Antistatic resin composition

Abstract

The present invention provides an antistatic resin composition, primarily composed of ionomer, with improved abrasion resistance. [Solution] An antistatic resin composition comprising a potassium ionomer (I) and a polyvalent hydroxy compound (II) that satisfies the following conditions: 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 at least a portion of the carboxyl groups and / or dicarboxylic acid anhydride groups in the copolymer (P) are converted to potassium ion-containing carboxylate salts, the proportion of the structural units (B) converted to potassium ion-containing carboxylate salts in the copolymer (P) is 1.5 mol% or more, and the phase angle δ at the absolute value of the complex modulus of elasticity G* = 0.1 MPa measured by a rotational rheometer is 50 to 75 degrees.

Description

[Technical Field]

[0001] This invention relates to an antistatic resin composition mainly composed of a novel potassium ionomer. [Background technology]

[0002] Ionomers are synthetic resins formed by agglomerating polymers with metal ions. Ethylene-based ionomers are known, which use ethylene-unsaturated carboxylic acid copolymers as precursor resins and are intermolecularly bonded with various metal ions (Patent Document 1). Ethylene-based ionomers are tough, highly elastic, flexible, and possess characteristics such as abrasion resistance and transparency.

[0003] It is already known that potassium ionomers of ethylene-unsaturated carboxylic acid copolymers that contain a substantial amount of potassium ions exhibit excellent non-static properties (Patent Document 2). It is also already known that the non-static performance in low-humidity atmospheres can be enhanced by adding polyvalent hydroxy compounds to the above potassium ionomer (Patent Document 3). Currently, commercially available potassium-based ionomers include "ENTIRA®" sold by Mitsui Dow Polychemicals.

[0004] However, the ethylene-unsaturated carboxylic acid copolymers used as precursor resins in commercially available ethylene-based ionomers all utilize polar group-containing olefin copolymers obtained by polymerizing ethylene and polar group-containing monomers such as unsaturated carboxylic acids using high-pressure radical polymerization. High-pressure radical polymerization has the advantage of being able to polymerize relatively inexpensively regardless of the type of polar group-containing monomer. However, the molecular structure of polar group-containing olefin copolymers produced by this high-pressure radical polymerization method has the disadvantage of being insufficient in terms of strength, as shown in the image diagram in Figure 1, which has many irregular long-chain and short-chain branches.

[0005] To improve the shortcomings of polar group-containing olefin copolymers obtained by high-pressure radical polymerization, methods have been sought to polymerize polar group-containing olefin copolymers with a linear molecular structure, as shown in the image diagram in Figure 2, using catalysts. However, polar group-containing monomers generally act as catalyst poisons, making catalyst polymerization difficult. Therefore, it has been difficult to obtain polar group-containing olefin copolymers with desired properties by an industrially inexpensive and stable method. However, in recent years, a method has been proposed to industrially obtain inexpensive and stable polar group-containing olefin copolymers with substantially linear molecular structures by using a new catalyst and new manufacturing method developed by the applicants of this application. Furthermore, the applicants of this application have reported that they have succeeded in producing a polar group-containing olefin copolymer, which serves as a precursor resin for ethylene-based ionomers, by using a late-period transition metal catalyst to produce a copolymer of ethylene and t-butyl acrylate, modifying the obtained polar group-containing olefin copolymer to an ethylene-acrylic acid copolymer by heat or acid treatment, and then reacting it with metal ions to produce a binary ionomer (Patent Document 4). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] U.S. Patent No. 3,264,272 [Patent Document 2] Japanese Patent Application Publication No. 3-106954 [Patent Document 3] Patent No. 3474285 [Patent Document 4] Japanese Patent Publication No. 2016-79408 [Overview of the project] [Problems that the invention aims to solve]

[0007] Various attempts have been made with antistatic resin compositions containing potassium ionomers. However, conventional potassium ionomers are manufactured by high-pressure radical polymerization and have a structure with many irregular long-chain and short-chain branches, resulting in a large number of molecular chain ends and inherently problems with abrasion resistance. Since the ionomer itself, which is the antistatic resin composition, has problems with abrasion resistance, molded articles using this antistatic resin composition also suffer from problems with abrasion resistance. In particular, when high antistatic properties are required, the amount of antistatic resin composition used increases, making the problem of abrasion resistance even more pronounced.

