Sealant resin composition and its uses

Abstract

The purpose of the present invention is to achieve a sealant resin composition which has good heat seal strength and excellent resistance to whitening during stretching, and which still has the good heat seal strength even after a heat treatment. The present invention relates to a sealant resin composition (X) which contains a 1-butene / ethylene copolymer (A) that satisfies a specific requirement and a propylene polymer (B), and which satisfies the requirement (X1) and the requirement (X1-2) described below. Requirement (X1): The Shore D hardness as measured in accordance with ASTM D2240 is within the range of 44 to 80. Requirement (X1-2): The melt flow rate (MFR) as measured at 230°C under a load of 2.16 kg in accordance with ASTM D1238 is within the range of 0.1 g / 10 minutes to 100 g / 10 minutes.

Description

Technical Field

[0001] The present invention relates to a sealant resin composition containing a 1-butene / ethylene copolymer and a propylene-based polymer, and its use.

Background Art

[0002] 1-Butene-based polymers are excellent in creep properties at high temperatures, abrasion resistance, flexibility, compatibility with polypropylene, etc., and are used for the modification of water supply and hot water supply pipes, sheets such as skin materials, polypropylene resins, hot melt adhesives, etc.

[0003] Patent Document 1 discloses a 1-butene-based polymer having a good balance of fluidity, tensile modulus and elongation, and secondary processability. The intrinsic viscosity [η] measured at 135°C in tetralin solvent is in the range of 0.01 to 0.5 dl / g, the melting point measured using a differential scanning calorimeter (DSC) is in the range of 0 to 100°C, and the stereoregularity index {(mmmm) / (mmrr+rmmr)} is 30 or less. A resin modifier composed of a highly fluid 1-butene-based polymer, and a hot melt adhesive containing the 1-butene-based polymer have been proposed.

[0004] Further, Patent Document 2 proposes a hot melt adhesive containing a 1-butene copolymer having a high melt flow rate having a melt mass flow rate (MFR) of 200 to 1500 when measured in accordance with ISO 1133 (190°C, 2.16 kg) and containing 2 to 6% by weight of ethylene-derived units.

[0005] However, when a resin composition containing a 1-butene copolymer is used as a sealant, there are problems that the whitening resistance during stretching in secondary processing such as deep drawing molding and the heat seal strength after heat treatment are not sufficient.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

[0007] The object of the present invention is to obtain a sealant resin composition that exhibits excellent whitening resistance during stretching, good heat seal strength, and good heat seal strength even after heat treatment. [Means for solving the problem]

[0008] The first aspect of the present invention relates to a sealant resin composition (X) containing a 1-butene-ethylene copolymer (A) and a propylene polymer (B), characterized in that the resin composition satisfies the following requirement (X1).

[0009] Requirement (X1): The Shore D hardness, measured according to ASTM D2240, is in the range of 44 to 80.

[0010] The second aspect of the present invention relates to a sealant resin composition (X) containing a 1-butene-ethylene copolymer (A) and a propylene polymer (B) that satisfy the following requirements (A1), (A2), and (A5), characterized in that the resin composition satisfies the following requirements (X1) and (X1-2).

[0011] Requirement (A1): The content of constituent unit (i) derived from 1-butene is in the range of 70 to 99.9 mol%, and the content of constituent unit (ii) derived from ethylene is in the range of 0.1 to 30 mol% [provided that the sum of constituent unit (i) and constituent unit (ii) is 100 mol%]. Requirements (A2): 13 Isotactic pen calculated by 13C NMR Ta ッ Do The fraction (mmmm) is in the range of 80-99.9%; Requirement (A5): Using a differential scanning calorimeter (DSC), the temperature is first cooled from 30°C to -70°C at a cooling rate of 20°C / min (first cooling), held at -70°C for 5 minutes, then heated from -70°C to 200°C at a heating rate of 20°C / min (first heating), held at 200°C for 10 minutes, then cooled to -70°C at a cooling rate of 20°C / min (second cooling), held at -70°C for 1 minute, and then heated again from -70°C to 200°C at a heating rate of 20°C / min (second heating), and no melting peak is observed during the second heating; Requirement (X1): The Shore D hardness, measured according to ASTM D2240, is in the range of 44 to 80; Requirement (X1 of 2): In accordance with ASTM D1238, the melt flow rate (MFR), measured at 230°C and a 2.16 kg load, is in the range of 0.1 to 100 g / 10 min.

[0012] The third aspect of the present invention is an energy storage device comprising a sealant resin composition (X), The present invention relates to an energy storage device in which the sealant resin composition (X) contains a 1-butene-ethylene copolymer (A) and a propylene polymer (B), and satisfies the following requirement (X1).

[0013] Requirement (X1): The Shore D hardness, measured according to ASTM D2240, is in the range of 44 to 80. [Effects of the Invention]

[0014] A single-layer or multi-layer film containing a layer formed from the resin composition of the present invention exhibits excellent resistance to whitening during stretching, good heat seal strength, and good heat seal strength even after heat treatment. Therefore, it can be suitably used as packaging for, for example, daily necessities, food, liquids, pharmaceuticals, electronic components, and lithium-ion batteries. [Modes for carrying out the invention]

[0015] <1-Butene-ethylene copolymer (A)> The 1-butene-ethylene copolymer (A), which is one of the components of the sealant resin composition (X) of the present invention, is preferably a 1-butene-ethylene copolymer (A) that satisfies the following requirements (A1) to (A5). Here, the 1-butene-ethylene copolymer (A) may satisfy only one of the following requirements (A1) to (A5), two or more, or all of them. In one preferred and exemplary embodiment of the present invention, the 1-butene-ethylene copolymer (A) satisfies the following requirements (A1), (A2), and (A5). In this embodiment, the 1-butene-ethylene copolymer (A) may further satisfy the following requirements (A3), requirement (A4), and one or more requirements selected from the group consisting of the following requirements (A5-2) to (A8) described later.

[0016] The monomers (1-butene and ethylene) contained in the 1-butene-ethylene copolymer (A) may be monomers derived from fossil fuels, monomers derived from biomass, or a combination of monomers derived from fossil fuels and monomers derived from biomass.

[0017] <Requirement (A1)> The content of constituent unit (i) derived from 1-butene is in the range of 70 to 99.9 mol%, and the content of constituent unit (ii) derived from ethylene is in the range of 0.1 to 30 mol% [provided that the sum of constituent unit (i) and constituent unit (ii) is 100 mol%].

[0018] The 1-butene-ethylene copolymer (A) according to the present invention has a lower limit of 70 mol% in the amount of constituent units derived from 1-butene. Preferably, the lower limit of the constituent units is 75 mol%, more preferably 80 mol%, and particularly preferably 85 mol%.

[0019] On the other hand, the upper limit of the amount of constituent units derived from 1-butene is 99.9 mol%, but it is preferably 98 mol%, more preferably 96 mol%, even more preferably 95 mol%, and particularly preferably 94.5 mol%.

[0020] The 1-butene-ethylene copolymer (A) according to the present invention has an upper limit of 30 mol% for the amount of constituent unit (ii) derived from ethylene. Preferably, this upper limit is 25 mol%, more preferably 20 mol%, and particularly preferably 15 mol%. When the 1-butene-ethylene copolymer (A) contains a certain amount or less of constituent unit (ii) derived from ethylene, the resulting sealant resin composition (X) tends to have sufficient whitening resistance and readily provides sealant films and laminates with excellent surface properties.

[0021] On the other hand, the lower limit of the amount of constituent unit (ii) derived from ethylene is 0.1 mol%, but it is preferably 2 mol%, more preferably 4 mol%, even more preferably 5 mol%, and particularly preferably 5.5 mol%. When the 1-butene-ethylene copolymer (A) contains a certain amount or more of constituent unit (ii) derived from ethylene, the resulting sealant resin composition (X) tends to have sufficient whitening resistance and readily yields sealant films and laminates with high mechanical strength.

[0022] The 1-butene-ethylene copolymer (A) according to the present invention can be made compatible with the propylene polymer (B) described later by keeping the amount of the constituent unit (ii) derived from ethylene within the above range. Quantity When the value is below the upper limit, it is preferable because, when used as a sealant, it improves resistance to whitening during stretching in secondary processing such as deep drawing, and provides excellent heat seal strength and heat seal strength after heat treatment.

[0023] The content (mol%) of each constituent unit of the 1-butene-ethylene copolymer (A) is: 13 The measurement is performed by 13C-NMR. Details of the measurement method are described in the examples below.

[0024] <Requirement (A2)> 13Isotactic pen calculated by 13C NMR Ta ッ Do The fraction (mmmm) is in the range of 80-99.9%.

[0025] The 1-butene-ethylene copolymer (A) according to the present invention preferably has a lower limit of isotactic pentad fraction (mmmm) of 85%, and more preferably 90%. Furthermore, the upper limit of the isotactic pentad fraction (mmmm) is preferably 99.5%, and more preferably 99.0%. By setting the isotactic pentad fraction (mmmm) within the above range, it becomes possible to design the copolymer with appropriate mechanical strength and flexibility even when copolymerizing ethylene and controlling its compatibility with the propylene-based polymer (B) described later.

[0026] The details of the measurement method for the isotactic pentad fraction (mmmm) are as described in the examples below.

[0027] <Requirements (A3)> At 135°C, the intrinsic viscosity [η] in decalin solvent is in the range of 0.7 to 4.0 dl / g.

[0028] The intrinsic viscosity [η] of the 1-butene-ethylene copolymer (A) according to the present invention is more preferably 0.8 to 3.0 dl / g, even more preferably 0.9 to 2.5 dl / g, and particularly preferably 1.0 to 2.2 dl / g. The 1-butene-ethylene copolymer (A) having an intrinsic viscosity [η] within the above range exhibits an excellent balance between fluidity and the mechanical strength of the resulting sealant.

[0029] The details of the method for measuring the intrinsic viscosity [η] are as described in the examples below.

[0030] <Requirements (A4)> In accordance with ASTM D1238, the melt flow rate (MFR), measured at 190°C and a 2.16 kg load, is in the range of 0.1 to 100 g / 10 min, preferably 0.5 to 50 g / 10 min, more preferably 1.0 to 30 g / 10 min, even more preferably 1.1 to 20 g / 10 min, even more preferably 1.1 to 5 g / 10 min, and particularly preferably 1.1 to 3.5 g / 10 min.

[0031] When the MFR is within the aforementioned range, the fluidity is good, and the resulting sealant has good mechanical properties. For example, when high fluidity is required, a sealant resin composition (X) containing a 1-butene-ethylene copolymer (A) preferably has a melt flow rate (MFR) in the range of 3 to 80 g / 10 min, measured in accordance with ASTM D1238 at 230°C and a 2.16 kg load. Furthermore, a sealant with excellent mechanical properties can be easily obtained. In addition, considering the appropriate balance between fluidity and mechanical properties for a film molding machine, it is particularly preferable that the MFR be 15 g / 10 min or less.

[0032] When the MFR is above the lower limit, the drawdown properties during film formation are good, making it suitable for high-speed film formation. When the MFR is below the upper limit, the mechanical properties of the 1-butene-ethylene copolymer (A) are excellent, and the sealant resin composition (X) containing the 1-butene-ethylene copolymer (A) is preferable because it has excellent heat seal strength, whitening resistance, and durability.

[0033] <Requirements (A5)> In calorimetry using differential scanning calorimeter (DSC), no melting peak was observed during the second heating phase.

