the viewpoint of synthesis, it is also preferable that R 10b and R 11b are hydrogen atoms. Alternatively, when n = 1, it is more preferable that R 9b and R 10b are bonded to each other to form a ring, and it is particularly preferable that the ring is a 6-membered ring such as a cyclohexane ring. In this case, R 11b is preferably a hydrogen atom. R 12b is preferably an alkyl group.

[0065] M is a Group 4 transition metal of the periodic table, such as Ti, Zr or Hf, preferably Zr or Hf, and particularly preferably Zr.

[0066] n is an integer of 1 to 3, preferably 1 or 2, and more preferably 1. When n is the above value, it is preferable from the viewpoint of efficiently obtaining the resulting polymer. j is an integer of 1 to 4, preferably 2.

[0067] Examples of the compound represented by the general formula (3) include (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)) zirconium dichloride and (8-(2,3,6,7-tetramethylfluoren)-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)) zirconium dichloride, which are particularly preferred. Here, the octamethylfluorene refers to 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorene.

[0068] <<Carrier (b)>> The carrier (b) is preferably particulate, and the metallocene catalyst is formed by immobilizing the metallocene compound (a) on its surface and inside. A catalyst in such a form is generally called a supported metallocene catalyst. The carrier (b) is mainly composed of an organoaluminum compound (b-1), an organoboron compound (b-2), or an inorganic compound (b-3), or a composite of two or more selected from these.

[0069] Examples of the organoaluminum compound (b-1) include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and trinormaloctylaluminum; dialkylaluminum hydrides such as diisobutylaluminum hydride; tricycloalkylaluminums; and organoaluminum oxy compounds typified by aluminoxane. Further, examples of the organoaluminum compound (b-1) also include organoaluminum oxy compounds containing a boron atom, aluminoxanes containing a halogen as exemplified in International Publication No. WO2005 / 066191 and International Publication No. WO2007 / 131010, and ionic aluminoxanes as exemplified in International Publication No. WO2003 / 082879.

[0070] Examples of the organic boron compound (b-2) include trialkylammonium tetraarylborate, trialkylammonium tetra(halogenated aryl)borate, dioctadecylmethylammonium tetraarylborate, dioctadecylmethylammonium tetra(halogenated aryl)borate, N,N-dialkylanilinium tetraarylborate, and N,N-dialkylanilinium tetra(halogenated aryl)borate.

[0071] Examples of the inorganic compound (b-3) include porous oxides, inorganic halides, clays, clay minerals, or ion-exchangeable layered compounds. Examples of the porous oxide include oxides such as SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, or composites or mixtures containing these. For example, natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO, etc. can be exemplified. Examples of the inorganic halide include MgCl2, MgBr2, MnCl2, and MnBr2. The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Further, after dissolving the inorganic halide in a solvent such as alcohol, a precipitate obtained by precipitation with a precipitating agent in fine particle form can also be used.

[0072] From the viewpoint of further suppressing the amount of the solvent-soluble part and having high activity, a carrier containing an aluminum atom is preferable as the carrier (b). The content of the aluminum atom in the carrier (b) is preferably 20% by mass or more, more preferably 20 to 60% by mass, still more preferably 30 to 50% by mass, and particularly preferably 35 to 47% by mass.

[0073] As such a carrier (b), solid aluminoxane is preferably used. For example, the solid aluminoxane disclosed in International Publication No. WO2010 / 055652, International Publication No. WO2013 / 146337, or International Publication No. WO2014 / 123212 is particularly preferably used.

[0074] "Solid state" means that the aluminoxane substantially maintains a solid state in the reaction environment where the solid aluminoxane is used. More specifically, for example, when preparing an olefin polymerization solid catalyst component by bringing each component constituting the olefin polymerization catalyst into contact, it means that the aluminoxane is in a solid state in an inert hydrocarbon medium such as hexane or toluene used in the reaction under a specific temperature and pressure environment.

[0075] The solid aluminoxane preferably contains an aluminoxane having at least one structural unit selected from the structural unit represented by the following formula (4) and the structural unit represented by the following formula (5), more preferably contains an aluminoxane having the structural unit represented by the following formula (4), and still more preferably contains polymethylaluminoxane consisting only of the structural unit represented by the following formula (4).

[0076]

Chemical formula

[0077]

Chemical formula

[0078] In general formula (4), Me is a methyl group. In general formula (5), R 1 is a hydrocarbon group having 2 to 20 carbon atoms, preferably a hydrocarbon group having 2 to 15 carbon atoms, more preferably a hydrocarbon group having 2 to 10 carbon atoms. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, and an aryl group.

[0079] The structure of solid aluminoxane has not necessarily been clarified, and it is generally presumed to have a structure in which the structural units represented by formula (4) and / or formula (5) are repeated about 2 to 50 times, but it is not limited to this structure. Further, the bonding mode of the structural units is various, such as linear, cyclic or cluster-like, and aluminoxane is generally presumed to consist of one of these or a mixture thereof. Further, aluminoxane may consist only of the structural units represented by formula (4) or formula (5).

[0080] As the solid aluminoxane, solid polymethylaluminoxane is preferable, and solid polymethylaluminoxane consisting only of the structural units represented by formula (4) is more preferable. Solid aluminoxane functions as a catalyst carrier. Therefore, in addition to solid aluminoxane, as the catalyst carrier, for example, solid inorganic carriers such as silica, alumina, silica-alumina, magnesium chloride, or solid organic carriers such as polystyrene beads may not be used. Solid aluminoxane can be prepared, for example, by the methods described in International Publication No. 2010 / 055652 and International Publication No. 2014 / 123212.

[0081] <<Organic compound component (c)>> The metallocene catalyst may further contain an organic compound component (c) as necessary. The organic compound component (c) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer as necessary. As the organic compound component (c), the above-described organoaluminum compound (b-1) may be used. In addition, for example, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates can be mentioned.

[0082] <<Polymerization conditions>> The polymerization of 4-methyl-1-pentene with ethylene and an α-olefin having 3 to 20 carbon atoms, if necessary, to obtain a 4-methyl-1-pentene copolymer can be carried out by any of liquid-phase polymerization methods such as solution polymerization and suspension polymerization or gas-phase polymerization. In the liquid-phase polymerization method, an inert hydrocarbon solvent can be used. Specifically, 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 a mixed solvent of two or more selected from these can be mentioned. Further, the olefin itself containing 4-methyl-1-pentene can be used as a polymerization solvent.