[0008] In view of the circumstances of the prior art, the present invention aims to provide a novel antistatic resin composition mainly composed of potassium ionomer with improved wear resistance. [Means for solving the problem]

[0009] In order to solve the above problems, the inventors conducted extensive research and found an antistatic resin composition that is excellent not only in terms of non-static properties but also in terms of abrasion resistance, by setting the proportion of structural units converted to potassium ion-containing carboxylates to a certain level or higher in a copolymer mainly composed of a novel ethylene-based potassium ionomer that is substantially linear.

[0010] In other words, the present invention relates to a resin composition mainly composed of potassium ionomer (I), wherein the potassium ionomer (I) is a copolymer 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 at least a portion of the carboxyl groups and / or dicarboxylic acid anhydride groups are converted to a metal-containing carboxylate salt containing potassium ions, the proportion of the structural units (B) converted to the potassium ion-containing carboxylate salt in the copolymer (P) is 1.5 mol% or more, and the absolute value G of the complex modulus measured by a rotational rheometer is... *The resin composition is a potassium ionomer whose phase angle δ at 0.1 MPa is 50 to 75 degrees, and which contains a polyvalent hydroxy compound (II), a compound having two or more hydroxyl groups in its molecule, as a minor component. [Effects of the Invention]

[0011] The present invention makes it possible to provide an antistatic resin composition that exhibits excellent non-static properties and superior abrasion resistance. The present invention, which includes a potassium ionomer having a substantially linear structure, has higher strength than potassium ionomers derived from resins produced by conventional high-pressure radical polymerization methods, and can therefore be applied to applications where conventional products could not be used. [Brief explanation of the drawing]

[0012] [Figure 1] Figure 1 shows a schematic diagram of the molecular structure of a polar group-containing olefin copolymer produced by high-pressure radical polymerization. [Figure 2] Figure 2 shows a schematic diagram of the molecular structure of a polar group-containing olefin copolymer obtained by catalytic polymerization. [Modes for carrying out the invention]

[0013] The present invention relates to an antistatic resin composition that primarily comprises a potassium ionomer (I) consisting of a copolymer obtained by substantially linear copolymerization, preferably random copolymerization, of structural units (A) derived from ethylene and / or α-olefins having 3 to 20 carbon atoms and structural units (B) derived from monomers having a carboxyl group and / or a dicarboxylic acid anhydride group, and further comprises a polyvalent hydroxy compound (II), which is a compound having two or more hydroxyl groups in its molecule, as a minor component.

[0014] The following describes in detail, item by item, the antistatic resin composition containing potassium ionomer related to the present invention. In this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid. Also, in this specification, "~" indicating a numerical range is used to mean that the values ​​written before and after it are included as the lower limit and upper limit.

[0015] 1. Potassium ionomer (I) The potassium ionomer of the present invention is characterized in that it contains as essential constituent units a structural unit (A) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms and a structural unit (B) derived from a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group, and a copolymer (P) obtained by substantially linear copolymerization, preferably random copolymerization, of these is used as a precursor 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 carboxylate salt containing potassium ions.

[0016] (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.

[0017] Specific examples of structural unit (A) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, and 4-methyl-1-pentene, and may also be ethylene. Furthermore, the structural unit (A) contained in the carboxylic acid-containing resin may be one type or multiple types. Examples of combinations of two types include ethylene-propylene, ethylene-1-butene, ethylene-1-hexene, ethylene-1-octene, propylene-1-butene, propylene-1-hexene, and propylene-1-octene. Examples of combinations of three types include ethylene-propylene-1-butene, ethylene-propylene-1-hexene, ethylene-propylene-1-octene, propylene-1-butene-hexene, and propylene-1-butene-1-octene.

[0018] 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 65 to 100 mol%, or 70 to 100 mol%, relative to the total moles of structural unit (A).

[0019] (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.

[0020] 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]hept-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. Specific examples of compounds include acrylic acid, methacrylic acid, and 5-norbornene-2,3-dicarboxylic acid anhydride, and acrylic acid may be particularly suitable. Furthermore, the monomer having a carboxyl group and / or a dicarboxylic acid anhydride group may be one type or multiple types.

[0021] 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.

[0022] (3) Other structural units (C) The copolymer (P) related to the present invention may contain structural units (C) other than the structural units represented by structural units (A) and structural units (B) (hereinafter sometimes referred to as "any monomer (C)"). Any monomer can be used to give structural unit (C), as long as it is not the same as the monomer that gives structural units (A) and structural units (B). Preferably, the monomer does not contain metal elements that can form cations. Any monomer that gives structural unit (C) is not limited to compounds that have one or more carbon-carbon double bonds in their molecular structure, but examples include acyclic monomers represented by the following general formula (1) and cyclic monomers represented by the following general formula (2).