[0034] In the present invention, calorimetry using a differential scanning calorimeter (DSC) is performed by accurately weighing approximately 6-10 mg of a sample, sealing it in an aluminum pan, first cooling it to -70°C (first cooling), then heating it from -70°C to 200°C at a heating rate of 20°C / min (first heating), measuring the DSC curve, holding it at 200°C for 10 minutes, then cooling it to -70°C at a cooling rate of 20°C / min (second cooling), measuring the DSC curve, holding it at -70°C for 1 minute, and then heating it again from -70°C to 200°C at a heating rate of 20°C / min (second heating), measuring the DSC curve. In an exemplary embodiment of the present invention, the first cooling performed before the first heating is done by first cooling it from 30°C to -70°C at a cooling rate of 20°C / min, holding it at -70°C for 5 minutes, and then performing the first heating.

[0035] Furthermore, in the DSC curve, if an endothermic peak (melting peak) due to melting is observed during the first heating phase, the temperature at which this melting peak (hereinafter referred to as "melting peak P1") is observed is defined as Tm1. If a melting peak is observed during the second heating phase, the temperature at which this melting peak (hereinafter referred to as "melting peak P2") is observed is defined as Tm2.

[0036] In this invention, "no melting peak observed during the second heating phase" means that the melting peak P2 is not observed during the second heating phase, that is, that Tm2 is not observed.

[0037] In this specification, the melting peak is measured by the measurement method described above, the melting point is the temperature at which the melting peak is observed, specifically the temperature at the peak of the melting peak, and the absence of a melting peak means that no crystal melting peak with a crystal melting enthalpy of 1 J / g or more is observed. If two or more melting peaks are observed, the melting point is the highest temperature among the temperatures at the peaks of these peaks.

[0038] <Requirements (A5-2)> In addition to the above requirements (A1) to (A5), the 1-butene-ethylene copolymer (A) according to the present invention preferably has a melting point (Tm) of 70°C or less, and more preferably 66°C or less, as measured by a differential scanning calorimeter (DSC) during the first heating stage. On the other hand, the melting point (Tm) is preferably 40°C or higher, and more preferably 44°C or higher. For example, the melting point (Tm) is preferably 40 to 70°C, and more preferably 44 to 66°C.

[0039] When the melting point (Tm) is below the upper limit, the crystallinity is low and flexibility is excellent. When the melting point is above the lower limit, mechanical properties are excellent and heat seal strength is improved. When the melting point (Tm) is within the aforementioned range, flexibility and low stickiness are well balanced.

[0040] Here, the "melting point (Tm) measured during the first heating phase of the differential scanning calorimeter (DSC)" can be measured by the "calorimetry using a differential scanning calorimeter (DSC)" as described in "Requirement (A5)" above. In this case, Tm is defined as the temperature Tm1 of the melting peak P1 that can be observed during the first heating phase.

[0041] <Requirements (A5-3)> The 1-butene-ethylene copolymer (A) according to the present invention preferably has a melting enthalpy of 1 to 60 J / g, and more preferably 2 to 50 J / g, as measured by the first heating stage of a differential scanning calorimeter (DSC), in addition to the above requirements (A1) to (A5) (or the above requirements (A1) to (A5-2)). Melting enthalpy is an indicator of crystallinity. If the melting enthalpy is below the upper limit, the crystallinity is low and flexibility is excellent, and if the melting enthalpy is above the lower limit, mechanical properties are excellent and heat seal strength is improved. If the melting enthalpy is within the above range, flexibility and low stickiness are well balanced.

[0042] Here, the "enthalpy of fusion measured in the first heating stage of the differential scanning calorimeter (DSC)" can be measured by the "calorimetry using a differential scanning calorimeter (DSC)" as described in "Requirement (A5)" above, and the enthalpy of fusion obtained for the melting peak P1 is defined as the "enthalpy of fusion measured in the first heating stage of the differential scanning calorimeter (DSC)".

[0043] The observation of a melting peak during the first heating phase, and the absence of a melting peak during the second heating phase despite the presence of crystallinity, indicates that the crystallization rate of 1-butene-ethylene copolymer (A) is extremely slow.

[0044] <Requirements (A6)> The 1-butene-ethylene copolymer (A) relating to the present invention has, in addition to the above requirements (A1) to (A5) (or the above requirements (A1) to (A5-3)), (A6): Weight-average molecular weight (Mw) is between 100,000 and 550,000. It is preferable.

[0045] When fluidity is required, the weight-average molecular weight (Mw) of the 1-butene-ethylene copolymer (A) is more preferably 100,000 to 520,000, even more preferably 100,000 to 500,000, and particularly preferably 100,000 to 490,000. When the weight-average molecular weight (Mw) is within the above range, the sealant resin composition containing the 1-butene-ethylene copolymer (A) is suitable for high-speed moldability. However, the weight-average molecular weight (Mw) of the 1-butene-ethylene copolymer (A) may exceed 550,000 in some cases. For example, when mechanical strength of the sealant is required, the weight-average molecular weight (Mw) is more preferably 150,000 to 600,000. 、 A weight-average molecular weight (Mw) of 200,000 to 600,000 is more preferable, and a weight-average molecular weight of 202,000 to 600,000 is particularly preferable. When the weight-average molecular weight (Mw) is within the above range, a sealant with excellent mechanical properties can be easily obtained.

[0046] <Requirements (A6-2)> The 1-butene-ethylene copolymer (A) according to the present invention further preferably has a molecular weight distribution (Mw / Mn) of 1.5 to 3.0, and more preferably 1.6 to 2.8. Mw / Mn is a polystyrene-based value measured by the GPC method. 1-butene-ethylene copolymer (A) with an Mw / Mn within the above range is preferred because it contains fewer low molecular weight components that reduce mechanical strength and fewer high molecular weight components that worsen fluidity.

[0047] <Requirements (A7) and (A8)> The 1-butene-ethylene copolymer (A) relating to the present invention has, in addition to the above requirements (A1) to (A5) (or the above requirements (A1) to (A6-2)), Requirement (A7): The maximum Shore A hardness (according to ASTM D2244) is 70-99. Requirement (A8): The maximum Shore D hardness (according to ASTM D2244) is 20-70. This is preferable. A more preferable range for Shore A hardness is 75 to 98. A more preferable range for Shore D hardness is 25 to 65. Shore A hardness or Shore D hardness is an indicator of crystallinity. If the Shore A hardness or Shore D hardness is below the upper limit, a sealant with low crystallinity and excellent flexibility and resistance to whitening during stretching can be easily obtained. If the Shore A hardness or Shore D hardness is above the lower limit, a sealant with excellent mechanical properties can be easily obtained.

[0048] The 1-butene-ethylene copolymer (A) may satisfy only one of the requirements (A7) and (A8), or it may satisfy both the requirements (A7) and (A8).

[0049] <Method for producing 1-butene-ethylene copolymer (A)> The 1-butene / ethylene copolymer (A) according to the present invention can be polymerized, for example, by a known polymerization method such as a gas-phase method, a bulk method, or a slurry method in the presence of a catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. Among these, not only does it result in a sealant resin composition having a narrow molecular weight distribution and composition distribution of the polymer and excellent balance between mechanical strength and flexibility, but particularly when combined with the propylene-based polymer (B) described later, good compatibility can be obtained, and it is preferable to use a metallocene catalyst that can uniformly control the reaction. It is particularly preferable to polymerize using a metallocene compound represented by the following general formula (1) or (2).

[0050]

Chemical formula

[0054] Preferably, the silicon-containing hydrocarbon group is an alkylsilyl group or arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms. Specific examples include trimethylsilyl, tert-butyldimethylsilyl, and triphenylsilyl.

[0055] Note, R 2 The substituent is a sterically bulky hydrocarbon group, specifically a silicon-containing hydrocarbon group, i.e., a secondary or tertiary substituent is preferred, and a substituent with four or more carbon atoms is more preferred. Specific examples of hydrocarbon groups include isopropyl, 1,1-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, and 1,1-dimethylbutyl. Tert-butyl is particularly preferred. Examples of silicon-containing hydrocarbon groups include compounds in which some or all of the carbon atoms of the above compounds are substituted with silicon.

[0056] R on the fluorene ring 5 From R 12 The adjacent substituents up to this point may bond to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl and dibenzofluorenyl. Also, R on the fluorene ring 5 From R 12 The substituents are symmetrical from left to right for ease of synthesis, i.e., R 5 =R 12 , R 6 =R 11, R 7 =R 10 , R 8 =R 9 It is preferable that it be unsubstituted fluorene, 3,6-disubstituted fluorene, 2,7-disubstituted fluorene, or 2,3,6,7-tetrasubstituted fluorene. Here, the 3, 6, 2, and 7 positions on the fluorene ring are R 7 , R 10 , R 6 , R 11 It corresponds to.

[0057] R in the above general formula (1) 3 and R 4 R is selected from hydrogen and hydrocarbon groups, and may be the same or different. Specific examples of preferred hydrocarbon groups are those similar to those mentioned above. Y is carbon or silicon. In the case of general formula (1), R 3 and R 4 Y is bonded to Y, forming a substituted methylene group or substituted silylene group as a crosslinking portion. Preferred specific examples include, for example, methylene, dimethylmethylene, diisopropylmethylene, methyl tert-butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene or dimethylsilylene, diisopropylsilylene, etc. A more preferred Y is carbon.

[0058] R in general formula (1) or (2) 2 When it is a tert-butyl group, R 1 It is preferable that it is a methyl or ethyl group. twist Preferably, it is a methyl group. In this case, R in general formula (1) 3 , R 4 R is a methyl or phenyl group, preferably a methyl group. 3 , R 4 It is preferable that they are the same as each other. Furthermore, R of the general formula (1) 2 is a tert-butyl group, R 1 When R is a methyl group, 5 ~R 12 It can also be hydrogen.

[0059] Furthermore, R in the general formula (1) 2 is a tert-butyl group, R 1 When it is an ethyl group, R 5 , R 7 , R 8 , R 9 , R 10 , R 12 is hydrogen, R 6 , R 11 Those in which the group is a tert-butyl group are preferably used.

[0060] In the case of general formula (2), Y is bonded to a divalent hydrocarbon group A having 2 to 20 carbon atoms, which may contain some unsaturated bonds and / or aromatic rings, and constitutes a cycloalkylidene group or a cyclomethylenesilylene group, etc. Preferred specific examples include, for example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, etc.

[0061] In general formulas (1) and (2), M is a metal selected from Group 4 of the periodic table, and examples of M include titanium, zirconium, and hafnium. Q is selected in the same or different combination from halogens, hydrocarbon groups having 1 to 20 carbon atoms, anionic ligands, or neutral ligands that can coordinate with a lone pair of electrons. Specific examples of halogens include fluorine, chlorine, bromine, and iodine, and specific examples of hydrocarbon groups are the same as those mentioned above. Specific examples of anionic ligands include alkoxy groups such as methoxy, tert-butoxy, and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can coordinate with a lone pair of electrons include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, or ethers such as tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxyethane. Of these, Q may be the same or a different combination, but it is preferable that at least one is a halogen or alkyl group.

[0062] Component (C) consists of at least one compound (C-3) selected from the group consisting of an organoaluminum oxy compound (C-1), a compound (C-2) that reacts with the metallocene compound (A) to form an ion pair, and an organoaluminum compound. Furthermore, it may also consist of a particulate support (D) as needed.

[0063] Conventionally known aluminoxanes can be used as the organoaluminum oxy compound (C-1) to be used.

[0064] Compounds (C-2) that react with metallocene compounds (A) to form ion pairs (hereinafter sometimes abbreviated as "ionic compounds") include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Japanese Patent Publication No. 1-501950 and Japanese Patent Publication No. 2004-51676, among others. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

[0065] Specifically, examples include triphenylborone, tris(o-tolyl)borone, tris(p-tolyl)borone, tris(3,5-dimethylphenyl)borone, trimethylborone, triisobutylborone; and halogen-containing aryl group compounds such as tris(4-fluorophenyl)borone, tris(3,5-difluorophenyl)borone, tris(4-fluoromethylphenyl)borone, and tris(pentafluorophenyl)borone; trifluoroborone is an example.

