Resin composition for film and ethylenic 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, the present invention relates to an ethylene-based film excellent in at least one of high rigidity, high strength, high transparency, high gloss, and low-temperature heat sealability. [Background technology]

[0002] Conventionally, known ethylene polymers for film formation include low-density polyethylene (LDPE), which has many branched chains and is obtained by high-pressure radical polymerization, and linear low-density polyethylene (LLDPE or metallocene PE), which is obtained by catalytic polymerization. However, the former has excellent moldability but low strength, and the latter has excellent strength but low moldability, making it difficult to satisfy all of these requirements.

[0003] On the other hand, ethylene-based ionomers are resins that use ethylene-unsaturated carboxylic acid copolymers as a base resin and are intermolecularly bonded with metal ions such as sodium and zinc (Patent Document 1). They are strong, elastic, flexible, abrasion-resistant, and transparent. Currently, commercially available ethylene-based ionomers include "Surlyn (registered trademark)", a sodium salt or zinc salt of ethylene-methacrylic acid copolymer developed by Dupont, and "Himilan (registered trademark)" sold by Dow Mitsui Polychemicals.

[0004] The ethylene-unsaturated carboxylic acid copolymers used as the base resins for these currently commercially available ethylene-based ionomers all use polar group-containing olefin copolymers obtained by polymerizing ethylene and polar group-containing monomers such as unsaturated carboxylic acids by high-pressure radical polymerization. The high-pressure radical polymerization method has the advantage that it is possible to polymerize relatively any type of polar group-containing monomer at low cost. However, the molecular structure of the polar group-containing olefin copolymer produced by the high-pressure radical polymerization method is a multi-branched molecular structure having many irregular long-chain branches and short-chain branches, as shown in the image diagram in Figure 1, and has the disadvantage of being insufficient in terms of strength.

[0005] Meanwhile, methods have been explored for producing polar group-containing olefin copolymers with a linear molecular structure, as shown in the image in Figure 2, using a polymerization method that uses a catalyst. However, polar group-containing monomers are generally catalyst poisons, making polymerization difficult. In fact, it has been considered difficult for many years to obtain polar group-containing olefin copolymers with the desired physical properties using an industrially inexpensive and stable method. However, in recent years, the applicants of the present application have proposed a method for industrially and inexpensively obtaining polar group-containing olefin copolymers having a substantially linear molecular structure in a stable manner by using a new catalyst and a new production method. The applicants of the present application have reported that they have succeeded in producing a copolymer of ethylene and t-butyl acrylate using a late transition metal catalyst as a method for producing a polar group-containing olefin copolymer that serves as the base resin for an ethylene-based ionomer, and modifying the resulting polar group-containing olefin copolymer by heat or acid treatment to form an ethylene-acrylic acid copolymer, which is then reacted with metal ions to produce a binary ionomer (Patent Document 2). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] U.S. Pat. No. 3,264,272 [Patent Document 2] JP 2016-79408 A Summary of the Invention [Problem to be solved by the invention]

[0007] Although the required degree varies depending on the application, films are generally required to have high strength, a good balance between rigidity and strength, high transparency, gloss, strength during heat sealing, low-temperature heat sealing property, etc., either individually or in combination. However, with conventional polyethylene resins, it has been difficult to obtain a film that satisfies any one of these physical properties in a dramatically improved form or satisfies a combination of these properties sufficiently using conventional techniques. In addition, films using conventional ethylene-based ionomers having a multi-branched molecular structure are also insufficient in resistance to impact in the normal to low temperature range, and the present inventors have found that they have poor bending resistance and are insufficient for packaging applications where the occurrence of pinholes is to be avoided. In view of the above-mentioned state of the art, the present application aims to provide a film and a resin composition for a 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. [Means for solving the problem]

[0008] As a result of extensive investigations conducted by the inventors to solve the above problems, it was discovered that molding a resin composition for film using a specific ionomer resin into a film has a much better effect than expected in terms of the physical properties required of the film. The ethylene-based ionomer is a novel ethylene-based ionomer that has not been seen before, in which the base resin has a substantially linear molecular structure and also functions as an ionomer, and its physical properties, etc. are significantly 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 discovery that an ethylene-based film obtained by molding a resin composition containing a substantially linear ethylene-based ionomer into a film has an excellent effect on improving the physical properties required of the film, exceeding the performance range of conventional ethylene-based resin films.

[0009] That is, the present invention is as described 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; In the copolymer (P), which contains the structural unit (B) derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group as an essential structural unit, at least a part of the carboxyl group and / or the dicarboxylic anhydride group is converted to a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table, Absolute value of complex modulus G measured by a rotational rheometer * The resin composition for films contains an ionomer, characterized in that the phase angle δ at a pressure of 0.1 MPa is 50 degrees to 75 degrees. [2] A structural unit (A) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms; a copolymer (P) including, as essential constituent units, 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 its molecular structure other than the structural unit (A) and the structural unit (B), wherein at least a part of the carboxyl groups and / or dicarboxylic anhydride groups are converted to a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the Periodic Table; Absolute value of complex modulus G measured by a rotational rheometer *The resin composition for films contains an ionomer, characterized in that the phase angle δ at a pressure of 0.1 MPa is 50 degrees to 75 degrees. [3] The resin composition for films according to [2] above, wherein the structural unit (C) in the copolymer (P) is a non-cyclic monomer represented by the following general formula (1) or a cyclic monomer represented by the following general formula (2): [ka] [In general formula (1), T 1 ~T 3 each independently represents 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. [ka] [In general formula (2), R 1 ~R 12 may be the same or different and are 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 11and R 12 may combine together to form a divalent organic group, R 9 or R 10 And, R 11 or R 12 may form a ring together. In addition, n represents 0 or a positive integer, and when n is 2 or more, R 5 ~R 8 may be the same or different in each repeating unit. [4] The resin composition for films according to [3], wherein the structural unit (C) in the copolymer (P) is a non-cyclic monomer represented by the general formula (1). [5] The resin composition for films according to [3], wherein the structural unit (C) in the copolymer (P) is a cyclic monomer represented by the general formula (2). [6] The copolymer (P) 13 The resin composition for films according to any one of [1] to [5], wherein the number of methyl branches calculated by C-NMR is 50 or less per 1,000 carbons. [7] The copolymer (P) 13 The resin composition for films according to any one of [1] to [5], wherein the number of methyl branches calculated by C-NMR is 5 or less per 1,000 carbons. [8] The resin composition for films according to any one of [1] to [7], wherein the copolymer (P) contains the structural unit (B) in an amount of 2 to 20 mol % (the total of all structural units constituting the copolymer being 100 mol %). [9] The resin composition for films according to any one of [1] to [8], wherein the copolymer (P) contains the structural unit (C) in an amount of 0.001 mol % to 20.0 mol % (the total of all structural units constituting the copolymer being 100 mol %).

[10] The resin composition for films 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 films 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 films 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 films according to any one of [1] to

[12] , characterized in that the copolymer (P) is a copolymer obtained by hydrolysis of 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 films according to

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

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

[14] above.

[16] A film containing an ethylene-based resin as a resin component, characterized in that, when molded to a thickness of 30 μm and measured, 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.

[17] An ethylene-based film containing an ethylene-based resin as a resin component, characterized in that the heat seal strength, when molded to a thickness of 30 μm and measured at a sealing temperature of 120° C., a sealing pressure of 0.2 MPa, a sealing time of 1 second, and a lower seal bar temperature of 60° C., is 10 N / 15 mm or more.

[18] An inflation film containing an ethylene-based resin as a resin component, characterized in that when molded to a thickness of 30 μm, the haze is 2% or less.

[19] An inflation film containing an ethylene-based resin as a resin component, characterized in that when molded to a thickness of 30 μm, the gloss (20°) is 120% or more. Effect of the Invention

[0010] The film of the present invention, which uses an ionomer having a substantially linear structure, has superior gloss, transparency, impact strength at room temperature as well as in low temperature environments, heat sealability, and pinhole resistance compared to existing films made of polyethylene or ionomer resins having a multibranched structure. [Brief description of the drawings]

[0011] [Figure 1] 1 is a conceptual diagram of the molecular structure of a multi-branched polar group-containing olefin copolymer produced by high-pressure radical polymerization. The circles in the diagram represent polar groups. [Diagram 2] 1 is a conceptual diagram of a linear olefin copolymer containing a polar group, in which the circles represent polar groups. [Diagram 3] 1 is a graph showing the amount of wear and the number of times of bending in Comparative Examples 1 to 9 and Examples 1 to 16. [Figure 4] 1 is a graph showing the results of evaluation of heat seal strength of the inflation films of Comparative Examples 10 to 13 and Examples 17 to 20. [Diagram 5] 1 is a graph showing the evaluation results of film impact at 23° C. and tensile modulus in the MD direction for Comparative Examples 10 to 13 and Examples 17 to 19. [Figure 6] 1 is a graph showing the evaluation results of film impact at −20° C. and tensile modulus in the MD direction for Comparative Examples 10 to 13 and Examples 17 to 20. [Figure 7] 1 is a graph showing the haze values ​​of the films of Comparative Examples 10 to 13, Examples 17 to 20, and a reference example (OPP film). [Figure 8] 1 is a graph showing the gloss values ​​of the films of Comparative Examples 10 to 13, Examples 17 to 20, and a reference example (OPP film). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The present invention provides a film using an ionomer, characterized in that the film contains, as a base resin, a copolymer (P) in which 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 are essential structural units, and optionally a structural unit (C) which is a compound having one or more carbon-carbon double bonds in its molecular structure, and which is copolymerized, preferably randomly, in a substantially linear manner, and in which at least a portion of the carboxyl groups and / or dicarboxylic anhydride groups of the structural unit (B) are converted to a metal-containing carboxylate containing at least one metal ion selected from Groups 1, 2, or 12 of the periodic table.

[0013] The ionomer, the film using the ionomer, and the uses thereof according to the present invention will be described in detail below. In this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid. In this specification, "to" indicating a numerical range is used to mean that the numerical values ​​before and after it are included as the lower and upper limits. In this specification, a copolymer means a binary or higher copolymer containing at least one type of unit (A) and at least one type of unit (B). In addition, in this specification, the ionomer refers to an ionomer of a binary or higher copolymer that contains the structural unit (A) and a structural unit (B') in which at least a portion of the structural unit (B) is converted to a metal-containing carboxylate, and may further contain the structural unit (B).

[0014] 1. Ionomer The ionomer of the present invention comprises, as a base resin, a copolymer (P) which 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 optionally also contains, as a constituent unit, a structural unit (C) which is a compound having one or more carbon-carbon double bonds in its molecular structure, and which is copolymerized, preferably randomly, in a substantially linear manner, and is characterized in that at least a portion of the carboxyl groups and / or dicarboxylic anhydride groups of the structural unit (B) are converted to 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 structural units derived from ethylene and structural units derived from an α-olefin having 3 to 20 carbon atoms. The α-olefins involved in the present invention have the structural formula: CH2=CHR 18 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 may be branched.) The α-olefin more preferably has 3 to 12 carbon atoms.

[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, and may be ethylene. As the ethylene, ethylene derived from a petroleum raw material or a non-petroleum raw material such as a plant raw material can be used. The structural unit (A) may be of one type or of multiple types. Examples of combinations of the two include ethylene-propylene, ethylene-1-butene, ethylene-1-hexene, ethylene-1-octene, propylene-1-butene, propylene-1-hexene, and propylene-1-octene. Examples of combinations of the three 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, the structural unit (A) preferably contains ethylene as an essential component and may further contain one or more α-olefins having 3 to 20 carbon atoms, if necessary. The amount of ethylene in the structural unit (A) may be 65 to 100 mol % or 70 to 100 mol % based on the total moles of the structural unit (A). In terms 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) has the same structure as the structural unit derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group, and as described later in the production method, it does not necessarily have to be produced using a monomer having a carboxyl group and / or a dicarboxylic anhydride group.