[0023] • Acyclic monomers [ka] [In general formula (1), T 1 ~T 3Each is independently a substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an ester group having 2 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, a halogen atom, or a cyano group. T 4 is a substituent selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an ester group having 2 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, a halogen atom, or a cyano group.

[0024] In the copolymer (P) of the present invention, T 1 and T 2 may be a hydrogen atom, T 3 may be a hydrogen atom or a methyl group, T 4 may be an ester group having 2 to 20 carbon atoms.

[0025] T 1 ~T 4 The hydrocarbon group, substituted alkoxy group, substituted ester group, alkoxy group, aryl group, ester group, and silyl group for T T 1 ~T 4 The carbon number of the hydrocarbon group for T T 1 ~T 4 The carbon number of the substituted alkoxy group for T 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.

[0026] Examples of acyclic monomers include (meth)acrylic acid esters. The (meth)acrylic acid ester related to this invention has the structural formula: CH2=C(R 21 )CO2(R 22 It is a compound represented by ). Here, R 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. As (meth)acrylic acid ester, R 21Examples include (meth)acrylic acid esters, which 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. Specific examples of (meth)acrylic acid esters 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). Furthermore, one type of acyclic monomer may be used, or multiple types may be used.

[0027] • 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 R10 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 8 These elements may be identical or different within each repeating unit.

[0028] Examples of cyclic monomers include norbornene-based olefins, such as norbornene, vinylnorbornene, ethylidenenorbornene, norbornadiene, tetracyclododecene, and tricyclo[4.3.0.1 2,5 Deca-1-en, 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.

[0029] (4) Copolymer (P) The copolymer (P) that serves as the precursor resin for the ionomer used in the present invention 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 is characterized in that these are 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 low, and the copolymer can be considered linear. Specifically, it refers to a state in which the phase angle δ of the copolymer measured under the following conditions is 50 degrees or more.

[0030] The copolymer (P) related 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 the copolymer (P) 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%.

[0031] Amount of structural units (A) derived from ethylene and / or α-olefins having 3 to 20 carbon atoms: The amount of structural unit (A) of the present invention is preferably selected from 60.0 mol% or more, more preferably 70.0 mol% or more, even more preferably 80.0 mol% or more, even more preferably 85.0 mol% or more, particularly preferably 90.0 mol% or more, and most preferably 91.2 mol% or more, from the viewpoint of improving the toughness of the multi-component copolymer and multi-component ionomer. The upper limit is preferably selected from 97.9 mol% or less, more preferably 97.5 mol% or less, even more preferably 97.0 mol% or less, even more preferably 96.7 mol% or less, particularly preferably 96.3 mol% or less, and most preferably 94.0 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 rigidity of the antistatic resin composition will be poor. If it is more than 97.9 mol%, the amount of structural units (B) that contribute to non-static properties will decrease, resulting in a decrease in non-static performance.

[0032] Amount of structural units (B) derived from monomers having a carboxyl group and / or a dicarboxylic acid anhydride group: The amount of structural unit (B) related to the present invention is preferably selected from a lower limit of 2.0 mol% or more, more preferably 3.0 mol% or more, even more preferably 3.2 mol% or more, even more preferably 4.2 mol% or more, and most preferably 5.2 mol% or more. The upper limit is preferably selected from a lower limit of 20.0 mol% or less, more preferably 15.0 mol% or less, even 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 5.5 mol% or less. The amount of structural unit (B) of the present invention is a part that contributes to the antistatic performance. If it is less than 2.0 mol%, the antistatic performance will decrease, and if it is more than 20.0 mol%, the rigidity of the antistatic resin composition will decrease. The monomer having a carboxyl group and / or dicarboxylic acid anhydride group used may be used alone or in combination of two or more types.

[0033] • Structural unit quantity of other structural units (C): The amount of structural unit (C) related to the present invention, when structural unit (C) is included, is selected from the following: lower limit 0.001 mol% or more, preferably 0.01 mol% or more, more preferably 0.02 mol% or more, even more preferably 0.1 mol% or more, even more preferably 1.0 mol% or more, particularly preferably 1.9 mol% or more, upper limit 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, particularly preferably 3.8 mol% or less. The monomers used may be used individually or in combination of two or more types.

