Resin composition for film and ethylene-based film using the same

Abstract

To provide a film excellent in glossiness, transparency, impact strength, heat sealability and pinhole resistance, or a resin composition giving the film.SOLUTION: There are provided a resin composition for a film that contains an ionomer in which at least a part of a carboxyl group and / or a dicarboxylic acid anhydride group in a copolymer (P) containing a structural unit (A) derived from ethylene and / or α-olefin having 3-20 carbon atoms and a structural unit (B) derived from a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group as essential structural units is converted into a metal-containing carboxylate containing at least one metal ion selected from Group I, II or XII in the periodic table, and a phase angle δ at an absolute value G*=0.1 MPa of complex modulus of elasticity measured by a rotary type rheometer is 50-75 degrees; and a film molded using the same.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition for films using a novel ethylene-based ionomer, and an ethylene-based film using the same. More specifically, it relates to an ethylene-based film excellent in at least one of high rigidity, high strength, high transparency, high glossiness, and low-temperature heat sealability.

Background Art

[0002] Conventionally, as ethylene-based polymers for film formation, low-density polyethylene (LDPE) having a large number of branched chains obtained by a high-pressure radical polymerization method, and linear low-density polyethylene (LLDPE or metallocene PE) obtained by a catalytic polymerization method are known. However, although the former has excellent moldability, its strength is low, and although the latter has excellent strength, its moldability is low, and it is difficult to satisfy all of these.

[0003] On the other hand, an ethylene-based ionomer is a resin in which an ethylene-unsaturated carboxylic acid copolymer is used as a base resin and is intermolecularly bonded with metal ions such as sodium and zinc (Patent Document 1). It is tough, rich in elasticity, and flexible, and has characteristics such as abrasion resistance and transparency. Currently, as commercially available ethylene-based ionomers, sodium salts and zinc salts of ethylene-methacrylic acid copolymers "Surlyn (registered trademark)" developed by Dupont, and "Hymilan (registered trademark)" sold by Mitsui Dow Polychemical Co., Ltd. are known.

[0004] As the ethylene-unsaturated carboxylic acid copolymer which is the base resin used in these currently commercially available ethylene-based ionomers, a polar group-containing olefin copolymer obtained by polymerizing ethylene and a polar group-containing monomer such as an unsaturated carboxylic acid by a high-pressure radical polymerization method is used in every case. The high-pressure radical polymerization method has an advantage that it can be polymerized at low cost without particularly selecting the kind of polar group-containing monomer. However, the molecular structure of the polar group-containing olefin copolymer produced by this high-pressure radical polymerization method is a multi-branched molecular structure having many long-chain branches and short-chain branches irregularly as shown in the image diagram of FIG. 1, and has a drawback that it is insufficient in strength.

[0005] On the other hand, a method for producing a polar group-containing olefin copolymer having a linear molecular structure as shown in the image diagram of FIG. 2 has been sought by using a polymerization method using a catalyst conventionally, but since the polar group-containing monomer generally acts as a catalyst poison, polymerization is difficult, and actually, it has been difficult for many years to obtain a polar group-containing olefin copolymer having desired physical properties by an industrially inexpensive and stable method. However, in recent years, a method has been proposed for industrially inexpensively and stably obtaining a polar group-containing olefin copolymer having a substantially linear molecular structure by using a new catalyst and a new production method developed by the applicant of the present application and the like. And, as a method for producing a polar group-containing olefin copolymer which is a base resin of an ethylene-based ionomer, a copolymer of ethylene and t-butyl acrylate is produced using a late transition metal catalyst, and the obtained polar group-containing olefin copolymer is heat-treated or acid-treated to be modified into an ethylene-acrylic acid copolymer, and then it has been reported by the applicant of the present application and the like that a binary ionomer has been successfully produced by reacting with metal ions (Patent Document 2).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] In films, although the degrees required for various applications are different, generally, high strength, good balance between rigidity and strength, high transparency, glossiness, and strength during heat sealing, low-temperature heat sealability, etc. are required respectively or in combination. However, with conventional polyethylene resins, it has been difficult with the conventional technology to obtain a resin that satisfies any one of these physical properties in a significantly improved form or that sufficiently satisfies them in combination. Also, films using conventional ethylene-based ionomers having a multi-branched molecular structure are not sufficiently resistant to impacts from room temperature to low temperature ranges. According to what the inventors have found, they have poor flex resistance and are insufficient for packaging applications where the occurrence of pinholes is to be avoided. In view of such a conventional technical situation, the present application aims to provide a film and a resin composition for film that are excellent in gloss, transparency, tensile strength, puncture strength, pinhole resistance, heat seal strength, and impact strength from room temperature to low temperature ranges.

Means for Solving the Problems

[0008] As a result of repeated studies by the inventors to solve the above problems, it has been found that by forming a resin composition for film using a specific ionomer resin, it has an unexpectedly excellent effect on the physical properties required for the film. The ethylene-based ionomer is a novel ethylene-based ionomer that has never existed before, in which the base resin has a substantially linear molecular structure and also has the function of an ionomer. Its physical properties and the like are very different from those of conventional ethylene-based ionomers having a multi-branched molecular structure, and its specific characteristics and suitable applications are also unknown. The present invention is based on the finding that an ethylene-based film obtained by film-forming a resin composition containing a substantially linear ethylene-based ionomer has excellent effects on improving the physical properties required for the film beyond the performance range of conventional ethylene-based resin films.

[0009] That is, the present invention is as shown in the following [1] to

[19] . [1] A structural unit (A) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms, and in a copolymer (P) containing, as an essential constituent unit, a structural unit (B) derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group, at least a part of the carboxyl group and / or the dicarboxylic anhydride group is converted into a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table, The absolute value G of the complex elastic modulus measured with a rotational rheometer * = 0.1 MPa, and the phase angle δ is 50 degrees to 75 degrees. A resin composition for a film containing an ionomer, characterized in that. [2] A structural unit (A) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms, and a structural unit (B) derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group, and a structural unit (C) which is a compound having one or more carbon-carbon double bonds in the molecular structure other than the structural unit (A) and the structural unit (B), in a copolymer (P) containing as an essential constituent unit, at least a part of the carboxyl group and / or the dicarboxylic anhydride group is converted into a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table, The absolute value G of the complex elastic modulus measured with a rotational rheometer *A resin composition for a film containing an ionomer, characterized in that the phase angle δ at 0.1 MPa is 50 degrees to 75 degrees. [3] The resin composition for a film according to [2] above, characterized in that the structural unit (C) in the copolymer (P) is an acyclic monomer represented by the following general formula (1) or a cyclic monomer represented by the following general formula (2).

Chemical formula

Chemical formula

[10] The resin composition for a film according to any one of [1] to [9], wherein the structural unit (A) is a structural unit derived from ethylene.

[11] The resin composition for a film according to any one of [1] to

[10] , wherein the metal ion is a metal ion of Group 1 of the periodic table.

[12] The resin composition for a film according to any one of [1] to

[10] , wherein the metal ion is a metal ion of Group 12 of the periodic table.

[13] The resin composition for a film according to any one of [1] to

[12] , wherein the copolymer (P) is a copolymer obtained by hydrolyzing a precursor copolymer produced using a transition metal catalyst containing a transition metal of Groups 8 to 11 of the periodic table.

[14] The resin composition for a film according to

[13] , wherein the transition metal catalyst is a transition metal catalyst composed of a phosphine sulfonic acid or a phosphine phenol ligand and nickel or palladium.

[15] An ethylene-based film formed using the resin composition for a film according to any one of [1] to

[14] .

[16] An ethylene-based film having an ethylene-based resin as a resin component, wherein the film impact at -20°C is 20 J / mm or more and the tensile modulus in the MD direction is 150 MPa or more when measured after being formed into a thickness of 30 μm.

[17] An ethylene-based film having an ethylene-based resin as a resin component, wherein the heat seal strength at a seal temperature of 120°C, a seal pressure of 0.2 MPa, a seal time of 1 second, and a lower seal bar temperature of 60°C is 10 N / 15 mm or more when measured after being formed into a thickness of 30 μm.

[18] An inflation film having an ethylene-based resin as a resin component, wherein the haze is 2% or less when formed into a thickness of 30 μm.

[19] An inflation film having an ethylene-based resin as a resin component, wherein the gloss (20°) is 120% or more when formed into a thickness of 30 μm. [Effect of the Invention]

[0010] The film of the present invention using an ionomer having a substantially linear structure is superior in gloss, transparency, impact strength under low temperature environment in addition to normal temperature, heat sealability, and pinhole resistance compared to films made of existing polyethylene or ionomer resins having a multi-branched structure.

Brief Description of Drawings

[0011]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Embodiments for Carrying Out the Invention

[0012] The present invention uses, as a base resin, a copolymer (P) in which structural units (A) derived from ethylene and / or α-olefins having 3 to 20 carbon atoms, and structural units (B) derived from monomers having a carboxyl group and / or a dicarboxylic anhydride group are essential constituent units, and further optionally contains structural units (C) which are compounds having one or more carbon-carbon double bonds in the molecular structure as constituent units, and these are substantially linearly copolymerized, preferably randomly copolymerized. At least a part of the carboxyl group and / or the dicarboxylic anhydride group of the structural unit (B) is converted into a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table. The film is an ionomer film.

[0013] Hereinafter, the ionomer related to the present invention, the film using the ionomer, and its uses will be described in detail item by item. In this specification, “(meth)acrylic acid” means acrylic acid or methacrylic acid. Also, in this specification, “~” indicating a numerical range is used to mean including the numerical values described before and after it as the lower limit value and the upper limit value. Further, in this specification, the copolymer means a binary or higher copolymer containing at least one kind of unit (A) and at least one kind of unit (B). Also, in this specification, the ionomer means an ionomer of a binary or higher copolymer containing the structural unit (A) and a structural unit (B') in which at least a part of the structural unit (B) is converted into a metal-containing carboxylate, and may further contain the structural unit (B).

[0014] 1. Ionomer The ionomer of the present invention contains, as essential constituent units, a structural unit (A) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms, and a structural unit (B) derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group, and further optionally contains, as a constituent unit, a structural unit (C) which is a compound having one or more carbon-carbon double bonds in the molecular structure. These are substantially linearly copolymerized, preferably randomly copolymerized, and a copolymer (P) is used as the base resin. At least a part of the carboxyl group and / or the dicarboxylic anhydride group of the structural unit (B) is converted into a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table.

[0015] (1) Structural unit (A) The structural unit (A) is at least one structural unit selected from the group consisting of a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 20 carbon atoms. The α-olefin related to the present invention has the structural formula: CH2=CHR 18 and is an α-olefin having 3 to 20 carbon atoms (R 18 is a hydrocarbon group having 1 to 18 carbon atoms, which may have a linear structure or a branch). The carbon number of the α-olefin is more preferably 3 to 12.

[0016] Specific examples of the structural unit (A) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, and 4-methyl-1-pentene, etc., and ethylene may also be used. As ethylene, in addition to those derived from petroleum raw materials, ethylene derived from non-petroleum raw materials such as plant raw materials can be used. Also, the structural unit (A) may be of one type or a plurality of types. Examples of the combination of two types include ethylene-propylene, ethylene-1-butene, ethylene-1-hexene, ethylene-1-octene, propylene-1-butene, propylene-1-hexene, and propylene-1-octene, etc. Examples of the three combinations include ethylene-propylene-1-butene, ethylene-propylene-1-hexene, ethylene-propylene-1-octene, propylene-1-butene-hexene, and propylene-1-butene-1-octene.

[0017] In the present invention, as the structural unit (A), preferably, ethylene is essentially included, and one or more α-olefins having 3 to 20 carbon atoms may be further included as necessary. Ethylene in the structural unit (A) may be 65 to 100 mol% or 70 to 100 mol% based on the total mol of the structural unit (A). From the viewpoint of impact resistance, the structural unit (A) may be a structural unit derived from ethylene.

[0018] (2) Structural unit (B) The structural unit (B) is a structural unit derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group. Note that the structural unit (B) represents the same structure as the structural unit derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group, and as described in the production method described later, it does not necessarily have to be produced using a monomer having a carboxyl group and / or a dicarboxylic anhydride group.

[0019] Examples of the structural unit derived from a monomer having a carboxyl group include, specifically, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornenedicarboxylic acid, and bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid. Examples of the structural unit derived from a monomer having a dicarboxylic anhydride group include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, and tetracyclo[6.2.1.1 3,6 .0 2,7Examples of the unsaturated dicarboxylic acid anhydrides include dodeca-9-ene-4,5-dicarboxylic anhydride and 2,7-octadien-1-yl succinic anhydride. As the structural unit derived from the monomer having a carboxyl group and / or a dicarboxylic anhydride group, acrylic acid, methacrylic acid, 5-norbornene-2,3-dicarboxylic anhydride are preferable from the viewpoint of easy availability in industry, and acrylic acid may be particularly used. The structural unit derived from the monomer having a carboxyl group and / or a dicarboxylic anhydride group may be of one kind or a plurality of kinds.

[0020] Although the dicarboxylic anhydride group may react with moisture in the air to open the ring and part of it may become a dicarboxylic acid, the dicarboxylic anhydride group may be open-ringed as long as the gist of the present invention is not deviated.

[0021] (3) Other structural unit (C) As the copolymer (P) used in the present invention, a binary copolymer composed only of the structural unit (A) and the structural unit (B), and a multi-component copolymer further containing the structural unit (A), the structural unit (B), and other structural units (C) can be used, but a multi-component copolymer further containing the structural unit (C) other than the structural units represented by the structural unit (A) and the structural unit (B) may also be used. The monomer that provides the structural unit (C) can be any monomer as long as it is not included in the monomers that provide the structural unit (A) and the structural unit (B). The monomer that provides the structural unit (C) is not limited as long as it is a compound having one or more carbon-carbon double bonds in the molecular structure, and examples thereof include an acyclic monomer represented by the general formula (1) described below and a cyclic monomer represented by the general formula (2). By using a terpolymer or higher-order copolymer containing a structural unit (C) as the base resin of the ionomer, compared to a binary copolymer consisting only of a structural unit (A) and a structural unit (B), an ionomer with a low melting point and crystallinity can be obtained. When formed into a film, the balance between rigidity and toughness is dramatically improved, and the transparency and gloss are also significantly excellent, and a film with excellent low-temperature heat sealability can be obtained. The structural unit (C) may be based on one type of monomer, or two or more types of monomers may be combined and used.

[0022] · Acyclic monomer [Chemical formula] [In general formula (1), T 1 ~T 3 are each independently a substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an ester group having 2 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, a halogen atom, or a cyano group, T 4 is a substituent selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an ester group having 2 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, a halogen atom, or a cyano group.]

