Group 2 metals in the periodic table contain アイオノマー

Abstract

To provide an ionomer which is excellent in a balance among flowability, impact resistance, and adhesion to a dissimilar material having high polarity.SOLUTION: There is provided an ionomer, wherein in a copolymer (P) containing a structural unit (A) derived from ethylene and / or 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 acid anhydride group as essential components, and has a ratio of the structural unit (B) of 1-20 mol%, at least a part of the carboxyl group and / or the dicarboxylic acid anhydride is converted into metal-containing carboxylate containing at least one kind of metal ions selected from the group 2 in the periodic table by neutralization, (a) a phase angle δ at an absolute value G* of 0.1 MPa of a complex elastic modulus measured by a rotary type rheometer is 50-75 degrees, and (b) a degree of neutralization is 1-90 mol%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to ionomers, and more specifically to ionomers containing Group 2 metals of the periodic table that have an excellent balance of fluidity, impact resistance, and adhesiveness. [Background technology]

[0002] Ethylene-based ionomers are resins that use ethylene-unsaturated carboxylic acid copolymers as a base resin, with intermolecular bonds formed by metal ions such as sodium and zinc. They are characterized by their toughness, high rigidity, and high transparency (Patent Document 1).

[0003] Currently, commercially available ethylene-based ionomers include "Surlyn®," a sodium and zinc salt of ethylene-methacrylic acid copolymer developed by Dupont, and "Hymiran®," sold by Mitsui Dow Polychemicals.

[0004] However, the ethylene-unsaturated carboxylic acid copolymers used as base resins in these currently commercially available ethylene-based ionomers all utilize polar group-containing olefin copolymers, which are polymerized by high-pressure radical polymerization of ethylene and polar group-containing monomers such as unsaturated carboxylic acids. The molecular structure of these polar group-containing olefin copolymers produced by high-pressure radical polymerization has many irregular long-chain and short-chain branches, as shown in the image diagram in Figure 1, and has the disadvantage of insufficient strength and impact resistance.

[0005] On the other hand, as another method for producing polar group-containing olefin copolymers that serve as the base resin for ethylene-based ionomers, it has been reported that a copolymer of ethylene and t-butyl acrylate is produced using a late-period transition metal catalyst, the resulting polar group-containing olefin copolymer is modified into an ethylene-acrylic acid copolymer by heat or acid treatment, and then reacted with metal ions such as sodium or zinc to produce ethylene-based ionomers (Patent Documents 2 and 3).

[0006] Furthermore, there have been reports of producing an ethylene-based ionomer using magnesium as a metal ion by grafting maleic anhydride onto an ethylene-cyclic olefin copolymer (COC) and then reacting it with magnesium stearate (Patent Document 4). [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] U.S. Patent No. 3,264,272 [Patent Document 2] Japanese Patent Publication No. 2016-079408 [Patent Document 3] Japanese Patent Publication No. 2020-143276 [Patent Document 4] Japanese Patent Publication No. 2020-158682 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] Patent Document 2 describes an ionomer produced using a late-period transition metal catalyst, which uses a polar group-containing olefin copolymer having a substantially linear structure as the base resin, resulting in an ionomer with excellent thermal properties and mechanical strength. However, only sodium ionomers have been substantially investigated, and there is no description of the effect of other metal ions on the properties. Furthermore, Patent Document 2 does not describe excellent adhesive performance to highly polar dissimilar materials such as synthetic resins other than polyolefins, metals, and wood.

[0009] Patent Document 3 describes a ternary ionomer produced using a late-period transition metal catalyst, with a base resin being a polar group-containing olefin copolymer having a substantially linear structure. It states that this ionomer exhibits excellent tensile strength, transparency, and metal adhesion. However, only sodium and zinc ions are substantially studied, and there is no description of the effects of other metal ions on the physical properties. Furthermore, Patent Document 3 does not describe how to achieve a high balance between fluidity, impact resistance, and adhesion. Moreover, using monomers other than ethylene and monomers having carboxyl groups and / or dicarboxylic acid anhydride groups leads to increased manufacturing costs.

[0010] Patent Document 4 describes a magnesium ionomer obtained using a maleic anhydride graft-modified ethylene-cyclic olefin copolymer (COC) as the base resin, which exhibits excellent high-temperature dimensional stability and transparency. However, since it is extremely difficult to produce copolymers containing a large amount of maleic anhydride by graft modification, these copolymers have the disadvantage of having a low acid content. In fact, the maleic anhydride content of the copolymer described in the examples of Patent Document 4 is about 1.5 wt% (0.86 mol%). Therefore, ethylene-based ionomers using graft-modified copolymers as the base resin have poor adhesive properties because the copolymer has few polar sites. Furthermore, because this ethylene-based ionomer has few reaction sites with metal ions, it is thought that it does not exhibit the full impact resistance expected of an ionomer. Furthermore, the ethylene-based ionomer base resin used in the examples of Patent Document 4 contains 21 mol% cyclic olefin, which has the disadvantage of having a high glass transition temperature (Tg) and being too hard.

[0011] In view of the circumstances of the prior art, the present invention aims to provide an ionomer that has an excellent balance of fluidity, impact resistance, and adhesion to dissimilar materials with high polarity. [Means for solving the problem]

[0012] To solve the above problems, the inventors have discovered that a specific ionomer having a linear structure such that the phase angle δ at the absolute value of the complex modulus G* = 0.1 MPa, measured with a rotary rheometer, is 50 to 75 degrees, and that has been neutralized with a metal ion from Group 2 of the periodic table, is an ionomer that exhibits superior fluidity, impact resistance, and adhesion to dissimilar materials with higher polarization than ionomers neutralized with metal ions from other groups, leading to the present invention.

[0013] In other words, the present invention relates to an ionomer comprising a copolymer (P) containing 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 acid anhydride group as essential constituent units, wherein the proportion of structural unit (B) is 1 to 20 mol%, and at least a portion of the carboxyl group and / or dicarboxylic acid anhydride group in the copolymer (P) is converted by neutralization to a metal-containing carboxylate containing at least one metal ion selected from Group 2 of the periodic table, characterized in that (a) the phase angle δ at the absolute value G* = 0.1 MPa of the complex modulus measured by a rotational rheometer is 50 to 75 degrees, and (b) the degree of neutralization is 1 to 90 mol%. In one aspect of the present invention, the copolymer (P) in the ionomer 13 The number of methyl branches calculated by 13C-NMR is 50 or less per 1,000 carbon atoms. In one aspect of the present invention, the structural unit (A) in the ionomer is a structural unit derived from ethylene. In one aspect of the present invention, the metal ion in the ionomer is Mg 2+ Ca 2+ It is at least one selected from the group consisting of the following: Furthermore, in one aspect of the present invention, the copolymer (P) is characterized in that it is produced using a transition metal catalyst containing a transition metal of groups 8 to 11 of the periodic table. In addition, in one aspect of the present invention, the transition metal catalyst in the ionomer is characterized in that it is a transition metal catalyst consisting of a phosphorusulfonic acid or phosphorphenol ligand and nickel or palladium. [Effects of the Invention]

[0014] According to the present invention, by using an ionomer with a substantially linear structure neutralized with Group 2 of the periodic table, it is possible to provide an ionomer with a better balance of fluidity, impact resistance, and adhesion than conventional multi-branched ionomers or linear ionomers neutralized with metals of other groups. [Brief explanation of the drawing]

[0015] [Figure 1] This is a schematic diagram illustrating the molecular structure of a highly branched olefin copolymer polymerized by a high-pressure radical polymerization process. [Figure 2] This is a conceptual diagram of the molecular structure of a linear olefin copolymer polymerized using a metal catalyst. [Figure 3] This figure shows the relationship between MFR (fluidity) and tensile impact strength (impact resistance) of the ionomers in Examples 1-3 and Comparative Examples 1-9. [Figure 4] This figure shows the relationship between the MFR (fluidity) and aluminum bonding strength (adhesion) of the ionomers in Examples 1-3 and Comparative Examples 1-9. [Modes for carrying out the invention]

[0016] The present invention is an ionomer characterized by comprising structural units (A) derived from ethylene and / or α-olefins having 3 to 20 carbon atoms and structural units (B) derived from monomers having carboxyl groups and / or dicarboxylic acid anhydride groups as essential constituent units, wherein at least a portion of the carboxyl groups and / or dicarboxylic acid anhydride groups in a copolymer (P) containing 1 to 20 mol% of structural unit (B) are converted by neutralization to a metal-containing carboxylate salt containing at least one metal ion selected from Group 2 of the periodic table, and having the following properties (a) and (b). (a) The phase angle δ at the absolute value G* = 0.1 MPa of the complex modulus measured by a rotary rheometer is between 50 and 75 degrees. (b) Degree of neutralization is 1-90 mol%

[0017] The ionomers related to the present invention will be described in detail below, item by item. In this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid. In this specification, "~" indicating a numerical range is used to mean that the values ​​written before and after it are included as the lower and upper limits. In this specification, copolymer means a binary or more copolymer containing at least one unit (A) and at least one unit (B). Furthermore, in this specification, "ionomer" means a binary or more copolymer ionomer comprising 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 salt, and which may further contain the structural unit (B).

[0018] 1. Ionomer The ionomer of the present invention is characterized in that it contains as essential structural units (A) a structural unit 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 acid anhydride group, and the copolymer (P) obtained by random copolymerizing these substantially in a linear manner is used as the base resin, and at least a portion of the carboxyl group and / or dicarboxylic acid anhydride group of the structural unit (B) is converted into a metal-containing carboxylate salt containing at least one metal ion selected from Group 2 of the periodic table.

[0019] (1) Structural unit (A) 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 α-olefins having 3 to 20 carbon atoms. The α-olefin related to this invention has the structural formula: CH2=CHR 18 It is an α-olefin with 3 to 20 carbon atoms, represented by (R 18 (The carbon group is a hydrocarbon group having 1 to 18 carbon atoms, and may have a linear or branched structure). The carbon number of the α-olefin is more preferably 3 to 12.

[0020] Specific examples of monomers that provide 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 ethylene may also be used. As for ethylene, in addition to ethylene derived from petroleum raw materials, ethylene derived from non-petroleum raw materials such as plant raw materials can be used. Furthermore, the structural unit (A) may be of one type or 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.

[0021] 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 as needed. The amount of ethylene in structural unit (A) may be 50-100 mol%, 70-100 mol%, or 90-100 mol% of the total moles of structural unit (A). From the standpoint of impact resistance, the preceding structural unit (A) may be a structural unit derived from ethylene.

[0022] (2) Structural unit (B) Structural unit (B) is a structural unit derived from a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group. Note that structural unit (B) has the same structure as the structural unit derived from a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group, and as described in the manufacturing method below, it does not necessarily have to be produced using a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group.