[0083] In the above-mentioned polymerization, the usage method and addition order of each component can be arbitrarily selected, and the following methods are exemplified. Hereinafter, the metallocene compound (a), the carrier (b), and the organic compound component (c) are also referred to as "components (a) to (c)", respectively. Further, the organoaluminum compound (b-1), the organoboron compound (b-2), and the inorganic compound (b-3) are also referred to as "components (b-1) to (b-c)", respectively. Method (i): A method of adding component (a) and component (b) to the polymerization reactor in an arbitrary order. Method (ii): A method of adding a catalyst component in which component (a) is supported on component (b) to the polymerization reactor.

[0084] In each of the above methods (i) to (ii), component (c) may be further added at an arbitrary stage. Further, at least two of each catalyst component may be contacted in advance. Further, in the solid catalyst component in which component (a) is supported on component (b), an olefin such as 4-methyl-1-pentene or 3-methyl-1-pentene may be prepolymerized, and a catalyst component may be further supported on the prepolymerized solid catalyst component.

[0085] When polymerizing monomers such as 4-methyl-1-pentene using a metallocene catalyst, the amounts of use of the respective components that can constitute the metallocene catalyst are as follows. Also, in the metallocene catalyst, the contents of the respective components can be adjusted as follows.

[0086] Component (a) is usually 10 -10 ~10 -2 moles, preferably 10 -8 ~10 -3 moles per liter of reaction volume. Component (b-1) can be used in an amount such that the molar ratio [Al / M] of the aluminum atom in component (b-1) to the total transition metal atoms (M) in component (a) is usually 10 to 10,000, preferably 30 to 2,000, particularly preferably 150 to 500. Component (b-2) can be used in an amount such that the molar ratio [(b-2) / M] of component (b-2) to the total transition metal atoms (M) in component (a) is usually 10 to 10,000, preferably 30 to 2,000, more preferably 150 to 500. Component (b-3) can be used in an amount such that the molar ratio [(b-3) / M] of component (b-3) to the total transition metal atoms (M) in component (a) is usually 10 to 10,000, preferably 30 to 2,000, more preferably 150 to 500.

[0087] When using component (c), when component (b) is component (b-1), the molar ratio [Al / (c)] of the aluminum atom in component (b-1) to component (c) is usually 0.002 to 500, preferably 0.01 to 60. When component (b) is component (b-2), the molar ratio [(b-2) / (c)] of component (b-2) to component (c) is usually 0.002 to 500, preferably 0.01 to 60. When component (b) is component (b-3), the molar ratio [(b-3) / (c)] of component (b-3) to component (c) is usually 0.002 to 500, preferably 0.01 to 60, and it can be used in such amounts.

[0088] The polymerization temperature is usually -50 to 200 °C, preferably 0 to 100 °C, more preferably 20 to 100 °C. The polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably under the conditions of normal pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out by any of the batch, semi-continuous and continuous methods. For the purpose of controlling the molecular weight or polymerization activity of the resulting polymer, hydrogen can be added to the polymerization system, and the appropriate amount of hydrogen to be added is about 0.001 to 100 NL per 1 kg of olefin.

[0089] As the polymerization conditions, it is also possible to adopt a multi-stage polymerization in which two or more stages of polymerization with different reaction conditions are carried out. For example, by carrying out the polymerization stepwise under two conditions with different hydrogen usage amounts or different ratios of 4-methyl-1-pentene to α-olefins having 10 to 20 carbon atoms, it is possible to obtain a polymer with a desired molecular weight distribution or composition distribution.

[0090] The 4-methyl-1-pentene-based polymer (A1) can be produced by polymerizing or copolymerizing 4-methyl-1-pentene and α-olefins having 10 to 20 carbon atoms, and optionally other polymerizable compounds, in the presence of a polymerization catalyst such as the above-mentioned metallocene catalyst.

[0091] 〔Multi-stage polymerization method〕 When the A layer contains two or more 4-methyl-1-pentene-based polymers, the first 4-methyl-1-pentene-based polymer and the second 4-methyl-1-pentene-based polymer may be separately produced and mixed in a desired blending ratio. Alternatively, for example, step (1) of producing the first 4-methyl-1-pentene-based polymer by slurry polymerization, and in the presence of the polymer obtained in step (1), the second 4-methyl-1-pentene-based polymer is produced by slurry polymerization such that the amount of the second polymer becomes the desired mass% when the total amount of the first and second polymers is 100 mass%. It can also be produced by a multi-stage polymerization method having step (2).

[0092] The multi-stage polymerization method has steps (1) and (2) with different polymerization conditions, and it may be a two-stage polymerization of steps (1) and (2), or may be a three-stage or higher polymerization further including other steps in addition to steps (1) and (2).

[0093] <<Step (1)>> In step (1), a first 4-methyl-1-pentene-based polymer is produced by slurry polymerization. In step (1), the ratio of 4-methyl-1-pentene, an α-olefin having 10 to 20 carbon atoms, and other polymerizable compounds used as required is set so that the content of the structural units derived from each monomer becomes a desired quantitative ratio.

[0094] In step (1), a slurry containing the first 4-methyl-1-pentene-based polymer is obtained. The slurry concentration, that is, the concentration of the first 4-methyl-1-pentene-based polymer particles, is usually 0.015 to 45% by mass, preferably 0.03 to 35% by mass.

[0095] <<Step (2)>> In step (2), a second 4-methyl-1-pentene-based polymer is produced by slurry polymerization in the presence of the first 4-methyl-1-pentene-based polymer obtained in step (1). In step (2), the supply amount ratio of 4-methyl-1-pentene, an α-olefin having 10 to 20 carbon atoms, and other polymerizable compounds used as required is set so that the content of the structural units derived from each monomer becomes a desired quantitative ratio.

[0096] In step (2), when the total amount of the first 4-methyl-1-pentene-based polymer obtained in step (1) and the second 4-methyl-1-pentene-based polymer obtained in step (2) is 100% by mass, the second 4-methyl-1-pentene-based polymer is produced so that the amount of the second 4-methyl-1-pentene-based polymer becomes a desired mass percentage.

[0097] In one embodiment of step (2), 4-methyl-1-pentene, an α-olefin having 10 to 20 carbon atoms, and, if necessary, other polymerizable compounds are added to a slurry containing a first 4-methyl-1-pentene-based polymer, and slurry polymerization of these monomers is carried out.

[0098] In step (2), a slurry containing particles containing a first 4-methyl-1-pentene-based polymer and a second 4-methyl-1-pentene-based polymer is obtained. The slurry concentration, that is, the particle concentration, is usually 3 to 50% by mass, preferably 5 to 40% by mass.