[0019] Examples of structural units derived from monomers having a carboxyl group include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, and bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid. Examples of structural units derived from monomers having a dicarboxylic acid 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 2,7] Unsaturated dicarboxylic acid anhydrides such as dodec-9-ene-4,5-dicarboxylic acid anhydride and 2,7-octadien-1-yl succinic acid anhydride are exemplified. As the structural unit derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group, from the viewpoint of industrial availability, preferred examples include acrylic acid, methacrylic acid, and 5-norbornene-2,3-dicarboxylic anhydride, and in particular acrylic acid. Furthermore, the structural unit derived from a monomer having a carboxyl group and / or a dicarboxylic anhydride group may be of one type or of multiple types.

[0020] In addition, the dicarboxylic anhydride group may react with moisture in the air to open the ring and become a part of the dicarboxylic acid, but the dicarboxylic anhydride group may be in a ring-opened state as long as it does not deviate from the gist of the present invention.

[0021] (3) Other structural units (C) The copolymer (P) used in the present invention may be a binary copolymer consisting of only the structural unit (A) and the structural unit (B), or a multicomponent copolymer containing the structural unit (A), the structural unit (B), and a structural unit (C) other than them. However, it may also be a multicomponent copolymer containing a structural unit (C) other than the structural units represented by the structural units (A) and (B). Any monomer can be used as the monomer that gives the structural unit (C) as long as it is not included in the monomers that give the structural unit (A) and the structural unit (B). The monomer that gives 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 acyclic monomers represented by the general formula (1) shown below and cyclic monomers represented by the general formula (2). Compared to a binary copolymer consisting of only the structural unit (A) and the structural unit (B), by using a ternary or higher multi-component copolymer containing the structural unit (C) as the base resin of the ionomer, it is possible to obtain an ionomer with a low melting point and a low degree of crystallinity, and when made into a film, it is possible to obtain a film with a dramatically improved balance between rigidity and toughness, outstanding transparency and gloss, and excellent low-temperature heat sealability. The structural unit (C) may be based on one type of monomer, or two or more types of monomers may be used in combination.

[0022] Acyclic Monomers [ka] [In general formula (1), T 1 ~T 3 each independently represents 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, T 3may be a hydrogen atom or a methyl group, T 4 may be an ester group having 2 to 20 carbon atoms.

[0024] T 1 ~T 4 The carbon skeleton of the hydrocarbon group, substituted alkoxy group, substituted ester group, alkoxy group, aryl group, ester group and silyl group may have a branch, a ring, and / or an unsaturated bond. T 1 ~T 4 The lower limit of the number of carbon atoms in the hydrocarbon group may be 1 or more, and the upper limit may be 20 or less, or may be 10 or less. T 1 ~T 4 The lower limit of the number of carbon atoms in the substituted alkoxy group may be 1 or more, and the upper limit may be 20 or less, or may be 10 or less. T 1 ~T 4 The lower limit of the number of carbon atoms in the substituted ester group may be 2 or more, and the upper limit may be 20 or less, or may be 10 or less. T 1 ~T 4 The lower limit of the number of carbon atoms in the alkoxy group may be 1 or more, and the upper limit may be 20 or less, or may be 10 or less. T 1 ~T 4 The lower limit of the number of carbon atoms in the aryl group in the above formula may be 6 or more, and the upper limit may be 20 or less, or may be 11 or less. T 1 ~T 4 The lower limit of the number of carbon atoms in the ester group may be 2 or more, and the upper limit may be 20 or less, or may be 10 or less. T 1 ~T 4 The number of carbon atoms in the silyl group in the above formula may be 3 or more, and may be 18 or less, or 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, T 1 ~T 3 However, each of them may be a hydrogen atom. In terms of impact resistance, T 4 may be an ester group having 2 to 20 carbon atoms.

[0026] Specific examples of the non-cyclic monomer include T 4 is an ester group having 2 to 20 carbon atoms. T 4 is an ester group having 2 to 20 carbon atoms, the acyclic monomer may be a monomer having the structural formula: CH2=C(R 21 )CO2(R 22 ) where R 21 R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, which may have a branch, a ring, and / or an unsaturated bond. 22 is a hydrocarbon group having 1 to 20 carbon atoms, which may have a branch, a ring, and / or an unsaturated bond. 22 It may contain a heteroatom at any position within the group. Structural formula: CH2=C(R 21 )CO2(R 22 ) as a compound represented by R 21 is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. 21 is a hydrogen atom, or R 21 Methacrylate esters in which the alkyl group is a methyl group are also included. Structural formula: CH2=C(R 21 )CO2(R 22Specific examples of the compound represented by the formula (1) include 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, and benzyl (meth)acrylate. Specific compounds include methyl acrylate, ethyl acrylate, n-butyl acrylate (nBA), isobutyl acrylate (iBA), t-butyl acrylate (tBA), and 2-ethylhexyl acrylate, and may in particular be n-butyl acrylate (nBA), isobutyl acrylate (iBA), and t-butyl acrylate (tBA). The non-cyclic monomer may be of one type or of multiple types.

[0027] Cyclic Monomers [ka] [In general formula (2), R 1 ~R 12 may be the same or different and are 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 combine together to form a divalent organic group, R 9 or R 10 And, R 11 or R 12 may form a ring together. In addition, n represents 0 or a positive integer, and when n is 2 or more, R 5 ~R 8may be the same or different in each repeating unit.

[0028] Examples of the cyclic monomer include norbornene-based olefins, such as norbornene, vinylnorbornene, ethylidenenorbornene, norbornadiene, tetracyclododecene, tricyclo[4.3.0.1 2,5 ]dec-3-ene, and other compounds having a cyclic olefin skeleton. 3,6 .0 2,7 ]dodec-4-ene and the like.

[0029] (4) Copolymer (P) The copolymer (P) used in the present invention as the base resin of the ionomer 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 may further contain an arbitrary structural unit (C) other than the above (A) and (B), and these structural units are copolymerized substantially linearly, preferably randomly. The term "substantially linear" refers to a state in which the copolymer has no branch or the frequency of branched structures is low, and the copolymer can be considered to be linear. Specifically, the copolymer has a phase angle δ of 50 degrees or more under the conditions described below.

[0030] The copolymer (P) according to the present invention must contain at least one type of structural unit (A) and at least one type of structural unit (B), that is, at least two types of monomer units in total. It may contain any structural unit (C) other than the above-mentioned (A) and (B). However, it is preferable that the copolymer (P) is a multicomponent copolymer containing such a structural unit (C). The structural units and the amounts of the structural units in the copolymer according to the present invention will be described below. A structure derived from one molecule each of ethylene and / or an α-olefin having 3 to 20 carbon atoms (A), a monomer having a carboxyl group and / or a dicarboxylic anhydride group (B), and any monomer (C) other than (A) and (B) is defined as one structural unit in the copolymer. The amount of structural units is the ratio of each structural unit expressed in mol % when all structural units in the copolymer are taken as 100 mol %.

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

[0032] Amount of structural units of 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 selected from the following: the lower limit is 2.0 mol% or more, preferably 2.9 mol% or more, and more preferably 5.2 mol% or more, and the upper limit is 20.0 mol% or less, preferably 15.0 mol% or less, more preferably 10.0 mol% or less, even 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 structural units derived from monomer (B) having a carboxyl group and / or a dicarboxylic anhydride group is less than 2.0 mol%, the copolymer may not have sufficient adhesion to different materials having high polarity, and if it exceeds 20.0 mol%, the copolymer may not have sufficient mechanical properties. Furthermore, the monomer having a carboxyl group and / or a dicarboxylic anhydride group to be used may be used alone or in combination of two or more kinds.

[0033] Amount of structural units of any monomer (C): When the components of the ionomer of the present invention contain an arbitrary monomer (C) other than the above-mentioned (A) or (B), the structural unit amount of the structural unit (C) related to the present invention is selected from the following: the lower limit is 0.001 mol% or more, preferably 0.010 mol% or more, more preferably 0.020 mol% or more, even more preferably 0.1 mol% or more, still more preferably 1.9 mol% or more, and particularly preferably 2.0 mol% or more, and the upper limit is 20.0 mol% or less, preferably 15.0 mol% or less, more preferably 10.0 mol% or less, even more preferably 5.0 mol% or less, and 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, the mechanical properties of the copolymer tend to be sufficient. Furthermore, any of the monomers used may be used alone or in combination of two or more kinds.

[0034] Method for measuring the amount of structural units of monomers having carboxyl groups and / or dicarboxylic anhydride groups and optional monomers in copolymers: The amount of structural units of the monomer having a carboxyl group and / or a dicarboxylic anhydride group and any other monomer in the copolymer of the present invention is 1 It can be determined using H-NMR spectroscopy. 1 H-NMR is measured by the following method. 200-250 mg of sample is placed in an NMR sample tube with an inner diameter of 10 mm together with 2.4 ml of o-dichlorobenzene / deuterated bromide benzene (C6D5Br) = 4 / 1 (volume ratio) and hexamethyldisiloxane, a chemical shift standard substance, and the tube is purged with nitrogen, sealed, heated to dissolve, and the resulting homogeneous solution is subjected to NMR measurement. NMR measurements are performed at 120°C using an AV400M NMR instrument from Bruker Japan Ltd. equipped with a 10 mmφ cryoprobe. 1 H-NMR is measured with a pulse angle of 4.5°, a pulse interval of 1.8 seconds, and an accumulation count of at least 256. The chemical shift is set to 0.088 ppm for the peak of the methyl proton of hexamethyldisiloxane, and the chemical shifts of peaks due to other protons are based on this.

[0035] Number of branches per 1,000 carbons in multicomponent copolymer: In the multicomponent copolymer of the present invention, in order to increase the elastic modulus and obtain sufficient mechanical properties, 13 The number of methyl branches calculated by C-NMR may be 50 or less, 5 or less, 1 or less, or 0.5 or less per 1,000 carbons, with no particular limit on the lower limit, and the smaller the better. The number of ethyl branches may be 3.0 or less, 2.0 or less, 1.0 or less, or 0.5 or less per 1,000 carbons, with no particular limit on the lower limit, and the smaller the better. The number of butyl branches may be 7.0 or less, 5.0 or less, 3.0 or less, or 0.5 or less per 1,000 carbons, with no particular limit on the lower limit, and the smaller the better.