[0034] • Number of branches per 1,000 carbon atoms in the copolymer: The molecular structure of polyolefins may include short carbon chains with approximately 1 to 4 carbon atoms, such as methyl, ethyl, and butyl, which appear as branches. The copolymer of the present invention has no branches or branches appear only infrequently, and has a structure that can be considered linear. In copolymers, 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, 1.0 or less, or 0.5 or less per 1,000 carbon atoms. The lower limit of the number of methyl branches is not particularly limited, and 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. The lower limit of the number of ethyl branches is not particularly limited, and 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. The lower limit of the number of butyl branches is not particularly limited, and the fewer the better.

[0035] • Method for measuring structural units and branching number derived from carboxyl groups and / or dicarboxylic acid anhydride group monomers in copolymers: Structural units derived from carboxyl groups and / or dicarboxylic acid anhydride group monomers in the multi-component copolymer of the present invention, 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 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, into an NMR sample tube with an inner diameter of 10 mmφ. 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. 13 1C-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. 13Set 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.

[0036] • 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, and typically 2,000,000 or less at the upper limit, preferably 1,500,000 or less, more preferably 1,000,000 or less, particularly suitable for 800,000 or less, and most preferably 56,000 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.

[0037] 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, and more preferably 1.9 to 2.3. 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. Furthermore, in this invention, (Mw / Mn) may be expressed as the molecular weight distribution parameter.

[0038] 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.

[0039] 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 standard polystyrene method is used, and the conversion from retention capacity to molecular weight is performed using a calibration curve prepared in advance using standard polystyrene. The standard polystyrenes used are all from Tosoh Corporation and are of the following brands: (F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000). A calibration curve is created by injecting 0.2 mL of a solution of each polystyrene dissolved in ODCB (containing 0.5 mg / mL of BHT) so that the concentration is 0.5 mg / mL. The calibration curve is approximated using a cubic equation obtained by the least squares method. 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

[0040] • 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. From the viewpoint of heat resistance, the melting point of the copolymer (P) of the present invention is preferably 50°C or higher at the lower limit, more preferably 60°C or higher, even more preferably 70°C or higher, preferably 140°C or lower at the upper limit, more preferably 110°C or lower, even more preferably 100°C or lower, even more preferably 98°C or lower, and particularly preferably 96°C or lower. The melting point can be determined from the absorption curve obtained by, for example, using a DSC (DSC7020) manufactured by SII Nanotechnology Co., Ltd., placing approximately 5.0 mg of the sample in 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.

[0041] • Crystallinity (%): In the copolymer (P) 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 greater. If the degree of crystallinity is 0%, the toughness of the copolymer may not be sufficient. Furthermore, the degree of crystallinity serves as an indicator of transparency, and the lower the degree of crystallinity of the copolymer, the better its transparency can be judged to be. In applications where transparency is required, the degree of crystallinity of the copolymer is preferably 30% or less, more preferably 25% or less, particularly preferably 25% or less, and most preferably 24% or less. The degree of crystallinity of a copolymer 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.

[0042] • Molecular structure of copolymer (P): The molecular chain end of the copolymer (P) 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).

[0043] Furthermore, the copolymer (P) related to the present invention includes random copolymers, block copolymers, and graft copolymers of structural units (A) of ethylene and / or α-olefins having 3 to 20 carbon atoms, structural units (B) of monomers having a carboxyl group and / or a dicarboxylic acid anhydride group, and structural units (C) of any monomer. 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.

[0044] [ka]

[0045] 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.

[0046] [ka]

[0047] 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%).

[0048] The copolymer (P) related to the present invention, which is a random copolymer, preferably satisfies the following formula (I) when the melting point (Tm, °C) observed by differential scanning calorimetry (DSC) and the total content [Z] (mol%) of the monomer structural units (B) having a carboxyl group and / or dicarboxylic acid anhydride group and the structural units (C) of any monomer. 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 heat resistance may be poor.

[0049] Furthermore, from the viewpoint of having a linear molecular structure, it is preferable that the copolymer (P) 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.

[0050] • 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 * The characteristic feature is that the phase angle δ at 0.1 MPa is between 50 and 75 degrees. The lower limit of the phase angle δ may be 51 degrees or more, 54 degrees or more, 56 degrees or more, or 58 degrees or more. The upper limit of the phase angle δ may be 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 *If the pressure (=0.1 MPa) is 50 degrees or higher, it indicates that the molecular structure of the copolymer is a linear structure, either completely free of long-chain branching or substantially linear, containing only 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.