[0099] In the above multi-stage polymerization method, slurry polymerization can be employed. Note that "slurry polymerization" refers to a polymerization in which the polymer produced by the polymerization is present in a form dispersed in the above medium as, for example, fine particles without substantially dissolving in the above medium used during the polymerization. The above multi-stage polymerization is not limited to the above slurry polymerization as long as the target 4-methyl-1-pentene-based polymer can be obtained, and may be, for example, solution polymerization or gas-phase polymerization.

[0100] <<Solid-liquid separation step>> The slurry containing 4-methyl-1-pentene-based polymer particles containing a first 4-methyl-1-pentene-based polymer and a second 4-methyl-1-pentene-based polymer obtained in step (2) is subjected to solid-liquid separation, for example, filtration, to separate and recover the particles.

[0101] <<Post-treatment step>> For the 4-methyl-1-pentene-based polymer particles obtained by the above multi-stage polymerization method, for example, the particles obtained in the above solid-liquid separation step, after being produced by the above method, post-treatment steps such as a known catalyst deactivation treatment step, a catalyst residue removal step, and a drying step may be carried out as necessary. In the above manner, a mixture of a first 4-methyl-1-pentene-based polymer and a second 4-methyl-1-pentene-based polymer can be obtained.

[0102] (B layer) The laminate according to the present invention includes a B layer. Hereinafter, each component of the B layer will be described in detail.

[0103] <Thermoplastic resin (B)> The B layer contains a thermoplastic resin (B). Examples of the thermoplastic resin (B) include known thermoplastic resins other than the above-mentioned 4-methyl-1-pentene polymers (A1) and (A2). Examples of the thermoplastic resin (B) include, for example, polyolefin polymers, polyamides, polyesters, polyacetals, styrene resins, acrylic resins, polycarbonates, polyphenylene oxides, chlorine resins, vinyl acetate resins, ethylene-(meth)acrylate copolymers, ethylene-(meth)acrylic resins and their ionomer resins, vinyl alcohol resins, cellulose resins, thermoplastic elastomers, various copolymer rubbers, and the like. Among these, the thermoplastic resin (B) is preferably a resin that can be molded at a temperature below 250°C, and more preferably has a melting point (Tm) of 210°C or lower.

[0104] Among these, the thermoplastic resin (B) is preferably a polyolefin polymer. Examples of the polyolefin polymer include, for example, polyethylene, polypropylene, poly-1-butene, polymethylbutene, ethylene·α-olefin·non-conjugated polyene copolymers, and the like. Among the polyolefin polymers, the thermoplastic resin (B) is particularly preferably polyethylene or polypropylene.

[0105] Polyethylene may be a homopolymer of ethylene or a copolymer of ethylene and a monomer other than ethylene. As an ethylene-based copolymer mainly composed of ethylene and copolymerized with ethylene and monomers other than ethylene, a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms is preferred. Examples of the α-olefin having 3 to 12 carbon atoms include linear or branched α-olefins such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, and 1-dodecene. The polyethylene is not particularly limited and may be, for example, ultra-high molecular weight polyethylene, high density polyethylene, medium density polyethylene, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), etc.

[0106] The polypropylene may be a propylene homopolymer or a copolymer of propylene and a monomer other than propylene with propylene as the main component. As the copolymer of propylene and a monomer other than propylene with propylene as the main component, a copolymer of propylene and ethylene and an α-olefin having 4 to 12 carbon atoms is preferred. Examples of the α-olefin having 4 to 12 carbon atoms include linear or branched α-olefins such as 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, and 1-dodecene.

[0107] The monomer other than ethylene constituting the polyethylene or the monomer other than propylene constituting the polypropylene may be a single species, two or more species, or may contain a copolymerizable monomer other than the α-olefin.

[0108] The thermoplastic resin (B) may be synthesized or may be a commercially available product. Examples of the commercially available product include those manufactured by Prime Polymer Co., Ltd., product name: Prime Polypro SP3010, etc.

[0109] The content of the thermoplastic resin (B) in the B layer is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, and still more preferably 98 to 100% by mass with respect to the total mass of the polymers contained in the B layer. The B layer may contain the thermoplastic resin (B) alone or in combination of two or more kinds.

[0110] The laminate according to the present invention is not particularly limited as long as it includes at least one layer of the A layer and the B layer, and may include a layer other than the A layer and the B layer (hereinafter, may also be referred to as "other layer") between the A layer and the B layer, or the A layer and the B layer may be in contact with each other. When the A layer and the B layer are in contact with each other in the laminate, examples of the layer structure of the laminate include A layer / B layer, A layer / A layer / B layer, A layer / B layer / A layer, A layer / B layer / B layer, B layer / A layer / B layer, A layer / B layer / A layer / B layer, and the like. Since the laminate includes the A layer containing the 4-methyl-1-pentene polymer (A1) and / or the polymer (A2) excellent in heat resistance and the like, heat sealing at a high temperature is possible, and when the A layer is provided on the outermost layer of the laminate, the releasability is also excellent.

[0111] When the laminate includes two or more A layers, the A layers may each contain the same 4-methyl-1-pentene polymer (A), or may each contain different 4-methyl-1-pentene polymers (A). Further, when the laminate includes two or more B layers, the B layers may each contain the thermoplastic resin (B), or may each contain different thermoplastic resins (B).

[0112] The shape of the laminate is preferably sheet-like or film-like. From the viewpoint of excellent bubble stability and being preferably manufactured by laminated inflation molding involving stretching, the laminate is preferably an inflation film. From the viewpoint that the thickness of the laminate can be preferably produced by laminated inflation molding with stretching, it is preferably 0.1 to 100 μm, more preferably 1 to 70 μm, and still more preferably 1 to 50 μm. The thicknesses of the respective layers constituting the laminate may be the same or different.

[0113] <Method for producing a laminate> The method for producing a laminate is not particularly limited, and it can be produced by a conventionally known method for molding a laminate. The method for producing a laminate according to the present invention includes a step of performing laminated inflation molding (hereinafter, also simply referred to as "laminated inflation molding step") on a resin composition (X) containing a 4-methyl-1-pentene polymer (A1) satisfying the above requirements (A1-1) to (A1-7) and a 4-methyl-1-pentene polymer (A2) satisfying the above requirements (A2-1) to (A2-7), and a thermoplastic resin (B) under conditions where the expansion ratio (bubble ratio) exceeds 1.0 and the molding temperature is less than 260°C. Since the 4-methyl-1-pentene polymers (A1) and (A2) are excellent in stretchability and have a relatively low melting point, as a method for producing a laminate, the laminated inflation molding method of the above resin composition (X) and the thermoplastic resin (B) can be preferably used. In such a production method, the bubble stability during laminated inflation molding is excellent, and the laminate can be molded more stably. Further, since the method for producing a laminate according to the present invention includes the step of performing the above inflation molding, the obtained laminate has suppressed variation in film thickness and excellent film thickness accuracy. Also, in a production method including the step of performing laminated inflation molding, a film with a uniform film thickness is easily obtained as a whole, removal of non-uniform portions is unnecessary, and the production yield is also excellent.