[0023] In the ionomer of the present invention, T 1 and T 2 may be a hydrogen atom, and T 3may be a hydrogen atom or a methyl group, and T 4 may be an ester group having 2 to 20 carbon atoms.

[0024] T 1 ~T 4 The hydrocarbon group, substituted alkoxy group, substituted ester group, alkoxy group, aryl group, ester group, and carbon skeleton of the silyl group related to T T 1 ~T 4 The number of carbon atoms of the hydrocarbon group related to T T 1 ~T 4 The lower limit of the number of carbon atoms of the substituted alkoxy group related to T T 1 ~T 4 The lower limit of the number of carbon atoms of the substituted ester group related to T T 1 ~T 4 The lower limit of the number of carbon atoms of the alkoxy group related to T T 1 ~T 4 The lower limit of the number of carbon atoms of the aryl group related to T T 1 ~T 4 The lower limit of the number of carbon atoms of the ester group related to T T 1 ~T 4 The lower limit of the number of carbon atoms of the silyl group related to T The upper limit may be 18 or less, and may be 12 or less. Examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triisopropylsilyl group, a dimethylphenylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group.

[0025] In the ionomer of the present invention, from the viewpoint of ease of production, T 1 and T 2 may be a hydrogen atom, T 3 may be a hydrogen atom or a methyl group, and T 1 ~T 3 may all be hydrogen atoms. Also, from the viewpoint of impact resistance, T 4 may be an ester group having 2 to 20 carbon atoms.

[0026] Specific examples of the acyclic monomer include cases where T 4 is an ester group having 2 to 20 carbon atoms, such as (meth)acrylate. T 4 When is an ester group having 2 to 20 carbon atoms, examples of the acyclic monomer include compounds represented by the structural formula: CH2 = C(R 21 )CO2(R 22 ). Here, R 21 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and may have a branch, a ring, and / or an unsaturated bond. R 22 is a hydrocarbon group having 1 to 20 carbon atoms, and may have a branch, a ring, and / or an unsaturated bond. Further, any position within R 22 may contain a hetero atom. As the compound represented by the structural formula: CH2 = C(R 21 )CO2(R 22 ), examples include compounds in which R 21 is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Also, examples include acrylic acid esters in which R 21 is a hydrogen atom or methacrylic acid esters in which R 21 is a methyl group. As the compound represented by the structural formula: CH2 = C(R 21 )CO2(R 22Specific examples of the compound represented by [formula] include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, and the like. Specific compounds include methyl acrylate, ethyl acrylate, n-butyl acrylate (nBA), isobutyl acrylate (iBA), t-butyl acrylate (tBA), 2-ethylhexyl acrylate, and the like, and particularly n-butyl acrylate (nBA), isobutyl acrylate (iBA), and t-butyl acrylate (tBA) may also be used. Note that the acyclic monomer may be of one kind or a plurality of kinds.

[0027] · Cyclic monomer [Chemical formula] [In general formula (2), R 1 ~R 12 may be the same or different from each other, and is selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 20 carbon atoms. R 9 and R 10 , and R 11 and R 12 may each integrally form a divalent organic group. R 9 or R 10 and R 11 or R 12 may form a ring with each other. In addition, n represents 0 or a positive integer. When n is 2 or more, R 5 ~R 8Within each repeating unit, they may be the same or different from each other.

[0028] Examples of the cyclic monomer include norbornene-based olefins and the like, such as norbornene, vinyl norbornene, ethylidene norbornene, norbornadiene, tetracyclododecene, tricyclo[4.3.0.1 2,5 deca-3-ene, and compounds having a cyclic olefin skeleton such as these, 2-norbornene (NB), and tetracyclo[6.2.1.1 3,6 .0 2,7 dodeca-4-ene and the like may be used.

[0029] (4) Copolymer (P) The copolymer (P) serving as the base resin of the ionomer used in the present invention contains, as essential constituent units, a structural unit (A) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms, and a structural unit (B) derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group, and further optionally contains an arbitrary structural unit (C) other than the above (A) and (B). It is characterized in that these respective structural units are copolymerized substantially linearly, preferably randomly copolymerized. "Substantially linearly" means that the copolymer has no branches or the frequency of the appearance of the branched structure is small, and it is a state in which the copolymer can be regarded as linear. Specifically, it refers to a state in which the phase angle δ of the copolymer is 50 degrees or more under the conditions described later.

[0030] The copolymer (P) related to the present invention needs to contain at least one kind of each of the structural unit (A) and the structural unit (B), and includes a total of two or more monomer units. It may contain an arbitrary structural unit (C) other than the above (A) and (B), but it is preferably a multi-component copolymer containing such a structural unit (C). The structural units and amounts of the structural units of the copolymer related to the present invention will be described. The structure derived from one molecule each of ethylene and / or an α-olefin (A) having 3 to 20 carbon atoms, a monomer (B) having a carboxyl group and / or a dicarboxylic anhydride group, and an arbitrary monomer (C) other than (A) and (B) is defined as one structural unit in the copolymer. And when the total of the structural units in the copolymer is 100 mol%, the ratio of each structural unit expressed in mol% is the amount of the structural unit.

[0031] · Amount of the structural unit of ethylene and / or an α-olefin (A) having 3 to 20 carbon atoms: The amount of the structural unit (A) according to the present invention is such that the lower limit is 60.0 mol% or more, preferably 70.0 mol% or more, more preferably 80.0 mol% or more, still more preferably 85.0 mol% or more, even more preferably 90.0 mol% or more, particularly preferably 91.2 mol% or more, and the upper limit is selected from 97.9 mol% or less, preferably 97.5 mol% or less, more preferably 97.0 mol% or less, still more preferably 96.5 mol% or less. If the amount of the structural unit derived from ethylene and / or an α-olefin (A) having 3 to 20 carbon atoms is less than 60.0 mol%, the toughness of the copolymer is inferior, and if it is more than 97.9 mol%, the crystallinity of the copolymer becomes high and the transparency may deteriorate.

[0032] · Amount of the structural unit of a monomer (B) having a carboxyl group and / or a dicarboxylic anhydride group: The amount of the structural unit (B) according to the present invention is such that the lower limit is 2.0 mol% or more, preferably 2.9 mol% or more, more preferably 5.2 mol% or more, and the upper limit is selected from 20.0 mol% or less, preferably 15.0 mol% or less, more preferably 10.0 mol% or less, still more preferably 8.0 mol% or less, particularly preferably 6.0 mol% or less, and most preferably 5.6 mol% or less. If the amount of the structural unit derived from the monomer (B) having a carboxyl group and / or a dicarboxylic anhydride group is less than 2.0 mol%, the adhesiveness of the copolymer to a highly polar different material is not sufficient, and if it is more than 20.0 mol%, sufficient mechanical properties of the copolymer may not be obtained. Furthermore, the monomer having a carboxyl group and / or a dicarboxylic anhydride group used may be used alone or in combination of two or more.

[0033] · Amount of the structural unit of any monomer (C): When the component of the ionomer of the present invention contains any monomer (C) other than the above (A) or (B), the amount of the structural unit of the structural unit (C) related to the present invention has a lower limit of 0.001 mol% or more, preferably 0.010 mol% or more, more preferably 0.020 mol% or more, still more preferably 0.1 mol% or more, still more preferably 1.9 mol% or more, particularly preferably 2.0 mol% or more, and an upper limit of 20.0 mol% or less, preferably 15.0 mol% or less, more preferably 10.0 mol% or less, still more preferably 5.0 mol% or less, particularly preferably 3.6 mol% or less. When the amount of the structural unit derived from any monomer (C) is 0.001 mol% or more, the flexibility of the copolymer tends to be sufficient, and when it is 20.0 mol% or less, sufficient mechanical properties of the copolymer are likely to be obtained. Furthermore, the any monomer used may be used alone or in combination of two or more.

[0034] · Method for measuring the amount of the structural unit of the monomer having a carboxyl group and / or a dicarboxylic anhydride group and any monomer in the copolymer: The amount of the structural unit of the monomer having a carboxyl group and / or a dicarboxylic anhydride group and any monomer in the copolymer related to the present invention 1 is determined using an H-NMR spectrum. 1 H-NMR is measured by the following method. 200 - 250 mg of the sample is placed in an NMR sample tube with an inner diameter of 10 mm φ together with 2.4 ml of o - dichlorobenzene / deuterated bromobenzene (C6D5Br) = 4 / 1 (volume ratio) and hexamethyldisiloxane which is a chemical shift reference substance. After nitrogen substitution, the tube is sealed, heated and dissolved to form a uniform solution for NMR measurement. NMR measurement is carried out at 120 °C using a Bruker Japan Co., Ltd.'s AV400M type NMR apparatus equipped with a 10 mm φ cryoprobe. 1 1H - NMR is measured with a pulse angle of 4.5°, a pulse interval of 1.8 seconds, and an integration number of 256 times or more. The chemical shift is set with the peak of the methyl proton of hexamethyldisiloxane at 0.088 ppm, and the chemical shifts of the peaks by other protons are based on this.

[0035] Number of branches per 1,000 carbons of the multi - copolymer: In the multi - copolymer of the present invention, from the viewpoint of increasing the elastic modulus and obtaining sufficient mechanical properties, 13 The number of methyl branches calculated by 13C - NMR may have an upper limit of 50 or less, 5 or less, 1 or less, 0.5 or less per 1,000 carbons, and the lower limit is not particularly limited, and the less the better. Also, the number of ethyl branches may have an upper limit of 3.0 or less, 2.0 or less, 1.0 or less, 0.5 or less per 1,000 carbons, and the lower limit is not particularly limited, and the less the better. Further, the number of butyl branches may have an upper limit of 7.0 or less, 5.0 or less, 3.0 or less, 0.5 or less per 1,000 carbons, and the lower limit is not particularly limited, and the less the better.

[0036] Measurement method for the amount of structural units and the number of branches derived from monomers having carboxy groups and / or dicarboxylic anhydride groups and acyclic monomers in the multi - copolymer: The amount of structural units derived from monomers having carboxy groups and / or dicarboxylic anhydride groups, and acyclic monomers, and the number of branches per 1,000 carbons in the multi-component copolymer of the present invention are 13 determined using a 13C-NMR spectrum. 13 13C-NMR is measured by the following method. Put 200 to 300 mg of the sample into an NMR sample tube with an inner diameter of 10 mmφ together with 2.4 ml of a mixed solvent of o-dichlorobenzene (C6H4Cl2) and deuterated benzene bromide (C6D5Br) (C6H4Cl2 / C6D5Br = 2 / 1 (volume ratio)) and hexamethyldisiloxane which is a chemical shift reference substance, replace with nitrogen, then seal the tube, heat and dissolve to make a uniform solution as an NMR measurement sample. NMR measurement is carried out at 120 °C using an AV400M type NMR apparatus of Bruker Japan Co., Ltd. equipped with a 10 mmφ cryoprobe. 13 13C-NMR is measured by the inverse gate decoupling method at a sample temperature of 120 °C, a pulse angle of 90°, a pulse interval of 51.5 seconds, and an integration number of 512 times or more. The chemical shift sets the 13C signal of hexamethyldisiloxane to 13 1.98 ppm, and the chemical shifts of signals from other 13C are based on this. 13 In the obtained 13 13C-NMR, by identifying signals specific to the monomers or branches of the multi-component copolymer and comparing their intensities, the amount of structural units of each monomer and the number of branches in the multi-component copolymer can be analyzed. The positions of signals specific to monomers or branches can be referred to known materials or identified independently according to the sample. Such an analysis method can be generally carried out by those skilled in the art.

[0037] · Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn): The weight average molecular weight (Mw) of the copolymer according to the present invention is usually 1,000 or more, preferably 6,000 or more, more preferably 10,000 or more, and the upper limit is usually 2,000,000 or less, preferably 1,500,000 or less, still more preferably 1,000,000 or less, particularly preferably 800,000 or less, and most preferably 100,000 or less. When Mw is less than 1,000, physical properties such as the mechanical strength and impact resistance of the copolymer are not sufficient. When Mw exceeds 2,000,000, the melt viscosity of the copolymer becomes very high, and it may be difficult to mold the copolymer.

[0038] The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the copolymer according to the present invention is usually in the range of 1.5 to 4.0, preferably 1.6 to 3.5, and more preferably 1.9 to 2.3. When Mw / Mn is less than 1.5, various processabilities such as molding of the copolymer are not sufficient. When it exceeds 4.0, the mechanical properties of the copolymer may be inferior. In this specification, (Mw / Mn) may be expressed as a molecular weight distribution parameter.

[0039] The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the copolymer according to the present invention are determined by gel permeation chromatography (GPC). The molecular weight distribution parameter (Mw / Mn) is obtained by gel permeation chromatography (GPC), further determining the number average molecular weight (Mn), and calculating the ratio of Mw to Mn, Mw / Mn.

[0040] An example of the measurement method of GPC according to the present invention is as follows. (Measurement conditions) Model used: Waters 150C Detector: FOXBORO MIRAN1A·IR detector (measurement wavelength: 3.42 μm) Measurement temperature: 140 °C Solvent: Orthodichlorobenzene (ODCB) Column: Showa Denko AD806M / S (3 columns) Flow rate: 1.0 mL / min Injection volume: 0.2 mL (Preparation of sample) The sample is prepared as a 1 mg / mL solution using ODCB (containing 0.5 mg / mL of BHT (2,6-di-t-butyl-4-methylphenol)) and dissolved at 140 °C for about 1 hour. (Calculation of molecular weight (M)) It is carried out by the standard polystyrene method, and the conversion from retention volume to molecular weight is performed using a calibration curve prepared in advance with standard polystyrene. The standard polystyrene to be used is, for example, the brands of Tosoh Corporation (F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000), the monodisperse polystyrene manufactured by Showa Denko (each 0.07 mg / ml solution of S-7300, S-3900, S-1950, S-1460, S-1010, S-565, S-152, S-66.0, S-28.5, S-5.05), etc. A 0.2 mL solution dissolved in ODCB (containing 0.5 mg / mL of BHT) so that each becomes 0.5 mg / mL is injected to prepare a calibration curve. The calibration curve uses a cubic equation approximated by the least squares method, or one approximated by a quartic equation for the elution time and the logarithmic value of the molecular weight. The following numerical values are used for the viscosity equation [η]=K×Mα used for the conversion to molecular weight (M). Polystyrene (PS): K = 1.38×10 -4 , α = 0.7 Polyethylene (PE): K = 3.92×10 -4 , α = 0.733 Polypropylene (PP): K = 1.03×10 -4 , α = 0.78

[0041] ·Melting point (Tm, °C): The melting point of the copolymer according to the present invention is indicated by the maximum peak temperature of the endothermic curve measured by a differential scanning calorimeter (DSC). The maximum peak temperature means that, in the DSC measurement, when multiple peaks are shown in the endothermic curve obtained with the heat flow (mW) on the vertical axis and the temperature (°C) on the horizontal axis, it indicates the temperature of the peak with the maximum height from the baseline among them. When there is only one peak, it indicates the temperature of that peak. The melting point is preferably 50°C to 140°C, more preferably 60°C to 138°C, and most preferably 70°C to 135°C. If it is lower than this range, the heat resistance is not sufficient, and if it is higher than this range, the adhesiveness may be inferior. The melting point can be determined, for example, from the absorption curve when using a DSC (DSC7020) manufactured by SII NanoTechnology Inc., filling about 5.0 mg of the sample into an aluminum pan, heating it to 200°C at 10°C / min, holding it isothermally at 200°C for 5 minutes, then cooling it to 20°C at 10°C / min, holding it isothermally at 20°C for 5 minutes, and then heating it to 200°C again at 10°C / min.