[0051] 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 for 5 minutes in a hot press at a surface temperature of 180°C. 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 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 with a thickness of approximately 1.0 mm. A circular press plate with a diameter of 25 mm was processed into a sample, and the 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 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 * Let = 0.1 MPa. logG is placed within 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 is calculated using linear interpolation. Also, all measurement points are logG. * When < 5, logG * Using the three largest values, we construct a quadratic curve with logG. * The δ value at =5.0 is obtained by extrapolation.

[0052] Regarding the manufacture of copolymers (P) From the viewpoint of having a linear molecular structure, the copolymer (P) related to the present invention is preferably manufactured in the presence of a transition metal catalyst.

[0053] • Polymerization catalyst The type of polymerization catalyst used in the production of copolymers according to the present invention is not particularly limited as long as it is capable of copolymerizing structural unit (A), structural unit (B), and any structural unit (C), but examples include transition metal compounds of groups 5 to 11 having a chelating ligand. Specific examples of preferred transition metals include vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, platinum, ruthenium, cobalt, rhodium, nickel, palladium, and copper. Of these, transition metals from groups 8 to 11 are preferred, transition metals from group 10 are preferred, and nickel (Ni) and palladium (Pd) are particularly preferred. These metals may be used individually or in combination. Chelating ligands contain ligands that have at least two atoms selected from the group consisting of P, N, O, and S, and are either bidentate or multidentate coordinated, and are electronically neutral or anionic. Examples of chelating ligand structures are provided in a review by Brookhart et al. (Chem. Rev., 2000, 100, 1169). Preferably, bidentate anionic P,O ligands are used as chelating ligands. Examples of bidentate anionic P,O ligands include phosphosulfonic acid, phosphocarboxylic acid, phosphorus phenol, and phosphorus enolate. Other chelating ligands include bidentate anionic N,O ligands. Examples of bidentate anionic N,O ligands include salicylaldehyde and pyridinecarboxylic acid. Other chelating ligands include diimine ligands, diphenoxide ligands, and diamide ligands.

[0054] The structure of the metal complex obtained from the chelating ligand is represented by the following structural formula (c1) or (c2), to which an arylphosphine compound, arylarsine compound, or arylantimony compound, which may have substituents, is coordinated.

[0055] [ka]

[0056] [ka]

[0057] [In structural formula (c1) and structural formula (c2), 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 represents phosphorus, arsenic or antimony. R 53 and R 54 each independently represent hydrogen or a hydrocarbon group which may contain heteroatoms and has 1 to 30 carbon atoms. R 55 each independently represent hydrogen, halogen, or a hydrocarbon group which may contain heteroatoms and has 1 to 30 carbon atoms. R 56 and R 57 each independently represent hydrogen, halogen, a hydrocarbon group which may contain heteroatoms and has 1 to 52 52 30 carbon atoms, OR 52 CO2R 51 CO2M’, C(O)N(R 52 )2, C(O)R 52 SR 52 SO2R 52 SOR 52 OSO2R 52 ) 2-y (R 51 ) y CN, NHR 52 N(R 52 )2, Si(OR 51 ) 3-x (R 51 ) x OSi(OR 51 ) 3-x (R 51 ) x NO2, SO3M’, PO3M’2, P(O)(OR 52 )2M’ or an epoxy-containing group. R 51 represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. R 52 represents a hydrocarbon group having 1 to 20 carbon atoms. M’ represents an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium or phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2. In addition, R 56 and R 57These 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. L 1 This represents the ligand coordinated to M. Also, R 53 and L 1 They may join together to form a ring.

[0058] More preferably, the complex that serves as the polymerization catalyst is a transition metal complex represented by the following structural formula (c3).

[0059] [ka]

[0060] [In structural formula (c3), 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(R51 )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 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.

[0061] 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).

[0062] • Polymerization method of copolymer (P): The polymerization method for the copolymer (P) 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, using the liquefied monomer itself as the medium; gas-phase polymerization, carried out in vaporized monomer; or 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 form may 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.

[0063] 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.

[0064] 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.

[0065] 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 viewpoint of reaction promoting effect, cost, and equipment corrosion, sodium hydroxide, potassium hydroxide, sodium carbonate, p-toluenesulfonic acid, and trifluoroacetic acid are preferred, and p-toluenesulfonic acid and trifluoroacetic acid are more preferred.

[0066] 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.

[0067] 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.

[0068] 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 atmospheres, and small amounts of oxygen or air may be present.