[0114] In the method for producing a laminate, the above requirements (A1-1) to (A1-7) and (A2-1) to (A2-7) are synonymous with the requirements (A1-1) to (A1-7) in the above-mentioned 4-methyl-1-pentene polymer (A1) and (A2-1) to (A2-7) in the 4-methyl-1-pentene polymer (A2), and the preferred embodiments are also the same.

[0115] <<Laminated inflation molding step>> The laminated inflation molding step is a step of performing laminated inflation molding on a resin composition (X) containing the above-mentioned 4-methyl-1-pentene polymer (A1) and the above-mentioned 4-methyl-1-pentene polymer (A2) and a thermoplastic resin (B). The 4-methyl-1-pentene polymers (A1) and (A2) used in the method for producing a laminate are synonymous with the 4-methyl-1-pentene polymers (A1) and (A2) contained in the A layer provided in the above-mentioned laminate, and the preferred embodiments are also the same. Further, the thermoplastic resin (B) used in the method for producing a laminate is synonymous with the thermoplastic resin (B) contained in the B layer provided in the above-mentioned laminate, and the preferred embodiments are also the same.

[0116] 〔Resin composition (X)〕 The composition (X) used in the method for producing a laminate contains a 4-methyl-1-pentene polymer (A1) and a 4-methyl-1-pentene polymer (A2).

[0117] The resin composition (X) has excellent physical properties such as heat resistance, transparency, light weight, mold release property, and stain resistance that conventional 4-methyl-1-pentene polymers have, while having a longer semi-crystallization time than compositions containing conventional 4-methyl-1-pentene polymers and having excellent stretchability. Further, the resin composition (X) can perform laminated inflation molding at a relatively low temperature.

[0118] The resin composition (X) preferably satisfies the following requirements (X-1) to (X-4), and more preferably satisfies one or more of the following requirements (X-5) to (X-8).

[0119] Requirement (X-1): The density measured in accordance with JIS K7112 (density gradient tube method) is 0.82 to 0.88 g / m 3 . The density is preferably 0.82 to 0.86 g / m 3 and more preferably 0.82 to 0.84 g / m 3 . When the density of the resin composition (X) is within the above range, a laminate containing the resin composition (X) can be made into a lighter film.

[0120] Requirement (X-2): The melting point (Tm) measured by differential scanning calorimetry (DSC) is 190°C to 220°C. The melting point (Tm) is preferably 190°C to 215°C, and more preferably 190°C to 210°C. The melting point (Tm) of the resin composition (X) satisfies the relatively low above range, while the melting point (Tm) of a general 4-methyl-1-pentene polymer is about 220 to 250°C. By satisfying the relatively low specific range of the melting point (Tm), the resin composition (X) can be molded under the same conditions as the above thermoplastic resin (B), and laminated inflation molding with the thermoplastic resin (B) can be preferably performed, and a layer excellent in adhesion to the layer containing the thermoplastic resin (B) can be formed.

[0121] Requirement (X-3): The melting enthalpy ΔH is less than 35 J / g. The melting enthalpy ΔH is a value measured in accordance with JIS K7122 using the resin composition (X). The melting enthalpy ΔH is preferably 5 J / g or more and less than 35 J / g, and more preferably 8 to 32 J / g. When the melting enthalpy ΔH of the resin composition (X) is within the above range, the moldability is improved, and laminated inflation molding with the thermoplastic resin (B) described below can be preferably performed.

[0122] Requirement (X-4): The half-crystallization time at 215 °C measured by DSC using the following measurement method is 220 seconds or more, or it cannot be measured. Measurement method for half-crystallization time: Using DSC8500 manufactured by PerkinElmer, Inc., heat from 30 °C to 280 °C at a heating rate of 500 °C / min, hold the temperature for 10 minutes, and then cool to 215 °C at a cooling rate of 500 °C / min, and measure the half-crystallization time at 215 °C. Preferably, the half-crystallization time is 500 seconds or more, or it cannot be measured; more preferably, it is 800 seconds or more, or it cannot be measured; even more preferably, it is 1000 seconds or more, or it cannot be measured; still more preferably, it is 1500 seconds or more, or it cannot be measured; particularly preferably, it is 2000 seconds or more, or it cannot be measured. By satisfying the above conditions for the half-crystallization time of the resin composition (X), the crystallization rate during melt molding becomes slow, the stretchability is improved, and the effect that the laminated inflation molding accompanied by stretching can be preferably performed can be obtained. In addition, even when using equipment similar to DSC8500 manufactured by PerkinElmer, Inc., the same value can be obtained for the above half-crystallization time.

[0123] Requirement (X-5): The content of the structural unit derived from 4-methyl-1-pentene is 90.0 mol% or more and less than 100 mol%, and the content of the structural unit derived from an α-olefin having 10 to 20 carbon atoms exceeds 0 mol% and is 10.0 mol% or less. The content of the structural unit derived from 4-methyl-1-pentene is preferably 95.0 to 99.5 mol%, more preferably 96.0 to 99.0 mol%, and even more preferably 96.5 to 98.5 mol%. The content of the structural unit derived from an α-olefin having 10 to 20 carbon atoms is preferably 0.5 to 5.0 mol%, more preferably 1.0 to 4.0 mol%, and even more preferably 1.5 to 3.5 mol%. By satisfying the above range for the content of the structural unit of the resin composition (X), the layer formed from the resin composition (X) is excellent in heat resistance, transparency, and mold release properties.

[0124] Requirement (X-6): The intrinsic viscosity [η] measured in decalin at 135 °C is 0.5 to 8.0 dl / g. Specifically, for example, it can be measured by the measuring method described in the examples below. The intrinsic viscosity [η] is preferably 0.5 to 7.0 dl / g, more preferably 0.5 to 6.0 dl / g, still more preferably 0.5 to 5.0 dl / g, even more preferably 0.5 to 4.0 dl / g, and particularly preferably 0.5 to 3.5 dl / g. Since the resin composition (X) has an intrinsic viscosity satisfying the above range, it is excellent in bubble stability, so that the moldability is good, and laminated inflation molding involving stretching can be suitably performed.

[0125] Requirement (X-7): The melt tension (melt tension: MT) measured at 260 °C is 25 mN or more. The melt tension is preferably 26 mN or more, more preferably 26 to 100 mN, and still more preferably 27 to 50 mN. The melt tension can be adjusted, for example, by controlling the molecular weight of the polymer. Since the resin composition (X) has a relatively high melt tension satisfying the above range, the stretchability is improved, and laminated inflation molding involving stretching can be suitably performed.