[0042] ·Molecular structure of the copolymer: The molecular chain ends of the copolymer according to the present invention may be structural units (A) of ethylene and / or α-olefins having 3 to 20 carbon atoms, structural units (B) of monomers having a carboxyl group and / or a dicarboxylic anhydride group, or any structural units (C) other than (A) and (B).

[0043] In addition, the copolymer according to the present invention includes random copolymers, block copolymers, and graft copolymers of structural units (A) of ethylene and / or α-olefins having 3 to 20 carbon atoms, structural units (B) of monomers having a carboxyl group and / or a dicarboxylic anhydride group, and structural units (C) of any monomers. Among these, a random copolymer that can contain a large amount of structural unit (B) may be used. A general example (1) of the molecular structure of a ternary copolymer is shown below. A random copolymer is a copolymer in which the probability of finding the structural units (A) of ethylene and / or α-olefins having 3 to 20 carbon atoms, the structural units (B) of monomers having a carboxyl group and / or a dicarboxylic anhydride group, and the structural units (C) of any monomers at any position in an arbitrary molecular chain is independent of the type of the adjacent structural unit. As shown below, in the molecular structure example (1) of the copolymer, the structural units (A) of ethylene and / or α-olefins having 3 to 20 carbon atoms, the structural units (B) of monomers having a carboxyl group and / or a dicarboxylic anhydride group, and the structural units (C) of any monomers form a random copolymer.

Chemical formula

[0044] In addition, when referring to the molecular structure example (2) of the copolymer in which the structural units (B) of monomers having a carboxyl group and / or a dicarboxylic anhydride group are introduced by graft modification, a part of the copolymer in which the structural units (A) of ethylene and / or α-olefins having 3 to 20 carbon atoms and the structural units (C) of any monomers are copolymerized is graft-modified to the structural units (B) of monomers having a carboxyl group and / or a dicarboxylic anhydride group.

Chemical formula

[0045] Also, although the random copolymerizability in the copolymer can be confirmed by various methods, the method for discriminating random copolymerizability from the relationship between the comonomer content and the melting point of the copolymer is described in detail in JP-A-2015-163691 and JP-A-2016-079408. When the melting point (Tm, °C) of the copolymer is higher than -3.74×[Z] + 130 (where [Z] is the comonomer content / mol%), it can be judged that the randomness is low.

[0046] The copolymer according to the present invention, which is a random copolymer, preferably satisfies the following formula (I) with respect to the melting point (Tm, °C) observed by differential scanning calorimetry (DSC) and the total content [Z] (mol%) of the structural unit (B) of the monomer having a carboxyl group and / or a dicarboxylic anhydride group and the structural unit (C) of any monomer. 50 < Tm < -3.74 × [Z] + 130 ··· (I) When the melting point (Tm, °C) of the copolymer is higher than -3.74 × [Z] + 130 (°C), the random copolymerizability is low, so the mechanical properties such as impact strength are inferior. When the melting point is lower than 50 °C, the heat resistance may be inferior.

[0047] Furthermore, from the viewpoint of making the molecular structure of the copolymer according to the present invention linear, it is preferably produced in the presence of a transition metal catalyst. It is known that the molecular structure of the copolymer varies depending on the production method, such as polymerization by a high-pressure radical polymerization process or polymerization using a metal catalyst. Although this difference in molecular structure can be controlled by selecting the production method, for example, as described in JP-A-2010-150532, the molecular structure can also be estimated from the complex elastic modulus measured with a rotational rheometer.

[0048] · Absolute value G of the complex elastic modulus * = Phase angle δ at 0.1 MPa: In the copolymer of the present invention, the absolute value G of the complex elastic modulus measured with a rotational rheometer * = The phase angle δ at 0.1 MPa is characterized by being 50 to 75 degrees. The lower limit of the phase angle δ may be 50 degrees or more, 51 degrees or more, 54 degrees or more, 56 degrees or more, 58 degrees or more, and the upper limit of the phase angle δ may be 75 degrees or less, 70 degrees or less. More specifically, the absolute value G of the complex elastic modulus measured with a rotational rheometer * = The phase angle δ at 0.1 MPa (G *When (the pressure) = 0.1 MPa is 50 degrees or higher, the molecular structure of the multi-component copolymer is a linear structure, showing a structure that does not contain any long-chain branches or a structure containing a small amount of long-chain branches that does not affect the mechanical strength. Also, the absolute value G of the complex elastic modulus measured with a rotational rheometer * of the phase angle δ (G * at = 0.1 MPa) is less than 50 degrees, the molecular structure of the multi-component copolymer shows a structure containing excessive long-chain branches, resulting in inferior mechanical strength. The absolute value G of the complex elastic modulus measured with a rotational rheometer * of the phase angle δ at = 0.1 MPa is affected by both the molecular weight distribution and the long-chain branches. However, only for multi-component copolymers with Mw / Mn ≤ 4, more preferably Mw / Mn ≤ 3, it becomes an indicator of the amount of long-chain branches. The more long-chain branches contained in its molecular structure, the smaller the δ (G * at = 0.1 MPa) value. In addition, if the Mw / Mn of the multi-component copolymer is 1.5 or more, even when the molecular structure does not contain long-chain branches, the δ (G * at = 0.1 MPa) value does not exceed 75 degrees.

[0049] The method for measuring the complex elastic modulus is as follows. Put the sample into a heating press mold with a thickness of 1.0 mm, preheat it in a hot press machine with a surface temperature of 180 °C for 5 minutes, then degas the residual gas in the molten resin by repeating pressurization and depressurization, and further pressurize it at 4.9 MPa and hold for 5 minutes. Then, transfer the sample to a press machine with a surface temperature of 25 °C and cool it by holding at a pressure of 4.9 MPa for 3 minutes to create a press plate composed of a sample with a thickness of about 1.0 mm. A sample obtained by processing the press plate composed of the sample into a 25 mm diameter circle is used as a sample, and an ARES type rotational rheometer manufactured by Rheometrics is used as a measuring device for dynamic viscoelastic properties, and the dynamic viscoelasticity is measured under the following conditions in a nitrogen atmosphere. · Plate: φ25 mm parallel plate · Temperature: 160 °C · Strain amount: 10% · Measurement angular frequency range: 1.0×10 -2 ~1.0×10 2rad / s ·Measurement interval: 5 points / decade Absolute value G of complex elastic modulus * Common logarithm logG of (Pa) * Plot the phase angle δ against it, and logG * Let the value of δ (degrees) at the point corresponding to logG = 5.0 be δ(G * = 0.1 MPa). When there is no point corresponding to logG * = 5.0 among the measurement points, use two points around logG * = 5.0 to obtain the δ value at logG * = 5.0 by linear interpolation. Also, when all measurement points are logG * < 5, use the values of three points from the larger logG * values to extrapolate the δ value at logG * = 5.0 using a quadratic curve.

[0050] ·Regarding the production of the copolymer From the viewpoint of making the molecular structure of the copolymer linear, it is preferably produced in the presence of a transition metal catalyst. ·Polymerization catalyst The type of polymerization catalyst used for the production of the copolymer according to the present invention is not particularly limited as long as it can copolymerize structural unit (A), structural unit (B), and optional structural unit (C). For example, transition metal compounds of Groups 5 to 11 having a chelating ligand can be mentioned. Specific examples of preferred transition metals include vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, manganese atom, iron atom, platinum atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom, copper atom, etc. Among these, preferably, transition metals of Groups 8 to 11, more preferably transition metals of Group 10, and particularly preferably nickel (Ni) and palladium (Pd). These metals may be used alone or in combination of a plurality. The chelating ligand contains a ligand having at least two atoms selected from the group consisting of P, N, O, and S, and is bidentate or multidentate, and is electronically neutral or anionic. The structure of the chelating ligand is illustrated in a review by Brookhart et al. (Chem. Rev., 2000, 100, 1169). Preferred chelating ligands include bidentate anionic P, O ligands. Examples of bidentate anionic P, O ligands include phosphinosulfonic acid, phosphinocarboxylic acid, phosphinophenol, and phosphinoenolate. Other chelating ligands include bidentate anionic N, O ligands. Examples of bidentate anionic N, O ligands include salicylaldiminato and pyridinecarboxylic acid. Other chelating ligands include diimine ligands, diphenoxide ligands, and diamide ligands, etc.

[0051] The structure of the metal complex obtained from the chelating ligand is represented by the following structural formula (a) or (b) coordinated with an arylphosphine compound, arylarsine compound, or arylantimony compound which may have a substituent. [Chemical formula] [Chemical formula] [In structural formula (a) and structural formula (b), M represents a transition metal belonging to any of Groups 5 to 11 of the periodic table of the elements, that is, various transition metals as described above. X 1 represents oxygen, sulfur, -SO3-, or -CO2-. Y 1 represents carbon or silicon. n represents an integer of 0 or 1. E 1 represents phosphorus, arsenic, or antimony. R 53 and R 54Each independently represents a hydrocarbon group which may contain hydrogen or a heteroatom and has 1 to 30 carbon atoms. R 55 Each independently represents hydrogen, a halogen, or a hydrocarbon group which may contain a heteroatom and has 1 to 30 carbon atoms. R 56 and R 57 Each independently represents hydrogen, a halogen, a hydrocarbon group which may contain a heteroatom and has 1 to 30 carbon atoms, OR 52 CO2R 52 CO2M’, C(O)N(R 51 )2, C(O)R 52 SR 52 SO2R 52 SOR 52 OSO2R 52 P(O)(OR 52 ) 2-y (R 51 ) y CN, NHR 52 N(R 52 )2, Si(OR 51 ) 3-x (R 51 ) x OSi(OR 51 ) 3-x (R 51 ) x NO2, SO3M’, PO3M’2, P(O)(OR 52 )2M’ or an epoxy-containing group. R 51 represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. R 52 represents a hydrocarbon group having 1 to 20 carbon atoms. M’ represents an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium or phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2. In addition, R 56 and R 57 may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, or sulfur. At this time, the number of ring members is 5 to 8, and the ring may or may not have a substituent. L1 represents a ligand coordinated to M. Also, R 53 and L 1 may combine with each other to form a ring.

[0052] More preferably, the complex serving as the polymerization catalyst is a transition metal complex represented by the following structural formula (c).

Chemical formula

[0053] Here, as the catalyst of the transition metal compound of Groups 5 to 11 having a chelating ligand, typically, catalysts such as so-called SHOP catalysts and Drent catalysts are known. The SHOP catalyst is a catalyst in which a phosphorus-based ligand having an aryl group which may have a substituent is coordinated to a nickel metal (see, for example, WO2010-050256). Also, the Drent catalyst is a catalyst in which a phosphorus-based ligand having an aryl group which may have a substituent is coordinated to a palladium metal (see, for example, JP-A-2010-202647).

[0054] · Method for polymerizing the copolymer: The method for polymerizing the copolymer according to the present invention is not limited. Examples of the polymerization method include slurry polymerization in which at least a part of the produced polymer becomes a slurry in a medium, bulk polymerization using the liquefied monomer itself as the medium, gas-phase polymerization carried out in the vaporized monomer, or high-pressure ionic polymerization in which at least a part of the produced polymer dissolves in the monomer liquefied at high temperature and high pressure. As the polymerization mode, any of batch polymerization, semi-batch polymerization, or continuous polymerization may be used. Also, living polymerization may be carried out, or polymerization may be carried out while concurrent chain transfer occurs. Furthermore, during the polymerization, a so-called chain shuttling agent (CSA) may be used in combination to carry out a chain shuttling reaction or coordinative chain transfer polymerization (CCTP). Specific production processes and conditions are disclosed, for example, in JP-A-2010-260913 and JP-A-2010-202647.

[0055] · Method for introducing a carboxyl group and / or a dicarboxylic anhydride group into the copolymer: The method for introducing a carboxyl group and / or a dicarboxylic anhydride group into the copolymer according to the present invention is not particularly limited. The carboxyl group and / or the dicarboxylic anhydride group can be introduced by various methods without departing from the gist of the present invention. Examples of the method for introducing a carboxyl group and / or a dicarboxylic anhydride group include a method of directly copolymerizing a comonomer having a carboxyl group and / or a dicarboxylic anhydride group, and a method of copolymerizing another monomer having a functional group that generates a carboxyl group and then introducing a carboxyl group and / or a dicarboxylic anhydride group by modification.

[0056] As a method for introducing a carboxyl group and / or a dicarboxylic anhydride group by modification, for example, when introducing a carboxylic acid, a method of copolymerizing an acrylic acid ester as a precursor and then hydrolyzing it to change it into a carboxylic acid, a method of copolymerizing t-butyl acrylate as a precursor and then changing it into a carboxylic acid by thermal decomposition, etc. can be mentioned.

[0057] When performing the above hydrolysis or thermal decomposition, a conventionally known acid-base catalyst may be used as an additive for accelerating the reaction. The acid-base catalyst is not particularly limited, but for example, hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide, lithium hydroxide, carbonates of alkali metals and alkaline earth metals such as sodium hydrogen carbonate and sodium carbonate, solid acids such as montmorillonite, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and organic acids such as formic acid, acetic acid, benzoic acid, citric acid, p-toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, etc. can be appropriately used. From the viewpoints of reaction acceleration effect, price, apparatus corrosiveness, etc., sodium hydroxide, potassium hydroxide, sodium carbonate, p-toluenesulfonic acid, trifluoroacetic acid are preferable, and p-toluenesulfonic acid and trifluoroacetic acid are more preferable.