[0023] Examples of 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, norbornenedicarboxylic acid, and bicyclo[2,2,1]hepta-2-ene-5,6-dicarboxylic acid. Examples of monomers having a dicarboxylic acid anhydride group include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, and tetracyclo[6.2.1.1 3,6 .0 2,7 Examples include unsaturated dicarboxylic acid anhydrides such as dodeca-9-ene-4,5-dicarboxylic acid anhydride and 2,7-octadiene-1-ylsuccinic acid anhydride. As monomers having a carboxyl group and / or dicarboxylic acid anhydride group, acrylic acid, methacrylic acid, or 5-norbornene-2,3-dicarboxylic acid anhydride are preferred from the viewpoint of industrial availability, and acrylic acid may be particularly preferred. Furthermore, the monomer having a carboxyl group and / or a dicarboxylic acid anhydride group may be one type or multiple types.

[0024] In addition, the dicarboxylic acid anhydride group may react with moisture in the air to open its ring, and a portion of it may become a dicarboxylic acid. However, the dicarboxylic acid anhydride group may remain ring-open as long as it does not depart from the spirit of the present invention.

[0025] (3) Other structural units (C) The copolymer (P) related to the present invention may contain a structural unit (C) other than the structural units (A) and (B). The monomer that provides the structural unit (C) can be any monomer as long as it is not included in the monomers that provide the structural units (A) and (B). The monomer that provides the structural unit (C) is not limited as long as it is a compound having one or more carbon-carbon double bonds in its molecular structure. Examples include acyclic monomers represented by the following general formula (1) and cyclic monomers represented by the following general formula (2).

[0026] ·Acyclic monomer [Chemical formula] [In general formula (1), T 1 ~T 3 are each independently a substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an ester group having 2 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, a halogen atom, or a cyano group, T 4 is a substituent selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an ester group having 2 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, a halogen atom, or a cyano group.]

[0027] T 1 ~T 4The carbon skeletons of the hydrocarbon groups, substituted alkoxy groups, substituted ester groups, alkoxy groups, aryl groups, ester groups, and silyl groups may have branching, rings, and / or unsaturated bonds. T 1 ~T 4 The number of carbon atoms in the hydrocarbon group related to this can be as follows: the lower limit is 1 or more, the upper limit is 20 or less, or it may be 10 or less. T 1 ~T 4 The number of carbon atoms in the substituted alkoxy group can be as follows: the lower limit is 1 or more, the upper limit is 20 or less, or it may be 10 or less. T 1 ~T 4 The number of carbon atoms in the substituted ester group can be as follows: the lower limit is 2 or more, the upper limit is 20 or less, and it may also be 10 or less. T 1 ~T 4 The number of carbon atoms in the alkoxy group can be as follows: the lower limit is 1 or more, the upper limit is 20 or less, or it may be 10 or less. T 1 ~T 4 The number of carbon atoms in the aryl group can be 6 or more at the lower limit, 20 or less at the upper limit, or 11 or less. T 1 ~T 4 The number of carbon atoms in the ester group can be as follows: the lower limit is 2 or more, the upper limit is 20 or less, and it may also be 10 or less. T 1 ~T 4 The number of carbon atoms in the silyl group can be 3 or more at the lower limit and 18 or less at the upper limit, or 12 or less. Examples of silyl groups include trimethylsilyl, triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, and triphenylsilyl.

[0028] In the ionomer of the present invention, in terms of ease of manufacture, T 1 and T 2 T may be a hydrogen atom, 3T may be a hydrogen atom or a methyl group. 1 ~T 3 However, all of them may be hydrogen atoms. Also, in terms of impact resistance, T 4 This may be an ester group having 2 to 20 carbon atoms.

[0029] Atypical monomers include, specifically, (meth)acrylic acid esters and the like. 4 Examples include cases where the group is an ester group with 2 to 20 carbon atoms. T 4 If the group is an ester group with 2 to 20 carbon atoms, the acyclic monomer is defined as follows: Structural formula: CH2=C(R 21 )CO2(R 22 Examples of compounds represented by ) are shown here. 21 R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and may have branching, rings, and / or unsaturated bonds. 22 R is a hydrocarbon group having 1 to 20 carbon atoms, and may have branching, ring, and / or unsaturated bonds. 22 Heteroatoms may be included at any position within the material. Structural formula: CH2=C(R 21 )CO2(R 22 As a compound represented by ), R 21 However, examples include compounds that are hydrogen atoms or hydrocarbon groups having 1 to 5 carbon atoms. Also, R 21 Acrylic acid ester or R, where is a hydrogen atom 21 Examples include methacrylate esters, which have a methyl group. Structural formula: CH2=C(R 21 )CO2(R 22Specific examples of compounds represented by ) include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, and benzyl (meth)acrylate. Specific examples of compounds include methyl acrylate, ethyl acrylate, n-butyl acrylate (nBA), isobutyl acrylate (iBA), t-butyl acrylate (tBA), and 2-ethylhexyl acrylate, and in particular n-butyl acrylate (nBA), isobutyl acrylate (iBA), and t-butyl acrylate (tBA). The acyclic monomer may be one type or multiple types.

[0030] • Cyclic monomer [ka] [In general formula (2), R 1 ~R 12 These 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 also, R 11 and R 12 These may each integrate to form a divalent organic group, R 9 or R 10 And, R 11 or R 12 These elements may form a ring with each other. Furthermore, n represents 0 or a positive integer, and if n is 2 or greater, R 5 ~R 8These elements may be identical or different within each repeating unit.

[0031] Examples of cyclic monomers include norbornene-based olefins, such as norbornene, vinylnorbornene, ethylidenenorbornene, norbornadiene, tetracyclododecene, and tricyclo[4.3.0.1 2,5 ], tricyclo[4.3.0.1 2,5 Examples include compounds having a cyclic olefin skeleton such as deca-3-ene, 2-norbornene (NB), and tetracyclo[6.2.1.1 3,6 .0 2,7 Dodeca-4-en may also be used.

[0032] (4) Metal ions Examples of metal ions for carboxylic acid bases include divalent metal ions selected from the group consisting of Group 2 of the periodic table. Specifically, these include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra) ions. From the viewpoint of ease of handling, magnesium (Mg) or calcium (Ca) ions may be used in particular. Carboxylic acid bases can be obtained, for example, by hydrolyzing or thermally decomposing the ester group of a copolymer, or by reacting it with a compound containing a Group 2 metal ion of the periodic table while hydrolyzing or thermally decomposing it, thereby converting the ester group portion of the copolymer into a metal-containing carboxylate salt. Furthermore, the metal ion may be one type or multiple types.

[0033] (5) Copolymer (P) The copolymer (P) that serves as the base resin for the ionomer used in the present invention is characterized in that it contains structural units (A) derived from ethylene and / or α-olefins having 3 to 20 carbon atoms, and structural units (B) derived from monomers having carboxyl groups and / or dicarboxylic acid anhydride groups as essential constituent units, and optionally includes arbitrary structural units (C), and each of these structural units is substantially copolymerized in a linear manner, preferably randomly copolymerized. "Substantially linear" means that the copolymer does not have branching or the frequency of branching structures is small, and the copolymer can be considered linear. Specifically, it means that the phase angle δ of the copolymer is 50 degrees or more.

[0034] The copolymer according to the present invention must contain at least one type of structural unit (A) and at least one type of structural unit (B), and a total of at least two types of monomer units, and may also contain other structural units (C). The structural units and quantities of structural units of the copolymer related to this invention will be described. A single structural unit in a copolymer is defined as 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 acid anhydride group (B), and any monomer (C). The amount of structural units is the ratio of each structural unit, expressed in mol%, when the total amount of structural units in the copolymer is considered to be 100 mol%.

[0035] Structural unit quantity of structural unit (A): The amount of structural unit (A) related to the present invention is selected from a lower limit of 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, even more preferably 90.0 mol% or more, particularly preferably 95.0 mol% or more, particularly more preferably 96.7 mol% or more, and an upper limit of 99.0 mol% or less, preferably 98.0 mol% or less, more preferably 97.0 mol% or less, even more preferably 96.7 mol% or less, even more preferably 95.0 mol% or less, particularly preferably 92.3 mol% or less. If the amount of structural units derived from ethylene and / or α-olefins (A) having 3 to 20 carbon atoms is less than 60.0 mol%, the toughness of the copolymer will be poor, and if it is more than 99.0 mol%, the crystallinity of the copolymer will be high, which may result in poor transparency.

[0036] • Structural unit quantity of structural unit (B): The amount of structural unit (B) related to the present invention is selected from the following ranges: a lower limit of 1.0 mol% or more, preferably 2.0 mol% or more, more preferably 3.3 mol% or more, even more preferably 5.0 mol% or more, even more preferably 7.5 mol% or more, and an upper limit of 20.0 mol% or less, preferably 15.0 mol% or less, more preferably 10.0 mol% or less, even more preferably 8.0 mol% or less, particularly preferably 6.0 mol% or less, and most preferably 5.0 mol% or less. If the amount of structural units derived from monomer (B) having a carboxyl group and / or dicarboxylic acid anhydride group is less than 1.0 mol%, the copolymer may not have sufficient adhesion to highly polar dissimilar materials, and if it is more than 20.0 mol%, the copolymer may not be able to obtain sufficient mechanical properties. Furthermore, the monomers having a carboxyl group and / or a dicarboxylic acid anhydride group used may be used individually or in combination of two or more types.

[0037] • Structural unit quantity of structural unit (C): The amount of structural units (C) related to the present invention is selected from an upper limit of 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 3.0 mol% or less, with no particular limit on the lower limit, which may be 0 mol%. When the amount of structural units derived from any monomer (C) is 20.0 mol% or less, sufficient mechanical properties of the copolymer are easily obtained. Furthermore, any monomer (C) used may be used alone or in combination of two or more types.

[0038] Number of branches per 1,000 carbon atoms in copolymer (P): In the copolymer of the present invention, in order to achieve a high elastic modulus and sufficient mechanical properties, 13 The number of methyl branches calculated by 13C-NMR may have an upper limit of 50 or less, 5.0 or less, 2.0 or less, 1.0 or less, or 0.5 or less per 1,000 carbon atoms, and there is no particular lower limit; the fewer the better. Similarly, the number of ethyl branches may have an upper limit of 3.0 or less, 2.0 or less, 1.0 or less, or 0.5 or less per 1,000 carbon atoms, and there is no particular lower limit; the fewer the better. Furthermore, the number of butyl branches may have an upper limit of 7.0 or less, 5.0 or less, 3.0 or less, or 0.5 or less per 1,000 carbon atoms, and there is no particular lower limit; the fewer the better.