[0069] There are no particular restrictions on the reactor used in the above process, as long as it can stir the copolymer substantially uniformly, it is not limited in any way. 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.

[0070] (5) Potassium ionomer The ionomer related to the present invention mainly comprises a potassium ionomer. The ionomer related to the present invention is an ionomer having a substantially linear structure in which at least a portion of the carboxyl groups and / or dicarboxylic acid anhydride groups of the structural unit (B) of the copolymer (P) of the present invention are converted to a metal-containing carboxylate salt containing potassium ions. The ionomers related to the present invention may optionally include ionomers composed of metal ions other than potassium. Applicable metal ions include monovalent or divalent metal ions from groups selected from the group consisting of groups 1, 2, and 12 of the periodic table. Specific examples of metal ions include lithium (Li), sodium (Na), rubidium (Rb), magnesium (Mg), calcium (Ca), and zinc (Zn) ions. Furthermore, as described later, ionomers are obtained by reacting an ionomer-based resin with a metal salt, and reactions that cleave the polymer's molecular chains do not usually occur during this process. Therefore, structural parameters such as the molar ratio of comonomers, the degree of branching, and randomness are usually conserved between the ionomer-based resin and the ionomer.

[0071] • Structure of ionomers The ionomers related to the present invention have a phase angle δ of 50 to 75 degrees at the absolute value of the complex modulus G* = 0.1 MPa, as measured by a rotational rheometer. If the phase angle δ(G*=0.1MPa) is lower than 50 degrees, the molecular structure of the multi-component ionomer will exhibit a structure containing an excessive amount of long-chain branching, resulting in inferior mechanical strength. Furthermore, even if the molecular structure does not contain long-chain branching, the δ(G*=0.1MPa) value will not exceed 75 degrees. In the present invention, the ionomer preferably has a lower limit of the phase angle δ of 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, with no particular upper limit, and the closer to 75 degrees the better.

[0072] ·Neutralization degree (mol%) The metal ion content is preferably such that it contains an amount that neutralizes some or all of the carboxyl groups and / or dicarboxylic acid anhydride groups in the multi-component copolymer as the base resin. The preferred degree of neutralization (average degree of neutralization) is 5 to 95 mol%, more preferably 10 to 90 mol%, and even more preferably 20 to 80 mol%, relative to the total molar amount of carboxyl groups in the multi-component copolymer. The degree of neutralization can be determined from the ratio of the sum of the values ​​of the valence × molar amount of each metal ion to the total molar amount of carboxyl groups that may be contained in the carboxyl groups and / or dicarboxylic acid anhydride groups in the multicomponent copolymer. 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. Higher neutralization levels result in higher tensile strength and tensile fracture stress of the ionomer, and lower tensile fracture strain, but tend to increase 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.

[0073] • Amount of structural units (mol%) of structural units (B) neutralized by potassium In the potassium ionomers related to this invention, the total potassium ion content is important. When structural units (B) (amount of structural units X mol%) contained in copolymer (P) are neutralized by potassium to a degree of neutralization Y (mol%), the amount of structural units (Z mol%) of the potassium-neutralized structural units (B) can be calculated using the formula Z = XY / 100. Here, "amount of structural units (B) neutralized by potassium" represents the amount (mol%) of structural units having carboxyl groups converted to carboxylate salts by potassium relative to the total monomer units constituting copolymer (P), and is different from the degree of neutralization based on the total amount of carboxyl groups. The amount of structural units (B) neutralized with potassium is proportional to the amount of potassium ions, and the non-static performance improves as the amount of potassium ions in the copolymer (P) increases. Therefore, the lower limit is preferably selected from 1.5 mol% or more, more preferably 1.7 mol% or more, even more preferably 1.9 mol% or more, even more preferably 2.0 mol% or more, particularly preferably 2.1 mol% or more, and most preferably 2.2 mol% or more. There is no particular limit to the upper limit as long as there is no problem with the moldability of the obtained potassium ionomer, but the maximum value is the same as the amount of structural units (B) when structural units (B) are 100% neutralized with potassium.

[0074] • Melting point of ionomers (Tm, °C) The melting point (Tm, °C) of the ionomer related to the present invention is preferably 50°C to 140°C, as observed by differential scanning calorimetry (DSC), in order to obtain sufficient adhesion with dissimilar materials that have high heat resistance and polarity. The melting point (Tm, °C) is preferably 60 °C or higher at the lower limit, more preferably 70 °C or higher, and even more preferably 80 °C or higher, from the viewpoint of heat resistance, and is preferably 120 °C or lower at the upper limit, more preferably 110 °C or lower, even more preferably 100 °C or lower, even more preferably 99 °C or lower, and particularly preferably 96 °C or lower, from the viewpoint of obtaining sufficient adhesion with highly polar dissimilar materials.