[0126] Requirement (X-8): By the method described in the examples below, the endothermic temperature (TmE) in the endothermic and exothermic curves (melting (endothermic) curve) measured with a differential scanning calorimeter (DSC) is preferably 230 °C or lower, more preferably 228 °C or lower, still more preferably 225 °C or lower, and even more preferably 220 °C or lower. Here, the endothermic end temperature means the temperature at which melting is completed, and is a different index from the onset and offset, which are generally the intersection points of the baseline and the tangent of the steady line. The endothermic end temperature can be set to a desired value, for example, by appropriately selecting an olefin polymerization catalyst when polymerizing a 4-methyl-1-pentene polymer, controlling the content ratio of the constitutional units, and the like. The resin composition (X) with the endothermic termination temperature within the above range is excellent in heat resistance. Therefore, the layer containing the resin composition (X) with the endothermic termination temperature within the above range also tends to be excellent in heat resistance.

[0127] The resin composition (X) preferably satisfies the above requirements (X-1) to (X-4), and more preferably further satisfies one or more of the requirements (X-5) to (X-8). As more preferable embodiments of the resin composition (X), there are mentioned a composition (X) satisfying the requirements (X-1) to (X-6), a resin composition (X) satisfying the requirements (X-1) to (X-4) and the requirement (X-7), a resin composition (X) satisfying all of the requirements (X-1) to (X-7), a resin composition (X) satisfying all of the requirements (X-1) to (X-8), etc.

[0128] The resin composition (X) may contain components other than the 4-methyl-1-pentene polymer (A1) and the 4-methyl-1-pentene polymer (A2) (hereinafter also referred to as "other components"). Examples of the other components include secondary antioxidants, heat stabilizers, weather stabilizers, antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, fillers, hydrochloric acid absorbers, etc. The content of the other components is not particularly limited, but is usually 0 to 50 parts by mass, preferably 0 to 10 parts by mass, respectively, based on 100 parts by mass of the polymer components such as the polymer (A1) and / or the polymer (A2) and the thermoplastic resin (B). The other components may be used alone or in combination of two or more.

[0129] The molding temperature in the laminated inflation molding process is under the condition of less than 260°C. Here, the molding temperature means the temperature at the time of molding, and usually means the die temperature. The molding temperature in the laminated inflation molding process is preferably less than 260°C and is a temperature not less than the melting points of the resin composition (X) and the thermoplastic resin (B), more preferably in the range of 180°C or more and less than 260°C, still more preferably in the range of 190°C or more and less than 260°C, and particularly preferably in the range of 200 to 245°C. When the melting point (Tm) of the resin composition (X) is lower than that of a normal 4-methyl-1-pentene polymer and the semi-crystallization time is long, and preferably when the resin composition (X) further has a higher melt tension than a normal 4-methyl-1-pentene polymer, the stretchability becomes good, and it is excellent in laminated inflation molding with a thermoplastic resin (B) having a melting point generally lower than that of a 4-methyl-1-pentene polymer.

[0130] There is no particular limitation on the molding apparatus used for laminated inflation molding, and a known inflation molding apparatus capable of laminated (multi-layer) molding can be used. As the laminated inflation molding method, preferably, the resin composition (X) and the thermoplastic resin (B) are co-extruded from an inflation die.

[0131] In the laminated inflation molding process, the co-extrusion of the resin composition (X) and the thermoplastic resin (B) is not particularly limited, but it is preferable to perform co-extrusion in the upward direction opposite to the gravitational direction.

[0132] The laminated inflation molding process performs laminated inflation molding under conditions where the expansion ratio (bubble ratio) exceeds 1.0. Here, the expansion ratio (bubble ratio) refers to the ratio of the maximum bubble diameter to the diameter of the die. When the expansion ratio (bubble ratio) exceeds 1.0, the co-extruded composition (X) and the thermoplastic resin (B) will be stretched. In the laminated inflation molding process, the expansion ratio (bubble ratio) is preferably 1.1 to 5.0, more preferably 1.2 to 4.5, still more preferably 1.5 to 4.0, and particularly preferably 1.8 to 3.0. Since the 4-methyl-1-pentene polymers (A1) and (A2) satisfy the above requirements, they are excellent in stretchability. Also, since laminated inflation molding with stretching where the expansion ratio (bubble ratio) exceeds 1.0 is performed, the variation in film thickness is suppressed, and the film thickness accuracy (thickness accuracy) of the obtained laminate is excellent.

[0133] In the lamination inflation molding process, the take-up speed of the laminated inflation film, which is a laminate, is generally 2 to 40 m / min, preferably 5 to 30 m / min. Also, the thickness of the resulting laminate is not particularly limited, but is preferably 0.1 to 100 μm, more preferably 1 to 50 μm. The thicknesses of the respective layers constituting the laminate may be the same or different.

[0134] The method for producing the laminate may include steps other than the lamination inflation molding step (hereinafter also referred to as "other steps"). Examples of the other steps include a step of preparing the 4-methyl-1-pentene polymer (A1) and the 4-methyl-1-pentene polymer (A2), a step of preparing the resin composition (X), a step of preparing the thermoplastic resin (B), and the like. Examples of the step of preparing the 4-methyl-1-pentene polymer (A1) and the 4-methyl-1-pentene polymer (A2) include the step of producing the above-mentioned 4-methyl-1-pentene polymer (A1) and the 4-methyl-1-pentene polymer (A2). Also, examples of the step of preparing the resin composition (X) include a step of mixing the polymer (A1) and the polymer (A2) obtained by the above-mentioned step of producing the 4-methyl-1-pentene polymer (A1) and the 4-methyl-1-pentene polymer (A2) with other components as necessary.

[0135] The laminate of the present invention can be suitably used as materials such as general household goods packaging materials, food packaging materials, food containers, retort containers, protective films, cosmetic films / sheets, shrink films, infusion bags, heat-sealing films, medical containers, release films, etc., and can be particularly suitably used for packaging. Further, when the laminate of the present invention is other than an inflation film, the method for producing the laminate is not particularly limited, and known molding methods can be mentioned. Examples of the method for producing the laminate include the T-die casting method.