[0039] Method for measuring the amount of structural units derived from monomers having carboxyl groups and / or dicarboxylic acid anhydride groups, acyclic monomers, and cyclic monomers in copolymers, and the number of branches per 1,000 carbon atoms: The amount of structural units derived from monomers having carboxyl groups and / or dicarboxylic acid anhydride groups, acyclic monomers, and cyclic monomers in the copolymer of the present invention, and the number of branches per 1,000 carbon atoms. 13 It can be determined using 1C-NMR spectroscopy. 13 1C-NMR is measured using the following method. 200-300 mg of the sample is placed in a 10 mm diameter NMR sample tube along with 2.4 mL of a mixed solvent of o-dichlorobenzene (C6H4Cl2) and deuterated bromidebenzene (C6D5Br) (C6H4Cl2 / C6D5Br = 2 / 1 (volume ratio)) and hexamethyldisiloxane, which is the reference substance for chemical shifts. After purging with nitrogen, the tube is sealed, and the sample is heated to dissolve and obtain a homogeneous solution, which is then used as the NMR measurement sample. NMR measurements are performed at 120°C using a Bruker Japan AV400M NMR spectrometer equipped with a 10 mmφ cryoprobe. 131C-NMR is measured using the reverse gate decoupling method with a sample temperature of 120°C, a pulse angle of 90°, a pulse interval of 51.5 seconds, and a total of 512 or more integration cycles. The chemical shift is hexamethyldisiloxane. 13 Set the C signal to 1.98 ppm, and the other 13 The chemical shift of the signal due to C is based on this. obtained 13 In 1C-NMR, by identifying signals specific to monomers or branches in a copolymer and comparing their intensities, the amount of structural units of each monomer and the number of branches in the copolymer can be analyzed. The location of the signals specific to monomers or branches can be determined by referring to known data or by independently identifying them depending on the sample. Such analytical techniques are generally possible for those skilled in the art.

[0040] • Weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn): The weight-average molecular weight (Mw) of the copolymer according to the present invention is typically 1,000 or more at the lower limit, preferably 6,000 or more, more preferably 10,000 or more, even more preferably 15,000 or more, and even more preferably 20,000 or more. The upper limit is typically 2,000,000 or less, preferably 1,500,000 or less, even more preferably 1,000,000 or less, particularly suitable for 800,000 or less, and most preferably 100,000 or less. If Mw is less than 1,000, the copolymer's physical properties such as mechanical strength and impact resistance are insufficient, and if Mw exceeds 2,000,000, the copolymer's melt viscosity becomes extremely high, which can make molding and processing difficult.

[0041] The ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) (Mw / Mn) of the copolymer related to the present invention is usually in the range of 1.5 to 4.0, preferably 1.6 to 3.5, more preferably 1.7 to 3.7, and even more preferably 1.9 to 2.4. If Mw / Mn is less than 1.5, the copolymer will not have sufficient processability, including molding, and if it exceeds 4.0, the copolymer may have poor mechanical properties. In this invention, (Mw / Mn) may be expressed as the molecular weight distribution parameter.

[0042] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) related to this invention are determined by gel permeation chromatography (GPC). Furthermore, the molecular weight distribution parameter (Mw / Mn) is calculated by determining the number-average molecular weight (Mn) using gel permeation chromatography (GPC), and then calculating the ratio of Mw to Mn, Mw / Mn.

[0043] An example of a GPC measurement method related to the present invention is as follows: (Measurement conditions) Model used: Waters 150C Detector: FOXBORO MIRAN1A IR detector (measurement wavelength: 3.42 μm) Measurement temperature: 140℃ Solvent: Orthodichlorobenzene (ODCB) Columns: Showa Denko AD806M / S (3 pieces) Flow rate: 1.0mL / min Injection volume: 0.2mL (Sample preparation) The sample is prepared by creating a 1 mg / mL solution using ODCB (containing 0.5 mg / mL of BHT (2,6-di-t-butyl-4-methylphenol)) and dissolving it at 140°C for approximately 1 hour. (Calculation of molecular weight (M)) The calibration is performed using the standard polystyrene method, and the conversion from retention capacity to molecular weight is performed using a calibration curve prepared in advance using standard polystyrene. Examples of standard polystyrenes used include those from Tosoh Corporation (F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000) and monodisperse polystyrenes from Showa Denko (S-7300, S-3900, S-1950, S-1460, S-1010, S-565, S-152, S-66.0, S-28.5, S-5.05, each in a 0.07 mg / mL solution). A calibration curve is created by injecting 0.2 mL of each solution, dissolved in ODCB (containing 0.5 mg / mL BHT) to a concentration of 0.5 mg / mL. The calibration curve is obtained by approximating it using the least squares method, using a cubic equation, or by approximating it using a quartic equation with the logarithm of the elution time and molecular weight. The viscosity formula [η] = K × Mα used for conversion to molecular weight (M) is as follows. Polystyrene (PS): K = 1.38 × 10 -4 α=0.7 Polyethylene (PE): K = 3.92 × 10 -4 , α=0.733 Polypropylene (PP): K = 1.03 × 10 -4 α = 0.78

[0044] • Melting point (Tm, °C): The melting point of the copolymer according to the present invention is indicated by the maximum peak temperature of the endothermic curve measured by differential scanning calorimeter (DSC). The maximum peak temperature refers to the temperature of the peak with the greatest height from the baseline when multiple peaks are shown in the endothermic curve obtained when heat flow (mW) is plotted on the vertical axis and temperature (°C) on the horizontal axis in a DSC measurement, or the temperature of that peak if there is only one 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 will not be sufficient, and if it is higher than this range, the adhesive properties may be poor. In this invention, the melting point can be determined from the absorption curve obtained by, for example, using DSC (DSC7020) manufactured by SII Nanotechnology Co., Ltd., packing approximately 5.0 mg of the sample into an aluminum pan, raising the temperature to 200°C at 10°C / min, holding it isothermally at 200°C for 5 minutes, then lowering the temperature to 20°C at 10°C / min, holding it isothermally at 20°C for 5 minutes, and then raising the temperature again to 200°C at 10°C / min.

[0045] • Crystallinity (%): In the copolymer of the present invention, the degree of crystallinity observed by differential scanning calorimetry (DSC) is not particularly limited, but is preferably greater than 0%. It is more preferably greater than 5%, and even more preferably 7% or more. If the degree of crystallinity is 0%, the toughness of the copolymer may not be sufficient. The degree of crystallinity is also an indicator of transparency, and transparency is preferable, but there is no particular upper limit to the degree of crystallinity. In the present invention, the degree of crystallinity can be determined, for example, by calculating the heat of fusion (ΔH) from the endothermic peak area obtained by DSC measurement using the same procedure as for measuring the melting point, and then dividing that heat of fusion by the heat of fusion of perfect high-density polyethylene (HDPE), which is 293 J / g.

[0046] • Molecular structure of copolymers: The molecular chain end of the copolymer according to the present invention may be an ethylene and / or α-olefin structural unit (A) having 3 to 20 carbon atoms, a monomer structural unit (B) having a carboxyl group and / or a dicarboxylic acid anhydride group, or any monomer structural unit (C).

[0047] Furthermore, copolymers related to the present invention include random copolymers, block copolymers, and graft copolymers of ethylene and / or α-olefin structural units having 3 to 20 carbon atoms (A), monomer structural units having a carboxyl group and / or a dicarboxylic acid anhydride group (B), and structural units of any monomer (C). Among these, a random copolymer that can contain a large amount of structural unit (B) may also 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 structural units of ethylene and / or α-olefins having 3 to 20 carbon atoms (A), the monomer structural units having a carboxyl group and / or a dicarboxylic acid anhydride group (B), and the structural units of any monomer (C) shown in molecular structure example (1) below, are found at any given molecular chain position, and the probability of finding each structural unit is independent of the type of adjacent structural units. As shown below, in the example molecular structure of the copolymer (1), structural units of ethylene and / or α-olefins having 3 to 20 carbon atoms (A), structural units of monomers having a carboxyl group and / or a dicarboxylic acid anhydride group (B), and structural units of any monomer (C) form a random copolymer. [ka]

[0048] For reference, an example of the molecular structure (2) of a copolymer into which a monomer structural unit (B) having a carboxyl group and / or a dicarboxylic acid anhydride group has been introduced by graft modification is also shown. In this example, a portion of the copolymer, which is copolymerized with a monomer structural unit (A) of ethylene and / or an α-olefin having 3 to 20 carbon atoms and a monomer structural unit (C) of any monomer, is graft-modified with a monomer structural unit (B) having a carboxyl group and / or a dicarboxylic acid anhydride group. [ka]

[0049] Furthermore, while random copolymerization in copolymers can be confirmed by various methods, a method for determining random copolymerization from the relationship between the comonomer content and melting point of a copolymer is described in detail in Japanese Patent Publication No. 2015-163691 and Japanese Patent Publication No. 2016-079408. From the above literature, it can be determined that the randomness is low if the melting point (Tm, °C) of the copolymer is higher than -3.74 × [Z] + 130 (where [Z] is the comonomer content / mol%).

[0050] In the present invention, which is a random copolymer, it is preferable that the melting point (Tm, °C) observed by differential scanning calorimetry (DSC) and the total content [Z] (mol%) of the monomer having a carboxyl group and / or dicarboxylic acid anhydride group (B) and the structural units of any monomer (C) satisfy the following formula (I). 50 <Tm<-3.74×[Z]+130···(I) If the melting point (Tm, °C) of the copolymer is higher than -3.74 × [Z] + 130 ( °C), the random copolymerization is poor, resulting in inferior mechanical properties such as impact strength. If the melting point is lower than 50 °C, the rigidity may be poor.

[0051] Furthermore, from the viewpoint of having a linear molecular structure, it is preferable that the copolymer related to the present invention is manufactured in the presence of a transition metal catalyst. It is known that the molecular structure of copolymers differs depending on the manufacturing method, such as polymerization by high-pressure radical polymerization or polymerization using metal catalysts. While these differences in molecular structure can be controlled by selecting a manufacturing method, the molecular structure can also be estimated by measuring the complex modulus of elasticity using a rotational rheometer, as described in Japanese Patent Publication No. 2010-150532.

[0052] • The absolute value G of the complex modulus of elasticity * Phase angle δ at =0.1MPa: In the copolymer of the present invention, the absolute value G of the complex modulus measured with a rotational rheometer * At 0.1 MPa, the phase angle δ may have a lower limit of 50 degrees or more, 51 degrees or more, 54 degrees or more, 56 degrees or more, 58 degrees or more, and an upper limit of 75 degrees or less, or 70 degrees or less. More specifically, the absolute value G of the complex modulus of elasticity measured with a rotational rheometer. * = Phase angle δ(G) at 0.1 MPa *When the pressure (=0.1 MPa) is 50 degrees Celsius or higher, the molecular structure of the copolymer is linear, either completely free of long-chain branching or containing a small amount of long-chain branching that does not affect its mechanical strength. Furthermore, the absolute value G of the complex modulus of elasticity measured with a rotary rheometer. * = Phase angle δ(G) at 0.1 MPa * If the pressure (=0.1 MPa) is below 50 degrees Celsius, the copolymer's molecular structure will exhibit excessive long-chain branching, resulting in inferior mechanical strength. The absolute value G of the complex modulus of elasticity measured with a rotary rheometer. * The phase angle δ at 0.1 MPa is influenced by both the molecular weight distribution and long-chain branching. However, for copolymers where Mw / Mn ≤ 4, more preferably Mw / Mn ≤ 3, it can serve as an indicator of the amount of long-chain branching, and the more long-chain branching there is in the molecular structure, the higher δ(G) * The value (=0.1MPa) will be smaller. Furthermore, if the Mw / Mn ratio of the copolymer is 1.5 or higher, even if the molecular structure does not include long-chain branching, δ(G * The value (=0.1MPa) will never exceed 75 degrees.