[0036] Method for measuring the amount of structural units derived from monomers having a carboxy group and / or a dicarboxylic anhydride group and non-cyclic monomers in a multicomponent copolymer, and the number of branches: The amount of structural units derived from monomers having a carboxy group and / or a dicarboxylic anhydride group and non-cyclic monomers in the multicomponent copolymer of the present invention, and the number of branches per 1,000 carbon atoms are 13 It can be determined using C-NMR spectroscopy. 13 C-NMR is measured by the following method. 200-300 mg of sample is placed in an NMR sample tube with an inner diameter of 10 mm together with 2.4 ml of a mixed solvent of o-dichlorobenzene (C6H4Cl2) and deuterated bromide benzene (C6D5Br) (C6H4Cl2 / C6D5Br = 2 / 1 (volume ratio)) and hexamethyldisiloxane, a chemical shift standard substance, and the tube is sealed after replacing with nitrogen. It is heated and dissolved to prepare a homogeneous solution, which is used as the NMR measurement sample. NMR measurements are performed at 120°C using an AV400M NMR instrument from Bruker Japan Ltd. equipped with a 10 mmφ cryoprobe. 13 C-NMR was measured using the inverse gate decoupling method with a sample temperature of 120°C, a pulse angle of 90°, a pulse interval of 51.5 seconds, and an accumulation count of 512 or more. The chemical shifts are those of hexamethyldisiloxane. 13 The C signal was set at 1.98 ppm, and the other 13 The chemical shifts of the C signals are based on this. Obtained 13 In C-NMR, the signals specific to the monomers or branches of the multicomponent copolymer are identified and their intensities are compared, so that the amount of structural units of each monomer in the multicomponent copolymer and the number of branches can be analyzed. The positions of the signals specific to the monomers or branches can be referred to publicly known materials, or can be independently identified depending on the sample. Such an analysis method is commonly known to 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 has a lower limit of usually 1,000 or more, preferably 6,000 or more, and more preferably 10,000 or more, and an upper limit of usually 2,000,000 or less, preferably 1,500,000 or less, even more preferably 1,000,000 or less, particularly preferably 800,000 or less, and most preferably 100,000 or less. If the Mw is less than 1,000, the physical properties such as mechanical strength and impact resistance of the copolymer will be insufficient, whereas if the Mw exceeds 2,000,000, the melt viscosity of the copolymer will be extremely high, making it 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. If Mw / Mn is less than 1.5, the copolymer may have insufficient processability, including molding, whereas if it exceeds 4.0, the copolymer may have poor mechanical properties. In this specification, (Mw / Mn) may be expressed as a molecular weight distribution parameter.

[0039] The weight average molecular weight (Mw) and 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 calculated by determining the number average molecular weight (Mn) by gel permeation chromatography (GPC) and then calculating the ratio of Mw to Mn, Mw / Mn.

[0040] An example of the GPC measurement method according to the present invention is as follows. (Measurement conditions) Machine used: Waters 150C Detector: FOXBORO MIRAN1A IR detector (measurement wavelength: 3.42 μm) Measurement temperature: 140℃ Solvent: orthodichlorobenzene (ODCB) Column: Showa Denko AD806M / S (3 columns) Flow rate: 1.0mL / min Injection volume: 0.2mL (Sample preparation) A 1 mg / mL solution of the sample is prepared using ODCB (containing 0.5 mg / mL BHT (2,6-di-t-butyl-4-methylphenol)), and dissolved at 140° C. for about 1 hour. (Calculation of molecular weight (M)) The standard polystyrene method is used, and the conversion from retention volume to molecular weight is performed using a calibration curve of standard polystyrene that has been prepared in advance. The standard polystyrene used is, for example, Tosoh's (F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000) brand, Showa Denko's monodisperse polystyrene (S-7300, S-3900, S-1950, S-1460, S-1010, S-565, S-152, S-66.0, S-28.5, S-5.05, each 0.07 mg / ml solution), etc. A calibration curve is prepared by injecting 0.2 mL of a solution in which each is dissolved in ODCB (containing 0.5 mg / mL BHT) so that the concentration is 0.5 mg / mL. The calibration curve is a cubic equation obtained by approximating the least squares method, or a quartic equation obtained by approximating the logarithm of the elution time and molecular weight. The following values ​​are used for the viscosity equation [η] = K × Mα used to convert to molecular weight (M): Polystyrene (PS): K = 1.38 x 10 -4 , α=0.7 Polyethylene (PE): K = 3.92 x 10 -4 , α=0.733 Polypropylene (PP): K = 1.03 x 10 -4 , α=0.78

[0041] Melting point (Tm, ℃): 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). When multiple peaks are shown in the endothermic curve obtained by DSC measurement, with heat flow (mW) on the vertical axis and temperature (°C) on the horizontal axis, the maximum peak temperature refers to the temperature of the peak with the maximum height from the baseline among the multiple peaks, or when there is only one peak, the maximum peak temperature refers to 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 insufficient, and if it is higher than this range, the adhesiveness may be poor. The melting point can be determined, for example, from the absorption curve obtained by using a DSC (DSC7020) manufactured by SII Nanotechnology Inc., packing approximately 5.0 mg of a sample into an aluminum pan, heating it to 200°C at 10°C / min, holding it isothermally at 200°C for 5 minutes, lowering it to 20°C at 10°C / min, holding it isothermally at 20°C for 5 minutes, and then heating it again to 200°C at 10°C / min.

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

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

[0044] For reference, an example of a molecular structure (2) of a copolymer into which structural unit (B) of a monomer having a carboxyl group and / or a dicarboxylic anhydride group has been introduced by graft modification is shown. A part of a copolymer in which structural unit (A) of ethylene and / or an α-olefin having 3 to 20 carbon atoms and structural unit (C) of an arbitrary monomer are copolymerized is graft modified with structural unit (B) of a monomer having a carboxyl group and / or a dicarboxylic anhydride group. [ka]

[0045] In addition, the random copolymerization of a copolymer can be confirmed by various methods, but a method for determining the random copolymerization from the relationship between the comonomer content and melting point of the copolymer is described in detail in JP 2015-163691 A and JP 2016-079408 A. From the above documents, it can be determined that the randomness is low when the melting point (Tm, °C) of the copolymer is higher than -3.74 × [Z] + 130 (where [Z] is the comonomer content / mol%).

[0046] The copolymer according to the present invention, which is a random copolymer, preferably has a melting point (Tm, °C) measured by differential scanning calorimetry (DSC) and a 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 an arbitrary monomer, which satisfy the following formula (I): 50 <Tm<-3.74×[Z]+130···(I) If the melting point of the copolymer (Tm, °C) is higher than -3.74 × [Z] + 130 (°C), the random copolymerization is low, resulting in poor mechanical properties such as impact strength. If the melting point is lower than 50°C, the heat resistance may be poor.

[0047] Furthermore, the copolymer according to the present invention is preferably produced in the presence of a transition metal catalyst, from the viewpoint of making the molecular structure thereof linear. 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. The difference in molecular structure can be controlled by selecting the production method, but the molecular structure can also be estimated from the complex modulus measured with a rotational rheometer, as described in JP 2010-150532 A, for example.

[0048] · Absolute value of complex elastic modulus G * Phase angle δ at =0.1MPa: In the copolymer of the present invention, the absolute value of the complex modulus G measured by a rotational rheometer * = 0.1 MPa, the phase angle δ is 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, or 58 degrees or more, and the upper limit of the phase angle δ may be 75 degrees or less, or 70 degrees or less. More specifically, the absolute value of the complex modulus G measured by a rotational rheometer * = Phase angle δ at 0.1 MPa (G *=0.1 MPa) is 50 degrees or more, the molecular structure of the multicomponent copolymer is a linear structure that does not contain any long chain branching or a structure that contains a small amount of long chain branching that does not affect the mechanical strength. In addition, the absolute value of the complex modulus G measured by a rotational rheometer * = Phase angle δ at 0.1 MPa (G * = 0.1 MPa) is lower than 50 degrees, the molecular structure of the multicomponent copolymer will contain excessive long chain branches, resulting in poor mechanical strength. Absolute value of complex modulus G measured by a rotational rheometer * The phase angle δ at G = 0.1 MPa is affected by both the molecular weight distribution and the long chain branching. However, for multicomponent copolymers with Mw / Mn ≦ 4, more preferably Mw / Mn ≦ 3, it is an index of the amount of long chain branching, and the more long chain branches there are in the molecular structure, the lower the δ(G * If the Mw / Mn of a multicomponent copolymer is 1.5 or more, the δ(G * =0.1MPa) value never exceeds 75 degrees.

[0049] The method for measuring the complex elastic modulus is as follows. The sample is placed in a 1.0 mm thick heat press mold and preheated for 5 minutes in a heat press machine with a surface temperature of 180°C. The residual gas in the molten resin is degassed by repeatedly applying and depressurizing pressure, and then the sample is pressurized to 4.9 MPa and held for 5 minutes. The sample is then 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 create a press plate made of the sample with a thickness of approximately 1.0 mm. The press plate made of the sample is processed into a circle with a diameter of 25 mm to use as a sample. A Rheometrics ARES type rotational rheometer is used as a measuring device for dynamic viscoelastic properties, and dynamic viscoelasticity is measured under the following conditions in a nitrogen atmosphere. Plate: φ25mm parallel plate ·Temperature: 160℃ Distortion: 10% Measurement angular frequency range: 1.0×10 -2 ~1.0×10 2rad / s Measurement interval: 5 points / decade Absolute value of complex elastic modulus G * Common logarithm logG of (Pa) * Plot the phase angle δ against logG * = 5.0, the value of δ (degrees) at the point * = 0.1MPa). * If there is no point corresponding to =5.0, logG * Using two points around =5.0, logG * The δ value at logG = 5.0 is calculated by linear interpolation. * <5, logG * Using the three largest values, we plot logG on a quadratic curve. * = 5.0.

[0050] - Copolymer production The copolymer according to the present invention is preferably produced in the presence of a transition metal catalyst, from the viewpoint of making the molecular structure thereof linear. Polymerization catalyst The type of polymerization catalyst used in the production of the copolymer according to the present invention is not particularly limited as long as it is capable of copolymerizing the structural unit (A), the structural unit (B), and the optional structural unit (C). For example, a transition metal compound 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, preferred are transition metals of Groups 8 to 11, more preferred are transition metals of Group 10, and particularly preferred are nickel (Ni) and palladium (Pd). These metals may be used alone or in combination. Chelating ligands have at least two atoms selected from the group consisting of P, N, O, and S, and include ligands that are bidentate or multidentate, and are electronically neutral or anionic. Exemplary chelating ligand structures are given in the review by Brookhart et al. (Chem. Rev., 2000, 100, 1169). The chelating ligand preferably includes a bidentate anionic P, O ligand. Examples of the bidentate anionic P, O ligand include phosphorus sulfonic acid, phosphorus carboxylic acid, phosphorus phenol, and phosphorus enolate. Other examples of the chelating ligand include a bidentate anionic N, O ligand. Examples of the bidentate anionic N, O ligand include salicylaldiminate and pyridine carboxylic acid. Other examples of the chelating ligand include a diimine ligand, a diphenoxide ligand, and a diamide ligand.

[0051] The structure of the metal complex obtained from the chelating ligand is represented by the following structural formula (a) or (b) in which an arylphosphine compound, an arylarsine compound or an arylantimony compound which may have a substituent is coordinated. [ka] [ka] [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 hydrogen or a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom. R 55 each independently represents hydrogen, halogen, or a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom. R 56 and R 57 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom, OR 52 , CO2R 52 , CO2M', C(O)N(R 51 )2, C(O)R 52 , S.R. 52 , SO2R 52 , SOR 52 , OSO2R 52 , P(O)(OR 52 ) 2-y (R 51 ) y , C.N., N.H.R. 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, a quaternary ammonium or a phosphonium; x represents an integer of 0 to 3; and y represents an integer of 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, in which case the ring has 5 to 8 members and may or may not have a substituent on the ring. L1 represents a ligand coordinated to M. Also, R 53 and L 1 may be bonded to 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). [ka] [In structural formula (c), 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 54 each independently represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom. R 55 each independently represents hydrogen, halogen, or a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom. R 58 , R 59 , R 60 and R 61 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom, OR 52 , CO2R 52 , CO2M', C(O)N(R 51 )2, C(O)R 52 , S.R. 52 , SO2R 52 , SOR 52 , OSO2R 52 , P(O)(OR 52 ) 2-y (R 51 ) y, C.N., N.H.R. 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, a quaternary ammonium or a phosphonium; x represents an integer of 0 to 3; and y represents an integer of 0 to 2. In addition, R 58 ~R 61 may be bonded to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, or sulfur. In this case, the number of ring members is 5 to 8, and the ring may or may not have a substituent. L 1 represents a ligand coordinated to M. Also, R 53 and L 1 may be bonded to each other to form a ring.