[0066] Examples of organoaluminum compounds (C-3) that form polymerization catalysts for olefins include organoaluminum compounds represented by the following general formula (3).

[0067] Ra m Al(ORb) n H p Q q ...(3) (In the formula, Ra and Rb may be the same as or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms; Q represents a halogen atom; m is a number satisfying 0 < m ≦ 3, n is a number satisfying 0 ≦ n < 3, p is a number satisfying 0 ≦ p < 3, q is a number satisfying 0 ≦ q < 3, and m + n + p + q = 3.) An organoaluminum compound represented by the formula.

[0068] Specific examples of such compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, and triisobutylaluminum; dialkylaluminum hydrides such as diisopropylaluminum hydride and diisobutylaluminum hydride; and alkylaluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide.

[0069] As the organoaluminum compound (C-3), tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, and trioctylaluminum, and tri-branched chain alkylaluminums such as triisobutylaluminum are preferable, and trimethylaluminum and triisobutylaluminum are particularly preferably used.

[0070] In the present invention, the polymerization of the 1-butene / ethylene copolymer (A) 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 may be used. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, and decane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; or mixtures thereof can be used. Further, bulk polymerization using olefins containing 1-butene itself as a solvent can also be carried out.

[0071] When carrying out the polymerization, component (A) is usually 10 -8 ~10 -2moles, preferably 10 -7 ~10 -3 It is used in amounts that are molars. Component (C-1) is used in amounts such that the molar ratio [(C-1) / M] of component (C-1) to the transition metal atom (M) in component (A) is usually 0.01 to 5000, preferably 0.05 to 2000. Component (C-2) is used in amounts such that the molar ratio [(C-2) / M] of component (C-2) to the transition metal atom (M) in component (A) is usually 1 to 10, preferably 1 to 5. Component (C-3) is used in amounts such that the molar ratio [(C- 3 The amount of ) / M is usually used in amounts of 10 to 5000, preferably 20 to 2000.

[0072] The polymerization temperature is typically in the range of -50 to 200°C, preferably 0 to 100°C, and more preferably 20 to 100°C. If the polymerization temperature is too low, it tends to be industrially disadvantageous in terms of polymerization activity per unit catalyst and heat recovery efficiency.

[0073] The polymerization pressure is typically atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in batch, semi-continuous, or continuous manner. Furthermore, polymerization can be carried out in two or more stages with different reaction conditions.

[0074] Hydrogen can be added during polymerization to control the molecular weight and polymerization activity of the 1-butene-ethylene copolymer (A) produced, and the appropriate amount is approximately 0.001 to 100 NL per 1 kg of 1-butene-ethylene copolymer (A).

[0075] <Propylene-based polymer (B)> The propylene polymer (B), which is one of the components contained in the sealant resin composition (X) of the present invention, is preferably a propylene polymer (B-1) that satisfies the following requirements (B1) and (B2).

[0076] <Requirements (B1)> A melting point measured by differential scanning calorimeter is preferably between 100 and 170°C. teeth The temperature range is 130 to 170°C, more preferably 132 to 150°C.

[0077] A sealant resin composition containing a propylene-based polymer (B) whose melting point satisfies the above range exhibits excellent heat resistance, good transparency, and a moderately slow crystallization rate.

[0078] <Requirement (B2)> The isotactic pentad fraction (mmmm) is in the range of 80-99.9%, more preferably 85-99.9%, and even more preferably 90-99.9%.

[0079] A sealant resin composition (X) containing a propylene polymer (B) whose isotactic pentad fraction (mmmm) satisfies the above range exhibits good heat seal strength.

[0080] The propylene polymer (B) according to the present invention preferably has one or more of the following requirements (B3) and (B4) in addition to the above requirements (B1) and (B2), and more preferably has both (B3) and (B4).

[0081] <Requirements (B3)> The crystallization temperature is in the range of 40°C to 120°C, preferably 60°C to 120°C, and more preferably 80°C to 120°C.

[0082] When the crystallization temperature of the propylene polymer (B) according to the present invention is within the above range, the sealant resin composition (X) containing the propylene polymer (B) is preferable from the viewpoint of heat resistance, as it has good heat seal strength.

[0083] The crystallization temperature of the propylene polymer (B) according to the present invention is defined as the temperature of the peak observed during the second cooling process of a differential scanning calorimeter (DSC). Here, the measurement of the propylene polymer (B) with a differential scanning calorimeter (DSC) can be performed in the same manner as the "calorimetry with a differential scanning calorimeter (DSC)" described above in "Requirement (A5)". If an exothermic peak due to crystallization is observed during the cooling process (second cooling) between the first and second heating stages, the temperature at which this exothermic peak is observed is defined as the crystallization temperature.

[0084] <Requirements (B4)> Preferably, the melt flow rate (MFR), measured at a temperature of 230°C and a load of 2.16 kg, is in the range of 0.1 to 150 g / 10 min. More preferably, it is in the range of 0.5 to 100 g / 10 min, even more preferably 1 to 50 g / 10 min, and particularly preferably 2 to 25 g / 10 min.

[0085] When the MFR is within the above range, the resulting sealant resin composition (X) has good moldability and excellent heat seal strength.

[0086] The propylene-based polymer (B) according to the present invention can be a propylene homopolymer or a copolymer of propylene and at least one α-olefin having 2 to 20 carbon atoms other than propylene. Here, examples of α-olefins having 2 to 20 carbon atoms other than propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene, with ethylene or α-olefins having 4 to 10 carbon atoms being preferred.

[0087] The copolymer of propylene and these α-olefins may be a random copolymer (random polypropylene) or a block copolymer (block polypropylene). The constituent units derived from these α-olefins may be included in the copolymer of α-olefin and propylene in a proportion of 35 mol% or less, preferably 30 mol% or less.

[0088] The propylene polymer (B) is preferably composed of one or more selected from the group consisting of random copolymers and block copolymers. The propylene polymer (B) is preferably a random copolymer, a block copolymer, or a combination of a random copolymer and a block copolymer, with a random copolymer being more preferred.

[0089] Furthermore, the propylene polymer (B) may be a single type or a combination of two or more types. For example, it may consist only of a propylene polymer (B-1) that satisfies the above requirements (B1) and (B2), or it may be a combination of the propylene polymer (B-1) and a propylene polymer (B-2) that does not satisfy either or both of the above requirements (B1) and (B2).

[0090] The monomers (propylene and α-olefins with 2 to 20 carbon atoms excluding propylene) contained in the propylene polymer (B) may be monomers derived from fossil fuels, monomers derived from biomass, or a combination of monomers derived from fossil fuels and monomers derived from biomass.

[0091] The method for producing the propylene polymer (B) according to the present invention is not particularly limited, and includes well-known methods using well-known catalysts such as Ziegler-Natta catalysts and metallocene catalysts.

[0092] <Ethylene-based polymer (C)> The sealant resin composition (X) of the present invention may further contain an ethylene-based polymer (C). The ethylene-based polymer (C) contains 60 to 100 mol% of structural units derived from ethylene. Specific examples of the ethylene-based polymer (C) according to the present invention include high-pressure low-density polyethylene (C1) and ethylene-α-olefin copolymer (C2).

[0093] By using an ethylene-based polymer (C), the resulting sealant resin composition (X) can easily provide a sealant that exhibits a particularly good balance of impact resistance and transparency.

[0094] The monomers (ethylene and α-olefins with 3 to 20 carbon atoms) contained in the ethylene polymer (C) may be monomers derived from fossil fuels, monomers derived from biomass, or a combination of monomers derived from fossil fuels and monomers derived from biomass.

[0095] ≪High-Pressure Low-Density Polyethylene (C1)≫ As high-pressure low-density polyethylene (C1), any known material can be used without restriction. High-pressure low-density polyethylene is generally polyethylene obtained by radical polymerization of ethylene under high temperature and high pressure. The manufacturing method is not particularly limited, but examples include radical polymerization carried out under conditions of 500 to 2000 atmospheres and 150 to 300°C, where organic peroxides can be used as polymerization initiators.

[0096] High-pressure low-density polyethylene (C1) has a density of 900-925 kg / m³ as measured in accordance with ASTM D1505. 3 It is preferable that it be within the range of 910 to 925 kg / m². 3 That is the case.

[0097] When the density is above the lower limit, it exhibits excellent resistance to stickiness, and when it is below the upper limit, it exhibits excellent flexibility.

[0098] High-pressure low-density polyethylene (C1) has a melt flow rate (MFR) measured at 190°C and a 2.16 kg load in accordance with ASTM D1238, preferably 0.1 g / 10 min or more, more preferably 0.5 g / 10 min or more, particularly preferably 1.0 g / 10 min or more, preferably 50 g / 10 min or less, more preferably 30 g / 10 min or less, and particularly preferably 20 g / 10 min or less.

[0099] If the MFR is above the lower limit, the film-forming properties are excellent; if it is below the upper limit, the heat resistance properties are excellent.

[0100] High-pressure low-density polyethylene (C1) has a melting point, as measured by differential scanning calorimeter (DSC), preferably 104-130°C, more preferably 105-125°C, and even more preferably 106-120°C.

[0101] If the melting point is above the lower limit, it exhibits excellent resistance to stickiness and heat resistance; if it is below the upper limit, it exhibits excellent flexibility.

[0102] Ethylene-α-olefin copolymer (C2) Ethylene-α-olefin copolymer (C2) contains at least one structural unit derived from ethylene and one structural unit derived from α-olefins having 3 to 20 carbon atoms.

[0103] The content of ethylene-derived structural units in the ethylene-α-olefin copolymer (C2) is 60 to 99 mol%, preferably 65 to 99 mol%, more preferably 70 to 99 mol%, and particularly preferably 80 to 99 mol%.

[0104] When the ethylene content is above the lower limit, it exhibits excellent resistance to stickiness and heat resistance, while when it is below the upper limit, it exhibits excellent flexibility.

[0105] Ethylene-α-olefin copolymer (C2) is characterized by having fewer long-chain branched structures compared to high-pressure low-density polyethylene (C1), and is generally sometimes referred to as linear low-density polyethylene (LLDPE).

[0106] The content of constituent units derived from α-olefins having 3 to 20 carbon atoms in the ethylene-α-olefin copolymer (C2) is 1 to 40 mol%, preferably 1 to 35 mol%, more preferably 1 to 30 mol%, and particularly preferably 1 to 20 mol%.

[0107] When the content of α-olefins with 3 to 20 carbon atoms is above the lower limit, it exhibits excellent flexibility and impact resistance, while when it is below the upper limit, it exhibits excellent resistance to stickiness and heat resistance. These amounts are relative to 100 mole% of the total constituent units derived from ethylene and α-olefins with 3 to 20 carbon atoms.

[0108] When the content of the constituent units is within the aforementioned range, a sealant with a good balance of impact resistance and flexibility can be easily obtained.

[0109] Examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-nonadecene, and 1-eicosene. Among these, α-olefins having 3 to 10 carbon atoms are preferred, α-olefins having 3 to 8 carbon atoms are more preferred, propylene, 1-butene, and 1-octene are even more preferred, and propylene is particularly preferred.

[0110] The α-olefin having 3 to 20 carbon atoms may be used individually or in combination of two or more types.

[0111] In addition to the aforementioned constituent units, the ethylene-α-olefin copolymer (C2) may contain one or more constituent units derived from other polymerizable monomers, to the extent that it does not impair the objectives of the present invention.