[0053] The method for measuring the complex modulus of elasticity is as follows: The sample was placed in a 1.0 mm thick heat press mold and preheated in a hot press machine at a surface temperature of 180°C for 5 minutes. After that, residual gas in the molten resin was removed by repeatedly applying and removing pressure, and then pressurized to 4.9 MPa and held for 5 minutes. Subsequently, the sample was transferred to a press machine at 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 from the sample with a thickness of approximately 1.0 mm. A 25 mm diameter circular press plate was processed from the sample and used as the sample. Dynamic viscoelasticity was measured under the following conditions in a nitrogen atmosphere using a Rheometrics ARES type rotary rheometer as the device for measuring dynamic viscoelastic properties. • Plate: φ25mm parallel plate ·Temperature: 160℃ • Distortion level: 10% • Measurement angular frequency range: 1.0 × 10 -2 ~1.0×10 2 rad / s ·Measurement interval: 5 points / decade Absolute value G of complex elastic modulus * Common logarithm logG of (Pa) * Plot the phase angle δ against it, and for logG * let the value of δ (degrees) at the point corresponding to logG = 5.0 be δ(G * = 0.1 MPa). When there is no point corresponding to logG * = 5.0 among the measurement points, use two points around logG * = 5.0 to obtain the δ value at logG * = 5.0 by linear interpolation. Also, when all measurement points are logG * < 5, use the values of three points with larger logG * values to extrapolate the δ value at logG * = 5.0 by a quadratic curve.

[0054] ·Regarding the production of the copolymer From the viewpoint of making the molecular structure of the copolymer linear, it is preferably produced in the presence of a transition metal catalyst. [[ID=Z1]]

[0055] ·Polymerization catalyst The type of polymerization catalyst used for the production of the copolymer according to the present invention is not particularly limited as long as it can copolymerize structural unit (A), structural unit (B), and optional structural unit (C). For example, transition metal compounds of Groups 5 to 11 having a chelating ligand can be mentioned. Specific examples of preferred transition metals include vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, manganese atom, iron atom, platinum atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom, copper atom, etc. Among these, preferably, transition metals of Groups 8 to 11, more preferably transition metals of Group 10, and particularly preferably nickel (Ni) and palladium (Pd). These metals may be used singly or in combination of a plurality. The chelating ligand contains a ligand having at least two atoms selected from the group consisting of P, N, O, and S, and is bidentate or multidentate, and is electronically neutral or anionic. The structure of the chelating ligand is illustrated in a review by Brookhart et al. (Chem. Rev., 2000, 100, 1169). Preferred chelating ligands include bidentate anionic P, O ligands. Examples of bidentate anionic P, O ligands include phosphinosulfonic acid, phosphinocarboxylic acid, phosphinophenol, and phosphinoenolate. Other chelating ligands include bidentate anionic N, O ligands. Examples of bidentate anionic N, O ligands include salicylaldiminato and pyridinecarboxylic acid. Other chelating ligands include diimine ligands, diphenoxide ligands, and diamide ligands, etc.

[0056] The structure of the metal complex obtained from the chelating ligand is represented by the following structural formula (a) or (b) coordinated with an arylphosphine compound, arylarsine compound, or arylantimony compound which may have a substituent. [Chemical formula] [Chemical formula] [In structural formula (a) and structural formula (b), M represents a transition metal belonging to any of Groups 5 to 11 of the periodic table of the elements, that is, various transition metals as described above. X 1 represents oxygen, sulfur, -SO3-, or -CO2-. Y 1 represents carbon or silicon. n represents an integer of 0 or 1. E 1 represents phosphorus, arsenic, or antimony. R 53 and R 54Each of these independently represents a hydrocarbon group which may contain hydrogen or a heteroatom having 1 to 30 carbon atoms. R 55 Each of these independently represents a hydrocarbon group which may contain hydrogen, a halogen, or a heteroatom having 1 to 30 carbon atoms. R 56 and R 57 Each of these independently contains hydrogen, a halogen, a hydrocarbon group which may contain a heteroatom having 1 to 30 carbon atoms, OR 52 CO2R 52 CO2M', C(O)N(R 51 )2, C(O)R 52 , SR 52 SO2R 52 SOR 52 OSO2R 52 , P(O)(OR 52 ) 2-y (R 51 ) y , CN, NHR 52 , N(R 52 )2, Si(OR 51 ) 3-x (R 51 ) x , OSi(OR 51 ) 3-x (R 51 ) x , NO2, SO3M', PO3M'2, P(O)(OR 52 ) Represents 2M' or epoxy-containing groups. R 51 This represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. R 52 This represents a hydrocarbon group having 1 to 20 carbon atoms. M' represents alkali metals, alkaline earth metals, ammonium, quaternary ammonium, or phosphonium, x is an integer from 0 to 3, and y is an integer from 0 to 2. Note, R 56 and R 57 These elements may be linked together to form an alicyclic ring, an aromatic ring, or a heterocycle 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 substituents. L1 This represents the ligand coordinated to M. Also, R 53 and L 1 They may join together to form a ring.

[0057] More preferably, it is a transition metal complex represented by the following structural formula (c). [ka] [In structural formula (c), M represents a transition metal belonging to one of groups 5 through 11 of the periodic table, i.e., the various transition metals mentioned above. X 1 represents oxygen, sulfur, -SO3-, or -CO2-. Y 1 represents carbon or silicon. n represents an integer, either 0 or 1. E 1 This represents phosphorus, arsenic, or antimony. R 53 and R 54 Each of these independently represents a hydrocarbon group which may contain hydrogen or a heteroatom having 1 to 30 carbon atoms. R 55 Each of these independently represents a hydrocarbon group which may contain hydrogen, a halogen, or a heteroatom having 1 to 30 carbon atoms. R 58 , R 59 , R 60 and R 61 Each of these independently contains hydrogen, a halogen, a hydrocarbon group which may contain a heteroatom having 1 to 30 carbon atoms, OR 52 CO2R 52 CO2M', C(O)N(R 51 )2, C(O)R 52 , SR 52 SO2R 52 SOR 52 OSO2R 52 , P(O)(OR 52 ) 2-y (R 51 ) y , CN, NHR52 , 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 ) Represents 2M' or epoxy-containing groups. R 51 This represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. R 52 This represents a hydrocarbon group having 1 to 20 carbon atoms. M' represents alkali metals, alkaline earth metals, ammonium, quaternary ammonium, or phosphonium, x is an integer from 0 to 3, and y is an integer from 0 to 2. Note, R 58 ~R 61 Multiple groups appropriately selected from these may be linked together to form an alicyclic ring, an aromatic ring, or a heterocycle 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 substituents. L 1 This represents the ligand coordinated to M. Also, R 53 and L 1 They may join together to form a ring.

[0058] Here, typical catalysts for transition metal compounds of groups 5 to 11 that have chelating ligands include so-called SHOP catalysts and Drent catalysts. SHOP catalysts are catalysts in which a phosphorus ligand having an aryl group, which may have substituents, is coordinated to a nickel metal (see, for example, WO2010-050256). Furthermore, Drent catalysts are catalysts in which a phosphorus ligand having an aryl group, which may have substituents, is coordinated to a palladium metal (see, for example, Japanese Patent Application Publication No. 2010-202647).

[0059] • Polymerization method for copolymers: The polymerization method for copolymers related to the present invention is not limited. Polymerization methods include slurry polymerization, in which at least a portion of the resulting polymer becomes a slurry in the medium; bulk polymerization, which uses the liquefied monomer itself as the medium; gas-phase polymerization, which is carried out in vaporized monomer; and high-pressure ionic polymerization, in which at least a portion of the resulting polymer dissolves in monomer liquefied at high temperature and pressure. The polymerization method can be batch polymerization, semi-batch polymerization, or continuous polymerization. Furthermore, living polymerization may be performed, or polymerization may be carried out while simultaneously undergoing chain transfer. Furthermore, during polymerization, a so-called chain shuttling agent (CSA) may be used in combination to perform chain shuttling reactions or coordinated chain transfer polymerization (CCTP). Specific manufacturing processes and conditions are disclosed, for example, in Japanese Patent Publication No. 2010-260913 and Japanese Patent Publication No. 2010-202647.

[0060] Method for introducing carboxyl groups and / or dicarboxylic acid anhydride groups into copolymers: The method for introducing carboxyl groups and / or dicarboxylic acid anhydride groups into the copolymer according to the present invention is not particularly limited. Within the scope of the present invention, carboxyl groups and / or dicarboxylic acid anhydride groups can be introduced by various methods. Methods for introducing carboxyl groups and / or dicarboxylic acid anhydride groups include, for example, directly copolymerizing a comonomer having carboxyl groups and / or dicarboxylic acid anhydride groups, or introducing carboxyl groups and / or dicarboxylic acid anhydride groups by modification after copolymerizing another monomer.

[0061] Methods for introducing carboxyl groups and / or dicarboxylic acid anhydride groups through modification include, for example, when introducing a carboxylic acid, methods such as copolymerizing an acrylic acid ester and then hydrolyzing it to convert it into a carboxylic acid, or copolymerizing t-butyl acrylate and then converting it into a carboxylic acid by thermal decomposition.

[0062] When hydrolyzing or thermally decomposing as described above, conventionally known acid-base catalysts may be used as additives to promote the reaction. There are no particular restrictions on the acid-base catalyst, but for example, alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; alkali metal or alkaline earth metal carbonates such as sodium bicarbonate and sodium carbonate; solid acids such as montmorillonite; inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid; and organic acids such as formic acid, acetic acid, benzoic acid, citric acid, p-toluenesulfonic acid, trifluoroacetic acid, and trifluoromethanesulfonic acid can be used as appropriate. From the viewpoints of reaction acceleration effect, cost, and equipment corrosivity, sodium hydroxide, potassium hydroxide, sodium carbonate, p-toluenesulfonic acid, and trifluoroacetic acid are preferred, with p-toluenesulfonic acid and trifluoroacetic acid being more preferred.

[0063] (6) Ionomer The ionomer according to the present invention is characterized in that at least a portion of the carboxyl groups and / or dicarboxylic acid anhydride groups of the structural unit (B) in the copolymer (P) of the present invention are converted by neutralization to a metal-containing carboxylate containing at least one metal ion selected from Group 2 of the periodic table, and has the following properties (a) and (b). (a) The phase angle δ at the absolute value G* = 0.1 MPa of the complex modulus measured by a rotary rheometer is between 50 and 75 degrees. (b) The degree of neutralization is 1 to 90 mol%. Here, in the copolymer (P), some of the carboxyl groups of the structural unit (B) are neutralized by a group 2 metal in the ionomer, but the amount of the portion corresponding to structural unit (B) is essentially the same between the copolymer (P) and the ionomer. Therefore, the amount of the portion corresponding to structural unit (B) contained in the ionomer has a lower limit of 1.0 mol% or more and an upper limit of 20.0 mol% or less.