[0053] Here, typical catalysts of Group 5 to 11 transition metal compounds having a chelating ligand include so-called SHOP catalysts and Drent catalysts. The SHOP catalyst is a catalyst in which a phosphorus-based ligand having an aryl group which may have a substituent is coordinated to nickel metal (see, for example, WO2010-050256). Furthermore, the Drent catalyst is a catalyst in which a phosphorus-based ligand having an aryl group which may have a substituent is coordinated to palladium metal (see, for example, JP-A-2010-202647).

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

[0055] Method for introducing carboxyl groups and / or dicarboxylic anhydride groups into copolymers: The method of introducing a carboxyl group and / or a dicarboxylic anhydride group into the copolymer according to the present invention is not particularly limited. A carboxyl group and / or a dicarboxylic anhydride group can be introduced by various methods within the scope of the present invention. Examples of methods 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] Examples of methods for introducing a carboxyl group and / or a dicarboxylic anhydride group by modification include, for example, a method in which an acrylic acid ester as a precursor is copolymerized and then hydrolyzed to convert it into a carboxylic acid, and a method in which t-butyl acrylate as a precursor is copolymerized and then thermally decomposed to convert it into a carboxylic acid, in the case of introducing a carboxylic acid.

[0057] A conventionally known acid-base catalyst may be used as an additive for promoting the reaction during the hydrolysis or thermal decomposition. The acid-base catalyst is not particularly limited, and examples of the acid-base catalyst that can be used include, for example, hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, or lithium hydroxide, alkali metals or carbonates of alkaline earth metals such as sodium hydrogencarbonate or sodium carbonate, solid acids such as montmorillonite, inorganic acids such as hydrochloric acid, nitric acid, or sulfuric acid, and organic acids such as formic acid, acetic acid, benzoic acid, citric acid, paratoluenesulfonic acid, trifluoroacetic acid, or trifluoromethanesulfonic acid. From the viewpoints of reaction promotion effect, cost, equipment corrosivity, etc., sodium hydroxide, potassium hydroxide, sodium carbonate, paratoluenesulfonic acid, and trifluoroacetic acid are preferred, and paratoluenesulfonic acid and trifluoroacetic acid are more preferred.

[0058] (5) Ionomer The ionomer according to the present invention is an ionomer having a substantially linear structure in which at least a part of the carboxyl groups and / or dicarboxylic anhydride groups of the structural unit (B) in the copolymer (P) is converted to a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table. As described below, the ionomer is obtained by reacting an ionomer base resin with a metal salt, and during this process, a reaction that cuts the molecular chain of the polymer does not usually occur. Therefore, parameters related to the structure, such as the molar ratio of the comonomer, the degree of branching, and randomness, are usually preserved between the ionomer base resin and the ionomer.

[0059] Ionomer structure The ionomer according to the present invention has a substantially linear structure like the copolymer according to the present invention, and therefore the absolute value of the complex modulus G measured by a rotational rheometer * The phase angle δ at pressure σ=0.1 MPa is 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. Phase angle δ(G * =0.1MPa) is lower than 50 degrees, the molecular structure of the ionomer contains excessive long chain branches, resulting in poor mechanical strength. As mentioned above, if Mw / Mn≦4, the phase angle δ is an index of the amount of long chain branches. If the Mw / Mn of an ionomer is 1.5 or more, the phase angle δ(G * =0.1MPa) value never exceeds 75 degrees.

[0060] Melting point of ionomer (Tm, °C) 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 insufficient, and if it is higher than this range, the adhesiveness may be poor. Of the ionomers related to the present invention, ionomers based on a binary copolymer consisting only of structural unit (A) and structural unit (B) have a melting point of 90°C or higher, preferably 95°C or higher, and more preferably 100°C or higher, while ionomers based on a ternary or higher multi-component copolymer have a melting point of less than 100°C, preferably less than 95°C, and more preferably less than 90°C.

[0061] Metal ions The metal ions contained in the ionomer of the present invention are not particularly limited, and may include metal ions used in conventionally known ionomers. Among them, metal ions of Groups 1, 2, or 12 of the periodic table are preferred, and Li + , Na + , K + , Rb + , Cs + , Mg2+ , Ca 2+ , Sr 2+ , B.A. 2+ and Zn 2+ More preferably, at least one selected from the group consisting of Li + , Na + , K + , Mg 2+ , Ca 2+ , and Zn 2+ , more preferably Na + , and Zn 2+ At least one selected from the group consisting of: Two or more of these metal ions may be mixed and contained as necessary.

[0062] ·Neutralization degree (mol%) The metal ion content is preferably 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, and the preferred degree of neutralization (average degree of neutralization) is 5 to 95 mol%, more preferably 10 to 90 mol%, and even more preferably 20 to 80 mol%. The degree of neutralization can be determined from the ratio of the total molar amount of the valence×molar amount of the metal ion to the total molar amount of the carboxy groups that may be contained in the carboxy groups and / or dicarboxylic anhydride groups in the copolymer. When a dicarboxylic anhydride group forms a carboxylate, it opens its ring to form a dicarboxylic acid, so the total molar amount of the carboxyl groups is calculated assuming that there are 2 mol of carboxyl groups per 1 mol of dicarboxylic anhydride group. 2+ For divalent metal ions such as those mentioned above, 1 mole of each can form a salt with 2 moles of carboxyl groups, and the total molar amount of molecules with the degree of neutralization is calculated by 2 x the molar amount. A high degree of neutralization results in an ionomer with high tensile strength and tensile stress at break, and low tensile strain at break, but the melt flow rate (MFR) of the ionomer tends to be low. On the other hand, a low degree of neutralization results in an ionomer with a moderate MFR, but low tensile modulus and tensile stress at break, and high tensile strain at break.

[0063] -Ionomer manufacturing method 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 above-mentioned method for introducing a carboxyl group and / or a dicarboxylic anhydride group into the copolymer to a conversion step of treating the copolymer 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 the copolymer into a metal-containing carboxylate. The ionomer according to the present invention may also be obtained by subjecting a copolymer of ethylene and / or an α-olefin having 3 to 20 carbon atoms / unsaturated carboxylic acid ester to a heat conversion step of heating the copolymer to convert at least a part of the ester groups in the copolymer 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 an ionomer is produced after introducing a carboxyl group and / or a dicarboxylic anhydride group into a polymer, the production method is, for example, as follows: A metal ion source is prepared by kneading a metal salt with a substance that captures metal ions, such as an ethylene / methacrylic acid (MAA) copolymer, optionally with heating, and then the metal ion source is added to an ionomer base resin in an amount that results in a desired degree of neutralization, followed by kneading.

[0065] In the thermal conversion step, (i) ethylene and / or an α-olefin having 3 to 20 carbon atoms / unsaturated carboxylic acid ester copolymer may be heated to convert the copolymer into an ethylene and / or an α-olefin having 3 to 20 carbon atoms / unsaturated carboxylic acid copolymer by hydrolysis or thermal decomposition, and then the copolymer may be 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 copolymer into the metal-containing carboxylate. In addition, (ii) ethylene and / or an α-olefin having 3 to 20 carbon atoms / unsaturated carboxylic acid ester copolymer may be heated to convert the ester group of the copolymer into the metal-containing carboxylate while reacting the copolymer with a compound containing a metal ion of Group 1, Group 2, or Group 12 of the periodic table to convert the ester group portion in the copolymer into the metal-containing carboxylate.

[0066] The metal ion-containing compound may be an oxide, hydroxide, carbonate, bicarbonate, acetate, formate, etc., of a metal from Groups 1, 2, or 12 of the Periodic Table. The compound containing metal ions may be supplied to the reaction system in the form of particles or fine powder, or may be dissolved or dispersed in water or an organic solvent and then supplied to the reaction system, or a master batch may be prepared using an ethylene / unsaturated carboxylic acid copolymer or an olefin copolymer as a base polymer and then supplied to the reaction system. In order to ensure smooth reaction, it is preferable to prepare a master batch and supply it to the reaction system.

[0067] Furthermore, the reaction with the compound containing metal ions may be carried out by melt kneading using various types of equipment such as a vent extruder, a Banbury mixer, a roll mill, etc., and the reaction may be a batch or continuous method. Since the reaction can be carried out smoothly by discharging water and carbon dioxide gas by-produced by the reaction using a degassing device, it is preferable to carry out the reaction continuously using an extruder equipped with a degassing device such as a vent extruder. In the reaction with the compound containing metal ions, a small amount of water may be injected to promote the reaction.

[0068] The temperature at which the ethylene and / or C3-20 α-olefin / unsaturated carboxylic acid ester copolymer is heated may be any temperature at which the ester becomes a carboxylic acid, and if the heating temperature is too low, the ester is not converted to a carboxylic acid, whereas if the heating temperature is too high, decarbonylation or decomposition of the copolymer may proceed. Therefore, the heating temperature in the present invention is preferably in the range of 80°C to 350°C, more preferably 100°C to 340°C, even 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, even more preferably 2 minutes to 10 hours, still more preferably 2 minutes to 3 hours, and particularly preferably 3 minutes to 2 hours.

[0070] In the above steps, the reaction atmosphere is not particularly limited, but it is generally preferable to carry out the reaction under an inert gas flow. Examples of the inert gas include nitrogen, argon, and carbon dioxide. A small amount of oxygen or air may be mixed in.

[0071] The reactor used in the above step is not particularly limited, and any method can be used as long as it can substantially uniformly stir the copolymer. A glass vessel or an autoclave (AC) equipped with a stirrer may be used, or any conventionally known kneading machine such as a Brabender plastograph, a single-screw or twin-screw extruder, a high-intensity screw-type kneader, a Banbury mixer, a kneader, or a roll may be used.

[0072] Whether or not a metal ion has been introduced into an ionomer-based resin and it has become an ionomer can be confirmed by measuring the IR spectrum of the resulting resin and examining the decrease in the peak derived from the carbonyl group of the carboxylic acid (dimer). Similarly, the degree of neutralization can be confirmed by calculating from the molar ratio described above, as well as 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 salt group.

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

[0074] MFR: In the ionomer of the present invention, the melt flow rate (MFR) at a temperature of 190° C. under 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 in this range, film formation is easy.

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

[0076] Tensile impact strength: The ionomer of the present invention has a tensile impact strength of 100 KJ / m 2 More than 700KJ / m, preferably tensile impact strength is 700KJ / m 2 More preferably, it is 800KJ / m or more. 2 That's all. Ionomers based on ternary or higher multi-component copolymers, especially those with a tensile impact strength of 700KJ / m 2 It is possible to obtain an ionomer that achieves the above. If the tensile impact strength of the ionomer is in this range, the risk of breakage is reduced even if the film is subjected to rubbing or the like accompanied by large deformation. There is no particular upper limit for the tensile impact strength as long as it is within the range obtainable from the materials used by those skilled in the art.