[0058] (5) Ionomer The ionomer related to the present invention is an ionomer having a substantially linear structure, in which at least a part of the carboxyl group and / or dicarboxylic anhydride group of the structural unit (B) in the copolymer (P) is converted into a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table. The ionomer is obtained by allowing a metal salt to act on an ionomer base resin as described later, and a reaction that cleaves the molecular chain of the polymer usually does not occur. For this reason, parameters related to the structure such as the molar ratio of comonomers, the degree of branching, randomness, etc. are usually preserved between the ionomer base resin and the ionomer.

[0059] · Structure of ionomer Since the ionomer according to the present invention has a substantially linear structure like the copolymer according to the present invention, the absolute value G of the complex elastic modulus measured with a rotational rheometer * The phase angle δ at = 0.1 MPa is characterized by being 50 to 75 degrees. The lower limit of the phase angle δ may be 51 degrees or more, and the upper limit of the phase angle δ may be 64 degrees or less. The phase angle δ (G * = 0.1 MPa) is lower than 50 degrees, the molecular structure of the ionomer shows a structure containing an excessive amount of long-chain branches, and the mechanical strength is inferior. As described above, if Mw / Mn ≤ 4, the value of the phase angle δ becomes an index of the amount of long-chain branches. If the Mw / Mn of the ionomer is 1.5 or more, even when the molecular structure does not contain long-chain branches, the δ (G * = 0.1 MPa) value does not exceed 75 degrees.

[0060] · Melting point (Tm, °C) of the ionomer The melting point (Tm, °C) of the ionomer according to the present invention is preferably 50°C to 140°C, more preferably 60°C to 138°C, and most preferably 70°C to 135°C. If it is lower than this range, the heat resistance is not sufficient, and if it is higher than this range, the adhesiveness may be inferior. Among the ionomers according to the present invention, the ionomer based on the binary copolymer composed only of the structural unit (A) and the structural unit (B) shows a melting point of 90°C or higher, preferably 95°C or higher, more preferably 100°C or higher, and the melting point of the ionomer based on the terpolymer or higher multi-component copolymer is less than 100°C, preferably less than 95°C, more preferably less than 90°C.

[0061] · Metal ions The metal ions contained in the ionomer according to the present invention are not particularly limited and can include metal ions used in conventionally known ionomers. Among the metal ions, in particular, metal ions of Group 1, Group 2, or Group 12 of the periodic table are preferable, and Li + , Na + , K + , Rb + , Cs + , Mg2+ 、Ca 2+ 、Sr 2+ 、Ba 2+ and Zn 2+ It is more preferable that at least one selected from the group consisting of is used. Particularly preferably, Li + 、Na + 、K + 、Mg 2+ 、Ca 2+ 、and Zn 2+ 、More preferably, at least one selected from the group consisting of Na + 、and Zn 2+ is included. These metal ions can be mixed and contained in two or more kinds as needed.

[0062] ·Degree of neutralization (mol%) As the content of the metal ions, it preferably contains an amount that neutralizes at least a part or all of the carboxyl groups and / or dicarboxylic anhydride groups in the copolymer as the base polymer. The preferable degree of neutralization (average degree of neutralization) is 5 to 95 mol%, more preferably 10 to 90 mol%, and still more preferably 20 to 80 mol%. The degree of neutralization can be determined from the ratio of the total mol amount of the valence of the metal ions × mol amount to the total mol amount of the carboxyl groups that can be contained in the carboxyl groups and / or dicarboxylic anhydride groups in the copolymer. Since the dicarboxylic anhydride group forms a carboxylic acid salt, it is ring-opened to become a dicarboxylic acid. Therefore, the total mol amount of the carboxyl groups is determined as having 2 mol of carboxyl groups per 1 mol of the dicarboxylic anhydride group. Also, for example, divalent metal ions such as Zn 2+ etc. are assumed to be able to form a salt with 2 mol of carboxyl groups per 1 mol, and the total mol amount of the molecules of the degree of neutralization is calculated by 2 × mol amount. When the degree of neutralization is high, the tensile strength and tensile fracture stress of the ionomer are high, and the tensile fracture strain is small, but the melt flow rate (MFR) of the ionomer tends to be small. On the other hand, when the degree of neutralization is low, an ionomer with an appropriate MFR can be obtained, but the tensile modulus and tensile fracture stress are low, and the tensile fracture strain tends to be high.

[0063] · Method for producing ionomer The ionomer according to the present invention may be obtained by subjecting a copolymer of ethylene and / or an α-olefin having 3 to 20 carbon atoms / unsaturated carboxylic acid obtained by the method for introducing a carboxyl group and / or a dicarboxylic acid anhydride group into the copolymer as described above to a conversion step of treating with a metal salt containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table to convert it into a metal-containing carboxylate. Further, the ionomer according to the present invention may be obtained by heating an ethylene and / or an α-olefin having 3 to 20 carbon atoms / unsaturated carboxylic acid ester copolymer and subjecting at least a part of the ester groups in the copolymer to a heat conversion step of converting them into a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table.

[0064] When producing an ionomer after introducing a carboxyl group and / or a dicarboxylic acid anhydride group into a polymer, the production method is, for example, as follows. That is, a metal ion source is prepared by heating and kneading a substance that captures metal ions, such as an ethylene / methacrylic acid (MAA) copolymer, and a metal salt as appropriate, and then the metal ion source is added to an ionomer base resin in an amount that gives a desired degree of neutralization and kneaded to obtain it.

[0065] In the heat conversion step, (i) an ethylene and / or C3-C20 α-olefin / unsaturated carboxylic acid ester copolymer may be heated and converted into an ethylene and / or C3-C20 α-olefin / unsaturated carboxylic acid copolymer by hydrolysis or thermal decomposition, and then reacted with a compound containing a metal ion of Group 1, Group 2, or Group 12 of the periodic table to convert the carboxylic acid in the ethylene and / or C3-C20 α-olefin / unsaturated carboxylic acid copolymer into the metal-containing carboxylate. Alternatively, (ii) an ethylene and / or C3-C20 α-olefin / unsaturated carboxylic acid ester copolymer may be heated and reacted with a compound containing a metal ion of Group 1, Group 2, or Group 12 of the periodic table while hydrolyzing or thermally decomposing the ester group of the copolymer to convert the ester group portion in the ethylene and / or C3-C20 α-olefin / unsaturated carboxylic acid ester copolymer into the metal-containing carboxylate.

[0066] The compound containing a metal ion may be an oxide, hydroxide, carbonate, bicarbonate, acetate, formate, etc. of a metal of Group 1, Group 2, or Group 12 of the periodic table. The compound containing a metal ion may be supplied to the reaction system in granular or fine powder form, or may be dissolved or dispersed in water or an organic solvent and then supplied to the reaction system. A masterbatch based on an ethylene / unsaturated carboxylic acid copolymer or an olefin copolymer may be prepared and supplied to the reaction system. To smoothly progress the reaction, it is preferable to prepare a masterbatch and supply it to the reaction system.

[0067] Furthermore, the reaction with the compound containing a metal ion may be carried out by melt-kneading using various types of apparatuses such as a vent extruder, Banbury mixer, or roll mill, and the reaction may be either batchwise or continuous. By discharging the water and carbon dioxide gas by-produced by the reaction using a degassing device, the reaction can proceed smoothly, so it is preferable to carry out the reaction continuously using an extruder equipped with a degassing device such as a vent extruder. When reacting with the compound containing a metal ion, a small amount of water may be injected to accelerate the reaction.

[0068] The temperature for heating the ethylene and / or α-olefin / unsaturated carboxylic acid ester copolymer having 3 to 20 carbon atoms may be any temperature at which the ester becomes a carboxylic acid. If the heating temperature is too low, the ester will not be converted into a carboxylic acid, and if it is too high, decarbonylation or decomposition of the copolymer may proceed. Therefore, the heating temperature of the present invention is preferably in the range of 80°C to 350°C, more preferably 100°C to 340°C, still more preferably 150°C to 330°C, and even more preferably 200°C to 320°C.

[0069] The reaction time varies depending on the heating temperature, the reactivity of the ester group portion, etc., but is usually 1 minute to 50 hours, more preferably 2 minutes to 30 hours, still more preferably 2 minutes to 10 hours, even more preferably 2 minutes to 3 hours, and particularly preferably 3 minutes to 2 hours.

[0070] In the above step, there is no particular limitation on the reaction atmosphere, but it is generally preferred to carry out the reaction under an inert gas stream. Examples of the inert gas that can be used include nitrogen, argon, and a carbon dioxide atmosphere. A small amount of oxygen or air may be mixed in.

[0071] There is no particular limitation on the reactor used in the above step, but any method that can substantially uniformly stir the copolymer is not limited at all. A glass container equipped with a stirrer or an autoclave (AC) may be used, or any conventionally known kneader such as a Brabender plastograph, a single-screw or twin-screw extruder, a powerful screw-type kneader, a Banbury mixer, a kneader, or a roll can also be used.

[0072] When metal ions are introduced into the ionomer-based resin, whether it has become an ionomer can be confirmed by measuring the IR spectrum of the obtained resin and examining the decrease in the peak derived from the carbonyl group of the carboxylic acid (dimer). Similarly, the degree of neutralization can also be confirmed by examining the decrease in the peak derived from the carbonyl group of the carboxylic acid (dimer) and the increase in the peak derived from the carbonyl group of the carboxylate group, in addition to the calculation from the aforementioned molar ratio.

[0073] <Ionomer physical properties> The ionomers used in the present invention, particularly the ionomers for films suitable for film applications, have any one or a combination of the following physical properties under the measurement conditions described in the columns of Examples 1 to 20 described later.

[0074] ·MFR: In the ionomer of the present invention, the melt flow rate (MFR) at a temperature of 190 °C and a load of 2.16 kg is 0.01 to 30 g / 10 min, preferably 0.1 to 15 g / 10 min, and more preferably 0.5 to 20 g / 10 min. When the MFR of the ionomer is within this range, film formation is easy.

[0075] ·Tensile modulus of elasticity: In the ionomer of the present invention, the tensile modulus of elasticity is 20 MPa or more, preferably 20 to 350 MPa, and preferably 20 to 300 MPa. When the tensile modulus of elasticity of the ionomer is within this range, the adhesion when formed into a film is good. In addition, the ionomer can be produced without difficulty in terms of designing the modulus of elasticity.

[0076] ·Tensile impact strength: In the ionomer of the present invention, the tensile impact strength is 100 KJ / m 2 or more, preferably the tensile impact strength is 700 KJ / m 2 or more, and more preferably 800 KJ / m 2 or more. In the ionomer based on a multi-component copolymer of more than a ternary system, an ionomer capable of achieving a tensile impact strength of 700 KJ / m 2 or more can be obtained. When the tensile impact strength of the ionomer is within this range, even if the film has rubbing or the like with large deformation, the risk of breakage is reduced. The upper limit of the tensile impact strength is not particularly limited within the range obtained from the materials used by those skilled in the art.

[0077] · Abrasion amount in the abrasion test: In the ionomer of the present invention, the abrasion amount in the abrasion test is less than 10 mg, preferably 9 mg or less. The conditions of the abrasion test are as described later. When the abrasion amount in the abrasion test is within this range, even when repeated rubbing and compression forces are applied, damage is less likely to occur on the film surface.

[0078] · Haze: In the ionomer of the present invention, the haze is 0.1 to 30%, preferably 0.1 to 20%. If the haze of the ionomer is 30% or less, it is preferable because it can be used without reducing transparency and without being restricted by the environment and applications.

[0079] · Additives In the ionomer related to the present invention, additives such as conventionally known antioxidants, ultraviolet absorbers, lubricants, antistatic agents, antiblocking agents, colorants, pigments, crosslinking agents, foaming agents, nucleating agents, flame retardants, conductive materials, and fillers may be blended within a range not departing from the gist of the present invention.

[0080] · Resin composition As a resin composition for films (including sheets) and other molded articles, the ionomer of the present invention may be used alone or as a resin composition blended with other resin components. Hereinafter, in the present invention, when referring to a "resin composition containing an ionomer" used in a molded article, it includes an ionomer resin alone or a composition blended with other resin components, additives, etc. Other resin components that can be blended in the ionomer resin composition of the present invention are not particularly limited as long as they are compatible with the ionomer and do not impair the effects of the present invention as a resin composition for films. For example, high-density polyethylene, medium-density polyethylene, low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, other ionomers, etc. can be mentioned. Also, two or more materials can be used in combination. The blending amount of these resin components is not particularly limited as long as it does not impair the effects of the present invention. The resin composition for films of the present invention is characterized by containing a specific ionomer according to the present application, and preferably, the content can be arbitrarily selected from the range of 1 to 100% by weight in combination with the intended film use and other various conditions. When using the specific ionomer according to the present application as a resin material for films, as the content in the resin composition, the resin material for films preferably contains 10% by weight or more of the ionomer of the present invention, more preferably 30% by weight or more, still more preferably 50% by weight or more, and particularly preferably 60% by weight or more. The upper limit value can be arbitrarily selected from 100% by weight or less, 90% by weight or less, 70% by weight or less, 50% by weight or less, or 40% by weight or less. The higher the content of the specific ionomer according to the present invention in the resin composition, the more fully the excellent physical properties and the like due to the use of the ionomer can be exhibited. However, the blending amount can be arbitrarily selected from the viewpoints of other processability, required physical properties, and cost. In addition, for use as a modifier for other resin materials for films, the resin material for films can contain 1% by weight or more, preferably 3% by weight or more, more preferably 10% by weight or more, and still more preferably 20% by weight or more of the ionomer of the present invention as the content in the resin composition.

[0081] For the ionomers used in the present invention, various additives and polymer components that are added or blended as necessary can be mixed using a Henschel mixer, super mixer, tumbler type mixer, etc., and then heat-kneaded and pelletized using a single-screw or twin-screw extruder, kneader, etc.

[0082] 2. Molded article (film) One embodiment of the present invention relates to a film-shaped molded article formed using a resin composition for films containing the ionomer, that is, an ethylene-based film. Here, the ethylene-based film refers to a film obtained from a resin mainly composed of a so-called ethylene monomer. The thickness of the film can be arbitrarily selected according to its use, but is usually about 1 to 500 μm, preferably 5 to 200 μm, and more preferably 10 to 100 μm. In this specification, even if the thickness is outside the above range, as long as the thickness is sufficiently small compared to the length in the remaining biaxial direction and the surface having no thickness direction is solely used for its utilization, it is represented as a film (film-shaped molded article). The molded article of the present invention can have an arbitrary shape such as a quadrilateral, circular, or triangular shape for the surface portion as long as it is in the form of a film. Preferably, it is bendable. Therefore, the "film" of the present application means not only a film in the narrow sense (thickness less than 250 μm), but also includes a sheet in the narrow sense with a thickness of 250 μm or more, tape, etc. However, considering that the most prominent feature of the film formed from the resin composition containing the ionomer of the present invention is its high optical properties along with high rigidity and high strength, particularly when the film thickness is thinner, the remarkable effects such as high strength and transparency of the film of the present invention are more likely to be significantly manifested. Therefore, a thickness of 1 to 100 μm, preferably 1 to 50 μm, and more preferably 1 to 30 μm is preferred. Depending on the compounding amount and application, it is also possible to reduce the thickness significantly to the range of 1 to 10 μm, and ultimately 1 to 5 μm.