[0064] • Metal ions The metal ions contained in the ionomer related to this invention are metal ions of Group 2 of the periodic table, such as Be. 2+ Mg 2+ Ca 2+ Sr 2+ Ba 2+ and Ra 2+ It is at least one selected from the group consisting of the following. Particularly preferred is Mg 2+ Ca 2+ , and Ba 2+ At least one selected from the group consisting of Mg 2+ These are some examples. These metal ions can be mixed in two or more types as needed. In addition to the metal ions of Group 2 of the periodic table, metal ions of Groups 1, 11, and 12 of the periodic table, which are conventionally known to be used in ionomers, can also be included to the extent that they do not impair the effects of the present invention.

[0065] (a) Phase angle δ (structure of the ionomer) Since the ionomers related to the present invention have a substantially linear structure, similar to the copolymers related to the present invention, the absolute value of the complex modulus G measured with a rotational rheometer * The phase angle δ at 0.1 MPa is characterized by being in the range of 50 to 75 degrees. * If the temperature (=0.1 MPa) is below 50 degrees Celsius, the molecular structure of the ionomer will exhibit a structure with excessive long-chain branching, resulting in inferior mechanical strength. Furthermore, even if the molecular structure does not contain long-chain branching, δ(G * The value (=0.1MPa) will never exceed 75 degrees. In the present invention, from the viewpoint of improving mechanical strength, the lower limit of the phase angle δ is preferably 51 degrees or more, more preferably 54 degrees or more, even more preferably 56 degrees or more, and even more preferably 58 degrees or more. The upper limit is not particularly limited, and the closer it is to 75 degrees, the better.

[0066] (b) Degree of neutralization (mol%) The metal ion content is preferably such that it neutralizes at least a portion of the carboxyl groups and / or dicarboxylic acid anhydride groups in the copolymer as the base polymer, and the preferred degree of neutralization (average degree of neutralization) is 1 to 90 mol%, more preferably 5 to 85 mol%, and even more preferably 10 to 80 mol%. The degree of neutralization can be determined from the ratio of the total amount of moles of metal ions (valence × moles) to the total amount of carboxyl groups that may be contained in the copolymer and / or dicarboxylic acid anhydride groups. Since the dicarboxylic acid anhydride group undergoes ring-opening to form a dicarboxylic acid when forming a carboxylate salt, the total amount of carboxyl groups is calculated by assuming that 1 mole of dicarboxylic acid anhydride group contains 2 moles of carboxyl groups. Since metal ions in Group 2 of the periodic table are +2 valence, the total amount of molecules of neutralization is calculated by assuming that 1 mole can form a salt with 2 moles of carboxyl groups, using 2 × moles. Higher neutralization levels result in higher tensile strength and tensile fracture stress of the ionomer, and lower tensile fracture strain, but tend to lower the melt flow rate (MFR) of the ionomer. On the other hand, lower neutralization levels yield an ionomer with a moderate MFR, but tend to result in lower tensile modulus and tensile fracture stress, and higher tensile fracture strain. If the degree of neutralization is lower than 1 mol%, the toughness (strength and impact resistance) of the ionomer may be insufficient, and if the degree of neutralization is higher than 90 mol%, the adhesion to highly polar dissimilar materials may be insufficient.

[0067] • Melt flow rate (MFR) (fluidity) of ionomers: In the ionomer of the present invention, in order to ensure sufficient fluidity of the ionomer, it is preferable that the lower limit of the MFR value measured under the conditions of a temperature of 190°C and a load of 21.18N (=2.16kg) according to Table 1-Condition 7 of JIS K-7210 (1999) exceeds 0.1, more preferably exceeds 0.3, even more preferably exceeds 0.5, and the upper limit is preferably 100 or less, more preferably 50 or less, and even more preferably 30 or less. Furthermore, MFR is an indicator of liquidity; the higher the MFR value, the better the liquidity is considered to be. The melt flow rate (MFR) can be measured by the method described in the examples below.

[0068] • Tensile impact strength (impact resistance) of ionomers: In the ionomer of the present invention, the tensile impact value obtained by the tensile impact test described in JIS K7160 (1996) Method B is 300 kJ / m², in order to ensure sufficient impact resistance of the ionomer. 2 Preferably, it should be 350 kJ / m³ or more. 2 It is more preferable that the value be greater than or equal to 400 kJ / m³. 2 It is even more preferable that the above conditions are met. The aforementioned tensile impact test can be measured by the method described in the embodiments below.

[0069] • Ionomer adhesive strength (bonding properties): In the ionomer of the present invention, in order to ensure sufficient adhesion of the ionomer to dissimilar materials with high polarity, the aluminum (Al) adhesive strength measured in the adhesive strength measurement test described in the examples below is preferably 0.3 N / 10 mm or more, more preferably 0.5 N / 10 mm or more, even more preferably 1.0 N / 10 mm or more, and particularly preferably 1.5 N / 10 mm or more.

[0070] • Crystallinity of the ionomer (%): In the ionomer of the present invention, the degree of crystallinity observed by differential scanning calorimetry (DSC) is preferably greater than 0%, more preferably greater than 5%, and even more preferably 7% or higher, from the viewpoint of sufficient toughness of the ionomer. From the viewpoint of transparency of the ionomer, the upper limit is preferably 50% or less, more preferably 40% or less, and even more preferably 35% or less. The degree of crystallinity serves as an indicator of transparency, and the lower the degree of crystallinity of the ionomer, the better its transparency can be judged to be.

[0071] • Tensile fracture strength of ionomers: In the ionomer of the present invention, the tensile breaking strength measured by the tensile impact test described in JIS K7161 (1994) is preferably 10 MPa or more, more preferably 20 MPa or more, and even more preferably 30 MPa or more, in order to ensure sufficient strength of the ionomer. The tensile test can be measured by the method described in the examples below.

[0072] The ionomer of the present invention preferably further possesses at least one of the above-mentioned properties: MFR, tensile impact strength, and adhesive strength, due to its excellent balance of fluidity, impact resistance, and adhesiveness.

[0073] • Method for manufacturing ionomers The ionomers according to the present invention may also be obtained by a conversion step in which a copolymer of ethylene and / or α-olefin / unsaturated carboxylic acid having 3 to 20 carbon atoms, obtained by the method of introducing carboxyl groups and / or dicarboxylic acid anhydride groups into the copolymer as described above, is treated with a metal salt containing at least one metal ion selected from Group 2 of the periodic table to convert it into a metal-containing carboxylate salt. Alternatively, the ionomers according to the present invention may also be obtained by a heating conversion step in which an ethylene and / or α-olefin / unsaturated carboxylic acid ester copolymer having 3 to 20 carbon atoms is heated and at least some of the ester groups in the copolymer are converted into a metal-containing carboxylate salt containing at least one metal ion selected from Group 2 of the periodic table.

[0074] When an ionomer is produced by introducing carboxyl groups and / or dicarboxylic acid anhydride groups into a polymer, the production method is as follows, for example: A metal ion source is prepared by heating and kneading a metal salt with a metal ion-capturing substance such as ethylene / (meth)acrylic acid ((M)AA) copolymer, and then the metal ion source is added to the ionomer precursor resin in an amount that results in a desired degree of neutralization and kneaded to obtain the ionomer.

[0075] Furthermore, in the heating conversion step, (i) the ethylene and / or C3-C20 α-olefin / unsaturated carboxylic acid ester copolymer may be heated to obtain an ethylene and / or C3-C20 α-olefin / unsaturated carboxylic acid copolymer by hydrolysis or thermal decomposition, and then reacted with a compound containing a Group 2 metal ion of the periodic table to convert the carboxylic acid in the ethylene and / or C3-C20 α-olefin / unsaturated carboxylic acid copolymer into the metal-containing carboxylate salt; or (ii) the ethylene and / or C3-C20 α-olefin / unsaturated carboxylic acid ester copolymer may be heated to hydrolyze or thermal decompose the ester groups of the copolymer, and reacted with a compound containing a Group 2 metal ion of the periodic table to convert the ester group portion in the ethylene and / or C3-C20 α-olefin / unsaturated carboxylic acid ester copolymer into the metal-containing carboxylate salt.

[0076] Furthermore, the compounds containing metal ions may also be oxides, hydroxides, carbonates, bicarbonates, acetates, formates, etc., of metals in Group 2 of the periodic table. Compounds containing metal ions may be supplied to the reaction system in granular or fine powder form, or they may be dissolved or dispersed in water or an organic solvent before being supplied to the reaction system. Alternatively, a masterbatch may be prepared using an ethylene / unsaturated carboxylic acid copolymer or an olefin copolymer as the base polymer and supplied to the reaction system. To ensure the reaction proceeds smoothly, it is preferable to prepare a masterbatch and supply it to the reaction system.

[0077] Furthermore, the reaction with the metal ion-containing compound may be carried out by melt-kneading using various types of equipment such as a vented extruder, Banbury mixer, or roll mill, and the reaction may be carried out in batch or continuous order. It is preferable to carry out the reaction continuously using an extruder equipped with a degasser, such as a vented extruder, as this allows the reaction to proceed smoothly by removing the water and carbon dioxide produced as by-products using a degasser. When reacting with compounds containing metal ions, a small amount of water may be added to accelerate the reaction.

[0078] The heating temperature for ethylene and / or α-olefin / unsaturated carboxylic acid ester copolymers having 3 to 20 carbon atoms should be such that the ester is converted to a carboxylic acid. If the heating temperature is too low, the ester will not be converted to a carboxylic acid, and if it is too high, decarbonylation or decomposition of the copolymer will occur. 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.

[0079] The reaction time varies depending on the heating temperature and the reactivity of the ester group, but is usually 1 minute to 50 hours, more preferably 2 minutes to 30 hours, even more preferably 2 minutes to 10 hours, even more preferably 2 minutes to 3 hours, and particularly preferably 3 minutes to 2 hours.

[0080] In the above process, there are no particular restrictions on the reaction atmosphere, but it is generally preferable to carry it out under an inert gas stream. Examples of inert gases that can be used include nitrogen, argon, and carbon dioxide. Small amounts of oxygen or air may be present.

[0081] There are no particular restrictions on the reactor used in the above process; any method that can stir the copolymer substantially uniformly is acceptable. A glass container or autoclave (AC) equipped with a stirrer may be used, or any conventionally known kneader such as a Brabender plastograph, a single-screw or twin-screw extruder, a heavy-duty screw kneader, a Banbury mixer, a kneader, or a roll can be used.