[0077] Wear amount in wear test: In the ionomer of the present invention, the amount of wear in the wear test is less than 10 mg, and preferably 9 mg or less. The conditions of the wear test are as described below. If the amount of wear in the wear test is within this range, the film surface is less likely to be damaged even when repeated rubbing and compression forces are applied.

[0078] Haze: The ionomer of the present invention has a haze of 0.1 to 30%, and preferably 0.1 to 20%. If the haze of the ionomer is 30% or less, the transparency is not reduced and the ionomer can be used without any environmental or application restrictions, which is preferable.

[0079] Additives The ionomer of the present invention may contain 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, as long as the additives do not deviate from the spirit of the present invention.

[0080] ·Resin composition As a resin composition for film used in a molded product such as a film (including a sheet), 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 the term "resin composition containing an ionomer" is used in a molded product, it includes the ionomer resin alone or a composition blended with other resin components, additives, etc. The 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 film. For example, high density polyethylene, medium density polyethylene, low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, other ionomers, etc. can be mentioned. In addition, two or more types of materials can be used in combination. The blending amount of these resin components is not particularly limited as long as it is within a range that does not impair the effects of the present invention. The resin composition for films of the present invention is characterized by containing the specific ionomer according to the present application, and the content thereof can be selected preferably from the range of 1 to 100% by weight in combination with the intended use of the film and other conditions. When the specific ionomer according to the present application is used as a resin material for a film, the resin material for a film preferably contains the ionomer of the present invention in an amount of 10% by weight or more, more preferably 30% by weight or more, even more preferably 50% by weight or more, and particularly preferably 60% by weight or more in terms of the content in the resin composition. The upper limit can be arbitrarily selected from 100% by weight or less to 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 it becomes possible to exhibit the excellent physical properties and the like that are achieved by using the ionomer, but the blending amount can be selected as desired from the standpoint of other processability, required physical properties, cost, and the like. Furthermore, when used as a modifier for other resin materials for films, the resin materials for films can contain the ionomer of the present invention in a content in the resin composition of 1% by weight or more, preferably 3% by weight or more, more preferably 10% by weight or more, and even more preferably 20% by weight or more.

[0081] The ionomer used in the present invention may be prepared by mixing various additives and polymer components to be added or blended as necessary using a Henschel mixer, a super mixer, a tumbler mixer or the like, and then heating and kneading the mixture using a single-screw or twin-screw extruder, a kneader or the like, and pelletizing the mixture.

[0082] 2. Molded products (films) One embodiment of the present invention relates to a film-shaped molded product, i.e., an ethylene-based film, molded using a resin composition for film containing the ionomer. Here, the ethylene-based film refers to a film obtained from a resin containing so-called ethylene monomer as a main component. The thickness of the film can be selected arbitrarily depending on the application, 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, the thickness is sufficiently small compared to the length in the remaining two axial directions, and the surface that does not have a thickness direction is used exclusively for its purpose, and is referred to as a film (film-like molded product). If the molded product of the present invention is in the form of a film, the surface portion can have any shape, such as a quadrilateral, a circle, or a triangle. It is preferably bendable. Therefore, the "film" of the present invention includes not only a film in the narrow sense (thickness less than 250 μm), but also a sheet in the narrow sense having a thickness of 250 μm or more, a tape, etc. However, considering that the greatest feature of the film formed from the resin composition containing the ionomer of the present invention is that it exhibits high rigidity and high strength together with high optical properties, the film thickness is particularly thin, which makes it easier to significantly exhibit the dramatic effects of the high strength, transparency, etc. of the film of the present invention. Therefore, the thickness is 1 to 100 μm, preferably 1 to 50 μm, or 1 to 30 μm, and depending on the blending amount and application, it is also possible to significantly reduce the thickness to 1 to 10 μm, and ultimately to 1 to 5 μm.

[0083] A film molded article can be obtained by molding the resin composition containing the ionomer of the present invention into a film. The method for producing the film or sheet can be a method known to those skilled in the art. Examples include various inflation molding methods, T-die film molding methods, and calendar molding methods. The resin composition containing the ionomer of the present invention can be subjected to a film forming process in which the resin composition is molded into a thin and long film, and thus a film that exhibits a dramatic effect that is unexpected from the ionomer copolymer alone can be obtained. For example, when a blown film molding method is used, a known blown film molding machine equipped with an annular die can be used. The temperature of the annular die is preferably 70 to 220°C. The blowing air ring in the blown film molding process is not particularly limited, but one having a plurality of blowing slits is preferable. The blow-up ratio in the blown film molding process is preferably in the range of 0.3 to 10, 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] An ethylene-based film molded using the resin composition for films containing the ionomer of the present invention is an ethylene-based film that has at least one or more dramatic physical properties that are in an unattained range that could not be achieved by ethylene-based films using conventional general ethylene-based resins, or a combination of both. That is, the film has the following properties, either or a combination of high rigidity, high strength, high transparency, high gloss, and low-temperature heat sealability. High rigidity and strength (toughness) One aspect of the present invention is a film containing an ethylene-based resin as a resin component, which has a film impact of 20 J / mm or more at -20°C when molded to a thickness of 30 μm and measured, and a tensile modulus in the MD direction of 150 MPa or more. Preferably, the film impact at 23° C. is 30 J / mm or more, 40 J / mm or more, or even 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, even 30 J / mm or more, or even 40 J / mm or more. On the other hand, the tensile modulus in the MD direction is preferably 200 MPa or more, or even 250 MPa or more. As shown in Figures 5 and 6, a balance between stiffness and toughness is important for a film. According to the present invention, both properties are well balanced to show high values, and the balance is good even at a low temperature range of -20°C, making it possible to obtain an ethylene-based film having physical properties in a range not previously attainable. High heat seal strength One embodiment of the present invention is an ethylene-based film containing an ethylene-based resin as a resin component, which has a heat seal strength of 10 N / 15 mm or more when molded to a thickness of 30 μm and measured at a sealing temperature of 120° C., a sealing pressure of 0.2 MPa, a sealing time of 1 second, and a lower seal bar temperature of 60° C. More preferably, the heat seal strength of the ethylene-based film is 6 N / 15 mm or more at a sealing temperature of 100°C, a sealing pressure of 0.2 MPa, a sealing time of 1 second, and a lower seal bar temperature of 60°C, and even more preferably, the heat seal strength of the ethylene-based film is 7 N / 15 mm or more under the above conditions. ·High transparency One aspect of the present invention is an ethylene-based film containing an ethylene-based resin as a resin component, particularly an inflation film obtained by inflation molding, which has a haze of 2% or less when molded to a thickness of 30 μm. Particularly preferred 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 containing an ethylene-based resin as a resin component, particularly an inflation film obtained by inflation molding, which has a gloss (20°) of 120% or more when molded to a thickness of 30 μm. Particularly preferred 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 known applications as an ethylene-based film using a conventional ethylene-based resin or ionomer, or in applications of other film materials in which ethylene-based films have not been used conventionally, for example, as a substitute for OPP film, either as a single layer or laminated with other materials. Examples of the applications include films, sheets, tapes, etc. Films include agricultural films, food films, electronic material films, and industrial films, and packaging films can be used as various packaging materials, such as food packaging materials, medical packaging materials, electronic material packaging materials, industrial material packaging materials, etc. For example, the film can be suitably used as a film for packaging heavy objects or contents containing liquids. Other applications include adhesive tapes or films for semiconductors, marking films, sanitary materials, protective films, sealant films, steel wire coating materials, clean room curtains, wallpaper, mats, flooring materials, FIBC inner bags, containers, shoes, battery separators, moisture permeable films, antifouling films, dustproof films, PVC alternative films, OPP alternative 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 physical properties in the examples and comparative examples were measured and evaluated by the methods shown below. In the tables, "no data" means that no measurement was performed, and "not detected" means that the value was 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 determining the number average molecular weight (Mn) by gel permeation chromatography (GPC) and then calculating the ratio of Mw to Mn, Mw / Mn. The measurements were performed according to the following procedures and conditions.

[0088] 1) Sample pretreatment When the sample contained a carboxylic acid group, it was subjected to an esterification treatment, such as methyl esterification using diazomethane or trimethylsilyl (TMS) diazomethane, before use in the measurement. When the sample contained a carboxylate group, it was subjected to an acid treatment to modify the carboxylate group to a carboxylic acid group, and then subjected to the above-mentioned esterification treatment before use in the measurement.

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

[0090] 3) Measurement A Waters Alliance GPCV2000 was connected to Showa Denko's high temperature GPC columns Showdex HT-G x 1 and HT-806M x 2, and measurements were performed using o-dichlorobenzene as the eluent at a temperature of 145°C and a flow rate of 1.0 mL / min.

[0091] 4) Calibration curve The column was calibrated using monodisperse polystyrene (S-7300, S-3900, S-1950, S-1460, S-1010, S-565, S-152, S-66.0, S-28.5, S-5.05, each 0.07 mg / ml solution) manufactured by Showa Denko, n-eicosane and n-tetracontane were measured under the same conditions as above, and the elution time and the logarithm of the molecular weight were approximated by a fourth-order equation. PS ) and polyethylene molecular weight (M PE The following formula was used to convert M PE =0.468×M PS

[0092] (2) Method for measuring the amount of structural units derived from monomers having a carboxyl group and / or a dicarboxylic anhydride group, and non-cyclic monomers, and the number of branches per 1,000 carbon atoms The amount of structural units derived from monomers having a carboxy group and / or a dicarboxylic anhydride group and non-cyclic monomers in the multicomponent copolymer of the present invention, and the number of branches per 1,000 carbon atoms are 13 It can be determined using C-NMR spectroscopy. 13 C-NMR was measured by the following method. 200-300 mg of sample was placed in an NMR sample tube with an inner diameter of 10 mm together with 2.4 ml of a mixed solvent of o-dichlorobenzene (C6H4Cl2) and deuterated bromide benzene (C6D5Br) (C6H4Cl2 / C6D5Br = 2 / 1 (volume ratio)) and hexamethyldisiloxane, a chemical shift standard substance, and the tube was purged with nitrogen, sealed, and heated to dissolve and prepare a homogeneous solution to be used as the NMR measurement sample. NMR measurements were performed at 120°C using an AV400M NMR instrument from Bruker Japan equipped with a 10 mmφ cryoprobe. 13 C-NMR was measured using the inverse gate decoupling method with a sample temperature of 120°C, a pulse angle of 90°, a pulse interval of 51.5 seconds, and an accumulation number of 512 or more. The chemical shifts are those of hexamethyldisiloxane. 13The C signal was set at 1.98 ppm, and the other 13 The chemical shifts of the C signals were based on this.