[0075] • Crystallinity of the ionomer (%) In the present invention, the degree of crystallinity observed by differential scanning calorimetry (DSC) of the ionomer preferably has a lower limit of over 0%, more preferably over 5%, and even more preferably over 7%, from the viewpoint of sufficient toughness of the multi-component ionomer. From the viewpoint of transparency of the multi-component ionomer, the upper limit is preferably 30% or less, more preferably 27% or less, even more preferably 24% or less, and even more preferably 22% or less. The degree of crystallinity serves as an indicator of transparency, and the lower the degree of crystallinity of the multi-component ionomer, the better its transparency can be judged to be.

[0076] • Method for manufacturing ionomers The method for producing the ionomer according to the present invention may 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 for introducing carboxyl groups and / or dicarboxylic acid anhydride groups into the copolymer (P) as described above, is treated with a metal salt containing potassium ions to convert it into a metal-containing carboxylate salt. Alternatively, the ionomer according to the present invention may be obtained by a heating conversion step in which an ethylene and / or α-olefin / unsaturated carboxylic acid ester copolymer (P) 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 potassium ions.

[0077] 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 potassium ion source is prepared by heating and kneading a metal ion-capturing substance such as an ethylene / methacrylic acid (MAA) copolymer with a metal salt, and then the potassium 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.

[0078] Furthermore, in the heating conversion step, (i) the ethylene and / or C3-C20 α-olefin / unsaturated carboxylic acid ester copolymer (P) may be heated to convert it to an ethylene and / or C3-C20 α-olefin / unsaturated carboxylic acid copolymer by hydrolysis or thermal decomposition, and then reacted with a compound containing potassium ions to convert the carboxylic acid in the ethylene and / or C3-C20 α-olefin / unsaturated carboxylic acid copolymer into a potassium-containing carboxylate salt; or (ii) the ethylene and / or C3-C20 α-olefin / unsaturated carboxylic acid ester copolymer (P) may be heated to convert the ester group portion in the ethylene and / or C3-C20 α-olefin / unsaturated carboxylic acid ester copolymer into a potassium-containing carboxylate salt while hydrolyzing or thermal decomposing the ester group of the copolymer with a compound containing potassium ions.

[0079] The metal ion-containing compound may be a metal oxide, hydroxide, carbonate, bicarbonate, acetate, formate, etc. The metal ion-containing compound may be supplied to the reaction system in granular or fine powder form, or it may be dissolved or dispersed in water or an organic solvent before being supplied to the reaction system, or 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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 atmospheres, and small amounts of oxygen or air may be present.

[0084] There are no particular restrictions on the reactor used in the above process, as long as it can stir the copolymer substantially uniformly, it is not limited in any way. 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.

[0085] Whether potassium ions have been introduced into the precursor resin to form a potassium 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.

[0086] 2. Polyvalent hydroxy compounds (II) The polyvalent hydroxy compound related to the present invention is a compound having two or more hydroxyl groups in its molecule. A mixture of potassium ionomer (I) and polyvalent hydroxy compound (II) is desirable because it can enhance non-static properties in a low-humidity atmosphere. Polyvalent hydroxy compounds play the role of water in high-humidity environments. In high-humidity environments, water hydrates potassium ions, causing some potassium salts to dissociate and making potassium ions more mobile, thus resulting in non-static properties. In low-humidity environments, polyvalent hydroxy compounds (II) perform the above role. Therefore, when compounds with relatively small molecular weights and many hydroxyl groups in their molecules are incorporated, they exhibit excellent non-static properties regardless of humidity.

[0087] The polyvalent hydroxy compound (II) should be selected based on the molecular structure and degree of neutralization of the potassium ionomer (I) it is combined with. It is also important that the polyvalent hydroxy compound (II) can withstand the molding temperature of the potassium ionomer (I). Therefore, it is preferable that the polyvalent hydroxy compound (II) has a boiling point of 200°C or higher, and more preferably 250°C or higher. The polyvalent hydroxy compound (II) has two or more hydroxyl groups per molecule, but it is preferable that it has three or more hydroxyl groups. A larger number of hydroxyl groups improves affinity with potassium ions and contributes to non-static properties. The molecular weight of the polyvalent hydroxy compound (II) is not particularly limited, but it is preferable that it is in a range where the boiling point is 200°C or higher, and more preferably relatively small. A smaller molecular weight results in better affinity with potassium ions, prevents the melting point from becoming too high, improves compatibility with the ionomer, and prevents bleed-out during mixing.