[0082] Whether 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 obtained resin and examining the decrease in the peak originating from the carbonyl group of the carboxylic acid (dimer). Similarly, the degree of neutralization can be confirmed by examining the decrease in the peak originating from the carbonyl group of the carboxylic acid (dimer) and the increase in the peak originating from the carbonyl group of the carboxylic acid base, in addition to the calculation from the molar ratio mentioned above.

[0083] • Additives The ionomers related to the present invention may contain additives such as conventionally known antioxidants, ultraviolet absorbers, lubricants, antistatic agents, colorants, pigments, crosslinking agents, foaming agents, nucleating agents, flame retardants, conductive materials, and fillers, to the extent that they do not depart from the spirit of the present invention.

[0084] (7) Highly polar dissimilar materials The ionomer of the present invention has excellent adhesive properties to highly polar dissimilar materials. Specific examples of highly polar dissimilar materials related to the present invention that can exhibit excellent adhesive properties include polyethylene resins such as ethylene-vinyl acetate copolymer and ethylene-acrylic acid ester copolymer; vinyl polymers such as polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylate, and polyacrylonitrile; polyamide resins such as nylon 6, nylon 66, nylon 10, nylon 11, nylon 12, nylon 610, and polymetaxylylene adipamide; polyester resins such as polyethylene terephthalate, polyethylene terephthalate / isophthalate, polybutylene terephthalate, polylactic acid, polybutylene succinate, and aromatic polyesters; polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and polycarbonate. Examples include thermosetting resins such as polycarbonate resins, adhesive fluororesins, phenolic resins, epoxy resins, urea resins, melamine resins, urea resins, alkyd resins, unsaturated polyesters, polyurethanes, thermosetting polyimides, and other thermosetting resins; thermoplastic resin films or sheets (stretched or printed) having film-forming ability, such as cellophane and other cellulose-based polymers; metal foils or metal plates of aluminum, iron, copper, or alloys mainly composed of these; vapor-deposited films of inorganic oxides such as silica vapor-deposited plastic films and alumina vapor-deposited plastic films; vapor-deposited films of metals such as gold, silver, and aluminum, or compounds other than oxides of these metals; papers such as fine paper, kraft paper, cardboard, glassine paper, and synthetic paper; cellophane; woven fabrics; and nonwoven fabrics. [Examples]

[0085] 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 using the methods described below. Additionally, "no data" in the table means no measurement was taken, and "not detected" means the value was below the detection limit.

[0086] <Measurement and Evaluation> (1) The absolute value G of the complex modulus of elasticity * = Phase angle δ(G) at 0.1 MPa * Measurement (=0.1MPa) 1) Sample preparation and measurement The sample was placed in a 1.0 mm thick heat press mold and preheated in a hot press machine at a surface temperature of 180°C for 5 minutes. After that, residual gas in the molten resin was removed by repeatedly applying and removing pressure, and then it was further pressurized to 4.9 MPa and held for 5 minutes. After that, it was transferred to a press machine at a surface temperature of 25°C and cooled by holding it at a pressure of 4.9 MPa for 3 minutes to produce a press plate made from the sample with a thickness of approximately 1.0 mm. A 25 mm diameter circular press plate was processed from the sample and used as the sample. Dynamic viscoelasticity was measured under the following conditions in a nitrogen atmosphere using a Rheometrics ARES type rotary rheometer as the device for measuring dynamic viscoelastic properties. • Plate: φ25mm (diameter) Parallel plate ·Temperature: 160℃ • Distortion level: 10% • Measurement angular frequency range: 1.0 × 10 -2 ~1.0×10 2 rad / s • Measurement interval: 5 points / decade The absolute value G of the complex modulus of elasticity * The common logarithm of (Pa) logG * We plot the phase angle δ against logG * The value of δ(degrees) for the point corresponding to =5.0 is δ(G * (=0.1MPa) was used. logG was placed inside the measurement point. * If there is no point corresponding to =5.0, then logG * Using two points around =5.0, logG * The δ value at =5.0 was determined by linear interpolation. Also, all measurement points were logG. * When < 5, logG * Using the three largest values, we construct a quadratic curve with logG. * The δ value at =5.0 was obtained by extrapolation.

[0087] (2) 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) using GPC, and then determining the ratio of Mw to Mn, Mw / Mn. The measurements were performed according to the following procedures and conditions.

[0088] 1) Sample pretreatment If the sample contained a carboxylic acid group, it was subjected to esterification treatment, such as methyl esterification using diazomethane or trimethylsilyl (TMS) diazomethane, before being used for measurement. If the sample contained a carboxylic acid base, it was treated with acid to convert the carboxylic acid base into a carboxylic acid group, and then subjected to the above-mentioned esterification treatment before being used for measurement.

[0089] 2) Preparation of sample solution 3 mg of the sample and 3 mL of o-dichlorobenzene were weighed into a 4 mL vial, sealed with a screw cap and a Teflon® septum, and then shaken at 150°C for 2 hours using a Senshu Scientific SSC-7300 high-temperature shaker. After shaking, the absence of insoluble components was visually confirmed.

[0090] 3) Measurement One Showdex HT-G and two Showdex HT-806M high-temperature GPC columns were connected to a Waters Alliance GPCV2000 column. 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 Column calibration was performed by measuring the molecular weights of 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 at 0.07 mg / mL solution), n-eicosane, and n-tetracontane under the same conditions as above, and elution time and the logarithm of molecular weight were approximated by a quartic equation. Note that the molecular weight of polystyrene (M PS) and polyethylene molecular weight (M PE The following formula was used for the conversion. M PE = 0.468 × M PS

[0092] (3) Melt Flow Rate (MFR) MFR was measured according to Table 1-Condition 7 of JIS K-7210 (1999), under conditions of a temperature of 190°C and a load of 21.18 N (= 2.16 kg). In the table, "<0.01" means that the resin did not flow under the test conditions and measurement was not possible.

[0093] (4) Melting point and degree of crystallinity The melting point is indicated by the peak temperature of the endothermic curve measured by a differential scanning calorimeter (DSC). A DSC (DSC7020) manufactured by SII Nanotechnology Co., Ltd. was used for the measurement, and the following measurement conditions were followed. Approximately 5.0 mg of the sample was placed in an aluminum pan and heated to 200°C at a rate of 10°C / min. After holding at 200°C for 5 minutes, the temperature was lowered to 30°C at a rate of 10°C / min. After holding at 30°C for 5 minutes, the temperature was raised again at a rate of 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 determined from the endothermic peak area. The degree of crystallinity (%) was then determined by dividing this heat of fusion by the heat of fusion of perfect high-density polyethylene (HDPE), which is 293 J / g.

[0094] (5) Method for measuring the amount of structural units and the number of branches per 1,000 carbon atoms derived from monomers having carboxyl groups and / or dicarboxylic acid anhydride groups, acyclic monomers, and cyclic monomers. The amount of structural units derived from monomers, acyclic monomers, and cyclic monomers having carboxyl groups and / or dicarboxylic acid anhydride groups in the copolymer of the present invention, and the number of branches per 1,000 carbon atoms. 13 It can be determined using 1C-NMR spectroscopy. 13 ¹ 200-300 mg of the sample was placed in 2.4 mL of a mixed solvent of o-dichlorobenzene (C6H4Cl2) and deuterated bromidebenzene (C6D5Br) (C6H4Cl2 / C6D5Br = 2 / 1 (volume ratio)) and hexamethyldisiloxane, a reference substance for chemical shifts, in an NMR sample tube with an inner diameter of 10 mmφ. After purging with nitrogen, the tube was sealed, heated to dissolve the sample, and prepared as a homogeneous solution for NMR measurement. NMR measurements were performed at 120°C using a Bruker Japan AV400M NMR spectrometer equipped with a 10 mmφ cryoprobe. 13 1C-NMR was measured using the reverse gate decoupling method with a sample temperature of 120°C, a pulse angle of 90°, a pulse interval of 51.5 seconds, and more than 512 integration cycles. The chemical shift is hexamethyldisiloxane. 13 Set the C signal to 1.98 ppm, and the other 13 The chemical shift of the signal due to C was based on this.

[0095] 1) Sample pretreatment If the sample contains a carboxylic acid base, it was treated with acid to convert the carboxylic acid base into a carboxyl group before being used for measurement. If the sample contains a carboxyl group, esterification treatment, such as methyl esterification using diazomethane or trimethylsilyl (TMS) diazomethane, may be performed as appropriate.

[0096] 2) Calculation of structural unit amounts derived from monomers having carboxyl groups and / or dicarboxylic acid anhydride groups, acyclic monomers, and cyclic monomers. <e tba> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 It is detected in the 1C-NMR spectrum between 79.6 and 78.8. 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 quantities given by the following equations, respectively. I(tBA)=I 79.6~78.8 I(E)=(I 180.0~135.0 +I 120.0~5.0 -I(tBA×7) / 2

[0097] <e tba iba> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 The C-NMR spectrum was detected at 79.6–78.8 ppm, the methylene signal of the isobutoxy group of iBA at 70.5–69.8 ppm, and the methyl signal of the isobutoxy group at 19.5–18.9 ppm. 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 represented by the following equations, respectively. I(tBA)=I 79.6~78.8 I(iBA)=(I 70.5~69.8 +I 19.5~18.9 ) / 3 I(E)=(I 180.0~135.0 +I 120.0~5.0 -I(iBA)×7-I(tBA)×7 / 2

[0098] <e tba nb> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 The C-NMR spectrum shows signals at 79.6–78.8 ppm, and the methine carbon signal of NB is detected at 41.9–41.1 ppm. 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 represented by the following equations, respectively. I(tBA)=I 79.6~78.8 I(NB)=(I 41.9~41.1 ) / 2 I(E)=(I 180.0~135.0 +I 120.0~5.0 -I(NB)×7-I(tBA)×7 / 2

[0099] Furthermore, if the structural unit amount of each monomer is indicated with an inequality sign, such as "<0.1", it means that it exists as a constituent unit in the copolymer, but the amount is less than 0.1 mol%, taking significant figures into consideration.

[0100] 3) Calculation of the number of branches per 1,000 carbon atoms Copolymers include isolated types, where branches exist individually in the main chain, and complex types (facing types, where branches face each other via the main chain; branched-branch types, where branches exist within the branched chain; and chained types). The following are examples of ethyl branched structures. In the examples of the opposite type, R represents an alkyl group.

[0101] [ka]

[0102] The number of branches per 1,000 carbon atoms can be determined by substituting one of the following I(B1), I(B2), or I(B4) into the I(branching) term in the following equation. B1 represents methyl branching, B2 represents ethyl branching, and B4 represents butyl branching. The number of methyl branchings is determined using I(B1), the number of ethyl branchings is determined using I(B2), and the number of butyl branchings is determined using I(B4). Number of branches (per 1,000 carbon atoms) = I (number of branches) × 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 integral intensity, and the subscript number of I indicates the range of the chemical shift. For example, I 180.0~135.0 It was detected between 180.0 ppm and 135.0 ppm. 13 This shows the integrated intensity of the C signal. Attributions are based on the non-patent literature Macromolecules 1984, 17, 1756-1761 and Macromolecules 1979, 12, 41. Note that when the number of branches is indicated with an inequality sign, such as "<0.1", it means that the component exists as a constituent unit in the copolymer, but the amount is less than 0.1 mol%, taking significant figures into consideration. Also, "not detected" means that it is below the detection limit.