[0093] 1) Sample pretreatment When the sample contained a carboxylate group, the sample was subjected to an acid treatment to convert the carboxylate group to a carboxyl group before the measurement. When the sample contained a carboxyl group, an esterification treatment such as methyl esterification using 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 non-cyclic monomers <e tba> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 It is detected at 79.6 to 78.8 in the C-NMR spectrum. Using these signal intensities, the amount of comonomer was calculated from the following formula. Total amount of tBA (mol%) = I(tBA) × 100 / 〔I(tBA) + I(E)〕 Here, I(tBA) and I(E) are the quantities shown in the following formulas. 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 The methylene signal of the butoxy group of nBA was detected at 64.1 to 63.4 ppm in the C-NMR spectrum and 79.6 to 78.8 ppm in the C-NMR spectrum. Using these signal intensities, the amount of comonomer was calculated from the following formula. 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 quantities expressed by the following formulas, 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) x 7 -I(tBA) x 7) / 2

[0096] <e tba iba> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 The methylene signal of the isobutoxy group of iBA is detected at 70.5 to 69.8 ppm, and the methyl signal of the isobutoxy group is detected at 19.5 to 18.9 ppm in the C-NMR spectrum. Using these signal intensities, the amount of comonomer was calculated from the following formula. 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 quantities expressed by the following formulas, 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) x 7 -I(tBA) x 7) / 2

[0097] <e tba nb> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 The methine carbon signal of NB was detected at 41.9 to 41.1 ppm in the C-NMR spectrum. Using these signal intensities, the amount of comonomer was calculated from the following formula. 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 quantities expressed by the following formulas. 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) x 7 -I(tBA) x 7) / 2

[0098] In addition, when the structural unit amount of each monomer is indicated by "<0.1" including an inequality sign, it means that it is present as a structural unit in the multi-component copolymer, but the amount is less than 0.1 mol %, taking into account significant digits.

[0099] 3) Calculation of the number of branches per 1,000 carbon atoms Multicomponent copolymers include isolated types in which a branch exists alone in the main chain, complex types (face-to-face types in which branches face each other via the main chain, branched-branch types in which branches exist within branched chains, and chain types). The following is an example of the structure of an ethyl branch. In the example of the facing type, R represents an alkyl group.

[0100] [ka]

[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 times: 16 to 512 Resolution: 4.0cm -1 Measurement wavelength: 5000~500cm -1

[0103] (4) Absolute value of complex elastic modulus G * Measurement of phase angle δ at 0.1 MPa 1) Sample preparation and measurement The sample was placed in a 1.0 mm thick mold for hot pressing, preheated for 5 minutes in a hot press machine with a surface temperature of 180°C, and then repeatedly pressurized and depressurized to remove residual gas in the molten resin. The sample was then pressed at 4.9 MPa and held for 5 minutes. The sample was then 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 pressed plate made of a sample with a thickness of approximately 1.0 mm. The pressed plate made of the sample was processed into a circle with a diameter of 25 mm to use as a sample, and a Rheometrics ARES type rotational rheometer was used as a measuring device for dynamic viscoelastic properties, and dynamic viscoelasticity was measured under the following conditions in a nitrogen atmosphere. Plate: φ25mm (diameter) parallel plate ·Temperature: 160℃ Distortion: 10% Measurement angular frequency range: 1.0×10 -2 ~1.0×10 2 rad / s Measurement interval: 5 points / decade Absolute value of complex elastic modulus G * Common logarithm logG of (Pa) * Plot the phase angle δ against logG * = 5.0, the value of δ (degrees) at the point * = 0.1MPa). * If there is no point corresponding to =5.0, logG * Using two points around =5.0, logG * The δ value at logG = 5.0 was calculated by linear interpolation. * <5, logG * Using the three largest values, we plot logG on a quadratic curve. * The δ value at =5.0 was extrapolated.

[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). The measurement was performed using a DSC (DSC7020) manufactured by SII Nano Technology Co., Ltd. under the following measurement conditions. Approximately 5.0 mg of the sample was packed into an aluminum pan, heated to 200°C at 10°C / min, held at 200°C for 5 minutes, and then cooled to 30°C at 10°C / min. After holding at 30°C for 5 minutes, the sample was again heated at 10°C / min. The maximum peak temperature in the absorption curve was taken as the melting point Tm, and the heat of fusion (ΔH) was calculated from the area of ​​the melting endothermic peak. The degree of crystallinity (%) was calculated by dividing the heat of fusion by the heat of fusion of perfect crystals of high density polyethylene (HDPE), 293 J / g.

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

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

[0107] How to adjust the press plate for the sample The sample was placed in a heat press mold with dimensions: 50 mm x 60 mm, thickness: 0.5 mm, preheated for 5 minutes in a heat press machine with a surface temperature of 180°C, and then the residual gas in the sample was degassed by repeatedly applying and depressurizing pressure, and the sample was then pressurized to 4.9 MPa and held for 3 minutes.The sample was then transferred to a press machine with a surface temperature of 25°C and cooled by holding the pressure at 4.9 MPa for 3 minutes to produce a press plate with a thickness of approximately 0.5 mm.

[0108] (8) Tensile test A 1 mm thick sheet was prepared as a sample by the method described in JIS K7151 (1995) (cooling method A), and this was punched out to prepare a small 5B type test piece described in JIS K7162 (1994). A tensile test was performed at a temperature of 23°C in accordance with JIS K7161 (1994) to measure the tensile modulus, tensile stress at break, and tensile strain at break. The test speed was 10 mm / min.

[0109] (9) Tensile impact strength 1) How to prepare samples for tensile impact strength test The sample was placed in a 1 mm thick mold for hot pressing, preheated for 5 minutes in a hot press machine with a surface temperature of 180 ° C., and then repeatedly pressurized and depressurized to melt the sample and degas the residual gas in the sample, and then pressurized at 4.9 MPa and held for 5 minutes. After that, while applying a pressure of 4.9 MPa, the sample was gradually cooled at a rate of 10 ° C. / min, and when the temperature had dropped to near room temperature, the molded plate was removed from the mold. The obtained molded plate was conditioned for more than 48 hours in an environment with a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5 ° C. A test piece in the shape of ASTM D1822 Type-S was punched out from the conditioned press plate to prepare a tensile impact strength test sample.

[0110] 2) Tensile impact strength test conditions The tensile impact strength was measured using the above test pieces with reference to JIS K 7160-1996 B method. The only difference from JIS K 7160-1996 was the shape of the test pieces. Other measurement conditions were performed in accordance with JIS K 7160-1996.

[0111] (10) Measurement of wear volume 1) How to prepare abrasion test samples The sample was placed in a mold for hot pressing with dimensions: 150 mm x 150 mm, thickness 1 mm, and preheated for 5 minutes in a hot press machine with a surface temperature of 180 ° C., and then the sample was melted and the residual gas in the sample was degassed by repeatedly applying pressure and reducing pressure, and the sample was further pressurized at 4.9 MPa and held for 3 minutes. After that, the sample was gradually cooled at a rate of 10 ° C / min under a pressure of 4.9 MPa, and the molded plate was removed from the mold when the temperature had dropped to near room temperature. 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 circle with a diameter of about 115 mm, and a hole with a diameter of about 6.5 mm was drilled in the center to prepare a wear test sample.

[0112] 2) Abrasion test conditions Using the above test pieces, the abrasion loss (mg) was measured under the following conditions in accordance with JIS K 7204-1999. · Equipment: Taber abrasion tester (rotary abrasion tester) manufactured by Toyo Seiki Seisakusho Co., Ltd. ·Wear wheel: CS-17 Rotational speed: 60 rpm Test count: 1000 rotations Load: 4.9N

[0113] (11) Measurement of bending resistance 1) How to prepare bending test samples The sample was placed in a mold for hot pressing with dimensions: 150 mm x 150 mm, thickness 1 mm, and preheated for 5 minutes in a hot press machine with a surface temperature of 180 ° C., and then the sample was melted and the residual gas in the sample was degassed by repeatedly applying pressure and reducing pressure, and the sample was further pressurized at 4.9 MPa and held for 3 minutes. After that, while applying a pressure of 4.9 MPa, the sample was gradually cooled at a rate of 10 ° C. / min, and when the temperature had dropped to near room temperature, the molded plate was removed from 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 pressed plate was cut into a width of 15 mm and a length of about 110 mm to prepare a bending test sample.

[0114] 2) Bending test conditions Using the above test piece, the number of bending cycles was measured under the following conditions with reference to JIS P 8115-2001. Note that the only differences from JIS P 8115-2001 were the material of the test piece and the load. Other measurement conditions were performed in accordance with JIS P 8115-2001. Equipment: MIT folding fatigue tester, manufactured by Toyo Seiki Co., Ltd. Load capacity: 29.4N -Bending speed: 175 times / min Bend angle: 135° Bend radius of bending clamp: 0.38mm

[0115] <How to make the film> (Comparative Examples 10 to 13, Example 17) A die with a die orifice diameter of 75 mm and a lip width of 3 mm was attached to a single-screw extruder with a diameter of 50 mm, and inflation molding was performed at a blow ratio of 2.0 under the conditions of setting the extruder and die temperatures to 190°C, to obtain films with a thickness of 30 μm as shown in Comparative Examples 10 to 13 and Example 9. The physical properties of this film were evaluated, and the results are shown in Table 7.

[0116] <Film haze evaluation method> The haze was measured in accordance with JIS K 7136.

[0117] <How to evaluate film gloss> The gloss of the film was measured with reference to JIS Z8741.

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

[0119] <Film impact strength evaluation method> Film impact at 23℃ and -20℃ A film impact tester (FILM·IMPACT·TESTER, hereafter simply referred to as the "testing machine") manufactured by Toyo Seiki Seisakusho was used to measure the work required for perforation destruction per unit film thickness. Specifically, the test film was stored in an atmosphere of 23°C-50% humidity, and after conditioning, the test film was fixed to the testing machine with a holder of 50 mm diameter, and a 1 / 2 inch (approximately 13.0 mm) hemispherical metal was struck on the penetration part from the inner surface of the test film, and the work required for perforation destruction was measured. At that time, the load was removed so that the maximum scale (work amount) was 3.0 J. The work amount divided by the film thickness was determined as the film impact value at 23°C. Similarly to the above, a tester equipped with a thermostatic chamber manufactured by Toyo Seiki Seisakusho was used to measure the work required for penetration destruction under conditions adjusted so that the holding portion fixing the film and the film were at -20°C. At that time, the load was removed as above, and the maximum scale (work load) was adjusted to 3.0 J. The value obtained by dividing the work load by the film thickness was taken as the film impact value at -20°C.

[0120] <Film puncture strength evaluation method> The film was fixed and a semicircular needle with a diameter of 1.0 mm and a tip 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 the film was measured.

[0121] <Method for evaluating film pinhole resistance> The film was bent 3,000 times using a Gelboflex device (manufactured by Tester Sangyo Co., Ltd.) and the number of pinholes was then measured.

[0122] <Heat seal strength of film> Two sheets of inflation film were stacked on top of each other, and a 12μm thick PET film was placed between them. Heat sealing was performed with the temperature of the lower seal bar at 60℃, the temperature of the upper seal bar at 80-150℃, the sealing pressure at 2.0MPa, and the sealing time at 1.0 second, and the 180 degree peel strength of a 15mm 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 prepared according to Synthesis Example 4 described in WO 2010 / 050256, using the following 2-bis(2,6-dimethoxyphenyl)phosphano-6-pentafluorophenylphenol ligand (B-27DM). A nickel complex (B-27DM / Ni) was synthesized in which B-27DM and Ni(COD)2 reacted in a 1:1 ratio using bis(1,5-cyclooctadiene)nickel(0) (referred to as Ni(COD)2) according to Example 1 of WO 2010 / 050256. [ka]

[0124] (2) Synthesis of B-423 / Ni complex 1) Ligand B-423: Synthesis of 2-bis(2,6-dimethoxyphenyl)phosphano-6-(2,6-diisopropylphenyl)phenol [ka] Ligand B-423 was synthesized according to the following scheme. In the following chemical formulas, -OMOM represents a methoxymethoxy group (-OCH2OCH3).