[0112] Other polymerizable monomers include, for example, vinyl compounds such as styrene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids or their derivatives such as maleic anhydride; and unconjugated polyenes such as dicyclopentadiene, cyclohexadiene, and 5-ethylidene-2-norbornene.

[0113] Specific examples of ethylene-α-olefin copolymers (C2) include ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-propylene-ethylidenenorbornene copolymer, ethylene-1-butene-1-octene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, and ethylene-1-octene copolymer. Among these, ethylene-propylene copolymer and ethylene-1-butene copolymer are preferred, for example.

[0114] The density of the ethylene-α-olefin copolymer (C2) is preferably 840 kg / m³. 3 More preferably 850 kg / m 3 In particular, 855 kg / m³ is preferred. 3 The above is preferable, preferably 940 kg / m 3 More preferably, 899 kg / m 3 More preferably, 890 kg / m 3 The following is particularly preferred: 885 kg / m 3 The following applies:

[0115] When the density is within the aforementioned range, a sealant resin composition with a good balance of impact resistance, rigidity, and transparency can be easily obtained.

[0116] The density can be measured using the density gradient pipe method.

[0117] The MFR (measured according to ASTM D1238, at 190°C and under a 2.16 kg load) of the ethylene-α-olefin copolymer (C2) is preferably 0.01 g / 10 min or more, more preferably 0.1 g / 10 min or more, preferably 40 g / 10 min or less, more preferably 20 g / 10 min or less, and particularly preferably 10 g / 10 min or less.

[0118] When the MFR is within the aforementioned range, a sealant resin composition with a good balance of impact resistance, rigidity, and transparency can be easily obtained.

[0119] The MFR of ethylene-α-olefin copolymer (C2) was measured in accordance with ASTM D1238 at 190°C and under a load of 10 kg. 10 And the ratio with MFR2 measured under the conditions of 190℃ and a load of 2.16kg (MFR 10 The MFR2 is preferably 4.0 or higher, more preferably 5.0 or higher, preferably 8.0 or lower, and more preferably 7.0 or lower.

[0120] MFR 10 When / MFR2 is within the aforementioned range, a sealant resin composition with a good balance of transparency and impact resistance can be easily obtained.

[0121] Ethylene-α-olefin copolymers (C2) can be produced by conventionally known methods using vanadium-based catalysts, titanium-based catalysts, or metallocene-based catalysts. Preferably, production using metallocene-based catalysts yields copolymers with narrow molecular weight and compositional distributions, which are more favorable in terms of mechanical properties, transparency, and impact resistance.

[0122] The ethylene-α-olefin copolymer (C2) has a melting point, as measured by differential scanning calorimetry (DSC), preferably 30 to 100°C, more preferably 31 to 90°C, and even more preferably 32 to 80°C.

[0123] If the melting point is within the above range, a sealant resin composition with a good balance of transparency and impact resistance can be easily obtained.

[0124] <Sealant resin composition (X)> The sealant resin composition (X) of the present invention is a resin composition containing the above-mentioned 1-butene-ethylene copolymer (A) and propylene polymer (B), and the composition satisfies the following requirements (X1) and (X1-2).

[0125] <Requirements (X1)> The Shore D hardness measured in accordance with ASTM D2240 is in the range of 44 to 80, preferably 44 to 71.

[0126] A sealant resin composition whose Shore D hardness meets the above range will be a flexible sealant with good mechanical properties.

[0127] <Requirements (X1-2)> The sealant resin composition (X) of the present invention is not particularly limited in terms of its melt flow rate (MFR), which is measured in accordance with ASTM D1238 at 230°C and a load of 2.16 kg, but is, for example, in the range of 0.1 to 100 g / 10 min, more preferably 1 to 30 g / 10 min.

[0128] If the MFR of the sealant resin composition (X) of the present invention, measured at 230°C and a 2.16 kg load, falls within the above range, the sealant will have good moldability and good mechanical properties.

[0129] In particular, when fluidity is required, the MFR is preferably 20 to 100 g / 10 min, more preferably 20 to 50 g / 10 min. However, even when high fluidity is required, an MFR of 3 to 80 g / 10 min may be preferable.

[0130] Furthermore, when superior mechanical strength is required, the MFR is preferably 1 g / 10 min or more and less than 20 g / 10 min.

[0131] The sealant resin composition (X) of the present invention may further contain, if necessary, the above-mentioned ethylene polymer (C) in addition to the above-mentioned 1-butene-ethylene copolymer (A) and the above-mentioned propylene polymer (B).

[0132] Examples of the sealant resin composition (X) of the present invention include a composition comprising a 1-butene-ethylene copolymer (A) and a propylene polymer (B), a composition comprising a 1-butene-ethylene copolymer (A), a propylene polymer (B), and high-pressure low-density polyethylene (C1), a composition comprising a 1-butene-ethylene copolymer (A), a propylene polymer (B), and ethylene-α-olefin copolymer (C2), and a composition comprising a 1-butene-ethylene copolymer (A), a propylene polymer (B), high-pressure low-density polyethylene (C1), and ethylene-α-olefin copolymer (C2).

[0133] In addition to (X1) and (X1-2) above, the sealant resin composition (X) of the present invention may preferably satisfy one or more of the following (X2), (X3), and (X4).

[0134] <Requirements (X2)> Using a differential scanning calorimeter (DSC), the enthalpy of fusion ΔHfus generated when the temperature is first lowered to -70°C (first cooling), then raised from -70°C to 200°C at a heating rate of 20°C / min (first heating), held at 200°C for 10 minutes, then lowered to -70°C at a cooling rate of 20°C / min (second cooling), held at -70°C for 1 minute, and then raised again from -70°C to 200°C at a heating rate of 20°C / min (second heating) is in the range of 20 to 100 J / g. In an exemplary embodiment of the present invention, the first cooling performed before the first heating is carried out by lowering the temperature from 30°C to -70°C at a cooling rate of 20°C / min, and after this first cooling, the temperature is held at -70°C for 5 minutes, and then the first heating is performed.

[0135] <Requirements (X3)> The content of 1-butene-ethylene copolymer (A) is in the range of 1 to 50% by mass, the content of propylene polymer (B) is in the range of 30 to 99% by mass, and the content of ethylene polymer (C) is in the range of 0 to 20% by mass [provided that the total of 1-butene-ethylene copolymer (A), propylene polymer (B), and ethylene polymer (C) is 100% by mass].

[0136] <Requirements (X4)> The Young's modulus (YM), measured according to ASTM D638, is 1100 MPa or less. Preferably, it is 10 to 1100 MPa, more preferably 100 to 1050 MPa, and even more preferably 200 to 1000 MPa. Young's modulus is also called the tensile modulus of elasticity.

[0137] If the Young's modulus is below the upper limit, a sealant with excellent flexibility and resistance to whitening during stretching can be easily obtained. If the Young's modulus is above the lower limit, a sealant with excellent mechanical properties and heat resistance can be easily obtained.

[0138] Furthermore, the sealant resin composition (X) of the present invention may contain a 1-butene-ethylene copolymer (A) that satisfies any one or more of the above requirements (A1), (A2), (A3), and (A4).

[0139] The sealant resin composition (X) of the present invention preferably has a melting enthalpy ΔHfus measured by a differential scanning calorimeter (DSC) at the second heating stage in the range of 20 to 100 J / g, preferably 20 to 90 J / g, more preferably 30 to 85 J / g, and even more preferably 35 to 80 J / g.

[0140] Enthalpy of fusion is an indicator of crystallinity. If the enthalpy of fusion is below the upper limit, a sealant with low crystallinity, excellent flexibility, and superior resistance to whitening during stretching can be easily obtained. If the enthalpy of fusion is above the lower limit, a sealant with excellent mechanical properties and heat resistance can be easily obtained.

[0141] The sealant resin composition (X) of the present invention may optionally contain at least one additive selected from the group consisting of conventionally known fluidity modifiers, crystal nucleating agents, antioxidants, heat stabilizers, weather stabilizers such as ultraviolet absorbers and light stabilizers, hydrochloric acid absorbers, pigments, dyes, antibacterial agents, antifungal agents, antistatic agents, lubricants, slip agents, antiblocking agents, antifogging agents, foaming agents, foaming aids, plasticizers such as mineral oil, and fillers, to the extent that the objectives of the present invention are not impaired.

[0142] [Method for producing sealant resin composition (X)] The method for producing the sealant resin composition (X) of the present invention is not particularly limited, but for example, it may be a method of mixing the above 1-butene-ethylene copolymer (A), a propylene polymer (B), and optionally an ethylene polymer (C), and optionally other optional components in the above-mentioned proportions using, for example, a Henschel mixer, V-blender, ribbon blender, tumbler blender, kneader-ruder, etc., or by melt-kneading after or without mixing using a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, etc. preparation This can be done. Furthermore, granulation, crushing, etc. may be performed as needed.

[0143] When mixing or kneading these ingredients, each component may be added at once or in stages.

[0144] The method of melt mixing is not particularly limited and can generally be carried out using commercially available melt mixing equipment such as extruders. For example, the temperature of the mixing section in the melt mixing equipment is usually 170 to 250°C, preferably 190 to 230°C. The mixing time is usually 0.5 to 30 minutes, particularly preferably 0.5 to 5 minutes.

[0145] <Sealant film> The sealant film of the present invention is a single-layer or multi-layer sealant film comprising at least one layer containing the sealant resin composition (X) of the present invention.

[0146] A sealant film can be obtained using a sealant resin composition (X) by conventionally known single-layer or multi-layer film molding machines.

[0147] The sealant resin composition (X) of the present invention is a single layer Film shape However, it can be used as a sealant film, but it is laminated with a base film made of polyolefin resin or the like to form a multilayer film. Shape It can also be used as a sealant film. That is, the sealant film of the present invention may be a single-layer or multi-layer film consisting only of a layer made of the sealant resin composition (X) of the present invention, or it may be a laminate including a layer made of the sealant resin composition (X) of the present invention and a layer made of a base film.

[0148] Examples of base films made of the above-mentioned polyolefin resin include single-layer or multi-layer films of polyolefin resin (e.g., polyethylene, polypropylene), polyester resin, polycarbonate resin, polyarylate resin, acrylic resin, polyphenylene sulfide resin, polystyrene resin, vinyl resin, vinyl chloride resin, polyimide resin, epoxy resin, etc. In a preferred and exemplary embodiment of the present invention, the base film is at least one selected from the group consisting of polyolefin film, polystyrene film, polyester film, polyamide film, laminated film of polyolefin and gas barrier resin film, metal foil such as aluminum foil, paper, and vapor-deposited film.

[0149] A laminate comprising a layer made of the sealant resin composition (X) of the present invention and a layer made of a base film can also be manufactured using a conventionally known single-layer or multi-layer film molding machine. For example, the laminate can be manufactured by bonding the sealant film layer and the base film by any of the methods selected from the group consisting of melt extrusion lamination, thermal lamination, and dry lamination. In a typical and exemplary embodiment of the present invention, the laminate can be obtained by a manufacturing method that includes the step of bonding a single-layer or multi-layer film consisting only of a layer made of the sealant resin composition (X) of the present invention and the base film by any of the methods selected from the group consisting of melt extrusion lamination, thermal lamination, and dry lamination.

[0150] The sealant film containing the sealant resin composition (X) of the present invention may be either a stretched film or an unstretched film, but it is preferably an unstretched film.

[0151] The unoriented film is not particularly limited as long as it is an unstretched film, and its shape, size (thickness), etc., can be appropriately selected according to the desired application. Furthermore, the unoriented film may be a single layer or a multilayer film. If it is a multilayer film, at least one of the layers may be a film containing the sealant resin composition (X) of the present invention. That is, the unoriented film may be a single-layer or multilayer film consisting only of a layer made of the sealant resin composition (X) of the present invention, or it may be a laminate containing a layer made of the sealant resin composition (X) of the present invention and a layer made of a substrate.