Examples

[0136] Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0137] <Amount of each structural unit> The amount of the structural unit derived from 4-methyl-1-pentene (4-methyl-1-pentene content) and the amount of the structural unit derived from α-olefins other than 4-methyl-1-pentene (α-olefin content) in the polymer obtained in the following production example were determined by the following apparatus and conditions. 13 They were calculated from the C-NMR spectrum. The results are shown in Tables 1 and 2. Using an ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., an o-dichlorobenzene / heavy benzene (80 / 20% by volume) mixed solvent was used as the solvent, the sample concentration was 55 mg / 0.6 mL, the measurement temperature was 120 °C, and the observed nucleus was 13 C (125 MHz), the sequence was single pulse proton decoupling, the pulse width was 4.7 μs (45° pulse), the repetition time was 5.5 s, and the number of integrations was 10,000 or more. Using 27.50 ppm as the reference value of the chemical shift, 13 a C-NMR spectrum was obtained. From the obtained 13 C-NMR spectrum, the 4-methyl-1-pentene and α-olefin contents were quantified.

[0138] <Intrinsic viscosity [η]> The intrinsic viscosity [η] of the polymer obtained in the following production example was measured at 135 °C using a decalin solvent. The results are shown in Tables 1 and 2. Specifically, about 20 mg of the polymer 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 intrinsic viscosity [η], which is the value of ηsp / C when extrapolating the concentration (C) to 0, was determined from the following formula. [η]=lim(ηsp / C) (C→0)

[0139] <Melting point (Tm)> The melting point (Tm) of the polymer obtained in the following production example was measured using a differential scanning calorimetry (DSC) apparatus (model number: DSC220C) manufactured by Seiko Instruments Inc. according to the following procedure. The results are shown in Tables 1 and 2. First, approximately 5 mg of the polymer was placed in an aluminum pan for measurement and sealed. The temperature was raised to 290°C at a rate of 100°C / min, held at 290°C for 5 minutes, then cooled to -100°C at a rate of 10°C / min, and then heated from -100°C to 290°C at a rate of 10°C / min. The melting point (Tm) was calculated from the peak top of the crystal melting peak observed in the heat quantity curve during the second heating. When multiple peaks were detected, the one with the highest temperature was taken as the melting point (Tm).

[0140] <Molecular weight distribution (Mw / Mn)> The molecular weight distribution (Mw / Mn) of the polymer obtained in the following production example was measured as follows using a gel permeation chromatograph (manufactured by Waters, model number: Alliance GPC-2000). The separation columns were two TSKgel GNH6-HT and two TSKgel GNH6-HTL, both with a column size of 7.5 mm in diameter and 300 mm in length, the column temperature was 140°C, the mobile phase used was o-dichlorobenzene (manufactured by Fujifilm Wako Pure Chemical Corporation) and 0.025 mass% of dibutylhydroxytoluene (BHT) (manufactured by Takeda Pharmaceutical Company Limited) as an antioxidant, it 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 was manufactured by Tosoh Corporation for Mw < 1000 and Mw > 4×10 6 For those, and for 1000 ≤ Mw ≤ 4×10 6 For those, products manufactured by Pressure Chemical were used.

[0141] <Melt tension> The melt tension at 260°C of the polymer obtained in the following production example was measured using a Capillograph 1D, an apparatus manufactured by Toyo Seiki Seisakusho, Ltd. After charging the measurement sample into a melting furnace (diameter 9.55 mm) set at 260°C and fully melting it, it was passed through a capillary with an L / D of 8 / 2.095 mm and an inlet angle of 180° at an extrusion rate of 15 mm / min. It was passed through a pulley fixed at a position 58 cm below the capillary, and the stress applied to the pulley when the molten resin was wound up at a speed of 15 m / min was measured, and that stress was taken as the melt tension.

[0142] [Production Examples A1-1 to A1-14] According to the method described in Comparative Example 1 of International Publication No. 2017 / 150265, the α-olefin species was changed to the α-olefins described in Table 1 below, and the usage ratios of 4-methyl-1-pentene, α-olefin, and hydrogen were changed so that the physical properties of the resulting polymer (A1) would be the values in Table 1 below, thereby synthesizing 4-methyl-1-pentene polymers (A1-1) to (A1-14).

[0143]

Table 1

[0144] [Production Examples A2-1 to A2-6] According to the method described in Comparative Example 1 of International Publication No. 2017 / 150265, the α-olefin species was changed to the α-olefins described in Table 2 below, and the usage ratios of 4-methyl-1-pentene, α-olefin, and hydrogen were changed so that the physical properties of the resulting polymer would be the values in Table 2 below, thereby synthesizing 4-methyl-1-pentene polymers (A2-1) to (A2-6).

[0145] [Production Examples A2-7 and A2-8] According to the method described in Comparative Example 9 of International Publication No. 2006 / 054613, the comonomer species was changed to the α-olefins listed in Table 1 below, and the usage ratios of 4-methyl-1-pentene, α-olefin, and hydrogen were changed so that the physical properties of the resulting polymer would be the values shown in Table 2 below, thereby synthesizing 4-methyl-1-pentene polymers (A2-7) and (A2-8). That is, 4-methyl-1-pentene polymers (A2-7) and (A2-8) were obtained by single-stage polymerization using a solid titanium catalyst obtained by reacting magnesium chloride anhydride, 2-ethylhexyl alcohol, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, and titanium tetrachloride as the polymerization catalyst.

[0146] [Table 2]

[0147] [Example 1] [Preparation of Resin Composition] To 100 parts by mass of the 4-methyl-1-pentene polymer (A1-1) obtained in the above Production Example, 0.1 part by mass of tris(2,4-di-t-butylphenyl) phosphate as a secondary antioxidant and 0.1 part by mass of n-octadecyl 3-(4'-hydroxy-3',5'-di-t-butylphenyl) propionate as a heat stabilizer were added to obtain a resin composition. Subsequently, the obtained resin composition was granulated using a twin-screw extruder BT-30 (screw diameter 30 mmφ, L / D = 46) manufactured by Plastic Engineering Laboratory Co., Ltd. under the conditions of a set temperature of 270°C, a resin extrusion rate of 60 g / min, and 200 rpm to prepare pellets of the resin composition.

[0148] [α-Olefin Content and Intrinsic Viscosity [η]] In the measurement of the above physical property values, the α-olefin content (i.e., the content of the structural unit derived from the α-olefin having 10 to 20 carbon atoms) and the intrinsic viscosity [η] contained in the prepared resin composition were measured and calculated in the same manner as the measurement method of the content of each structural unit and the intrinsic viscosity [η] in the polymer, except that the prepared resin composition was used instead of the 4-methyl-1-pentene polymer. The results are shown in Tables 3 and 4.