[0083] By forming the resin composition containing the ionomer of the present invention into a film shape, a film molded body can be obtained. As the method for manufacturing the film or sheet, a method known to those skilled in the art can be used. Examples include various inflation molding methods, T-die film molding methods, calender molding methods, etc. The resin composition containing the ionomer of the present invention can, in particular, obtain a film that exhibits unexpected and remarkable effects from the ionomer copolymer alone through the film-forming process of being formed thinly and in a long strip shape. For example, when using the inflation molding method, a known inflation molding machine equipped with an annular die can be used. The temperature of the annular die is preferably 70 to 220°C. Also, the blowing air ring in the process of inflation film molding is not particularly limited, but those having a plurality of blowing slits are preferred. The blow-up ratio in the process of inflation film molding is preferably in the range of 0.3 to 10, and more preferably in the range of 1 to 8. A known bubble internal cooling device can also be used to increase the stability of the bubble.

[0084] The ethylene-based film formed using the resin composition for films containing the ionomer of the present invention is an ethylene-based film that has at least one or combines the leapfrog physical property performances in the unreachable region that could not be achieved by conventional general ethylene-based resins. That is, it is a film having the following performance, any one or a combination thereof, such as high rigidity, high strength, high transparency, high gloss, and low-temperature heat sealability. · High rigidity and high strength (toughness) One aspect of the present invention is a film containing an ethylene-based resin as a resin component, wherein the film impact at -20°C when formed into a thickness of 30 μm and measured is 20 J / mm or more, and the tensile elastic modulus in the MD direction is 150 MPa or more. It is an ethylene-based film. Preferably, the film impact at 23°C is 30 J / mm or more, the film impact is 40 J / mm or more, more preferably 50 J / mm or more, and the film impact at -20°C is 20 J / mm or more, more preferably 22 J / mm or more, further preferably 30 J / mm or more, and even more preferably 40 J / mm or more. On the other hand, the tensile elastic modulus in the MD direction is preferably 200 MPa or more, more preferably 250 MPa or more. As shown in FIGS. 5 and 6, the balance between rigidity and toughness is important for the film. According to the present invention, both are appropriately balanced and show high values, and the balance is good even at -20°C, which is a low-temperature range. An ethylene-based film having physical properties in a region that has not been obtained so far can be obtained. · High heat seal strength One aspect of the present invention is a film containing an ethylene-based resin as a resin component, wherein the heat seal strength at a seal temperature of 120°C, a seal pressure of 0.2 MPa, a seal time of 1 second, and a lower seal bar temperature of 60°C when formed into a thickness of 30 μm and measured is 10 N / 15 mm or more. It is an ethylene-based film. More preferably, it is an ethylene-based film in which the heat seal strength at a seal temperature of 100°C, a seal pressure of 0.2 MPa, a seal time of 1 second, and a lower seal bar temperature of 60°C is 6 N / 15 mm or more, and even more preferably, the heat seal strength under the above conditions is 7 N / 15 mm or more. · High transparency One aspect of the present invention is an ethylene-based film having an ethylene-based resin as a resin component, particularly an inflation film obtained by inflation molding, which is an ethylene-based film having a haze of 2% or less when formed to a thickness of 30 μm. Particularly preferably, it is an ethylene-based film having a haze of 1% or less, more preferably 0.5% or less, under the above conditions. · High gloss One aspect of the present invention is an ethylene-based film having an ethylene-based resin as a resin component, particularly an inflation film obtained by inflation molding, which is an ethylene-based film having a gloss (20°) of 120% or more when formed to a thickness of 30 μm. Particularly preferably, it is an ethylene-based film having a gloss of 130% or more under the above conditions.

[0085] The film of the present embodiment can be used in applications known for ethylene-based films using conventional ethylene-based resins or ionomers, or in applications of other film materials that have not been conventionally used for ethylene-based films, for example, as a single layer as a film for replacing OPP films, or laminated with other materials. For example, various applications such as films, sheets, tapes, etc. can be mentioned. As films, agricultural films, food films, electronic material films, industrial films can be mentioned. As packaging films, they can be used as various packaging materials, for example, food packaging materials, medical packaging materials, electronic material packaging materials, industrial material packaging materials, etc. For example, it can be suitably used as a film for packaging heavy objects or contents containing liquids. Other examples include adhesive tapes or films for semiconductors, marking films, sanitary materials, protective films, sealant films, steel wire coating materials, clean room curtains, wallpapers, mats, floor materials, inner bags for flexible containers, containers, shoes, battery separators, moisture-permeable films, antifouling films, dust-proof films, PVC replacement films, OPP replacement films, etc.

Examples

[0086] The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The measurement and evaluation of physical properties in the Examples and Comparative Examples were carried out by the methods shown below. In the tables, "no data" means not measured, and "not detected" means below the detection limit.

[0087] <Measurement and Evaluation> (1) Measurement of weight average molecular weight (Mw) and molecular weight distribution parameter (Mw / Mn) The weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC). The molecular weight distribution parameter (Mw / Mn) was calculated by further determining the number average molecular weight (Mn) by gel permeation chromatography (GPC) and taking the ratio of Mw to Mn, Mw / Mn. The measurement was carried out according to the following procedures and conditions.

[0088] 1) Pretreatment of sample When the sample contains a carboxylic acid group, for example, esterification treatment such as methylation using diazomethane or trimethylsilyl (TMS) diazomethane was carried out and used for measurement. When the sample contains a carboxylate group, acid treatment was carried out to modify the carboxylate group to a carboxylic acid group, and then the above esterification treatment was carried out and used for measurement.

[0089] 2) Preparation of sample solution 3 mg of the sample and 3 mL of o-dichlorobenzene were weighed into a 4 mL vial, covered with a screw cap and a septum made of Teflon (registered trademark), and then shaken at 150 °C for 2 hours using a SSC-7300 type high-temperature shaker manufactured by Senshu Science Co., Ltd. After the shaking was completed, it was visually confirmed that there were no insoluble components.

[0090] 3) Measurement One Showa Denko high-temperature GPC column Showdex HT-G and two HT-806M columns were connected to an Alliance GPCV2000 type manufactured by Waters Corporation, o-dichlorobenzene was used as the eluent, and the measurement was carried out at a temperature of 145 °C and a flow rate of 1.0 mL / min.

[0091] 4) Calibration curve The calibration of the column was carried out under the same conditions as above for the measurement of monodisperse polystyrene (0.07 mg / ml solutions of S-7300, S-3900, S-1950, S-1460, S-1010, S-565, S-152, S-66.0, S-28.5, S-5.05, each manufactured by Showa Denko), n-eicosane and n-tetracosane, and the elution time and the logarithmic value of the molecular weight were approximated by a fourth-order equation. Note that for the conversion between polystyrene molecular weight (M PS ) and polyethylene molecular weight (M PE ), the following equation was used. M PE = 0.468 × M PS

[0092] (2) Method for measuring the amount of structural units derived from monomers having a carboxy group and / or a dicarboxylic anhydride group and acyclic monomers, and the number of branches per 1,000 carbons The amount of structural units derived from monomers having a carboxy group and / or a dicarboxylic anhydride group, and acyclic monomers, and the number of branches per 1,000 carbons in the multi-component copolymer of the present invention are 13 determined using a C-NMR spectrum. 13 C-NMR was measured by the following method. 200 - 300 mg of the sample was placed in an NMR sample tube with an inner diameter of 10 mmφ together with 2.4 ml of a mixed solvent of o-dichlorobenzene (C6H4Cl2) and deuterated benzene bromide (C6D5Br) (C6H4Cl2 / C6D5Br = 2 / 1 (volume ratio)) and hexamethyldisiloxane as a chemical shift reference substance, purged with nitrogen, sealed, heated and dissolved to obtain a uniform solution as an NMR measurement sample. NMR measurement was carried out at 120 °C using an AV400M type NMR apparatus of Bruker Japan Co., Ltd. equipped with a 10 mmφ cryoprobe. 13 C-NMR was measured by the inverse gate decoupling method at a sample temperature of 120 °C, a pulse angle of 90°, a pulse interval of 51.5 seconds, and an integration number of 512 times or more. The chemical shift was that of hexamethyldisiloxane 13The C signal was set at 1.98 ppm, and the chemical shift of the signal due to the other 13 C signals was based on this.

[0093] 1) Pretreatment of the sample When the sample contained a carboxylate group, it was acid-treated to modify the carboxylate group to a carboxy group and then used for measurement. When the sample contained a carboxy group, esterification treatment such as methylation using, for example, diazomethane or trimethylsilyl (TMS) diazomethane may be appropriately performed.

[0094] 2) Calculation of the amount of structural units derived from monomers having a carboxy group and / or a dicarboxylic anhydride group, and acyclic monomers <e tba> The quaternary carbon signal of the t-butyl acrylate group of tBA is detected at 79.6 to 78.8 in the 13C-NMR spectrum. Using these signal intensities, the comonomer amount was calculated from the following formula. 13 The total amount of tBA (mol%) = I(tBA) × 100 / [I(tBA) + I(E)] Here, I(tBA) and I(E) are the amounts represented by the following formulas, respectively. I(tBA) = I I(tBA)=I 79.6~78.8 I(E)=(I 180.0~135.0 +I 120.0~5.0 -I(tBA)×7) / 2

[0095] <e tba nba> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 detected at 79.6 - 78.8 ppm in the 13C-NMR spectrum, and the methylene signal of the butoxy group of nBA is detected at 64.1 - 63.4 ppm. Using these signal intensities, the comonomer amounts were calculated from the following equations. Total amount of tBA (mol%) = I(tBA) × 100 / [I(tBA) + I(nBA) + I(E)] Total amount of nBA (mol%) = I(nBA) × 100 / [I(tBA) + I(nBA) + I(E)] Here, I(tBA), I(nBA), and I(E) are the amounts represented by the following equations, respectively. I(tBA) = I 79.6~78.8 I(nBA) = I 64.1~63.4 I(E) = (I 180.0~135.0 + I 120.0~5.0 - I(nBA) × 7 - I(tBA) × 7) / 2

[0096] <e tba iba> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 detected at 79.6 - 78.8 ppm in the 13C-NMR spectrum. The methylene signal of the isobutoxy group of iBA is detected at 70.5 - 69.8 ppm, and the methyl signal of the isobutoxy group is detected at 19.5 - 18.9 ppm. Using these signal intensities, the comonomer amounts were calculated from the following equations. Total amount of tBA (mol%) = I(tBA) × 100 / [I(tBA) + I(iBA) + I(E)] Total amount of iBA (mol%) = I(iBA) × 100 / [I(tBA) + I(iBA) + I(E)] Here, I(tBA), I(iBA), and I(E) are the amounts represented by the following equations, respectively. I(tBA) = I 79.6~78.8 I(iBA) = (I 70.5~69.8 + I 19.5~18.9 ) / 3 I(E) = (I 180.0~135.0 + I 120.0~5.0 - I(iBA) × 7 - I(tBA) × 7) / 2

[0097] <e tba nb> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 detected at 79.6 - 78.8 ppm in the 13C-NMR spectrum, and the methine carbon signal of NB is detected at 41.9 - 41.1 ppm. Using these signal intensities, the comonomer amounts were calculated from the following equations. Total amount of tBA (mol%) = I(tBA) × 100 / [I(tBA) + I(NB) + I(E)] Total amount of NB (mol%) = I(NB) × 100 / [I(tBA) + I(NB) + I(E)] Here, I(tBA), I(NB), and I(E) are the amounts represented by the following equations, respectively. I(tBA) = I 79.6~78.8 I(NB) = (I 41.9~41.1 ) / 2 I(E) = (I 180.0~135.0 + I 120.0~5.0 - I(NB) × 7 - I(tBA) × 7) / 2

[0098] When the structural unit amount of each monomer is indicated by "<0.1" including an inequality sign, it means that it exists as a constitutional unit in the copolymer but is less than 0.1 mol% considering significant figures.

[0099] 3) Calculation of the number of branches per 1,000 carbons In the copolymer, there are isolated types where branches exist alone in the main chain, and composite types (face-to-face type where branches face each other through the main chain, branched-branch type with branches in the branched chain, and chain type). The following are examples of the structure of ethyl branches. In the example of the face-to-face type, R represents an alkyl group.

[0100]

Chemical formula

[0101] The number of branches per 1,000 carbons is calculated by substituting either I(B1), I(B2), or I(B4) below into the I (branch) term in the following formula. B1 represents methyl branches, B2 represents ethyl branches, and B4 represents butyl branches. The number of methyl branches is calculated using I(B1), the number of ethyl branches using I(B2), and the number of butyl branches using I(B4). Number of branches (per 1,000 carbons) = I (branches) x 1000 / I (total) Here, I(total), I(B1), I(B2), and I(B4) are quantities expressed by the following formulas. I(total)=I 180.0~135.0 +I 120.0~5.0 I(B1)=(I 20.0~19.8 +I 33.2~33.1 +I 37.5~37.3 ) / 4 I(B2)=I 8.6~7.6 +I 11.8~10.5 I(B4)=I 14.3~13.7 -I 32.2~32.0 Here, I is the integrated intensity, and the subscripts of I indicate the range of chemical shifts. For example, I 180.0~135.0 was detected between 180.0 ppm and 135.0 ppm. 13 C The integrated intensity of the signal is shown. The attribution was based on the non-patent literature Macromolecules 1984, 17, 1756-1761 and Macromolecules 1979, 12, 41. In addition, when each branch number is indicated by "<0.1" including an inequality sign, it means that it exists as a structural unit in the multi-component copolymer, but the amount is less than 0.1 mol% considering significant figures. Also, "not detected" means below the detection limit.