[0152] The method for producing the unoriented film is not particularly limited as long as the objective of the present invention is not impaired. The unoriented film may be produced by co-extruding using known multilayer film molding methods such as the T-die film molding method or the inflation film molding method, or by laminating a layer containing the sealant resin composition (X) of the present invention onto a pre-molded substrate. heightThis includes, for example, the unstretched film may be obtained by a manufacturing method that includes a step of laminating a substrate with a layer of a single-layer or multi-layer sealant film (for example, a single-layer or multi-layer film consisting only of layers made of the sealant resin composition (X) of the present invention), which includes at least one layer containing the sealant resin composition (X), by melt extrusion lamination, thermal lamination, and dry lamination.

[0153] The base material is not particularly limited, but it may be a metal such as aluminum foil, steel foil, or stainless steel foil, or it may be a thermoplastic resin. The base material often takes the form of a base film, and may be a base film as exemplified above as "a base film made of polyolefin resin, etc.," or it may be a metal foil such as aluminum foil. When the unoriented film is multilayered, "unoriented" means that none of the layers are stretched.

[0154] The thickness of the unstretched film (total thickness in the case of a multilayer film) is preferably 5 μm or more, more preferably 10 μm or more, even more preferably 20 μm or more, preferably 150 μm or less, more preferably 130 μm or less, and even more preferably 100 μm or less.

[0155] In this specification, there is no particular distinction made between film and sheet, but generally, a film refers to a membrane-like material with a thickness of less than 250 μm, and a sheet refers to a thin plate-like material with a thickness of 250 μm or more.

[0156] Specific applications of the aforementioned unoriented film include, for example, packaging films for packaging food, liquids, pharmaceuticals, electronic components, etc., and packaging materials obtained therefrom.

[0157] <Applications of sealant film> The sealant film and laminates of the sealant film and a base film laminated together (for example, a single-layer or multi-layer sealant film consisting only of a layer made of the sealant resin composition (X), and a laminate including a layer made of the sealant resin composition (X) and a layer made of a base film) of the present invention can be suitably used as packaging for all kinds of articles, including daily necessities, food (food packaging materials), liquids, pharmaceuticals, electronic components, and building materials, by taking advantage of the properties of the sealant film. Furthermore, the sealant film and the laminate may be included in energy storage devices such as lithium-ion batteries and lithium-ion capacitors, and can be suitably used, for example, as packaging for lithium-ion batteries. From another perspective, the present invention can also be said to provide an energy storage device containing the sealant resin composition (X). An example of such an energy storage device is an energy storage device containing the sealant film or the laminate, and a specific example thereof is packaging for lithium-ion batteries containing the sealant film or the laminate.

[0158] A lithium-ion battery typically contains a positive electrode, a negative electrode, a separator between the positive and negative electrodes, and a non-aqueous electrolyte. The positive electrode usually includes a positive electrode current collector made of a metallic or carbon material, and a positive electrode active material capable of intercalating and releasing lithium, such as a composite oxide made of lithium and a transition metal. The negative electrode usually includes a negative electrode current collector made of a carbon material, and a negative electrode active material capable of intercalating and releasing lithium ions, such as metallic lithium, a lithium-containing alloy, or a metal or alloy that can be alloyed with lithium. The non-aqueous electrolyte contains a lithium salt as an electrolyte and a non-aqueous solvent. In a lithium-ion battery, the positive electrode, the negative electrode, and the separator are impregnated with the non-aqueous electrolyte. Details regarding the non-aqueous solvent will be described later in the section "Non-aqueous Solvent".

[0159] In most cases, lithium-ion batteries have packaging (packaging for lithium-ion batteries) around their periphery, and the positive electrode, negative electrode, separator, and non-aqueous electrolyte are sealed inside the packaging. Typically, the positive electrode and negative electrode are connected to positive and negative electrode terminals, respectively, with a portion of the positive and negative electrode terminals exposed to the outside of the packaging.

[0160] When the sealant film or laminate of the present invention is used as the packaging, a lithium-ion battery is obtained by sandwiching the positive electrode and the negative electrode, etc., between a pair of sealant films or a pair of laminates, and heat-sealing the peripheral edges of the pair of sealant films or a pair of laminates in such a manner that a portion of the positive electrode terminal and a portion of the negative electrode terminal are exposed to the outside of the pair of sealant films or a pair of laminates. Here, when the laminate of the present invention is used as the packaging, the laminate may include a base material made of metal such as aluminum foil.

[0161] Lithium-ion batteries using lithium-ion battery packaging can be used, for example, in portable electronic devices, personal computers, robots, drones, automobiles, aircraft, wearable devices, and energy storage systems (ESS) for home or renewable energy generation.

[0162] <Non-aqueous solvent> Non-aqueous electrolytes for lithium-ion batteries generally contain a non-aqueous solvent.

[0163] Various known non-aqueous solvents can be appropriately selected, but it is preferable to use at least one selected from the group consisting of cyclic aprotic solvents and chain-like aprotic solvents.

[0164] To improve battery safety, if the goal is to raise the flash point of the solvent, it is preferable to use a cyclic aprotic solvent as the non-aqueous solvent.

[0165] (Cyclic aprotic solvent) As cyclic aprotic solvents, cyclic carbonates, cyclic carboxylic acid esters, cyclic sulfones, and cyclic ethers can be used.

[0166] The cyclic aprotic solvent may be used alone or in a mixture of several types. The mixing ratio of the cyclic aprotic solvent in the non-aqueous solvent is 10% to 100% by mass, more preferably 20% to 90% by mass, and particularly preferably 30% to 80% by mass. By using such a ratio, the conductivity of the electrolyte, which is related to the charge and discharge characteristics of the battery, can be increased.

[0167] Examples of cyclic carbonates include ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, and 2,3-pentylene carbonate. Of these, ethylene carbonate and propylene carbonate, which have high dielectric constants, are preferably used. In the case of batteries using graphite as the negative electrode active material, ethylene carbonate is more preferable. Furthermore, two or more of these cyclic carbonates may be used in mixture form.

[0168] Examples of cyclic carboxylic acid esters include γ-butyrolactone, δ-valerolactone, or alkyl-substituted derivatives such as methyl-γ-butyrolactone, ethyl-γ-butyrolactone, and ethyl-δ-valerolactone.

[0169] Cyclic carboxylic acid esters have low vapor pressure, low viscosity, and high dielectric constant, and can reduce the viscosity of the electrolyte without lowering the flash point or the degree of dissociation of the electrolyte. Therefore, they have the characteristic of being able to increase the conductivity of the electrolyte, which is an indicator related to the charge-discharge characteristics of the battery, without increasing the flammability of the electrolyte. For this reason, when aiming to improve the flash point of the solvent, it is preferable to use a cyclic carboxylic acid ester as the cyclic aprotic solvent. γ-Butyrolactone is the most preferred.

[0170] Furthermore, cyclic carboxylic acid esters are preferably used in mixture with other cyclic aprotic solvents. For example, a mixture of a cyclic carboxylic acid ester with a cyclic carbonate and / or a linear carbonate is used.

[0171] Examples of combinations of cyclic carboxylic acid esters with cyclic carbonates and / or linear carbonates include, specifically, γ-butyrolactone and ethylene carbonate, γ-butyrolactone and ethylene carbonate and dimethyl carbonate, γ-butyrolactone and ethylene carbonate and methyl ethyl carbonate, γ-butyrolactone and ethylene carbonate and diethyl carbonate, γ-butyrolactone and propylene carbonate, γ-butyrolactone and propylene carbonate and dimethyl carbonate, and γ-butyrolactone and propylene carbonate and methyl ethyl carbonate. Diethyl carbonate, γ-butyrolactone and propylene carbonate and diethyl carbonate, γ-butyrolactone and ethylene carbonate and propylene carbonate, γ-butyrolactone and ethylene carbonate and propylene carbonate and dimethyl carbonate, γ-butyrolactone and ethylene carbonate and propylene carbonate and methyl ethyl carbonate, γ-butyrolactone and ethylene carbonate and propylene carbonate and diethyl carbonate, γ-butyrolactone and ethylene carbonate and dimethyl carbonate and methyl ethyl carbonate Gamma-butyrolactone and ethylene carbonate and dimethyl carbonate and diethyl carbonate, gamma-butyrolactone and ethylene carbonate and methyl ethyl carbonate and diethyl carbonate, gamma-butyrolactone and ethylene carbonate and dimethyl carbonate and methyl ethyl carbonate and diethyl carbonate, gamma-butyrolactone and ethylene carbonate and propylene carbonate and dimethyl carbonate and methyl ethyl carbonate, gamma-butyrolactone and ethylene carbonate and propylene carbonate and dimethyl carbonate γ-Butyrolactone and diethyl carbonate, γ-Butyrolactone and ethylene carbonate and propylene carbonate and methyl ethyl carbonate and diethyl carbonate, γ-Butyrolactone and ethylene carbonate and propylene carbonate and dimethyl carbonate and methyl ethyl carbonate and diethyl carbonate, γ-Butyrolactone and sulfolane, γ-Butyrolactone and ethylene carbonate and sulfolane, γ-Butyrolactone and propylene carbonate and sulfolane, γ-Butyrolactone and ethylene carbonate and propylene carbonate and sulfolane,Examples include γ-butyrolactone, sulfolane, and dimethyl carbonate.

[0172] Examples of cyclic sulfones include sulfolane, 2-methylsulfolane, 3-methylsulfolane, dimethylsulfone, diethylsulfone, dipropylsulfone, methylethylsulfone, and methylpropylsulfone. Dioxolane can be cited as an example of a cyclic ether.

[0173] (Chain-like aprotic solvent) Examples of chain-like aprotic solvents include chain-like carbonates, chain-like carboxylic acid esters, chain-like ethers, and chain-like phosphate esters.

[0174] The mixing ratio of the chain-like aprotic solvent in the non-aqueous solvent is 10% to 100% by mass, more preferably 20% to 90% by mass, and particularly preferably 30% to 80% by mass.

[0175] Specific examples of chain-like carbonates include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, dipropyl carbonate, methyl butyl carbonate, ethyl butyl carbonate, dibutyl carbonate, methyl pentyl carbonate, ethyl pentyl carbonate, dipentyl carbonate, methyl heptyl carbonate, ethyl heptyl carbonate, diheptyl carbonate, methyl hexyl carbonate, ethyl hexyl carbonate, dihexyl carbonate, methyl octyl carbonate, ethyl octyl carbonate, dioctyl carbonate, and methyl trifluoroethyl carbonate. Two or more of these chain-like carbonates may be used in combination.

[0176] Examples of linear carboxylic acid esters include methyl pivalate. Examples of chain-like ethers include dimethoxyethane.

[0177] Examples of chain-like phosphate esters include trimethyl phosphate.

[0178] (combination of solvents) The non-aqueous electrolyte may contain only one type of non-aqueous solvent, or it may contain two or more types.

[0179] Furthermore, using only one or more cyclic aprotic solvents, or using only one or more linear aprotic solvents, or using a cyclic aprotic solvent and a linear Non A mixture of protic solvents may be used. When particularly aiming to improve the load characteristics and low-temperature characteristics of the battery, it is preferable to use a combination of a cyclic aprotic solvent and a chain-like aprotic solvent as the non-aqueous solvent.

[0180] Furthermore, due to the electrochemical stability of the electrolyte, it is most preferable to use cyclic carbonates for cyclic aprotic solvents and linear carbonates for linear aprotic solvents. Additionally, the conductivity of the electrolyte, which is related to the battery's charge-discharge characteristics, can also be improved by combining cyclic carboxylic acid esters with cyclic carbonates and / or linear carbonates.