[0125] [ka]

[0126] (i) Synthesis of Compound 2 It was 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. The reaction mixture was stirred at 25° C. for 1 h, and then PCl (618 mg, 4.50 mmol) was added at −78° C. The reaction mixture was warmed to 25° C. over 3 hours to give a yellow suspension. The solvent was removed under reduced pressure to give 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), n-BuLi (2.5 M, 96 ml) was added at 0° C. and stirred at 30° C. for 1 hour. i Pr)3 (123 g, 651 mmol) was added 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 (5.00g, 27.5mmol), compound 6 (4.42g, 18.3mmol), Pd2(dba)3 (168mg, 0.183mmol), s-Phos (2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl) (376mg, 0.916mmol), and K3PO4 (7.35g, 34.6mmol) were weighed into a reaction vessel, and toluene (40ml) was added. This solution was reacted at 110°C for 12 hours to obtain a black suspension. H2O (50ml) was added, and the mixture was extracted with EtOAc (55ml x 3). The organic layer was washed with brine (20ml) and dehydrated with Na2SO4. The organic layer was filtered and the solvent was removed under reduced pressure, and then purified with a silica gel column to obtain 1.3g of an oily substance.

[0130] (v) Synthesis of compound 8 n-BuLi (2.5M, 9.15ml) was added dropwise to a solution of compound 7 (6.5g, 22mmol) in THF (40ml) at 0°C, and the mixture was heated to 30°C and stirred for 1 hour. The reaction solution was cooled to -78°C, CuCN (2.1g, 23mmol) was added, and the mixture was stirred at 30°C for 1 hour. The reaction solution was cooled to -78°C, a solution of compound 3 (6.7g, 20mmol) in THF (40ml) was added, and the mixture was stirred at 30°C for 12 hours to obtain a white suspension. When H2O (50ml) was added to the suspension, a white precipitate was formed. The white precipitate was collected by filtration and dissolved in dichloromethane (20ml), and ammonia water (80ml) was added and stirred for 3 hours. The product was extracted with dichloromethane (50ml x 3), dehydrated with Na2SO4, and then concentrated to obtain a yellow oily substance. This oily substance was purified using a silica gel column 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), HCl / EtOAc (4 M, 50 ml) was added at 0° C. and stirred at 30° C. for 2 hours to obtain a pale yellow solution. The solvent was removed under reduced pressure, and then dichloromethane (50 ml) was added. The mixture was washed with saturated aqueous NaHCO3 solution (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 bisacetylacetonate nickel(II) (referred to as Ni(acac)2) in a 1:1 reaction between B-423 and Ni(acac)2, in accordance with Example 1 of WO 2010 / 050256.

[0133] <(Production Examples 1 to 10): Production of Ionomer-Based Resin Precursors> Using a transition metal complex (B-27DM / Ni complex or B-423 / Ni complex), ethylene / tBu acrylate / acrylic acid ester copolymer and ethylene / tBu acrylate / norbornene copolymer were produced. The copolymer was produced with reference to Production Example 1 or Production Example 3 described in JP 2016-79408 A, and the production conditions, such as the metal catalyst type, metal catalyst amount, trioctyl aluminum (TNOA) amount, toluene amount, comonomer type, comonomer amount, ethylene partial pressure, polymerization temperature, and polymerization time, were appropriately changed, as shown in Table 1, and the physical properties of the obtained ionomer-based resin precursor are shown in Table 2. However, in the table, "no data" means not measured, and "not detected" means below the detection limit.

[0134] [Table 1]

[0135] [Table 2]

[0136] <(Resin 1, Resin 2, Resin 10): Production of ionomer-based resins-1> Internal volume 1.6m 3 In a SUS316L autoclave equipped with an agitator, 100 kg of any one of the copolymers obtained in Production Example 1, Production Example 2, and Production Example 10, 2.0 kg of paratoluenesulfonic acid monohydrate, and 173 L of toluene were added and stirred at 105 ° C for 4 hours. 173 L of ion-exchanged water was added, stirred, and allowed to stand, and then the aqueous layer was extracted. Thereafter, the addition and withdrawal of ion-exchanged water was repeated until the pH of the extracted aqueous layer became 5 or more. The remaining solution was added to a twin-screw extruder (L / D = 45.5) equipped with a 42 mm φ vent device, and the solvent was distilled off by drawing a vacuum through the vent. Furthermore, the resin extruded continuously in the form of a strand 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 850 cm -1 The disappearance of the peak near 1730 cm -1 The decrease in the peak near 1700 cm originates from the carbonyl group of the carboxylic acid (dimer). -1 An increase in the peak near As a result, decomposition of t-Bu ester and generation of carboxylic acid were confirmed, and ionomer base resin 1, resin 2, and resin 10 were obtained. The physical properties of the obtained resins are shown in Table 3. In the table, "no data" means not measured, and "not detected" means below the detection limit.

[0137] <(Resin 3 to Resin 9): Production of Ionomer-Based Resins-2> In a 500 ml separable flask, 40 g of the copolymers obtained in Production Examples 3 to 9, 0.8 g of paratoluenesulfonic acid monohydrate, and 185 ml of toluene were added and 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 extracted. Thereafter, the addition and withdrawal of ion-exchanged water was repeated until the pH of the extracted aqueous layer reached 5 or more. The solvent was distilled off under reduced pressure from the remaining solution, and the solution was dried until it reached a constant weight. In the IR spectrum of the obtained resin, the 850 cm -1 The disappearance of the peak near 1730 cm -1 The decrease in the peak near 1700 cm originates from the carbonyl group of the carboxylic acid (dimer). -1 An increase in the peak near As a result, decomposition of t-Bu ester and generation of carboxylic acid were confirmed, and ionomer base resins 3 to 9 were obtained. The physical properties of the obtained resins are shown in Table 3. In the following table, "AA", "NB", "iBA", and "nBA" are abbreviations for "acrylic acid", "norbornene", "isobutyl acrylate", and "n-butyl acrylate" as structural units contained in the base resin, respectively. However, in the table, "no data" means not measured, and "not detected" means below the detection limit.

[0138] [Table 3]

[0139] <(I-1, I-3~6, I-8~I-14, I-16): Production of ionomers-1> 1) Preparation of Na ion source A Na ion source was prepared by adding 22 g of ethylene / methacrylic acid (MAA) copolymer (Mitsui Dow Polychemicals, brand: Nucrel N1050H) and 18 g of sodium carbonate to a Labo Plastomill (Roller Mixer R60) manufactured by Toyo Seiki Co., Ltd., equipped with a small mixer with a capacity of 60 ml, and kneading the mixture at 180°C and 40 rpm for 3 minutes.

[0140] 2) Preparation of Zn ion source A Zn ion source was prepared by adding 21.8 g of ethylene / methacrylic acid (MAA) copolymer (Mitsui Dow Polychemicals, brand: Nucrel N1050H) to a Toyo Seiki Co., Ltd. Labo Plastomill: Roller Mixer R60 equipped with a 60 ml small mixer, 18 g of zinc oxide, and 0.2 g of zinc stearate, and kneading at 180 °C and 40 rpm for 3 minutes.

[0141] 3): Preparation of ionomer 40 g of resins 1 to 9 were added to a Labo Plastomill (Roller Mixer R60 type) manufactured by Toyo Seiki Co., Ltd., equipped with a small mixer with a capacity of 60 ml, and dissolved by kneading for 3 minutes at 160°C and 40 rpm. Thereafter, a Na ion source or a Zn ion source was added so as to achieve a desired degree of neutralization, and kneading was performed for 5 minutes at 250°C and 40 rpm. In the IR spectrum of the obtained resin, the 1700 cm -1 The peak at 1560 cm originating from the carbonyl group of the carboxylate group decreased. -1 The peak around 1700 cm originating from the carbonyl group of the carboxylic acid (dimer) increased. -1 It was confirmed that an ionomer with the desired degree of neutralization had been produced from the reduction in the peak in the vicinity. The pressed sheet physical properties of the obtained ionomer are shown in Tables 5 and 6.

[0142] <(I-2, I-7, I-15, I-17): Production of ionomers -2> 1) Preparation of Na ion source Ethylene / methacrylic acid (MAA) copolymer (Mitsui Dow Polychemicals, brand: Nucrel N1050H) was continuously fed into a Toshiba Machine twin-screw extruder (L / D=64) equipped with a 26mmφ vent device so that the blending ratio was 55wt% and sodium carbonate was 45wt%. The mixture was extruded under the conditions of a barrel set temperature of 150°C and a screw rotation speed of 150rpm, while removing gas and water generated during the blending from the vent part with a vacuum pump. Furthermore, 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 as a source of sodium ions. 2) Preparation of Zn ion source Ethylene / methacrylic acid (MAA) copolymer (Mitsui Dow Polychemicals, brand: Nucrel N1050H) was continuously fed into a Toshiba Machine twin-screw extruder (L / D=64) equipped with a 26mmφ vent device so that the blending ratio was 55wt% and sodium carbonate was 45wt%. The mixture was extruded under the conditions of a barrel set temperature of 150°C and a screw rotation speed of 150rpm, while removing gas and water generated during the blending from the vent part with a vacuum pump. Furthermore, 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 as a source of sodium ions.

[0143] 3): Preparation of ionomer Resin 1, resin 2, or resin 10 and a Na ion source or a Zn ion source were continuously fed into a Toshiba Machine 26mmφ vented twin-screw extruder (L / D=65) in a blending ratio that would give a predetermined degree of neutralization, and extrusion was performed under kneading conditions of barrel setting temperature 200°C and screw rotation speed 150 rpm, while injecting water at a ratio of 4 parts per 100 parts of the fed resin, and removing gas and water generated during kneading from the vent part with a vacuum pump. Furthermore, the resin continuously extruded in the form of a strand from the die at the tip of the extruder was cooled in water and cut with a cutter to obtain ionomer pellets. In the IR spectrum of the obtained resin, the 1700 cm -1 The peak at 1560 cm originating from the carbonyl group of the carboxylate group decreased. -1 The peak around 1700 cm originating from the carbonyl group of the carboxylic acid (dimer) increased. -1 From the decrease in the peak near the peak, it was confirmed that ionomers with the desired degree of neutralization had been produced. The pressed sheet properties of the obtained ionomers I-2, I-7, and I-15 are shown in Table 5, and the inflation film properties 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, 10 to 12, 14, and 15): Existing polyethylene Comparative example 1 (PE-1) Manufactured by Japan Polyethylene Co., Ltd., product name: Novatec HD, Ziegler-Natta high density polyethylene, ethylene-α-olefin copolymer, grade name: HS430P, MFR = 0.8g / 10min, density = 0.955g / cm 3 Ethylene-butene-1 copolymer Comparative example 2 (PE-2) Manufactured by Japan Polyethylene Co., Ltd., product name: Kernel, metallocene-based 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 Co., Ltd., product name: Kernel, metallocene-based 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 Co., Ltd., product name: Novatec LD, high pressure radical process low density polyethylene, grade name: LF405M, MFR = 2.0g / 10min, density = 0.919g / cm 3 Comparative example 10 (PE-5) Manufactured by Japan Polyethylene Co., Ltd., product name: Novatec LL, Ziegler-Natta linear low-density polyethylene, grade name: UF421, MFR = 0.9g / 10min, density = 0.926g / cm 3 Ethylene-1-butene copolymer Comparative example 11 (PE-6) Manufactured by Japan Polyethylene Co., Ltd., product name: Harmolex, metallocene-based 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 Japan Polyethylene Co., Ltd., product name: Kernel, metallocene-based 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 Japan Polyethylene Co., Ltd., product 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 Japan Polyethylene Co., Ltd., product name: Harmolex, metallocene-based 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 PE-4 are shown in Table 4, and the physical properties of the inflation films of PE-5 to PE-9 are shown in Table 7.