[0102] (3) Infrared absorption spectrum The sample was melted at 180° C. for 3 minutes and compression molded to prepare a film with a thickness of about 50 μm. This film was analyzed by Fourier transform infrared spectroscopy to obtain an infrared absorption spectrum. Product name: FT / IR-6100 manufactured by JASCO Corporation Measurement method: Transmission method Detector: TGS (Triglycine sulfate) Number of integration times: 16 - 512 times Resolution: 4.0 cm -1 Measurement wavelength: 5000 - 500 cm -1

[0103] (4) Absolute value G of complex elastic modulus * = Measurement of phase angle δ at 0.1 MPa 1) Preparation and measurement of sample The sample was placed in a heating press mold with a thickness of 1.0 mm, preheated in a hot press machine with a surface temperature of 180 °C for 5 minutes, and then degassed of the residual gas in the molten resin by repeating pressurization and depressurization. Further, it was pressurized at 4.9 MPa and held for 5 minutes. Then, it was transferred to a press machine with a surface temperature of 25 °C and cooled by holding at a pressure of 4.9 MPa for 3 minutes to produce a press plate made of a sample with a thickness of about 1.0 mm. A sample obtained by processing the press plate made of the sample into a circle with a diameter of 25 mm was used, and a Rheometrics ARES type rotational rheometer was used as a dynamic viscoelasticity measurement device, and the dynamic viscoelasticity was measured under the following conditions in a nitrogen atmosphere. · Plate: φ25 mm (diameter) parallel plate · Temperature: 160 °C · Strain amount: 10% · Measurement angular frequency range: 1.0×10 -2 ~1.0×10 2 rad / s · Measurement interval: 5 points / decade Absolute value G of complex elastic modulus * (Pa) common logarithm logG * Plot the phase angle δ against it, and the value of δ (degree) at the point corresponding to logG * = 5.0 was taken as δ(G * = 0.1 MPa). When there is no point corresponding to logG * = 5.0 among the measurement points, two points around logG * = 5.0 were used to obtain the δ value at logG * = 5.0 by linear interpolation. Also, when all the measurement points are logG * When it is <5, logG * Using the three values from the larger value of the logG value, the δ value at logG = 5.0 was obtained by extrapolation using a quadratic curve. * = 5.0 was obtained by extrapolating the δ value.

[0104] (5) Melting point (Tm, °C): The melting point is indicated by the peak temperature of the endothermic curve measured by a differential scanning calorimeter (DSC). For the measurement, a DSC (DSC7020) manufactured by SII NanoTechnology Inc. was used and carried out under the following measurement conditions. Approximately 5.0 mg of the sample was packed into an aluminum pan, heated to 200 °C at a rate of 10 °C / min, held at 200 °C for 5 minutes, and then cooled to 30 °C at a rate of 10 °C / min. After holding at 30 °C for 5 minutes, among the absorption curves when heating again at a rate of 10 °C / min, the maximum peak temperature was taken as the melting point Tm, the heat of fusion (ΔH) was obtained from the melting endothermic peak area, and the crystallinity (%) was obtained by dividing the heat of fusion by the heat of fusion of the perfect crystal of high-density polyethylene (HDPE), which is 293 J / g.

[0105] (6) Melt flow rate (MFR) The MFR was measured according to Table 1 - Condition 7 of JIS K - 7210 (1999) under the conditions of a temperature of 190 °C and a load of 21.18 N (= 2.16 kg).

[0106] (7) Haze measurement method The haze was measured in accordance with JIS K 7136.

[0107] Sample press plate adjustment method The sample was placed in a heating press mold with dimensions: 50 mm × 60 mm and a thickness of 0.5 mm, preheated in a hot press machine with a surface temperature of 180 °C for 5 minutes, and the residual gas in the sample was degassed by repeating pressurization and depressurization. Then, it was pressurized at 4.9 MPa and held for 3 minutes. After that, it was transferred to a press machine with a surface temperature of 25 °C and cooled by holding at a pressure of 4.9 MPa for 3 minutes to produce a press plate with a thickness of approximately 0.5 mm.

[0108] (8) Tensile test The sample was made into a 1-mm thick sheet by the method described in JIS K7151 (1995) (cooling method A), and using a 5B-shaped small test piece described in JIS K7162 (1994) produced by punching this, a tensile test was carried out under the condition of a temperature of 23°C in accordance with JIS K7161 (1994), and the tensile elastic modulus, tensile fracture stress, and tensile fracture strain were measured. The test speed was 10 mm / min.

[0109] (9) Tensile impact strength 1) Method for producing a tensile impact strength test sample The sample was placed in a heating press mold with a thickness of 1 mm, preheated in a hot press machine with a surface temperature of 180°C for 5 minutes, and then the sample was melted and the residual gas in the sample was degassed by repeating pressurization and depressurization, and further pressurized at 4.9 MPa and held for 5 minutes. Then, while applying a pressure of 4.9 MPa, it was gradually cooled at a rate of 10°C / min, and when the temperature dropped to near room temperature, the molded plate was taken out of the mold. The obtained molded plate was conditioned for 48 hours or more in an environment of a temperature of 23 ± 2°C and a humidity of 50 ± 5°C. A test piece of the shape of ASTM D1822 Type-S was punched out from the conditioned press plate to obtain a tensile impact strength test sample.

[0110] 2) Tensile impact strength test conditions Using the above test piece, the tensile impact strength was measured with reference to Method B of JIS K 7160-1996. The only difference from JIS K 7160-1996 is the shape of the test piece. Regarding other measurement conditions, etc., the test was carried out by a method in accordance with JIS K 7160-1996.

[0111] (10) Measurement of wear amount 1) Method for producing a wear test sample The sample was placed in a heating press mold with dimensions of 150 mm × 150 mm and a thickness of 1 mm. After preheating in a hot press machine with a surface temperature of 180 °C for 5 minutes, the sample was melted and the residual gas in the sample was degassed by repeating pressurization and depressurization. Then, it was pressurized at 4.9 MPa and held for 3 minutes. After that, with a pressure of 4.9 MPa applied, it was gradually cooled at a rate of 10 °C / min. When the temperature dropped to near room temperature, the molded plate was taken out of the mold. The obtained molded plate was conditioned for 48 hours or more in an environment with a temperature of 23 ± 2 °C and a humidity of 50 ± 5 °C. The conditioned press plate was cut into a circular shape with a diameter of about 115 mm, and a hole with a diameter of about 6.5 mm was drilled in the center to obtain a wear test sample.

[0112] 2) Abrasion test conditions Using the above test piece, the wear loss amount (mg) was measured under the following conditions in accordance with JIS K 7204-1999. · Apparatus: Taber abrasion tester (Rotary Abrasion Tester), manufactured by Toyo Seiki Seisakusho Co., Ltd. · Abrasion wheel: CS-17 · Rotation speed: 60 rotations / min · Number of test rotations: 1000 rotations · Load: 4.9 N

[0113] (11) Measurement of the number of flexure resistance 1) Method for preparing a flexure test sample The sample was placed in a heating press mold with dimensions of 150 mm × 150 mm and a thickness of 1 mm. After preheating in a hot press machine with a surface temperature of 180 °C for 5 minutes, the sample was melted and the residual gas in the sample was degassed by repeating pressurization and depressurization. Then, it was pressurized at 4.9 MPa and held for 3 minutes. After that, with a pressure of 4.9 MPa applied, it was gradually cooled at a rate of 10 °C / min. When the temperature dropped to near room temperature, the molded plate was taken out of the mold. The obtained molded plate was conditioned for 48 hours or more in an environment with a temperature of 23 ± 2 °C and a humidity of 50 ± 5 °C. The conditioned press plate was cut into a width of 15 mm and a length of about 110 mm to obtain a flexure test sample.

[0114] 2) Flexure test conditions Using the above test pieces, the number of flexing cycles was measured under the following conditions with reference to JIS P 8115-2001. The only differences from JIS P 8115-2001 were the material of the test piece and the load. Regarding other measurement conditions, etc., the test was carried out in a method conforming to JIS P 8115-2001. · Apparatus: MIT folding fatigue tester, manufactured by Toyo Seiki Seisakusho Co., Ltd. · Load: 29.4 N · Folding speed: 175 cycles / min · Folding angle: 135° · Bending radius of the folding clamp: 0.38 mm

[0115] <Method for producing the film> (Comparative Examples 10 to 13, Example 17) A die with a die diameter of 75 mmφ and a lip width of 3 mm was attached to a single-screw extruder with a diameter of 50 mmφ. Under the condition that the set temperature of the extruder and the die was set to 190°C, inflation molding was performed with a blow ratio of 2.0 to obtain films with a thickness of 30 μm shown in Comparative Examples 10 to 13 and Example 9. The results of the physical property evaluation of this film are shown in Table 7.

[0116] <Method for evaluating the haze of the film> The haze was measured in accordance with JIS K 7136.

[0117] <Method for evaluating the gloss of the film> The gloss of the film was measured with reference to JIS Z8741.

[0118] <Method for measuring the tensile elastic modulus of the film> The MD and TD directions were measured in accordance with JIS K 7127.

[0119] <Method for evaluating the impact strength of the film> · Film impact at 23°C and -20°C Using a film impact tester (FILM·IMPACT·TESTER, hereinafter simply referred to as the "testing machine") manufactured by Toyo Seiki Seisakusho, the work amount required for through - destruction per unit film thickness was measured. Specifically, the test film was stored in an atmosphere of 23°C - 50%, and after conditioning, the test film was fixed to the testing machine with a holder having a diameter of 50 mm. A 1 / 2 - inch (about 13.0 mm) hemispherical metal was struck at the penetration part from the inner layer surface of the test film, and the work amount required for through - destruction was measured. At that time, the load was removed, and the maximum scale (work amount) was set to 3.0 J. Then, the value obtained by dividing the work amount by the film thickness was defined as the film impact value at 23°C. Similarly to the above, using a testing machine equipped with a thermostat also manufactured by Toyo Seiki Seisakusho, the holding part where the film was fixed and the work amount required for through - destruction under the condition that the film was adjusted to - 20°C were measured. At that time, similarly to the above, the load was removed, and the maximum scale (work amount) was set to 3.0 J. Then, the value obtained by dividing the work amount by the film thickness was defined as the film impact value at - 20°C.

[0120] <Film puncture strength evaluation method> The film was fixed, and a semi - circular needle with a diameter of 1.0 mm and a tip shape radius of 0.5 mm was pierced into the film at a speed of 50 ± 0.5 mm per minute, and the maximum load (N) until the needle penetrated was measured.

[0121] <Film pinhole resistance evaluation method> The film was bent 3000 times with a gelbo flex device (manufactured by Tester Sangyo). Then, the number of pinholes was measured.

[0122] <Film heat - seal strength> Two inflation - formed films were stacked, and with a 12 - μm - thick PET film in between, the temperature of the lower seal bar was 60°C, the temperature of the upper seal bar was 80 - 150°C, the seal pressure was 2.0 MPa, and heat - sealing was performed with a seal time of 1.0 second. The 180 - degree peel strength of a 15 - mm width was measured. The measurement results are shown in Table 8 and Figure 2.

[0123] <Synthesis of Metal Complexes> (1) Synthesis of B-27DM / Ni Complex The B-27DM / Ni complex was synthesized according to Synthesis Example 4 described in International Publication No. 2010 / 050256, using the following 2-bis(2,6-dimethoxyphenyl)phosphano-6-pentafluorophenylphenol ligand (B-27DM). According to Example 1 of International Publication No. 2010 / 050256, using bis(1,5-cyclooctadiene)nickel(0) (referred to as Ni(COD)2), a nickel complex (B-27DM / Ni) in which B-27DM and Ni(COD)2 reacted in a 1:1 ratio was synthesized.

Chemical Formula

[0124] (2) Synthesis of B-423 / Ni Complex 1) Synthesis of Ligand B-423: 2-bis(2,6-dimethoxyphenyl)phosphano-6-(2,6-diisopropylphenyl)phenol

Chemical Formula

[0125]

Chemical Formula

[0126] (i) Synthesis of Compound 2 Synthesized according to Patent Document WO2010 / 050256.

[0127] (ii) Synthesis of Compound 3 To a solution of compound 2 (2.64 g, 10.0 mmol) in THF (5.0 ml) was added i-PrMgCl (2 M, 5.25 ml) at 0 °C. After the reaction mixture was stirred at 25 °C for 1 hour, PCl3 (618 mg, 4.50 mmol) was added at -78 °C. The reaction mixture was warmed to 25 °C over 3 hours to obtain a yellow suspension. The solvent was distilled off under reduced pressure to obtain a yellow solid. This mixture was used in the next reaction without purification.

[0128] (iii) Synthesis of compound 5 To a solution of compound 4 (30 g, 220 mmol) in THF (250 ml) was added n-BuLi (2.5 M, 96 ml) at 0 °C, and the mixture was stirred at 30 °C for 1 hour. To this solution was added B(O i Pr)3 (123 g, 651 mmol) at -78 °C, and the mixture was stirred at 30 °C for 2 hours to obtain a white suspension. Hydrochloric acid (1 M) was added to adjust the pH to 6 - 7, and the organic layer was concentrated to obtain a mixture. The obtained mixture was washed with petroleum ether (80 ml) to obtain 26 g of compound 5.

[0129] (iv) Synthesis of compound 7 Compound 5 (5.00 g, 27.5 mmol), compound 6 (4.42 g, 18.3 mmol), Pd2(dba)3 (168 mg, 0.183 mmol), s-Phos (2-dicyclohexylphosphino-2’,6’-dimethoxybiphenyl) (376 mg, 0.916 mmol), and K3PO4 (7.35 g, 34.6 mmol) were weighed into a reaction vessel, and toluene (40 ml) was added. This solution was reacted at 110 °C for 12 hours to obtain a black suspension. H2O (50 ml) was added, and the mixture was extracted with EtOAc (55 ml × 3). The organic layer was washed with brine (20 ml) and dried over Na2SO4. The organic layer was filtered, the solvent was distilled off under reduced pressure, and purification by silica gel column chromatography gave 1.3 g of an oily substance.

[0130] (v) Synthesis of compound 8 To a solution of compound 7 (6.5 g, 22 mmol) in THF (40 ml) was added dropwise n-BuLi (2.5 M, 9.15 ml) at 0 °C, and the temperature was raised to 30 °C and stirred for 1 hour. The reaction solution was cooled to -78 °C, CuCN (2.1 g, 23 mmol) was added, and the mixture was stirred at 30 °C for 1 hour. The reaction solution was cooled to -78 °C, and a solution of compound 3 (6.7 g, 20 mmol) in THF (40 ml) was added. The mixture was stirred at 30 °C for 12 hours to obtain a white suspension. When H2O (50 ml) was added to the suspension, a white precipitate formed. The white precipitate was collected by filtration, dissolved in dichloromethane (20 ml), aqueous ammonia (80 ml) was added, and the mixture was stirred for 3 hours. The product was extracted with dichloromethane (50 ml × 3), dried over Na2SO4, and concentrated to obtain a yellow oily substance. This oily substance was purified by silica gel column chromatography to obtain 2.9 g of compound 8.