[0103] (6) Infrared absorption spectrum The sample was melted at 180°C for 3 minutes, and then compressed to produce a film with a thickness of approximately 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) Cumulative number of times: 16-512 Resolution: 4.0cm -1 Measurement wavelength: 5000~500cm -1

[0104] (7) Tensile test A 1 mm thick sheet was prepared from the sample using the method described in JIS K7151 (1995) (cooling method A). A 5B type small test specimen, as described in JIS K7162 (1994), was prepared by punching out the sheet. Tensile tests were then performed at a temperature of 23°C according to JIS K7161 (1994), and the tensile modulus, tensile breaking stress, and tensile breaking elongation were measured. The test speed was 10 mm / min.

[0105] (8) Tensile impact strength 1) Method for preparing tensile impact strength test samples The sample was placed in a 1 mm thick heat press mold and preheated in a hot press machine at a surface temperature of 180°C for 5 minutes. Then, the sample was melted by repeatedly applying and removing pressure, and any residual gas in the sample was removed. Further pressurization was applied at 4.9 MPa and held for 5 minutes. After that, the sample was gradually cooled at a rate of 10°C / min while maintaining the 4.9 MPa pressure, and the molded plate was removed from the mold when the temperature had dropped to near room temperature. The resulting molded plate was conditioned for more than 48 hours in an environment of 23 ± 2°C and 50 ± 5°C humidity. Test specimens in the shape of ASTM D1822 Type-S were punched out from the conditioned press plate and used as tensile impact strength test samples.

[0106] 2) Tensile impact strength test conditions Using the above-mentioned test specimens, the tensile impact strength was measured according to Method B of JIS K 7160-1996. The only difference from JIS K 7160-1996 was the shape of the test specimens. Other measurement conditions were carried out in accordance with the method of JIS K 7160-1996.

[0107] (9) Aluminum (Al) bonding strength The Al (aluminum) adhesion strength was measured by preparing a laminate by overlapping a sample processed into a press plate and an aluminum sheet and performing a hot press, and then conducting a peel test. The adjustment method of the press plate, the adjustment method of the laminate, and the measurement method of the adhesion strength will be described in order.

[0108] 1) Method for adjusting the press plate of the sample The sample was placed in a hot press mold with dimensions of 50 mm × 60 mm and a thickness of 0.5 mm, preheated in a hot press machine with a surface temperature of 180°C for 5 minutes, and then the residual gas in the sample was degassed by repeating pressurization and depressurization. Further, it was pressurized at 4.9 MPa and held for 3 minutes. Then, it was transferred to a press machine with a surface temperature of 25°C and cooled by holding at a pressure of 4.9 MPa for 3 minutes to prepare a press plate with a thickness of approximately 0.5 mm.

[0109] 2) Method for preparing a laminate of the sample and an aluminum (Al) sheet The press plate of the sample obtained by the press plate preparation method and a commercially available 50-μm-thick aluminum sheet (manufactured by UACJ Corporation, 1N30_H18_B1-1 (1N30 standard, hard double-sided glossy specification)) were cut into dimensions of 50 mm × 60 mm. The surfaces of the press plate of the sample and the aluminum sheet were wiped with a cloth impregnated with ethanol, and the press plate of the sample and the aluminum sheet were overlapped with the wiped surfaces. Then, they were placed in a hot press mold with dimensions of 50 mm × 60 mm and a thickness of 0.5 mm, and pressurized at 4.9 MPa for 5 minutes using a hot press machine with a surface temperature of 180°C. Then, it was transferred to a press machine with a surface temperature of 25°C and cooled by holding at a pressure of 4.9 MPa for 3 minutes to prepare a laminate of the press plate of the sample and the aluminum sheet.

[0110] 3) Method for measuring the adhesion strength of the laminate The laminate obtained by the laminate fabrication method was cut into 10 mm widths, and the adhesive strength was measured by peeling it off at a speed of 50 mm / min using a Tensilon (manufactured by Toyo Seiki Co., Ltd.) tensile testing machine. The unit of adhesive strength is expressed as N / 10 mm. Furthermore, if the adhesive strength is very strong, the sample layer or the base layer will yield and even break during the peel test. This phenomenon occurs because the adhesive strength of the laminate is higher than the lower of the tensile breaking strengths of the sample layer or the base layer, and it can be judged that the adhesion is very high. If the adhesive strength cannot be measured due to this phenomenon, "Not Peelable" is written in the adhesive strength measurement result, and it is judged that the adhesion is higher than the measured adhesive strength value.

[0111] <Synthesis of Metal Complexes> (1) Synthesis of B-27DM / Ni complex The B-27DM / Ni complex was synthesized using the following 2-bis(2,6-dimethoxyphenyl)phosphano-6-pentafluorophenylphenol ligand (B-27DM) according to Synthesis Example 4 described in International Publication No. 2010 / 050256. Following Example 1 of International Publication No. 2010 / 050256, a nickel complex (B-27DM / Ni) was synthesized by reacting B-27DM and Ni(COD)2 in a 1:1 ratio using bis(1,5-cyclooctadiene)nickel(0) (referred to as Ni(COD)2). [ka]

[0112] (2) Synthesis of B-423 / Ni complex The B-423 / Ni complex was synthesized according to Synthesis Example 1 described in Patent No. 2019 / 156764, using the following 2-bis(2,6-dimethoxyphenyl)phosphano-6-(2,6-diisopropylphenyl)phenol ligand (B-423). Following Example 1 of Patent No. 2019 / 156764, a nickel complex (B-423 / Ni) was synthesized by reacting B-423 and Ni(COD)2 in a 1:1 ratio using bis(1,5-cyclooctadiene)nickel(0) (referred to as Ni(COD)2). [ka]

[0113] <(Manufacturing Examples 1-7): Manufacturing of Ionomer-Based Resin Precursors> Using transition metal complexes (B-27DM / Ni complex or B-423 / Ni complex), ethylene / acrylic acid tBu copolymer, ethylene / acrylic acid tBu / acrylic acid ester copolymer, and ethylene / acrylic acid tBu / norbornene copolymer were produced. Production Examples 1-3 and 5-7 were produced with reference to Production Example 1 described in Japanese Patent Publication No. 2016-79408, and Production Example 4 was produced with reference to Production Example 3 described in Japanese Patent Publication No. 2016-79408. The production conditions and results, with appropriate changes to the metal complex species, amount of metal complex, amount of aluminum compound (trioctylaluminum (TNOA), triisopropoxyaluminum (Al(OiPr)3)), amount of toluene, comonomer species, amount of comonomer, ethylene partial pressure, polymerization temperature, polymerization time, etc., are shown in Tables 1 and 2, and the physical properties of the obtained copolymers are shown in Table 3.

[0114] [Table 1]

[0115] [Table 2]

[0116] [Table 3]

[0117] <(Resin 1-4, Resin 7-9): Manufacturing of ionomer-based resins> Into a separable flask with a capacity of 500 mL, 40 g of the copolymers obtained in Production Examples 1 to 4 and Production Examples 5 to 7, 0.8 g of p-toluenesulfonic acid monohydrate, and 185 mL of toluene were added, and the mixture was stirred at 105 °C for 4 hours. 185 mL of ion-exchanged water was added, stirred, allowed to stand, and then the aqueous layer was extracted. Thereafter, the addition and extraction of ion-exchanged water were repeated until the pH of the extracted aqueous layer became 5 or more. The solvent was distilled off under reduced pressure from the remaining solution, and drying was performed until a constant weight was obtained. In the IR spectrum of the obtained resin, disappearance of the peak around 850 cm -1 derived from the tBu group and decrease of the peak around 1730 cm -1 derived from the carbonyl group of the ester, and increase of the peak around 1700 cm -1 derived from the carbonyl group of the carboxylic acid (dimer) were observed. Thereby, decomposition of the t-Bu ester and formation of the carboxylic acid were confirmed, and ionomer base resins 1 to 4 and resins 7 to 9 were obtained. The physical properties of the obtained resins are shown in Table 4.

[0118] <(Resin 5): Ionomer base resin> It is a copolymer of ethylene and acrylic acid, and an acid copolymer (brand name: PRIMACOR 3440, manufactured by SK Chemicals Co., Ltd.) produced by a high-pressure radical process was used as the ionomer base resin. The physical properties are shown in Table 4.

[0119] <(Resin 6): Ionomer base resin> It is a copolymer of ethylene and methacrylic acid, and an acid copolymer (brand name: NUCREL 1108C, manufactured by Mitsui Dow Polychemical Co., Ltd.) produced by a high-pressure radical process was used as the ionomer base resin. The physical properties are shown in Table 4.

[0120]

Table 4

[0121] <Examples 1 to 10, Comparative Examples 1 to 25: Production of ionomers> 1) Preparation of a Na ion supply source A Na ion source was prepared by adding 22g of ethylene / methacrylic acid (MAA) copolymer (manufactured by Mitsui Dow Polychemicals Ltd., brand name: Nucrel N1050H) and 18g of sodium carbonate to a Toyo Seiki Co., Ltd. Laboplast Mill: Roller Mixer R60 equipped with a 60mL capacity mixer, and kneading at 180°C and 40rpm for 3 minutes.

[0122] 2) Preparation of a Zn ion source A Zn ion source was prepared by adding 21.8g of ethylene / methacrylic acid (MAA) copolymer (manufactured by Mitsui Dow Polychemicals Ltd., brand name: Nucrel N1050H), 18g of zinc oxide, and 0.2g of zinc stearate to a Toyo Seiki Co., Ltd. Laboplast Mill: Roller Mixer R60 equipped with a 60mL capacity mixer, and mixing at 180°C and 40rpm for 3 minutes.

[0123] 3) Preparation of a Mg ion supply source A Mg ion source was prepared by adding 21.8g of polyethylene (manufactured by Nippon Polyethylene Co., Ltd., brand: KS571), 18g of magnesium hydroxide, and 0.2g of magnesium stearate to a Toyo Seiki Co., Ltd. Laboplast Mill: Roller Mixer R60 equipped with a 60mL capacity mini mixer, and mixing at 180°C and 40rpm for 3 minutes.

[0124] 4) Preparation of a Ca ion source A Ca ion source was prepared by adding 21.8g of polyethylene (manufactured by Nippon Polyethylene Co., Ltd., brand: KS571), 18g of calcium oxide, and 0.2g of calcium stearate to a Toyo Seiki Co., Ltd. Laboplast Mill: Roller Mixer R60 equipped with a 60mL capacity mini mixer, and mixing at 180°C and 40rpm for 3 minutes.