[0181] Specifically, combinations of cyclic carbonates and linear carbonates include: ethylene carbonate and dimethyl carbonate, ethylene carbonate and methyl ethyl carbonate, ethylene carbonate and diethyl carbonate, propylene carbonate and dimethyl carbonate, propylene carbonate and methyl ethyl carbonate, propylene carbonate and diethyl carbonate, ethylene carbonate, propylene carbonate and methyl ethyl carbonate, ethylene carbonate, propylene carbonate and diethyl carbonate, ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, and ethylene carbonate and dimethyl carbonate. Examples include diethyl carbonate, ethylene carbonate and methyl ethyl carbonate and diethyl carbonate, ethylene carbonate and dimethyl carbonate and methyl ethyl carbonate and diethyl carbonate, ethylene carbonate and propylene carbonate and dimethyl carbonate and methyl ethyl carbonate, ethylene carbonate and propylene carbonate and dimethyl carbonate and diethyl carbonate, ethylene carbonate and propylene carbonate and methyl ethyl carbonate and diethyl carbonate, ethylene carbonate and propylene carbonate and dimethyl carbonate and methyl ethyl carbonate and diethyl carbonate, and ethylene carbonate and propylene carbonate and dimethyl carbonate and methyl ethyl carbonate and diethyl carbonate.

[0182] The mixing ratio of cyclic carbonate to linear carbonate, expressed as a mass ratio, is 5:95 to 80:20, more preferably 10:90 to 70:30. By using this ratio, the increase in viscosity of the electrolyte can be suppressed and the degree of dissociation of the electrolyte can be increased, thereby improving the conductivity of the electrolyte, which is related to the charge and discharge characteristics of the battery. Furthermore, the solubility of the electrolyte can be further increased. Therefore, an electrolyte with excellent electrical conductivity at room temperature or low temperature can be obtained, and the load characteristics of the battery can be improved from room temperature to low temperature.

[0183] Lithium-ion batteries contain a non-aqueous electrolyte containing the non-aqueous solvent described above. Therefore, the packaging for lithium-ion batteries (lithium-ion battery packaging) must be resistant to elution into the non-aqueous solvent and swelling caused by the non-aqueous solvent, and must maintain a certain level of mechanical strength even when exposed to contact with the non-aqueous solvent. The sealant film and laminate of the present invention, containing the sealant resin composition (X), exhibit excellent whitening resistance, are resistant to elution into the non-aqueous solvent and swelling caused by the non-aqueous solvent, and maintain a certain level of mechanical strength even when exposed to contact with the non-aqueous solvent. Therefore, they can be suitably used as packaging for lithium-ion batteries. [Examples]

[0184] The present invention will be described in more detail below based on examples, but the present invention is not limited in any way to these examples.

[0185] The polymers used in the examples and comparative examples are shown below.

[0186] [1-Butene-ethylene copolymer (A)] 1-butene-ethylene copolymers (A-1) to (A-6) obtained by the manufacturing example described later were used. (A-1); 1-Butene-ethylene copolymer (ethylene content: 14.6 mol%, MFR (190℃, 2.16 kg load): 3.0 g / 10 min, intrinsic viscosity [η]: 1.72 dl / g, mmmm fraction: 95.9%) (A-2); 1-Butene-ethylene copolymer (ethylene content: 14.3 mol%, MFR (190℃, 2.16 kg load): 1.1 g / 10 min, intrinsic viscosity [η]: 2.14 dl / g, mmmm fraction: 96.2%) (A-3); 1-Butene-ethylene copolymer (ethylene content: 12.2 mol%, MFR (190℃, 2.16 kg load): 3.3 g / 10 min, intrinsic viscosity [η]: 1.68 dl / g, mmmm fraction: 94.6%) (A-4); 1-Butene-ethylene copolymer (ethylene content 10.1 mol%, MFR (190℃, 2.16 kg load): 3.0 g / 10 min, intrinsic viscosity [η]: 1.68 dl / g, mmmm fraction: 93.6%) (A-5); 1-Butene-ethylene copolymer (ethylene content 8.1 mol%, MFR (190℃, 2.16 kg load): 3.1 g / 10 min, intrinsic viscosity [η]: 1.65 dl / g, mmmm fraction: 92.8%) (A-6); 1-Butene-ethylene copolymer (ethylene content 5.7 mol%, MFR (190℃, 2.16 kg load): 3.0 g / 10 min, intrinsic viscosity [η]: 1.66 dl / g, mmmm fraction: 92.3%)

[0187] [Propylene polymer (B)] As the propylene polymer (B), random polypropylene (manufactured by Prime Polymer Co., Ltd., trade name Prime PolyPro F327, MFR (230℃, 2.16kg load): 7g / 10min, melting point: 140℃, crystallization temperature: 93℃, mmmm: 95.3%) (B-1) was used.

[0188] [Ethylene-based polymer (C)] As an ethylene polymer (C), High-pressure low-density polyethylene (manufactured by Mitsui Dow Polychemicals, product name Mirason 11P, MFR (190℃, 2.16kg load) 7.2g / 10min, density: 0.917g / cm³) 3 (917kg / m 3 ), melting point: 108℃) (C-1), or, Ethylene-propylene copolymer (MFR (190℃, 2.16kg load): 0.6g / 10min, density: 0.869g / cm³) 3 (869kg / m 3 (Propylene content: 19 mol%, Melting point: 40℃) (C-2) I used it.

[0189] [Other ingredients] As another component, propylene-ethylene copolymer (ethylene content 20.6 mol%, MFR (190℃, 2.16 kg load): 1.4 g / 10 min, melting point 44℃) (PER) was used.

[0190] 《Example of production of 1-butene-ethylene copolymer (A)》 [Manufacturing Example 1] n-hexane is supplied at a rate of 14.2 L / h to one feed port of a 300-liter continuous polymerizer, and a mixed hexane solution of isopropylidene (3-tert-butyl-5-methylcyclopentadienyl-fluorenyl) zirconium dichloride (main catalyst 1), modified methylaluminoxane, and triisobutylaluminum (main catalyst 1) is supplied from the other feed port. of A zirconium equivalent concentration of 0.5 mmol / L, a modified methylaluminoxane equivalent to 4 mmol / L, and a triisobutylaluminum equivalent to 100 mmol / L were continuously supplied at 0.22 L / h (total hexane 10 L / h). Simultaneously, 1-butene was continuously supplied at a rate of 27 kg / h, ethylene at 1.0 kg / h, and hydrogen at 0.6 NL / h from another supply port of the polymerizer. Continuous solution polymerization was carried out under conditions of polymerization temperature of 60°C, polymerization pressure of 0.8 MPaG, and residence time of 1.5 hours to obtain 1-butene-ethylene copolymer (A-1).

[0191] [Manufacturing Example 2] 1-butene-ethylene copolymer (A-2) was produced in the same manner as in the production method of Production Example 1, except that the 1-butene was adjusted to 27 kg / h, the ethylene to 0.9 kg / h, and the hydrogen to 0.1 NL / h.

[0192] [Manufacturing Example 3] 1-butene-ethylene copolymer (A-3) was produced in the same manner as in the production method of Production Example 1, except that the 1-butene was adjusted to 27 kg / h, the ethylene to 0.8 kg / h, and the hydrogen to 0.6 NL / h.

[0193] [Manufacturing Example 4] 1-butene-ethylene copolymer (A-4) was produced in the same manner as in the production method of Production Example 1, except that the 1-butene was adjusted to 27 kg / h, the ethylene to 0.7 kg / h, and the hydrogen to 0.7 NL / h.

[0194] [Manufacturing Example 5] 1-butene-ethylene copolymer (A-5) was produced in the same manner as in the production method of Production Example 1, except that the amount of 1-butene was adjusted to 27 kg / h, ethylene to 0.6 kg / h, and hydrogen to 0.7 NL / h, and the polymerization pressure was set to 0.7 MPaG.

[0195] [Manufacturing Example 6] 1-butene-ethylene copolymer (A-6) was produced in the same manner as in the production method of Production Example 1, except that the 1-butene was adjusted to 27 kg / h, ethylene to 0.4 kg / h, and hydrogen to 0.6 NL / h, and the polymerization pressure was set to 0.6 MPaG.

[0196] The physical properties of the 1-butene-ethylene copolymer (A) obtained in the manufacturing example were measured by the following method. The results are shown in Table 1.

[0197] [Table 1]

[0198] [1-butene and ethylene content in 1-butene-ethylene copolymer (A)] The quantification of 1-butene and ethylene content was performed using a Bruker BioSpin AVANCE cryo-500 nuclear magnetic resonance spectrometer as follows: o-dichlorobenzene / deuterated benzene (volume ratio: 80 / 20) mixed solvent, sample concentration 20 mg / 0.6 mL, measurement temperature 120°C, observation. nuclear teeth 13 The C (125 MHz) sequence was single-pulse proton broadband decoupling, with a pulse width of 4.7 μs (45° pulse), a repetition time of 5.5 seconds, 128 integration cycles, and a chemical shift reference value of 27.50 ppm for the carbon signal of the butene side-chain methylene group. 13The composition of 1-butene (C4 content; mol%) and ethylene (C2 content; mol%) was quantified by 13C-NMR spectroscopy.

[0199] [MFR of 1-butene-ethylene copolymer (A)] MFR was measured at 190°C and a 2.16 kg load in accordance with ASTM D1238.

[0200] [IsoTactic Pen] Ta ッ Do [Measurement of fractions (mmmm)] The pentad isotacticity (mmmm) of 1-butene-ethylene copolymer (A) was calculated using the following formula, assuming a chemical shift of 27.5 ppm at the peak top of the pentads represented in mmmm. This involved determining the peak area S with a peak top of 27.5 ppm and the total peak area S' appearing in the range of 27.3 ppm to 26.3 ppm. (Detection limit: 0.01%) (mmmm) = S / (S+S') × 100(%) Here, the main peaks appearing in the range of 27.3 ppm to 26.3 ppm are attributed to mmmr (27.3 ppm), mmrr and rmmr (27.2 ppm), and mrrm (26.3 ppm).

[0201] [Intrinsic viscosity [η](dl / g)] 1-Butene-ethylene copolymer (A) intrinsic viscosity [η] This value was measured using an Ubbelohde viscometer in decalin solvent at 135°C. Polymerization powder 、 Approximately 20 mg of pellets or resin lumps were taken and dissolved in 15 mL of decalin. The specific viscosity ηsp was measured in an oil bath heated to 135°C. After diluting this decalin solution by adding 5 mL of decalin solvent, the specific viscosity ηsp was measured again in the same manner. This dilution procedure was repeated two more times, and the intrinsic viscosity [η] was calculated as the ηsp / C value when the concentration (C) was extrapolated to zero. [η] = lim(ηsp / C) (C→0)

[0202] [Weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn)] A Waters Alliance GPC-2000 gel permeation chromatograph was used as the GPC instrument, and Mw and Mn in polystyrene equivalent were measured under the following conditions, and the Mw / Mn ratio was calculated.

[0203] Separation columns: Two TSKgel GNH6-HT columns and two TSKgel GNH6-HTL columns manufactured by Tosoh Corporation (both columns are 7.5 mm in diameter and 300 mm in length). Column temperature: 140℃ Mobile phase: o-dichlorobenzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) containing 0.025% by weight of BHT (manufactured by Takeda Pharmaceutical Company Limited) as an antioxidant. Travel speed: 1.0mL / min Sample concentration: 15 mg / 10 mL Sample injection volume: 400 μL Detector: Differential refractometer Standard polystyrene: Molecular weight Mw < 1000, and Mw > 4 × 10⁻¹⁰ 6 In this case, use products manufactured by Tosoh Corporation, with a molecular weight of 1000 ≤ Mw ≤ 4 × 10 6 In this case, a product from Pressure Chemical Co., Ltd. was used.