[0131] (vi) Synthesis of B-423 To a solution of compound 8 (2.9 g, 4.8 mmol) in dichloromethane (20 ml) was added HCl / EtOAc (4 M, 50 ml) at 0 °C, and the mixture was stirred at 30 °C for 2 hours to obtain a pale yellow solution. After the solvent was distilled off under reduced pressure, dichloromethane (50 ml) was added. The mixture was washed with saturated aqueous NaHCO3 (100 ml) to obtain 2.5 g of B-423. The NMR assignment values of the obtained ligand B-423 are shown below. [NMR] 1 H NMR (CDCl3, δ, ppm): 7.49 (t, 1H), 7.33 (t, 1H), 7.22 (m, 4H), 6.93 (d, 1H), 6.81 (t, 1H), 6.49 (dd, 4H), 6.46 (br, 1H), 3.56 (s, 12H), 2.63 (sept, 2H), 1.05 (d, 6H), 1.04 (d, 6H); 31 P NMR (CDCl3, δ, ppm): -61.6 (s).

[0132] 2) Synthesis of B-423 / Ni complex The B-423 / Ni complex was synthesized using the B-423 ligand and bis(acetylacetonato)nickel(II) (referred to as Ni(acac)2) according to Example 1 of International Publication No. 2010 / 050256, and reacting B-423 and Ni(acac)2 in a 1:1 ratio to obtain a nickel complex (B-423 / Ni).

[0133] <(Production Examples 1 to 10): Production of Ionomer Base Resin Precursor> Using a transition metal complex (B-27DM / Ni complex or B-423 / Ni complex), an ethylene / t-butyl acrylate / acrylate copolymer and an ethylene / t-butyl acrylate / norbornene copolymer were produced. The production of the copolymer was carried out with reference to Production Example 1 or Production Example 3 described in JP-A-2016-79408, and the production conditions such as the metal catalyst species, the amount of the metal catalyst, the amount of trioctylaluminum (TNOA), the amount of toluene, the comonomer species, the amount of the comonomer, the ethylene partial pressure, the polymerization temperature, and the polymerization time were appropriately changed. Table 1 shows the production conditions, and Table 2 shows the physical properties of the obtained ionomer base resin precursor. However, "no data" in the table means unmeasured, and "not detected" means below the detection limit.

[0134]

Table 1

[0135]

Table 2

[0136] <(Resin 1, Resin 2, Resin 10): Production of Ionomer Base Resin - 1> Internal volume 1.6 m 3 Into an autoclave made of SUS316L with a stirring blade, 100 kg of any one of the copolymers obtained in Production Example 1, Production Example 2, and Production Example 10, 2.0 kg of p-toluenesulfonic acid monohydrate, and 173 L of toluene were charged, and the mixture was stirred at 105 °C for 4 hours. 173 L of ion-exchanged water was added, stirred, allowed to stand, and then the aqueous layer was withdrawn. Thereafter, the addition and withdrawal of ion-exchanged water were repeated until the pH of the withdrawn aqueous layer became 5 or more. The remaining solution was charged into a twin-screw extruder (L / D = 45.5) equipped with a 42 mmφ vent device, and the solvent was distilled off by pulling the vent to a vacuum. Further, the resin extruded continuously in the form of strands from the die at the tip of the extruder was cooled in water and cut with a cutter to obtain resin pellets. In the IR spectrum of the obtained resin, the disappearance of the peak around 850 cm -1 derived from the tBu group and the decrease in the peak around 1730 cm -1 derived from the carbonyl group of the ester, and the increase in the peak around 1700 cm -1 derived from the carbonyl group of the carboxylic acid (dimer) were observed. Thereby, the decomposition of the t-Bu ester and the formation of the carboxylic acid were confirmed, and ionomer base resins 1, 2, and 10 were obtained. The physical properties of the obtained resins are shown in Table 3. However, no data in the table means unmeasured, and not detected means below the detection limit.

[0137] <(Resins 3 to 9): Production of Ionomer Base Resin - 2> Into a 500 ml separable flask, 40 g of the copolymers obtained in Production Examples 3 to 9, 0.8 g of p-toluenesulfonic acid monohydrate, and 185 ml of toluene were charged, and the mixture was stirred at 105 °C for 4 hours. 185 ml of ion-exchanged water was added, stirred, allowed to stand, and then the aqueous layer was withdrawn. Thereafter, the addition and withdrawal of ion-exchanged water were repeated until the pH of the withdrawn aqueous layer became 5 or more. The solvent was distilled off from the remaining solution under reduced pressure, and drying was carried out until a constant weight was obtained. In the IR spectrum of the obtained resin, the disappearance of the peak around 850 cm -1 derived from the tBu group and the decrease in the peak around 1730 cm -1 Decrease in the peak near 1700 cm−1 derived from the carbonyl group of the carboxylic acid (dimer) was observed. -1 Increase in the peak near 1700 cm−1 was observed. Thereby, decomposition of the t-Bu ester and formation of the carboxylic acid were confirmed, and ionomer base resins 3 to 9 were obtained. Physical properties of the obtained resins are shown in Table 3. In the following table, “AA”, “NB”, “iBA”, and “nBA” are abbreviations of “acrylic acid”, “norbornene”, “isobutyl acrylate”, and “n-butyl acrylate”, respectively, as structural units contained in the base resin. However, no data in the table means unmeasured, and not detected means below the detection limit.

[0138]

Table 3

[0139] <(I-1, I-3 to 6, I-8 to I-14, I-16): Production of ionomer-1> 1) Preparation of Na ion source To a Laboplastmill: Roller Mixer R60 type manufactured by Toyo Seiki Seisaku-sho, Ltd. equipped with a small mixer with a capacity of 60 ml, 22 g of an ethylene / methacrylic acid (MAA) copolymer (brand: Nucrel N1050H manufactured by Mitsui Dow Chemical Co., Ltd.) and 18 g of sodium carbonate were charged, and kneaded at 180 °C and 40 rpm for 3 minutes to prepare a Na ion source.

[0140] 2) Preparation of Zn ion source To a Laboplastmill: Roller Mixer R60 type manufactured by Toyo Seiki Seisaku-sho, Ltd. equipped with a small mixer with a capacity of 60 ml, 21.8 g of an ethylene / methacrylic acid (MAA) copolymer (brand: Nucrel N1050H manufactured by Mitsui Dow Chemical Co., Ltd.), 18 g of zinc oxide, and 0.2 g of zinc stearate were charged, and kneaded at 180 °C and 40 rpm for 3 minutes to prepare a Zn ion source.

[0141] 3): Preparation of ionomer Laboratory Plastomill manufactured by Toyo Seiki Co., Ltd. with a small mixer of 60 ml capacity: Roller Mixer R60 type. 40 g of Resin 1 to Resin 9 were charged, and kneaded and dissolved at 160 °C and 40 rpm for 3 minutes. Then, a Na ion source or a Zn ion source was added so as to achieve a desired neutralization degree, and kneading was carried out at 250 °C and 40 rpm for 5 minutes. In the IR spectrum of the obtained resin, the peak around 1700 cm -1 derived from the carbonyl group of carboxylic acid (dimer) decreased, and the peak around 1560 cm -1 derived from the carbonyl group of carboxylate increased. It was confirmed that an ionomer with the desired neutralization degree was successfully produced from the decrease amount of the peak around 1700 cm -1 derived from the carbonyl group of carboxylic acid (dimer). The press sheet physical properties of the obtained ionomer are shown in Table 5 and Table 6.

[0142] <(I-2, I-7, I-15, I-17): Production of Ionomer - 2> 1) Preparation of Na ion source Into a twin-screw extruder (L / D = 64) with a 26 mmφ vent device manufactured by Toshiba Machine Co., Ltd., an ethylene / methacrylic acid (MAA) copolymer (brand: Nucrel N1050H, manufactured by Mitsui Dow Chemical Co., Ltd.) was continuously charged at a blending ratio of 55 wt% and sodium carbonate at 45 wt%. Extrusion was carried out under kneading conditions of a barrel set temperature of 150 °C and a screw rotation speed of 150 rpm, while removing the gas and water generated during kneading from the vent part with a vacuum pump. Further, the resin extruded continuously in the form of strands from the die at the tip of the extruder was cooled in water and cut with a cutter to obtain pellets of the Na ion source. 2) Preparation of Zn ion source A biaxial extruder (L / D = 64) with a 26 mmφ vent device manufactured by Toshiba Machine was continuously charged with 55 wt% of an ethylene / methacrylic acid (MAA) copolymer (brand name: Nucrel N1050H, manufactured by Mitsui Dow Chemical Co., Ltd.) and 45 wt% of sodium carbonate so that the blending ratio was as follows. Extrusion was carried out under kneading conditions of a barrel set temperature of 150°C and a screw rotation speed of 150 rpm while removing the gas and water generated during kneading from the vent part with a vacuum pump. Further, the resin continuously extruded in the form of strands from the die at the tip of the extruder was cooled in water and cut with a cutter to obtain pellets of the Na ion source.

[0143] 3): Preparation of ionomer A biaxial extruder (L / D = 65) with a 26 mmφ vent device manufactured by Toshiba Machine was continuously charged with any one of Resin 1, Resin 2, and Resin 10 and a Na ion source or a Zn ion source at a blending ratio such that a predetermined neutralization degree was obtained. Extrusion was carried out under kneading conditions of a barrel set temperature of 200°C and a screw rotation speed of 150 rpm while injecting water at a ratio of 4 parts per 100 parts of the charged resin amount and removing the gas and water generated during kneading from the vent part with a vacuum pump. Further, the resin continuously extruded in the form of strands from the die at the tip of the extruder was cooled in water and cut with a cutter to obtain pellets of the ionomer. In the IR spectrum of the obtained resin, the peak near 1700 cm−1 derived from the carbonyl group of carboxylic acid (dimer) decreased, and the peak near 1560 cm−1 derived from the carbonyl group of carboxylate increased. It was confirmed that an ionomer with the desired neutralization degree could be produced from the decrease amount of the peak near 1700 cm−1 derived from the carbonyl group of carboxylic acid (dimer). The physical properties of the press sheets of the obtained ionomers I-2, I-7, and I-15 are shown in Table 5, and the physical properties of the inflation films of I-2, I-7, I-15, and I-17 are shown in Table 7. -1 near decreased, and the peak near 1560 cm−1 -1 derived from the carbonyl group of the carboxylate increased. The peak near 1700 cm−1 -1 derived from the carbonyl group of carboxylic acid (dimer). From the decrease amount of the peak near 1700 cm−1, it was confirmed that an ionomer with the desired neutralization degree was successfully produced. The physical properties of the press sheets of the obtained ionomers I-2, I-7, and I-15 are shown in Table 5, and the physical properties of the inflation films of I-2, I-7, I-15, and I-17 are shown in Table 7.

[0144] The raw materials used as comparative examples will be described. (Comparative Examples 1 to 4, Comparative Examples 10 to 12, 14, and 15): Existing polyethylene Comparative Example 1 (PE-1) Manufactured by Japan Polyethylene Corporation, trade name: Novatec HD, Ziegler-Natta type high density polyethylene, ethylene-α-olefin copolymer, grade name: HS430P, MFR = 0.8 g / 10 min, density = 0.955 g / cm 3 ethylene-butene-1 copolymer Comparative Example 2 (PE-2) Manufactured by Japan Polyethylene Corporation, trade name: Kernel, metallocene type linear low density polyethylene, ethylene-α-olefin copolymer, grade name: KF360T, MFR = 3.5 g / 10 min, density = 0.898 g / cm 3 ethylene-propylene-1-hexene copolymer Comparative Example 3 (PE-3) Manufactured by Japan Polyethylene Corporation, trade name: Kernel, metallocene type linear low density polyethylene, ethylene-α-olefin copolymer, grade name: KF560T, MFR = 16.5 g / 10 min, density = 0.898 g / cm 3 ethylene-propylene-1-hexene copolymer Comparative Example 4 (PE-4) Manufactured by Japan Polyethylene Corporation, trade name: Novatec LD, high pressure radical method low density polyethylene, grade name: LF405M, MFR = 2.0 g / 10 min, density = 0.919 g / cm 3 Comparative Example 10 (PE-5) Manufactured by Japan Polyethylene Corporation, trade name: Novatec LL, Ziegler-Natta type linear low density polyethylene, grade name: UF421, MFR = 0.9 g / 10 min, density = 0.926 g / cm 3 ethylene-1-butene copolymer Comparative Example 11 (PE-6) Manufactured by Japan Polyethylene Corporation, trade name: Harmolex, metallocene type linear low density polyethylene, ethylene-α-olefin copolymer, grade name: NF324A, MFR = 1.0 g / 10 min, density = 0.906 g / cm 3 ethylene-1-hexene copolymer Comparative Example 12 (PE-7) Manufactured by Nippon Polyethylene Co., Ltd., trade name Kernel, metallocene linear low density polyethylene, ethylene·α-olefin copolymer, grade name: KS240T, MFR = 2.2 g / 10 min, density = 0.880 g / cm 3 ethylene·propylene·1-hexene copolymer Comparative Example 14 (PE-8) Manufactured by Nippon Polyethylene Co., Ltd., trade name Novatec LL, Ziegler-Natta linear low density polyethylene, grade name: UF641, MFR = 2.1 g / 10 min, density = 0.927 g / cm 3 ethylene·1-butene copolymer Comparative Example 15 (PE-9) Manufactured by Nippon Polyethylene Co., Ltd., trade name Harmolex, metallocene linear low density polyethylene, ethylene·α-olefin copolymer, grade name: NF444N, MFR = 2.0 g / 10 min, density = 0.912 g / cm 3 ethylene·1-hexene copolymer The physical properties of the press sheets of PE-1 to 4 are shown in Table 4, and the physical properties of the inflation films of PE-5 to 9 are shown in Table 7.

[0145] (Comparative Examples 5 to 7, Comparative Example 13): E / MAA-based binary ionomer (HIM-1 to 3) A copolymer of ethylene, methacrylic acid and sodium methacrylate, an ionomer resin produced by a high-pressure radical process (manufactured by Mitsui Dow Chemical Co., Ltd., brand names: HIMILAN HIM1605 (HIM-1), HIM1707 (HIM-2), HIM1555 (HIM-3)) was used as a reference ionomer. These ionomers have a phase angle δ of 46 to 49° and a structure containing an excessive amount of long-chain branches. The physical properties of the press sheets are shown in Table 4, and the physical properties of the inflation films are shown in Table 7.