[0125] 5) Preparation of ionomers 40g each of resins 1 to 6 were added to a Toyo Seiki Co., Ltd. Laboplast Mill: Roller Mixer R60, equipped with a 60mL capacity mini mixer, and mixed at 160°C and 40rpm for 3 minutes until dissolved. Subsequently, a Na ion source, Zn ion source, Mg ion source, or Ca ion source was added to achieve the desired degree of neutralization, and the mixture was kneaded at 250°C and 40rpm for 5 minutes. In the IR spectrum of the obtained resin, a 1700 cm⁻¹ spectrum originating from the carbonyl group of the carboxylic acid (dimer) was observed. -1 The peak in the vicinity decreases, and the 1560 cm peak originates from the carbonyl group of the carboxylic acid base. -1 The peak in the vicinity was increasing. This was due to the carbonyl group of the carboxylic acid (dimer) at 1700 cm². -1 The decrease in the surrounding peaks confirmed that the desired degree of neutralization of the ionomer was achieved. The physical properties of the obtained ionomer are shown in Tables 5 to 8.

[0126] [Table 5]

[0127] [Table 6]

[0128] [Table 7]

[0129] [Table 8]

[0130] <Discussion of the results from the examples and comparative examples> [Comparison of the ionomer of the present invention with conventional ionomers] Examples 2 and 3 in Table 6 are ionomers consisting of a base resin and a metal ion source produced with a specific transition metal catalyst; therefore, their molecular structure is substantially linear, and the phase angle δ(G) * The pressure (=0.1 MPa) is 50° or higher. On the other hand, Comparative Examples 1-3 in Table 8 are conventional ionomers, and since they are ionomers consisting of a base resin and a metal ion source produced by the high-pressure radical method, their molecular structure has many long-chain branches, and the absolute value of the complex modulus G * = Phase angle δ(G) at 0.1 MPa * =0.1MPa)) is less than 50°. Example 2 and Comparative Example 1, and Example 3 and Comparative Examples 2 and 3, are all similar in terms of structural unit (B) content, metal type, and degree of neutralization, and can be directly compared and evaluated; therefore, the comparisons are explained below. The MFR (fluidity) values ​​of the ionomers of the present invention in Examples 2 and 3 are similar to those of the conventional ionomers in Comparative Examples 1 to 3. However, the tensile impact values ​​and aluminum bonding strength of Examples 2 and 3 are significantly higher than those of Comparative Examples 1 to 3. Therefore, the ionomers of the present invention in Examples 2 and 3 have superior impact resistance and adhesion compared to the conventional ionomers in Comparative Examples 1, 2, and 3. This means that the phase angle δ(G * The linear ionomer of the present invention, with a pressure of 50° or higher (0.1 MPa), demonstrates a relatively superior balance of fluidity, impact resistance, and adhesion compared to conventional multi-branched ionomers.

[0131] [Regarding the metal ion species of the ionomer in this invention] Examples 1 to 10 in Table 6 are ionomers consisting of a base resin produced with a specific transition metal catalyst and a group 2 element of the periodic table. On the other hand, Comparative Examples 4 to 17 and 20 to 25 in Table 8 are conventional ionomers consisting of a base resin produced with a specific transition metal catalyst and a group 1 or 12 element of the periodic table. Examples 1-3 and Comparative Examples 4-9, Examples 4-6 and Comparative Examples 10-15, Example 7 and Comparative Examples 16 and 17, Example 8 and Comparative Examples 20 and 21, Example 9 and Comparative Examples 22 and 23, Example 10 and Comparative Examples 24 and 25 are ionomers with different metal ion species produced from the same base resin. Since those with similar degrees of neutralization can be directly compared and evaluated, the comparisons are explained below. The magnesium ionomers (Mg-IO) of Examples 1 to 3 have similar MFR values ​​(fluidity) to the sodium ionomers (Na-IO) of Comparative Examples 4 to 6, but exhibit higher tensile impact values ​​and significantly superior Al adhesion strength. On the other hand, compared to the zinc ionomers (Zn-IO) of Comparative Examples 7 to 9, they have larger MFR values, superior fluidity, and also superior tensile impact values ​​and Al adhesion strength. The same applies to comparisons between Examples 4-6, 8, 9, and 10 (Mg-IO) and Comparative Examples 10-12, 20, 22, and 24 (Na-IO), 13-15, 21, 23, and 25 (Zn-IO), as well as between Example 7 (calcium ionomer (Ca-IO)) and Comparative Examples 16 (Na-IO) and 17 (Zn-IO). This indicates that the Group 2 ionomers of the present invention have a superior balance of fluidity, impact resistance, and adhesiveness compared to Group 1 and Group 12 ionomers of the periodic table.

[0132] [Regarding the amount of structural units (B) of the copolymer (P) and the degree of neutralization of the ionomer in this invention] Examples 1 to 10 in Table 6 show that the amount of structural units (B) of the copolymer (P) and the degree of neutralization of the ionomer are within the range of the present invention, and exhibit excellent MFR values ​​(fluidity), tensile impact values ​​(impact resistance), and Al adhesive strength (adhesion). On the other hand, Comparative Example 18 in Table 8 has a low amount of structural units (B) of copolymer (P) at 0.6 mol%, which is outside the scope of the present invention, and its tensile impact value and Al adhesive strength are significantly lower. Furthermore, the ionomer in Comparative Example 19 had a high degree of neutralization of 95 mol%, which is outside the scope of the present invention, and its MFR value and Al adhesive strength were significantly lower. In other words, Comparative Examples 18 and 19 have an inferior balance of fluidity, impact resistance, and adhesiveness. This indicates that the ionomer of the present invention exhibits an excellent balance of fluidity, impact resistance, and adhesion by having a specific range of copolymer (P) structural unit (B) content and degree of ionomer neutralization.

[0133] The reason why the Group 2 ionomer of the periodic table described in this application has superior fluidity, impact resistance, and adhesion compared to Group 1 and Group 12 ionomers of the periodic table is likely due to the significant influence of the valence and electronegativity of the metal ions. Metal ions in Groups 2 and 12 of the periodic table have a valency of 2, while metal ions in Group 1 have a valency of 1. It is presumed that the higher the metal ion valency, the more polymer chains can ionically bond with a single metal ion, thus forming stronger crosslinking points and increasing the material strength of the polymer. Therefore, it is thought that ionsomers in Groups 2 and 12 of the periodic table, which have high metal ion valencies, have superior impact resistance compared to ionsomers in Group 1 of the periodic table. On the other hand, metal ions in Group 2 and Group 1 of the periodic table have lower electronegativity than metal ions in Group 12 of the periodic table. Generally, ion-crosslinkable resins such as ions exhibit fluidity because the rearrangement of metal-carboxylic acid bonds becomes easier upon heating. It is presumed that the lower the electronegativity of the metal ion, the stronger the ionic bonding of the metal-carboxylic acid bond, and the easier the rearrangement of the metal-carboxylic acid bond upon heating, thus improving the fluidity of the ionomer. Therefore, it is thought that ionsomers from Group 2 and Group 1 of the periodic table, which have lower electronegativity, have superior fluidity compared to ionsomers from Group 12 of the periodic table. Furthermore, adhesive strength is evaluated by a value measured by a peel test, as exemplified in JIS K6854-1~4 (1999) "Adhesives - Peel Adhesion Strength Test Method". However, the value measured by this method is thought to be the sum of the chemical and physical bonding forces at the interface between dissimilar materials and the cohesive force or stress during deformation of the materials, and is therefore presumed to be greatly influenced by the material strength. For this reason, as mentioned above, ionomers of Group 2 and Group 12 of the periodic table, which have high material strength, are considered to have superior adhesive properties compared to ionomers of Group 1 of the periodic table. From the above, it can be inferred that the Group 2 ionomer of the present invention, which uses metal ions with a high metal ion valency and low electronegativity, has an excellent balance of fluidity, impact resistance, and adhesiveness.

[0134] The present invention relates to the ionomers described in the following sections. [1] An ionomer characterized by comprising a copolymer (P) containing structural units (A) derived from ethylene and / or α-olefins having 3 to 20 carbon atoms and structural units (B) derived from monomers having carboxyl groups and / or dicarboxylic acid anhydride groups as essential constituent units, wherein the proportion of structural units (B) is 1 to 20 mol%, and at least a portion of the carboxyl groups and / or dicarboxylic acid anhydride groups in the copolymer (P) is converted by neutralization to a metal-containing carboxylate salt containing at least one metal ion selected from Group 2 of the periodic table, and having the following properties (a) and (b). (a) The phase angle δ at the absolute value G* = 0.1 MPa of the complex modulus measured by a rotary rheometer is between 50 and 75 degrees. (b) The degree of neutralization is 1 to 90 mol%. [2] The copolymer (P) 13 The ionomer according to [1], characterized in that the number of methyl branches calculated by 13C-NMR is 50 or less per 1,000 carbon atoms. [3] The ionomer of [1] or [2], characterized in that the structural unit (A) is a structural unit derived from ethylene. [4] The metal ion is Mg 2+ Ca 2+ An ionomer according to any one of the above [1] to [3], characterized in that it is selected from the group consisting of the following. [5] The ionomer according to any one of [1] to [4], characterized in that the copolymer (P) is produced using a transition metal catalyst containing a transition metal of Group 8 to 11 of the periodic table. [6] The ionomer according to [5], characterized in that the transition metal catalyst is a transition metal catalyst comprising a phosphorusulfonic acid or phosphorphenol ligand and nickel or palladium. [Industrial applicability]

[0135] The ionomers disclosed herein offer a superior balance of fluidity, impact resistance, and adhesiveness compared to conventional ionomers, making them highly useful.< / e> < / e> < / e>

Claims

1. An ionomer characterized by comprising 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 acid anhydride group as essential constituent units, wherein the proportion of structural unit (B) is 1 to 20 mol%, and at least a portion of the carboxyl group and / or dicarboxylic acid anhydride group in the copolymer (P) is converted by neutralization to a metal-containing carboxylate salt containing at least one metal ion selected from Group 2 of the periodic table, and having the following properties (a) and (b). (a) The phase angle δ at the absolute value G* = 0.1 MPa of the complex modulus measured by a rotary rheometer is between 50 and 75 degrees. (b) The degree of neutralization is 1 to 90 mol%.

2. The copolymer (P) １３ The ionomer according to claim 1, characterized in that the number of methyl branches calculated by C-NMR is 50 or less per 1,000 carbon atoms.

3. The ionomer according to claim 1, characterized in that the structural unit (A) is a structural unit derived from ethylene.

4. The aforementioned metal ion is Mg ２＋ Ca ２＋ The ionomer according to claim 1, characterized in that it is at least one selected from the group consisting of the following.

5. The ionomer according to any one of claims 1 to 4, characterized in that the copolymer (P) is produced using a transition metal catalyst containing a transition metal of groups 8 to 11 of the periodic table.

6. The ionomer according to claim 5, characterized in that the transition metal catalyst is a transition metal catalyst comprising a phosphorusulfonic acid or phosphorphenol ligand and nickel or palladium.

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