[0149] [Production of Multilayer Film] A multilayer film was produced using a three-layer upblown inflation molding machine having a circular die with a die diameter of 30φ, three hopper inlets, and a 20 mmφ screw. The pellets of the resin composition prepared above were charged into one hopper, and the cylinder temperature was set at 270°C. Further, as the thermoplastic resin (B), polyethylene (manufactured by Prime Polymer Co., Ltd., product name: Prime Polypro SP3010, MFR (230°C, 2.16 kg load): 1.0 g / 10 min) was charged into the remaining two hoppers, and the cylinder temperatures for these hoppers were set at 200°C, respectively. The die temperature was set at 260°C, and the pellets of the resin composition and the melt-kneaded product of polyethylene were co-extruded from the die as a multilayer film and taken up under the condition of an air-cooling take-up speed of 2.0 m / min, thereby cooling and solidifying to obtain an unstretched multilayer film (i.e., a raw film) having a layer structure of "A layer / B layer / B layer" with an overall thickness of 60 μm. The obtained multilayer film was a laminate in which an A layer having a thickness of 30 μm and two B layers each containing polyethylene having a thickness of 15 μm were laminated in this order. The thickness of each layer was calculated from the extrusion amount and is shown in Table 3.

[0150] <Shrinkage after Heat Sealing (HS Shrinkage Rate)> Two test pieces having a length of 150 mm and a width of 30 mm were prepared from the multilayer film obtained above. The length direction of the film was the direction corresponding to the flow direction (MD direction) in the raw film production process. Two obtained test pieces were overlapped such that the B layer containing polyethylene, which is the outermost layer (i.e., the B layer not in contact with the A layer), faced each other, and heat-sealed using a heat sealer under the conditions of a temperature of 180 °C and a gauge pressure of 2.0 MPa for 2 seconds. Using a vernier caliper, the length and width of the test pieces before and after heat sealing were measured, and the shrinkage rates (%) in the MD direction and TD direction were calculated from the following formulas. The results are shown in Tables 3 and 4. HS shrinkage rate in the MD direction = (LM0 - LM1) / LM0 × 100 (%) HS shrinkage rate in the TD direction = (LT0 - LT1) / LT0 × 100 (%) [LM0: Length of the test piece before heat sealing, LM1: Length of the test piece after heat sealing, LT0: Width of the test piece before heat sealing, LT1: Width of the test piece after heat sealing]

[0151] <Thickness evaluation of A layer and B layer> A test piece with a length of 50 mm and a width of 50 mm was prepared from the multilayer film obtained above, cut with a razor, and the cross-section was observed with the above optical microscope, and the thickness of the original fabric and the total thickness of the A layer and B layer were measured respectively.

[0152] <Measurement of tensile elastic modulus> The multilayer film prepared above was cut into strips with a width of 50 mm and a length of 150 mm with a razor. Using the obtained test pieces, a tensile test was performed with a tensile testing machine (manufactured by A&D Company, Limited, model number: RTG - 1250), and the elastic modulus was calculated from the slope of the initial strain and stress. The measurement temperature was room temperature (23 °C), and the tensile speed was 50 mm / min.

[0153] <Bubble stability> In the production of the multilayer film, the stability of the bubble during inflation molding was visually observed and evaluated according to the following criteria. ◎: The bubble was stable for a long time, and a good film was obtained. ○: Slight movement occurred in the bubble, but stable molding was possible. ×: The bubble fluctuated up and down, causing a fluctuation in the film width, or molding could not be performed.

[0154] <Surface smoothness (melt fracture)> The surface roughness of the film prepared above was measured using a surface roughness measuring instrument manufactured by Tokyo Seimitsu Co., Ltd. From the obtained roughness curve, a measurement length (l) was extracted in the direction of the mean line. When the x-axis was taken in the direction of the mean line of the extracted portion and the y-axis was taken in the direction of the vertical magnification, and the roughness curve was expressed as y = f(x), the value obtained by the following formula was expressed in nanometers (nm) and defined as the surface roughness (Ra), which was used as an index of surface smoothness. The measurement length was 10 mm.

[0155] [Equation]

[0156] [Examples 2 to 16 and Comparative Examples 3 to 6] A resin composition was prepared in the same manner as in Example 1 except that the polymers shown in Table 3, Table 4, or Table 5 were used. Using this resin composition and polyethylene, inflation molding was performed to produce a multilayer film. Each evaluation was carried out using the obtained multilayer film. The results are shown in Table 3, Table 4, or Table 5.

[0157]

Table 3

[0158] [Comparative Examples 1 and 2] A multilayer film was produced in the same manner as in Example 1 except that only the polymers shown in Table 4 were extruded and inflation molded from three extruders. Each evaluation was carried out using the obtained multilayer film. The results are shown in Table 4.

[0159]

Table 4

[0160] [Example 17] The polymer A1-1 and A2-1 were used in the composition ratios shown in Table 5. Except that 0.1 part by mass of tris(2,4-di-t-butylphenyl) phosphate was used as a secondary antioxidant and 0.1 part by mass of n-octadecyl 3-(4'-hydroxy-3',5'-di-t-butylphenyl) propionate was used as a heat stabilizer with respect to 100 parts by mass of the polymer component, pellets of the resin composition were prepared in the same manner as in Example 1, and the α-olefin content and the intrinsic viscosity [η] contained in the resin composition were measured and calculated. Furthermore, by the same method for producing a multilayer film as in Example 1, the resin composition pellets prepared above and polyethylene ((manufactured by Prime Polymer Co., Ltd., product name: Prime Polypro SP3010, MFR (230 °C, 2.16 kg load): 1.0 g / 10 min)) as the thermoplastic resin (B) were co-extruded as a multilayer film, and inflation molding was performed under the same conditions as in the method for producing the multilayer film of Example 1 to produce a multilayer film. Using the obtained multilayer film, each evaluation was carried out in the same manner as in Example 1. The results are shown in Table 5.

[0161] [Examples 18 to 38 and Comparative Examples 7 and 8] A resin composition was prepared in the same manner as in Example 17 except that the polymers A1 and A2 were mixed in the composition ratios shown in Table 5 or Table 6, and pellets of the resin composition were produced. Except that the pellets of this resin composition were used, inflation molding was performed under the same conditions as in the method for producing the laminate in Example 1 to produce a multilayer film. Using the obtained multilayer film, each evaluation was carried out. The results are shown in Table 5 or Table 6.

[0162]

Table 5

[0163]

Table 6

[0164] It can be seen that the multilayer films of Examples 1 to 38 are laminates that are excellent in bubble stability when subjected to inflation molding as compared with the multilayer films of Comparative Examples 1 to 8.