[0204] [Press forming conditions] Press sheets prepared under the following conditions and stored at room temperature for more than 10 days were used in the tests. In the following tests, unless otherwise specified, the press sheets stored at room temperature for more than 10 days were used as test specimens or test specimens for mechanical properties.

[0205] Press machine: Manufactured by Kansai Roll Co., Ltd. (Model number: PEWE-70 / 50 35) Preheating time: 4 min Preheating and pressurizing temperature: 120℃ Pressure: 10 MPa Pressurization time: 3 min Cooling rate: 40°C / min (Pressurized at 10 MPa for 4 minutes in a separate press machine set to 20°C, then cooled to room temperature)

[0206] [Melting point and enthalpy of melting] The melting point and enthalpy of melting ΔHfus (1st, 2nd) were measured using the measurement method described above (i.e., the measurement method described in the "Requirement (A5)" section above).

[0207] Specifically, the calorimetry of polymers such as 1-butene-ethylene copolymer (A) using differential scanning calorimeter (DSC) was performed by accurately weighing approximately 6-10 mg of the sample, sealing it in an aluminum pan, first cooling it to -70°C (first cooling), then heating it from -70°C to 200°C at a rate of 20°C / min (first heating), measuring the DSC curve, holding it at 200°C for 10 minutes, then cooling it to -70°C at a rate of 20°C / min (second cooling), measuring the DSC curve, holding it at -70°C for 1 minute, and then heating it again from -70°C to 200°C at a rate of 20°C / min (second heating), measuring the DSC curve. Here, the first cooling, performed before the first heating, was done by first cooling it from 30°C to -70°C at a rate of 20°C / min, holding it at -70°C for 5 minutes, and then performing the first heating.

[0208] Here, DSC measurements of polymers such as 1-butene-ethylene copolymer (A) were performed using an X-DSC7000 (differential scanning calorimeter, manufactured by Hitachi High-Tech Science Corporation).

[0209] Furthermore, in the DSC curve, if an endothermic peak (melting peak) due to melting is observed during the first heating phase, the temperature at which this melting peak (hereinafter referred to as "melting peak P1") is observed, specifically the temperature at the peak of "melting peak P1", was defined as Tm1 or "melting point (1st)". If a melting peak is observed during the second heating phase, the temperature at which this melting peak (hereinafter referred to as "melting peak P2") is observed, specifically the temperature at the peak of "melting peak P2", was defined as Tm2 or "melting point (2nd)". Here, if two or more melting peaks are observed for each of "melting peak P1" and "melting peak P2", the highest temperature among the peak temperatures of these peaks was defined as the melting point.

[0210] Furthermore, if the "melting peak P1" exists in the DSC curve, the enthalpy of melting determined for that melting peak P1 was defined as ΔHfus(1st) or "enthalpy of melting (1st)". Similarly, if the "melting peak P2" exists, the enthalpy of melting determined for that melting peak P2 was defined as ΔHfus(2nd) or "enthalpy of melting (2nd)".

[0211] Furthermore, if no crystalline melting peak with a crystalline melting enthalpy of 1 J / g or more was observed as "melting peak P1" or "melting peak P2," it was determined to be either "no melting peak observed" or "na."

[0212] [Mechanical properties (at room temperature)] The aforementioned test specimens for mechanical properties were subjected to yield stress, fracture strength (TS), elongation at fracture (between chucks, EL), and Young's modulus (YM) measurements in accordance with JIS K 6251 (measurement temperature 23°C, tensile speed = 200 mm / min, maximum strain = 800%). For specimens that did not fracture at 800% strain, the stress at that point was defined as the TS.

[0213] [Shore A hardness (instantaneous value) and Shore D hardness] Using a Type A measuring instrument, the scale was read immediately after contact with the test specimen with the indenter, and the Shore A hardness was determined (in accordance with ASTM D2240).

[0214] Using a Type D measuring instrument, the Shore D hardness was determined by reading the maximum value on the scale after contacting the test specimen with the indenter (in accordance with ASTM D2240).

[0215] During press molding, a 100 μm thick release PET film (manufactured by Toray, product name Lumirror) was used as the release film.

[0216] The physical properties of the sealant resin compositions obtained in the examples and comparative examples were measured by the following method. The results are shown in Tables 2-1 and 2-2.

[0217] [Melting point and enthalpy of fusion (sealant resin composition)] The measurement method described above (i.e., the measurement method described in the "Requirement (X2)" section above) determines the melting point and enthalpy of melting ΔHfus(2nd) of It was measured.

[0218] Specifically, the melting point and enthalpy of melting of the sealant resin composition (X) were measured by DSC measurement. This DSC measurement was performed using an X-DSC7000 (differential scanning calorimeter, manufactured by Hitachi High-Tech Science Corporation) in the same manner as described above in "Melting Point and Enthalpy of Melting". Then, the "2nd melting point" and "2nd enthalpy of melting" were determined from the DSC curve obtained by the DSC measurement in the same manner as described above in "Melting Point and Enthalpy of Melting".

[0219] In comparative examples where a single polymer was used instead of the sealant resin composition (X), similar DSC measurements were performed on the polymer.

[0220] [Tensile modulus of elasticity (sealant resin composition)] Using a φ40 mm single-screw extruder, pellets were prepared by melt-kneading various polymers in the proportions (parts by mass) listed in Tables 2-1 and 2-2 under conditions of a melting temperature of 210°C and a rotation speed of 40-50 rpm. The sealant resin composition (X) obtained in pellet form was heated for 5 minutes using a hydraulic hot press molding machine set to 190°C, molded for 2 minutes under a pressure of 10 MPa, and then cooled for 4 minutes under a pressure of 10 MPa at 20°C to produce a 2 mm thick sheet (test specimen). In comparative examples where a single polymer was used instead of the sealant resin composition (X), pellets and sheets (test specimens) were prepared similarly for that polymer.

[0221] After molding, the test pieces were stored at room temperature for 7 days or more, and then dumbbell-shaped test pieces (Type ASTM-4) specified in ASTM D638 were prepared from this sheet. For the dumbbell-shaped test pieces, a tensile test was conducted in accordance with ASTM D638 (measurement temperature: 23 °C, tensile speed = 50 mm / min), and the tensile modulus (Young's modulus (YM)) was determined from the obtained stress / strain curve.

[0222] [Shore D hardness (sealant resin composition)] Using a φ40 mm single-screw extruder, pellets were prepared by melt-kneading various polymers in the proportions (parts by mass) described in Tables 2-1 and 2-2 under the conditions of a melting temperature of 210 °C and a rotation speed of 40 to 50 rpm. The sealant resin composition (X) obtained in the form of the pellets was heated for 5 minutes using a hydraulic hot press molding machine set at 190 °C, then molded under a pressure of 10 MPa for 2 minutes, and then cooled under a pressure of 10 MPa at 20 °C for 4 minutes to prepare a 2-mm-thick sheet (test piece). Here, in the comparative example where a single polymer was used instead of the sealant resin composition (X), pellets and a sheet (test piece) were similarly prepared for the polymer.

[0223] After molding, the test pieces were stored at room temperature for 7 days or more, and then the Shore D hardness was measured.

[0224] [MFR (sealant resin composition)] In accordance with ASTM D1238, the MFR at 230 °C and a load of 2.16 kg was measured.

[0225] [Anti-whitening test] Pellets were prepared by melt-kneading various polymers in the proportions (parts by mass) listed in Tables 2-1, 2-2, and 3, using a φ40 mm single-screw extruder, under conditions of a melting temperature of 210°C and a rotation speed of 40-50 rpm. A 0.5 mm thick sheet (test specimen) was prepared by heating the sealant resin composition (X) obtained in pellet form for 5 minutes using a hydraulic hot press molding machine set to 190°C, molding it under a pressure of 10 MPa for 2 minutes, and then cooling it under a pressure of 10 MPa at 20°C for 4 minutes. In comparative examples where a single polymer was used instead of the sealant resin composition (X), pellets and sheets (test specimens) were prepared similarly for that polymer.

[0226] The resulting sheets (test specimens) were stored at room temperature for at least 7 days after molding.

[0227] From the sheet, a No. 2 dumbbell (dumbbell-shaped No. 2 dumbbell test piece) as specified in JIS K 6251 was prepared, and the hue before stretching (L value (before stretching)) and the hue after stretching it by 15 mm at a tensile speed of 50 mm / min (L value (after stretching)) were measured using a spectrophotometer (Konica Minolta, Inc., CM-3700d), and the hue change (ΔL) was calculated based on the following formula.

[0228] Furthermore, the hue change (ΔL) was similarly calculated using sheets that had been heat-treated at 85°C for 5 days.

[0229] A smaller ΔL value indicates better resistance to whitening. The results are shown in Table 1.

[0230] Evaluation criteria for whitening resistance ΔL = L value (after stretching) - L value (before stretching) ○:ΔL≦15 ×:ΔL≧16

[0231] [Heat seal strength] The polymers listed in Tables 2-1 and 2-2 were kneaded in the proportions (parts by mass) specified in Tables 2-1 and 2-2 using an extruder (φ40 mm). The resulting pellets were extruded at 230°C using a cast film molding machine to produce a 100 μm thick single-layer unoriented film. Next, a 25 μm thick stretched PET film (manufactured by Toray) was laminated onto the substrate layer surface of the obtained unoriented film via a dry lamination method, with an adhesive layer in between, to produce a laminate (hereinafter sometimes referred to as "laminated film" in this section). That is, this laminate has, in this order, a layer made of a sealant resin composition such as sealant resin composition (X), an adhesive layer, and a substrate layer made of stretched PET film, with the adhesive layer in direct contact with the layer made of the sealant resin composition and the substrate layer made of stretched PET film. The following evaluation was performed using this laminate.

[0232] <Heat seal (HS) strength (before heat treatment)> A test specimen was prepared by stacking a 50 μm thick Teflon® sheet, two of the resulting laminated films, and another 50 μm thick Teflon® sheet in this order. Here, the two laminated films were stacked so that the surfaces having layers made of sealant resin composition faced each other.

[0233] A heat seal bar (TB-701B, manufactured by Tester Industries Co., Ltd.) was set to 15 mm wide x 300 mm long. The temperature on the lower side of the seal bar was set to 70°C and the temperature on the upper side of the seal bar was set to 190°C. The test specimen was sandwiched between the seal bars and heat-sealed for 1.0 second at a pressure of 0.2 MPa. After that, the two Teflon® sheets were removed to obtain a laminated film, which was left at 23°C for one day. A 15 mm wide slit was made in the laminated film, including the heat-sealed portion, and the unheat-sealed portion was chucked into a tensile testing machine (IM-20ST, manufactured by Intesco Co., Ltd.). The maximum load when peeling the heat-sealed portion in a 180° direction at a speed of 300 mm / min was measured. This measurement was performed five times, and the average of the maximum loads was defined as the heat seal strength.

[0234] <Heat seal (HS) strength (after heat treatment)> In the test of HS strength (before heat treatment), except that a film obtained by heat-treating the monolayer non-stretched film at 85°C for 5 days was used instead of the monolayer non-stretched film, the heat seal strength after heat treatment was measured in the same manner as the test of HS strength (before heat treatment).

[0235] Evaluation criteria for HS strength (after heat treatment) ○: HS strength is 35 N / 15 mm or more.

[0236] ×: HS strength is less than 35 N / 15 mm.

[0237] <Heat seal (HS) strength retention rate> The HS strength retention rate was determined from the HS strength before and after heat treatment by the following formula. The larger this value, the better the heat resistance can be said. Also, based on the HS strength retention rate, the HS strength retention was evaluated according to the following criteria.