[0145] (Comparative Examples 5 to 7, Comparative Example 13): E / MAA-based binary ionomers (HIM-1 to 3) Ionomer resins (manufactured by Mitsui Dow Polychemicals Co., Ltd., brands: HIMILAN HIM1605 (HIM-1), HIM1707 (HIM-2), HIM1555 (HIM-3)) which are copolymers of ethylene, methacrylic acid, and sodium methacrylate and were produced by a high-pressure radical process were used as reference ionomers. 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 pressed sheet and the physical properties of the inflation film are shown in Table 4 and Table 7, respectively.

[0146] (Comparative Examples 8 and 9): E / MAA-based binary ionomers (HIM-4 and 5) Ionomer resins (manufactured by Mitsui Dow Polychemicals, brand: HIMILAN HIM1652 (HIM-4), HIM1706 (HIM-5)) which are copolymers of ethylene, methacrylic acid and zinc methacrylate and were produced by a high pressure radical process were used as reference ionomers. These ionomers have a phase angle δ of 41° or 45° and a structure containing an excess of long chain branches. The pressed sheet properties are shown in Table 4.

[0147] [Table 4]

[0148] [Table 5]

[0149] [Table 6]

[0150] [Table 7]

[0151] [Table 8]

[0152] <Evaluation 1: Press sheet physical properties> ·Transparency The haze values ​​in Tables 4 to 6 are the evaluation index 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 a haze value lower than any of Comparative Examples 1 to 4, and was approximately equal to or lower than the films of the existing ionomers (Comparative Examples 5 to 9). It can be seen that the ionomers of the present invention have better transparency than existing polyethylenes and existing ionomers.

[0153] Impact strength The values ​​of tensile modulus and tensile impact strength in Tables 4 to 6 are examined. It can be seen that, in the case of existing polyethylene, the tensile impact strength tends to decrease with an increase in the tensile modulus, which is an evaluation index of rigidity. In view of this, when the values ​​of tensile modulus and tensile impact strength of the existing ionomers in Comparative Examples 5 to 9 are examined, it can be seen that the strength per tensile modulus is higher than that of the existing polyethylene, but the ionomers of the present invention, particularly in Examples 1 to 8, have a higher tensile modulus than Comparative Examples 5 to 9, but have the same or higher tensile impact strength, and are excellent in the balance between rigidity and strength. It can be seen that Examples 9 to 16 have the same or lower tensile modulus compared to the existing ionomers, and generally have high tensile impact strength. Therefore, it can be seen that the ionomers of the present invention are materials excellent in flexibility and strength.

[0154] -Pinhole resistance The values ​​of the amount of wear and the number of times of bending in Tables 4 to 6 are shown. FIG. 3 is a graph in which the amount of wear of each press sheet is plotted on the horizontal axis and the number of times of bending is plotted on the vertical axis. When evaluating pinhole resistance, it is desirable that the amount of wear is small and the number of times of bending is large. By satisfying both of these conditions, it can be said that the material has high resistance to bending and wear in the actual usage environment, and is therefore less likely to cause pinholes. Looking at Comparative Examples 1 to 9 and Examples 1 to 16, the plots for Examples 1 to 16 are located to the upper left of the plots for Comparative Examples 1 to 9. Therefore, it can be seen that the ionomer of the present invention has a small amount of wear and a large number of times of bending, and can be said to have excellent pinhole resistance.

[0155] <Evaluation 2: Film properties> ·Optical properties The haze and gloss values ​​are shown in Table 7. The haze is an evaluation index of the degree of cloudiness, and the lower the value, the better the transparency. Generally, a value below 10% is judged to be excellent in transparency. On the other hand, the gloss is an evaluation index of the gloss of the film, and the higher the value, the better the gloss. Table 7 shows that the haze and gloss values ​​of Examples 17 to 20 are significantly superior to those of Comparative Examples 10 to 13, 14, and 15. The transparency of the film of the present invention is in a range that has not been achieved by an ethylene-based resin film, and is superior to the haze value of 1.2% and gloss value of 135.5% of a 20 μm OPP film (stretched polypropylene film) known as a highly transparent film.

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

[0157] -Puncture strength The puncture strength values ​​in Table 7 are shown. Puncture strength is an evaluation index that indicates the force required for a sharp tip to pierce a film. The ionomers of the present invention in Examples 17 to 20 exhibit values ​​that are 2.4 to 3.8 times higher than the existing polyethylene in Comparative Examples 10 to 12, and 1.0 to 1.6 times higher than the existing ionomer in Comparative Example 13. This shows that the films made from the ionomers of the present invention have superior puncture strength compared to films made from existing polyethylene and ionomers.

[0158] -Pinhole resistance The Gelbo Flex value in Table 7 is shown. This value is an evaluation index showing how many pinholes occur when the film is bent multiple times, and the lower the value, the less pinholes occur and the better the pinhole resistance. From Comparative Example 10 and Comparative Example 14, it can be said that Comparative Example 14 has more pinholes even though it is the same LLDPE. From this, it can be seen that molding at 160°C, which is lower than 190°C, is disadvantageous in terms of pinhole resistance. Based on this, Comparative Examples 10 to 12, Comparative Examples 14 and 15, and Comparative Example 13 show that the existing ionomers are equivalent to or inferior to the existing PE in terms of pinhole resistance, even though they are molded at 190°C. Here, from Examples 17 to 19, the ionomers of the present invention have better performance than the existing ionomers in that the number of pinholes is zero not only when molded at 190°C but also when molded at 160°C. The film of Example 20 had fewer pinholes than LLDPE molded at the same 160°C, and the number of pinholes was about the same as that of existing ionomer molded at the favorable condition of 190°C. This shows that the film has higher or similar performance, and when considered comprehensively with other physical properties introduced in this application, it is clear that the film has physical properties superior to existing PE and ionomers.

[0159] Heat seal strength The values ​​of heat seal strength shown in Table 8 and Figure 4 are used as an evaluation index to indicate the strength at which a portion of films melt-pressed together at a specified temperature and constant pressure breaks in tension. Generally, it is desirable that the heat seal strength is high, and that high strength is obtained when sealing is performed at a lower temperature. As shown in Examples 17 to 20, it can be seen that the films made with 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] - Balance between rigidity and toughness Let's look at the balance between stiffness (tensile modulus of elasticity) and toughness (tensile impact strength) shown in Table 7 and Figure 5. Both need to be well balanced and have high values, and in Figure 5, the upper right side shows the good direction. The films using conventional linear low density polyethylene (LLDPE) shown in Comparative Examples 10 to 12, 14, and 15, and the films using the ionomer resin based on a hyperbranched structure shown in Comparative Example 13 are insufficient in either rigidity or toughness. Compared to these comparative examples, the films using the ionomer having a linear structure in Examples 17 to 20 of the present application are shown to be ethylene-based resin films having rigidity and toughness in a range not previously seen.

[0161] -Transparency and gloss The comparison of transparency shown in Table 7 and FIG. 6 is made based on the haze value. The smaller 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, 14, and 15, and the films using the ionomer resin based on a multi-branched structure shown in Comparative Example 13, the films using the ionomer having a linear structure in Examples 17 to 20 of the present application are ethylene-based resin films having a dramatically superior haze value of 0.2% to 1.2% when molded to a thickness of 30 μm. This is a region that has almost never been reached as an ethylene-based resin film having transparency in this range, and is superior to the value of 1.2% of a 20 μm OPP film (stretched polypropylene film) known as a highly transparent film. The comparison of glossiness shown in Table 7 and FIG. 7 is made by gloss value. The higher the gloss value, the higher the glossiness. Compared with the films using conventional linear low density polyethylene (LLDPE) shown in Comparative Examples 10 to 12, 14, and 15, and the films using the ionomer resin based on a multi-branched structure shown in Comparative Example 13, the films using the ionomer having a linear structure in Examples 17 to 20 of the present application have a gloss value of 137.8 to 145.4% when molded to a thickness of 30 μm, which indicates that they are ethylene-based resin films having dramatically superior gloss values. This is a region that has almost never been reached as an ethylene-based resin film having a glossiness in this range, and is superior to the value of 135.5% of a 20 μm OPP film (stretched polypropylene film) known as a film with a high glossiness. [Industrial Applicability]

[0162] The film using the ionomer of the present invention is superior in gloss, transparency, tensile strength, impact strength, puncture strength, pinhole resistance, and heat seal strength compared to films made using existing polyethylenes 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, such as food packaging materials, medical packaging materials, and industrial material packaging materials.< / e> < / e> < / e> < / e>

Claims

1. a structural unit (A) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms; a copolymer (P) comprising, as essential constituent units, 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 its molecular structure other than the structural unit (A) and the structural unit (B), wherein at least a portion of the carboxyl groups and / or dicarboxylic anhydride groups in the copolymer (P) are converted to a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the Periodic Table; Absolute value of complex modulus G measured by a rotational rheometer ＊ A resin composition for films containing an ionomer, characterized in that a phase angle δ at σ = 0.1 MPa is 50 degrees to 75 degrees.

2. A resin composition for film as described in claim 1, characterized in that the structural unit (C) in the copolymer (P) is a non-cyclic monomer represented by the following general formula (1) or a cyclic monomer represented by the following general formula (2): 【Chemistry 14】 [In general formula (1), T 1 to T 3 each independently represent 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. 【Chemistry 15】 [In general formula (2), R 1 to R 12 may be the same or different and are selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups having 1 to 20 carbon atoms; R 9 and R 10 , and R 11 and R 12 may each combine together to form a divalent organic group; and R 9 or R 10 and R 11 or R 12 may together form a ring.] Furthermore, n represents 0 or a positive integer, and when n is 2 or greater, R 5 to R 8 may be the same or different in each repeating unit.]

3. A resin composition for film as described in Claim 2, characterized in that the structural unit (C) in the copolymer (P) is a non-cyclic monomer represented by the general formula (1).

4. A resin composition for film as described in Claim 2, characterized in that the structural unit (C) in the copolymer (P) is a cyclic monomer represented by the general formula (2).

5. The resin composition for films according to claim 1, wherein the number of methyl branches of the copolymer (P) calculated by 13 C-NMR is 50 or less per 1,000 carbon atoms.

6. The resin composition for films according to claim 1, wherein the number of methyl branches of the copolymer (P) calculated by 13 C-NMR is 5 or less per 1,000 carbon atoms.

7. A resin composition for film described in any one of claims 1 to 6, characterized in that the copolymer (P) contains 2 to 20 mol% of the structural unit (B) in the copolymer (the sum of all structural units constituting the copolymer being 100 mol%).

8. A resin composition for film described in any one of claims 1 to 7, characterized in that the copolymer (P) contains the structural unit (C) in an amount of 0.001 mol% to 20.0 mol% (the total of all structural units constituting the copolymer is 100 mol%).

9. A resin composition for film described in any one of claims 1 to 8, characterized in that the structural unit (A) is a structural unit derived from ethylene.

10. A resin composition for film according to claim 1, wherein the metal ion is a metal ion of Group 1 of the periodic table.

11. A resin composition for film according to claim 1, wherein the metal ion is a metal ion of Group 12 of the periodic table.

12. A resin composition for films described in any one of claims 1 to 11, characterized in that 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.

13. The resin composition for film according to claim 12, wherein the transition metal catalyst is a transition metal catalyst consisting of a phosphorus sulfonic acid or phosphorus phenol ligand and nickel or palladium.

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