[0146] (Comparative Examples 8, 9): E / MAA-based binary ionomer (HIM-4, 5) An ionomer resin copolymerized from ethylene, methacrylic acid, and zinc methacrylate, and manufactured by a high-pressure radical process (brand name: HIMILAN HIM1652 (HIM-4), HIM1706 (HIM-5) manufactured by Mitsui Dow Chemical Co., Ltd.) was used as a reference ionomer. These ionomers have a phase angle δ of 41° or 45° and have a structure with excessive long-chain branching. The physical properties of the press sheet are shown in Table 4.

[0147]

Table 4

[0148]

Table 5

[0149]

Table 6

[0150]

Table 7

[0151]

Table 8

[0152] <Evaluation 1: Regarding the physical properties of the press sheet> · Transparency The haze values in Tables 4 to 6 are the evaluation indices for transparency. The haze value indicates the degree of cloudiness, and the lower this value, the better the transparency. The press sheets of each example had lower haze values than those of Comparative Examples 1 to 4 and were almost equal to or lower than those of the films of existing ionomers (Comparative Examples 5 to 9). It can be seen that the ionomers of the present invention are superior in transparency to existing polyethylene and existing ionomers.

[0153] · Impact strength Look at the values of the tensile elastic modulus and tensile impact strength in Tables 4 to 6. It can be seen that in existing polyethylene, as the tensile elastic modulus, which is an evaluation index of rigidity, increases, the tensile impact strength tends to decrease. In view of this, when looking at the values of the tensile elastic modulus and tensile impact strength of the existing ionomers in Comparative Examples 5 to 9, it can be seen that the strength per tensile elastic modulus is higher than that of existing polyethylene. However, for the ionomers of the present invention, particularly in Examples 1 to 8, they have a higher tensile elastic modulus than Comparative Examples 5 to 9 and have equivalent or higher tensile impact strength, indicating that they have an excellent balance between rigidity and strength. Examples 9 to 16 have tensile elastic modulus values equivalent to or lower than those of the existing ionomers, and generally have a high tensile impact strength. Therefore, it can also be seen that the ionomers of the present invention are materials excellent in flexibility and strength.

[0154] · Pinhole resistance Look at the values of the wear amount and the number of bending cycles in Tables 4 to 6. Fig. 3 is a graph with the wear amount of each press sheet on the horizontal axis and the number of bending cycles on the vertical axis. When evaluating pinhole resistance, it is desirable that the wear amount is small and the number of bending cycles is large. By satisfying both of these conditions, it can be said that the material has high durability against bending and wear in the actual use environment, and thus is less likely to generate pinholes. When looking at Comparative Examples 1 to 9 and Examples 1 to 16, for Examples 1 to 16, they are located above and to the left of the plots of Comparative Examples 1 to 9. Therefore, it can be seen that the ionomers of the present invention have a small wear amount and a large number of bending cycles, indicating that they are excellent in pinhole resistance.

[0155] <Evaluation 2: Film physical properties> · Optical properties Look at the haze value and gloss value in Table 7. The haze value is an evaluation index for cloudiness. The lower the value, the better the transparency. Generally, when it is less than 10%, it is judged to have excellent transparency. On the other hand, the gloss value is an evaluation index for the gloss of the film. The higher the value, the better the gloss. Looking at Table 7, it can be seen that the haze values and gloss values of Examples 17 to 20 are significantly better than those of Comparative Examples 10 to 13, Comparative Examples 14 and 15. The transparency of the film of the present invention is in a region that is almost unattainable as an ethylene-based resin film. It is more excellent even when compared with the haze value of 1.2% and gloss value of 135.5% of a 20-μm OPP film (biaxially oriented polypropylene film), which is known as a film with high transparency.

[0156] · Impact strength Look at the tensile modulus and film impact values in Table 7. The tensile modulus is an evaluation index representing the rigidity of the film, and the film impact value is an evaluation index representing the impact strength of the film. From the trends of Comparative Examples 10 to 12, Comparative Examples 14 and 15, it can be seen that the impact strength tends to improve as the rigidity decreases, and thus the flexibility increases. Considering this trend, when comparing general linear polyethylene with existing ionomers, the rigidity of Comparative Example 13 is 1.6 times that of Comparative Example 10, and the impact strength shows a value 2.5 times that of Comparative Example 10. It can be seen that the existing ionomer has a better balance between rigidity and strength compared with existing linear low-density polyethylene. Next, compare the existing ionomer with the ionomer of the present invention. It can be seen that the films of Examples 17 to 19 maintain better rigidity than polyethylene films like existing ionomers, and there is a large difference in impact strength, which is 1.25 to 3.3 times. In particular, since the strength level shown by Example 17 is higher than that of the very flexible metallocene-based polyethylene shown in Comparative Example 12, it can be seen that the film made of the ionomer of the present invention is very excellent in the balance between rigidity and strength compared with the films made of existing polyethylene and ionomers. Next, looking at the film impact values at -20°C in Table 7 as well, the films of Comparative Examples 13 to 15 are 17 to 19 J / mm and do not exceed 20 J / mm, while the films of Examples 17 to 20 are 28.0 to 35.0 J / mm, showing a strength about 1.5 to 2.0 times higher. From this, it can be seen that the ionomer of the present invention is excellent in impact strength not only at room temperature but also in the low temperature range.

[0157] ·Puncture strength Looking at the puncture strength values in Table 7. The puncture strength is an evaluation index representing the force required for a sharp tip to penetrate the film. When comparing the ionomers of the present invention in Examples 17 to 20 with the existing polyethylene in Comparative Examples 10 to 12, the values are 2.4 to 3.8 times higher, and when compared with the existing ionomer in Comparative Example 13, they are about 1.0 to 1.6 times higher. From this, it can be seen that the film made of the ionomer of the present invention is excellent in strength against puncture compared with the films made of existing polyethylene and ionomers.

[0158] ·Pinhole resistance performance Look at the gel flex values in Table 7. This numerical value is an evaluation index representing how many pinholes are generated when the film is bent multiple times. The lower the numerical value, the fewer pinholes are generated, and it can be evaluated that the film has excellent pinhole resistance. From a comparison between Comparative Example 10 and Comparative Example 14, it can be seen that although they are the same LLDPE, the number of pinholes is larger in Comparative Example 14. From this, it can be understood that molding at 160°C, which is lower than 190°C, is disadvantageous for pinhole resistance. Based on this, when looking at Comparative Examples 10 - 12, Comparative Example 14, 15 and Comparative Example 13, it can be seen that the existing ionomer, despite being molded at 190°C, has performance equivalent to or inferior to that of the existing PE from the perspective of pinhole resistance. Here, when looking at Examples 17 - 19, the ionomer of the present invention has excellent performance compared to the existing ionomer in that the number of pinholes is 0 not only when molded at 190°C but also when molded at 160°C. Regarding the film of Example 20, the number of pinholes is less than that of LLDPE molded at the same 160°C, and it has the same number of pinholes as the existing ionomer molded at 190°C, which is an advantageous condition. Therefore, it can be seen that it has higher performance or equivalent performance. Considering comprehensively with other physical properties introduced in this application, it can be seen that it has physical properties superior to those of the existing PE and ionomer.

[0159] · Heat seal strength Look at the heat seal strength values shown in Table 8 and Figure 4. This is an evaluation index indicating the strength when the part where the films are melt-bonded at a predetermined temperature and a constant pressure is tensilely broken. Generally, it is desirable that the heat seal strength is high, and moreover, high strength can be obtained when sealing at a lower temperature. As shown in Examples 17 - 20, it can be seen that the films made of the ionomer of the present invention have the highest seal strength in the temperature range of 90°C to 150°C. As described above, from the physical properties of the press sheet and the inflation film, the film made of the ionomer of the present invention is excellent in gloss, transparency, impact strength, puncture strength, pinhole resistance, and heat seal strength.

[0160] · Regarding the balance between rigidity and toughness Look at the balance between the rigidity (tensile elastic modulus) and toughness (tensile impact strength) shown in Table 7 and Figure 5. Both need to be moderately balanced and take high values, and in Figure 5, the upper right side indicates a good direction. For the films using conventional linear low-density polyethylene (LLDPE) shown in Comparative Examples 10 to 12, Comparative Examples 14, 15, and the ionomer resin based on a multi-branched structure shown in Comparative Example 13, either the rigidity or the toughness is insufficient. Compared with these comparative examples, the films using the ionomers having a linear structure of Examples 17 to 20 of the present application have been shown to be ethylene-based resin films having rigidity-toughness in an unprecedented region.

[0161] ·Regarding transparency and gloss The comparison of transparency shown in Table 7 and Figure 6 is made based on the haze value. The lower the haze value, the higher the transparency. Compared with the films using conventional linear low-density polyethylene (LLDPE) shown in Comparative Examples 10 to 12, Comparative Examples 14, 15, and the ionomer resin based on a multi-branched structure shown in Comparative Example 13, the films using the ionomers having a linear structure of Examples 17 to 20 of the present application have been shown to be ethylene-based resin films having a remarkably excellent haze with a haze value of 0.2% to 1.2% when formed into a thickness of 30 μm. As an ethylene-based resin film having transparency in this region, it is an almost unachieved region, and it is more excellent than the value of 1.2% of a 20-μm OPP film (oriented polypropylene film), which is known as a film having high transparency. The comparison of the glossiness shown in Table 7 and FIG. 7 is performed based on the gloss value. The higher the gloss value, the higher the glossiness. Compared with the films using the conventional linear low-density polyethylene (LLDPE) shown in Comparative Examples 10 to 12 and 14 to 15, and the ionomer resin based on the multi-branched structure shown in Comparative Example 13, the films using the ionomers having a linear structure in Examples 17 to 20 of the present application have been shown to be ethylene-based resin films having a gloss value of 137.8 to 145.4% when formed into a thickness of 30 μm, which is a significantly excellent gloss value. As an ethylene-based resin film having the glossiness in this region, it is an almost unachieved region, and it is more excellent even compared with the value of 135.5% of a 20-μm OPP film (stretched polypropylene film), which is known as a film having a high glossiness.

Industrial Applicability

[0162] The film using the ionomer of the present invention is excellent in film gloss, transparency, tensile strength, impact strength, puncture strength, pinhole resistance, and heat seal strength as compared with the films made using existing polyethylene or existing ionomers. The film of the present invention can be used as a packaging film and can be suitably used as various packaging materials, for example, food packaging materials, medical packaging materials, industrial material packaging materials, etc.< / e> < / e> < / e> < / e>

Claims

1. A random copolymer containing, as essential constituent units, a structural unit (A) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms, and a structural unit (B) derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group, wherein at least a part of the carboxyl group and / or the dicarboxylic anhydride group in the random copolymer (P) containing ethylene as an essential component of the structural unit (A) is converted into a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table, The absolute value G of the complex elastic modulus measured with a rotational rheometer ＊ An ethylene-based film formed using a resin composition for a film containing an ionomer, characterized in that the phase angle δ at = 0.1 MPa is 50 degrees to 75 degrees, When formed into a thickness of 30 μm and measured, the haze is 2% or less, the film impact at -20 °C is 20 J / mm or more, and the tensile elastic modulus in the MD direction is 150 MPa or more. An ethylene-based film.

2. The ethylene-based film according to claim 1, wherein the ionomer is a random copolymer (P) containing, as an essential constituent unit, a structural unit (C) which is a compound having one or more carbon-carbon double bonds in its molecular structure other than the structural unit (A) and the structural unit (B).

3. The ethylene-based film according to claim 2, wherein the structural unit (C) in the random copolymer (P) is an acyclic monomer represented by the following general formula (1) or a cyclic monomer represented by the following general formula (2). 【Chemical Formula 14】 [In the general formula (1), T １ ~T ３Each is independently a substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an ester group having 2 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, a halogen atom, or a cyano group. T ４ is a substituent selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an ester group having 2 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, a halogen atom, or a cyano group. 【Chemical Formula 15】 [In General Formula (2), R １ ~R １２ may be the same or different and are each selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 20 carbon atoms. R ９ and R １０ , and R １１ and R １２ may each integrally form a divalent organic group. R ９ or R １０ and R １１ or R １２ may form a ring with each other. Further, n represents 0 or a positive integer. When n is 2 or more, R ５ ~R ８ may be the same or different in each repeating unit. ]

4. The ethylene-based film according to claim 3, wherein the structural unit (C) in the random copolymer (P) is an acyclic monomer represented by the general formula (1).

5. The ethylene-based film according to claim 3, wherein the structural unit (C) in the random copolymer (P) is a cyclic monomer represented by the general formula (2).

6. of the random copolymer (P) １３ The ethylene-based film according to any one of claims 1 to 5, wherein the number of methyl branches calculated by C-NMR of the random copolymer (P) is 50 or less per 1,000 carbons.

7. of the random copolymer (P) １３ The ethylene-based film according to any one of claims 1 to 5, wherein the number of methyl branches calculated by C-NMR of the random copolymer (P) is 5 or less per 1,000 carbons.

8. The ethylene-based film according to any one of claims 1 to 7, wherein the random copolymer (P) contains 2 to 20 mol% of the structural unit (B) in the copolymer (the total of all constitutional units constituting the copolymer is 100 mol%).

9. The ethylene-based film according to any one of claims 1 to 8, wherein the random copolymer (P) contains 0.001 mol% to 20.0 mol% of the structural unit (C) in the copolymer (the total of all constitutional units constituting the copolymer is 100 mol%).

10. The melting point (Tm, °C) of the random copolymer (P) and the total content [Z] (mol%) of the structural unit (B) and optionally the structural unit (C) contained therein satisfy the following formula (I): 50 < Tm < -3.74 × [Z] + 130... (I) The ethylene-based film according to any one of claims 1 to 9, characterized in that it satisfies the above.

11. The ethylene-based film according to any one of claims 1 to 10, wherein the structural unit (A) is a structural unit derived from ethylene.

12. The ethylene-based film according to any one of claims 1 to 11, wherein the metal ion is a metal ion of Group 1 of the periodic table.

13. The ethylene-based film according to any one of claims 1 to 11, wherein the metal ion is a metal ion of Group 12 of the periodic table.

14. The ethylene-based film according to claim 1, wherein the heat seal strength at a seal temperature of 120°C, a seal pressure of 0.2 MPa, a seal time of 1 second, and a lower seal bar temperature of 60°C, when measured after being formed into a thickness of 30 μm, is 10 N / 15 mm or more.

15. The ethylene-based film according to claim 1, which is an inflation film.

16. The ethylene-based film according to claim 1, which is an inflation film and has a gloss (20°) of 120% or more when formed into a thickness of 30 μm.

Images