[0238] HS strength retention rate (%) = 100 × HS strength (after heat treatment) / HS strength (before heat treatment)

[0239] Evaluation criteria for HS strength retention ○: HS strength retention rate is 80% or more. ×: HS strength retention rate is less than 80%.

[0240] The presence or absence of appearance change on the film surface before and after heat-treating the monolayer non-stretched film at 85°C for 5 days was evaluated.

[0241] ○: No appearance change △: A bleed component occurred in a part of the surface (a part of the surface became sticky).

[0242] ×: A bleed component occurred on the entire surface (the entire surface became sticky).

[0243] [Resistance to non-aqueous solvents] To evaluate the resistance to non-aqueous solvents, the sealant resin composition was evaluated as described below. In this evaluation, the contact between the packaging and the electrolyte when the sealant resin composition is used in packaging for lithium-ion batteries was assumed, and a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) was used as the non-aqueous solvent.

[0244] The densities of ethylene carbonate (EC) and diethyl carbonate (DEC) are 1.32 g / cm³, respectively. 3 and 0.975 g / cm³ 3 Therefore, the mass ratio of EC to DEC in a 1:1 (v / v) mixed solvent of EC and DEC is approximately 58:42.

[0245] <Percentage change in weight after immersion in a non-aqueous solvent> Using a φ40 mm single-screw extruder, pellets were prepared by melt-kneading various polymers in the proportions (parts by mass) listed in Table 3 under conditions of a melting temperature of 210°C and a rotation speed of 40-50 rpm. The sealant resin composition (X) obtained in pellet form was heated for 5 minutes using a hydraulic hot press molding machine set to 190°C, molded for 2 minutes under a pressure of 10 MPa, and then cooled for 4 minutes under a pressure of 10 MPa at 20°C to produce a 0.3 mm thick sheet (test specimen). In comparative examples where a single polymer was used instead of the sealant resin composition (X), pellets and sheets (test specimens) were prepared similarly for that polymer.

[0246] A dumbbell conforming to ASTM 638-4 was prepared from a 0.3 mm thick sheet obtained by the above press molding process. After immersion in ethylene carbonate (EC) / diethyl carbonate (DEC) = 1 / 1 (v / v%) (manufactured by Kishida Chemical Co., Ltd., trade name "EC:DEC (1:1v / v%)") at 80°C for 24 hours, the weight change rate was measured using the following formula.

[0247] Weight change rate (%) = 100 × (Weight after immersion - Weight before immersion) / Weight before immersion A negative value for the weight change rate indicates that the resin composition is eluting into EC / DEC, while a positive value indicates that the resin composition is swelling due to EC / DEC.

[0248] Evaluation criteria for weight change rate ○: Weight change rate is between -4.5% and 4.5%. ×: The weight change rate is less than -4.5% or greater than 4.5%.

[0249] <Mechanical properties after EC / DEC immersion> ASTM-4 dumbbells were prepared from 0.3 mm thick sheets obtained by press molding in the same manner as described above in "Weight change rate after immersion in non-aqueous solvent". After immersion in EC / DEC = 1 / 1 (v / v%, manufactured by Kishida Chemical Co., Ltd.) at 80°C for 24 hours, the yield stress, breaking strength (TS), breaking elongation (between chucks, EL), and Young's modulus (YM) of the test specimens before and after immersion were measured in accordance with ASTM D638 (measurement temperature 23°C, tensile speed = 50 mm / min).

[0250] The Young's modulus (YM) retention rate and fracture strength (TS) retention rate were measured using the following formulas.

[0251] YM retention rate (%) = 100 × Young's modulus after immersion / Young's modulus before immersion TS retention rate (%) = 100 × Breaking point strength after immersion / Breaking point strength before immersion Evaluation Criteria for YM Maintenance Rate and TS Maintenance Rate ○: YM maintenance rate and TS maintenance rate are 81% or higher. ×: YM maintenance rate and TS maintenance rate are less than 81%.

[0252] [Physical properties and heat seal characteristics of sealant resin compositions] [Example A1] 10 parts by mass of the 1-butene-ethylene copolymer (A-1) described above as 1-butene-ethylene copolymer (A), and the propylene polymer (B) described above as Random PolypropyleneUsing 90 parts by mass of (B-1), a sealant resin composition was obtained by the method described above, and then the physical properties of the sealant resin composition were measured by the method described above. The obtained physical properties are shown in Table 2-1.

[0253] [Examples A2-A9] A sealant resin composition was obtained in the same manner as in Example A1, except that the polymers shown in Tables 1 and 2-1 were used instead of the polymer constituting the sealant resin composition used in Example 1. The physical properties of the obtained sealant resin composition were measured by the method described above. The obtained physical properties are shown in Table 2-1.

[0254] [Comparative examples a1 to a4] A sealant resin composition was obtained in the same manner as in Example A1, except that the polymers shown in Tables 1 and 2-2 were used instead of the polymer constituting the sealant resin composition used in Example 1. However, in Comparative Example a1, the above random polypropylene (B-1) was used as is. The physical properties of the obtained sealant resin composition or polymer were measured by the method described above. The obtained physical properties are shown in Table 2-2.

[0255] [Table 2-1]

[0256] [Table 2-2]

[0257] [Physical properties of sealant resin compositions after immersion in a non-aqueous solvent] [Examples B1, B10-B11, B8-B9, and Comparative Examples b1-b4] In Examples B1 and B8-B9, Comparative Example b1, and Comparative Examples b2-b4, the weight change rate was measured for each of the sealant resin compositions obtained in Examples A1 and A8-A9, the polymer used in Comparative Example a1, and the sealant resin compositions obtained in Comparative Examples a2-a4, using the method described in "Weight Change Rate After Immersion in Non-Aqueous Solvent" above, as well as the mechanical properties measured using the method described in "Mechanical Properties After Immersion in EC / DEC" above.

[0258] On the other hand, in Examples B10 to B11, sealant resin compositions were obtained in the same manner as in Example A1, except that the polymers shown in Tables 1 and 3 were used instead of the polymers constituting the sealant resin composition used in Example A1. For each of the obtained sealant resin compositions, a whitening resistance test was performed according to the method described in "Whitening Resistance Test" above, the weight change rate was measured according to the method described in "Weight Change Rate After Immersion in Non-Aqueous Solvent" above, and measurements were performed according to the method described in "Mechanical Properties After Immersion in EC / DEC" above.

[0259] The obtained physical properties are shown in Table 3. For reference, Table 3 also shows the whitening resistance data described in Tables 2-1 and 2-2 above for the sealant resin compositions obtained in Examples A1 and A8-A9, the polymer used in Comparative Example a1, and the sealant resin compositions obtained in Comparative Examples a2-a4.

[0260] [Table 3]

[0261] Table 3 shows the comparison results between Examples B10 and B11 and Comparative Example b2, and between Example B9 and Comparative Example b4. It can be seen that the sealant resin composition of the present invention exhibits a smaller weight change rate after immersion in a non-aqueous solvent, less decrease in Young's modulus after EC / DEC immersion, and higher whitening resistance compared to compositions containing a propylene-ethylene copolymer instead of 1-butene-ethylene copolymer (A). The comparison results between Example B1 and Comparative Example b1 show that when only random polypropylene is used instead of the sealant resin composition of the present invention, the physical properties after immersion in a non-aqueous solvent are good, but the whitening resistance is insufficient.

Claims

1. A resin composition containing a 1-butene-ethylene copolymer (A) and a propylene polymer (B) that satisfy the following requirements (A1), (A2), and (A5), wherein the resin composition is a sealant resin composition (X) that satisfies the following requirements (X1) and (X1-2); Requirement (A1): The content of constituent unit (i) derived from 1-butene is in the range of 70 to 99.9 mol%, and the content of constituent unit (ii) derived from ethylene is in the range of 0.1 to 30 mol% [provided that the sum of constituent unit (i) and constituent unit (ii) is 100 mol%]. Requirement (A2): 13 The isotactic pentad fraction (mmmm) calculated by C-NMR is in the range of 80–99.9%; Requirement (A5): Using a differential scanning calorimeter (DSC), the temperature is first lowered from 30°C to -70°C at a cooling rate of 20°C / min (first cooling), held at -70°C for 5 minutes, then heated from -70°C to 200°C at a heating rate of 20°C / min (first heating), held at 200°C for 10 minutes, then lowered to -70°C at a cooling rate of 20°C / min (second cooling), held at -70°C for 1 minute, and then heated again from -70°C to 200°C at a heating rate of 20°C / min (second heating), and no melting peak is observed during the second heating. Requirement (X1): The Shore D hardness measured according to ASTM D2240 is in the range of 44 to 80; Requirement (X1-2): The melt flow rate (MFR), measured at 230°C and a 2.16 kg load, conforms to ASTM D1238 and is in the range of 0.1 to 100 g / 10 min.

2. A sealant resin composition (X) according to claim 1 that satisfies the following requirement (X2); Requirement (X2): Using a differential scanning calorimeter (DSC), the enthalpy of fusion ΔHfus is in the range of 20 to 100 J / g when the temperature is first cooled from 30°C to -70°C at a cooling rate of 20°C / min (first cooling), held at -70°C for 5 minutes, heated from -70°C to 200°C at a heating rate of 20°C / min (first heating), held at 200°C for 10 minutes, then cooled to -70°C at a cooling rate of 20°C / min (second cooling), held at -70°C for 1 minute, and then heated again from -70°C to 200°C at a heating rate of 20°C / min (second heating).

3. The sealant resin composition (X) according to claim 1, comprising an ethylene polymer (C).

4. A sealant resin composition (X) according to claim 1 that satisfies the following requirement (X3); Requirements (X3): The content of 1-butene-ethylene copolymer (A) is in the range of 1 to 50% by mass, the content of propylene polymer (B) is in the range of 30 to 99% by mass, and the content of ethylene polymer (C) is in the range of 0 to 20% by mass [provided that the total of 1-butene-ethylene copolymer (A), propylene polymer (B), and ethylene polymer (C) is 100% by mass].

5. A sealant resin composition (X) according to claim 1, wherein the 1-butene-ethylene copolymer (A) satisfies the following requirement (A3); Requirement (A3): The intrinsic viscosity [η] in decalin solvent at 135°C is in the range of 0.7 to 4.0 dl / g.

6. The sealant resin composition (X) according to claim 1, wherein the propylene polymer (B) is one or more selected from the group consisting of random copolymers and block copolymers.

7. A single-layer or multi-layer sealant film comprising at least one layer containing the sealant resin composition (X) described in claim 1.

8. A laminate comprising a layer of sealant film according to claim 7, wherein at least one base film selected from the group consisting of polyolefin film, polystyrene film, polyester film, polyamide film, laminated film of polyolefin and gas barrier resin film, metal foil, paper, and vapor-deposited film is laminated.

9. The laminate according to claim 8, characterized in that the sealant film layer and the base film are bonded together by a melt extrusion lamination method, a heat lamination method, or a dry lamination method.

10. The laminate according to claim 8, wherein the base film is aluminum foil.

11. A packaging body comprising the laminate according to claim 9 or 10.

12. A power storage device comprising the laminate according to claim 9 or 10.

13. A packaging for a lithium-ion battery comprising the laminate according to claim 9 or 10.

14. A power storage device comprising a sealant resin composition (X), A storage device comprising a sealant resin composition (X) containing a 1-butene-ethylene copolymer (A) and a propylene polymer (B), and satisfying the following requirement (X1); Requirement (X1): The Shore D hardness, measured according to ASTM D2240, is in the range of 44 to 80.

15. The energy storage device according to claim 14, which is a lithium-ion battery.

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