Claims

1. An A layer containing a 4-methyl-1-pentene polymer (A1) satisfying the following requirements (A1-1) to (A1-7), a B layer containing a thermoplastic resin (B), A laminate comprising: Requirement (A1-1): The density measured in accordance with JIS K7112 (density gradient tube method) is 0.82 to 0.88 g / m ３ ; Requirement (A1-2): The melting point (Tm) measured by differential scanning calorimetry (DSC) is 190°C or higher and less than 220°C; Requirement (A1-3): The melting enthalpy ΔH is less than 35 J / g; Requirement (A1-4): The half-crystallization time at 215°C measured by the following measurement method using a differential scanning calorimeter is 220 seconds or longer, or not measured; Measurement method for half-crystallization time: Using DSC8500 manufactured by PerkinElmer, Inc., heat from 30°C to 280°C at a heating rate of 500°C / min, hold the temperature for 10 minutes, and then cool to 215°C at a cooling rate of 500°C / min, and measure the half-crystallization time at 215°C; Requirement (A1-5): The molecular weight distribution (Mw / Mn), which is the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn), is 6.0 or less; Requirement (A1-6): The content of the structural unit derived from 4-methyl-1-pentene is 90.0 mol% or more and less than 100 mol%, and the content of the structural unit derived from an α-olefin having 10 to 20 carbon atoms exceeds 0 mol% and is 10.0 mol% or less (however, the total content of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from the α-olefin having 10 to 20 carbon atoms is 100 mol%); Requirement (A1-7): The intrinsic viscosity [η] measured in decalin at 135°C exceeds 0.6 and is 4.0 dl / g or less.

2. In the A layer, the content of the 4-methyl-1-pentene polymer (A1) is 60 to 100% by mass, The content of the 4-methyl-1-pentene polymer (A2) satisfying the following requirements (A2-1) to (A2-7) is 0 to 40% by mass (however, the total content of the polymer (A1) and the polymer (A2) is 100% by mass), The laminate according to Claim 1; Requirement (A2-1): The density measured in accordance with JIS K7112 (density gradient tube method) is 0.82 to 0.88 g / m ３ ; Requirement (A2-2): The melting point (Tm) measured by differential scanning calorimetry (DSC) is 210°C to 240°C; Requirement (A2-3): The melting enthalpy ΔH is less than 40 J / g; Requirement (A2-4): The half-crystallization time at 215°C measured by the following measurement method using a differential scanning calorimeter is 220 seconds or less; Method for measuring semi-crystallization time: Using DSC8500 manufactured by PerkinElmer, Inc., heat the temperature from 30°C to 280°C at a heating rate of 500°C / min, hold the temperature for 10 minutes, and then measure the semi-crystallization time at 215°C when cooling to 215°C at a cooling rate of 500°C / min; Requirement (A2-5): The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 6.0 or less; Requirement (A2-6): The content of the structural unit derived from 4-methyl-1-pentene is 90.0 mol% or more and less than 100 mol%, and the content of the structural unit derived from an α-olefin having 10 to 20 carbon atoms exceeds 0 mol% and is 10.0 mol% or less (however, the total content of the structural unit derived from the 4-methyl-1-pentene and the structural unit derived from the α-olefin having 10 to 20 carbon atoms is 100 mol%); Requirement (A2-7): The intrinsic viscosity [η] measured in decalin at 135°C is 0.5 to 5.0 dl / g.

3. The laminate according to claim 1 or 2, wherein the 4-methyl-1-pentene polymer (A1) further satisfies the following requirement (A1-8); Requirement (A1-8): The melt tension measured at 260°C is 10 mN or more.

4. The laminate according to claim 1 or 2, wherein the thermoplastic resin (B) is polyethylene or polypropylene.

5. The laminate according to claim 1 or 2, having a thickness of 1 to 70 μm.

6. The laminate according to claim 1 or 2, which is an inflation film.

7. The laminate according to claim 1 or 2, which is for packaging.

8. A resin composition (X) containing a 4-methyl-1-pentene polymer (A1) satisfying the following requirements (A1-1) to (A1-7) and a 4-methyl-1-pentene polymer (A2) satisfying the following requirements (A2-1) to (A2-7), and a thermoplastic resin (B), and a step of performing laminated inflation molding under conditions where the expansion ratio (bubble ratio) exceeds 1.0 and the molding temperature is less than 260°C, a method for manufacturing a laminate; Requirement (A1-1): The density measured in accordance with JIS K7112 (density gradient tube method) is 0.82 to 0.88 g / m ３ ; Requirement (A1-2): The melting point (Tm) measured by differential scanning calorimetry (DSC) is 190°C or more and less than 220°C; Requirement (A1-3): The melting enthalpy ΔH is less than 35 J / g; Requirement (A1-4): The semi-crystallization time at 215°C measured by the following measurement method using a differential scanning calorimeter is 220 seconds or more, or not measured; Measurement method of semi-crystallization time: Using DSC8500 manufactured by PerkinElmer, Inc., heat the temperature from 30°C to 280°C at a heating rate of 500°C / min, hold the temperature for 10 minutes, and then measure the semi-crystallization time at 215°C when cooling down to 215°C at a cooling rate of 500°C / min; Requirement (A1-5): The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 6.0 or less; Requirement (A1-6): The content of the structural unit derived from 4-methyl-1-pentene is 90.0 mol% or more and less than 100 mol%, and the content of the structural unit derived from α-olefin with 10 to 20 carbon atoms exceeds 0 mol% and is 10.0 mol% or less (however, the total content of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from α-olefin with 10 to 20 carbon atoms is 100 mol%); Requirement (A1-7): The intrinsic viscosity [η] measured in decalin at 135°C exceeds 0.6 and is 4.0 dl / g or less; Requirement (A2-1): The density measured in accordance with JIS K7112 (density gradient tube method) is 0.82 to 0.88 g / m ３ ; Requirement (A2-2): The melting point (Tm) measured by differential scanning calorimetry (DSC) is 220°C to 240°C; Requirement (A2-3): The melting enthalpy ΔH is less than 40 J / g; Requirement (A2-4): The semi-crystallization time at 215°C measured by the following measurement method using DSC is 220 seconds or less; Measurement method of semi-crystallization time: Using DSC8500 manufactured by PerkinElmer, Inc., heat the temperature from 30°C to 280°C at a heating rate of 500°C / min, hold the temperature for 10 minutes, and then measure the semi-crystallization time at 215°C when cooling down to 215°C at a cooling rate of 500°C / min; Requirement (A2-5): The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 6.0 or less; Requirement (A2-6): The content of the structural unit derived from 4-methyl-1-pentene is 90.0 mol% or more and less than 100 mol%, and the content of the structural unit derived from α-olefin with 10 to 20 carbon atoms exceeds 0 mol% and is 10.0 mol% or less (however, the total content of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from α-olefin with 10 to 20 carbon atoms is 100 mol%); Requirement (A2-7): The intrinsic viscosity [η] measured in decalin at 135°C is 0.5 to 5.0 dl / g.

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