[0088] Examples of polyvalent hydroxy compounds (II) include, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, glycerin, diglycerin, trimethylolethane, trimethylolpropane, di(trimethylolpropane)sorbitol, xylose, arabinose, glucose, galactose, sorbose, fructose, and low molecular weight polyethylene glycol. Furthermore, if the compound has three or more hydroxyl groups, one or more hydroxyl groups may be modified for performance adjustment, provided that at least two hydroxyl groups remain. These polyvalent hydroxy compounds may also be used individually or in combination of two or more types.

[0089] 3. Antistatic resin composition The antistatic resin composition related to the present invention is a resin composition mainly composed of potassium ionomer (I) and containing polyhydric hydroxy compound (II), which is a compound having two or more hydroxyl groups in its molecule, as a minor component. The amount of potassium ionomer (I) in the resin composition is preferably 80% to 99.9% by weight, more preferably 85% to 99.9% by weight, even more preferably 90% to 99.9% by weight, and particularly preferably 92% to 99.9% by weight, based on the total amount with polyvalent hydroxy compound (II). The amount of polyvalent hydroxy compound (II) in the resin composition is preferably 0.1% to 20% by weight, more preferably 0.1% to 15% by weight, even more preferably 0.1% to 10% by weight, and particularly preferably 0.1% to 8% by weight, based on the total amount with potassium ionomer (I). By setting the amounts within this range, it is possible to obtain an antistatic resin composition that satisfies the required physical properties such as moldability as a resin and has excellent non-static properties.

[0090] The antistatic resin composition according to the present invention may contain resins other than the potassium ionomer (I) and polyvalent hydroxy compound (II) described above, in order to introduce other physical properties, without departing from the spirit of the present invention. Examples of such resins include polyolefin resins such as high molecular weight polyethylene, homopolymer of ethylene alone, ethylene-α-olefin copolymer, and polypropylene. The resins that can be blended are preferably polymers obtained by polymerizing monomers consisting of carbon-hydrogen, which may optionally contain oxygen and / or nitrogen atoms. The amount of these resins blended is not particularly limited as long as it does not impair the strength and antistatic properties of the resin composition of the present invention, but as described above, it is desirable that the amount of potassium ionomer (I) in the antistatic resin composition is 80% by weight or more and 99.9% by weight or less, and the amount of polyvalent hydroxy compound (II) is 0.1% by weight or more and 20% by weight or less.

[0091] Furthermore, the resin composition as an antistatic resin composition related to the present invention may contain additives such as conventionally known antioxidants, ultraviolet absorbers, lubricants, colorants, pigments, crosslinking agents, foaming agents, nucleating agents, conductive materials, and fillers, without departing from the spirit of the present invention. Those skilled in the art can use appropriate amounts of each of these additives.

[0092] The antistatic resin composition according to the present invention can be manufactured by mixing the above-mentioned components in any order according to the above-mentioned mixing ratios, and then kneading and granulating them using a conventional kneader such as a single-screw extruder, twin-screw extruder, super mixer, Henschel mixer, Banbury mixer, roll mixer, Brabender plastograph, or kneader. In this case, it is preferable to select a kneading and granulation method that can ensure good dispersion of each component, and it is particularly preferable to use a twin-screw extruder for kneading and granulation from the standpoint of economy and other factors. The kneader may also be a multi-stage kneading process using multiple machines with different kneading methods.

[0093] 4. Molded products The antistatic resin composition according to the present invention may be used as a molded article uniformly mixed with other resins, or as part of a multilayer structure in which the antistatic resin composition is the outermost layer or a layer near the outermost layer. In particular, when used as the outermost layer, high strength is required, so it is thought that this will enable applications that could not be addressed with conventional antistatic resin compositions produced by high-pressure radical polymerization. [Examples]

[0094] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The physical properties in the examples and comparative examples were measured and evaluated by the methods shown below. In the table, "no data" means no measurement was taken, and "not detected" means below the detection limit.

[0095] (1) 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 21.18N.

[0096] (2) Non-static performance (surface resistivity Ω / □) 1) Sample preparation The sample was placed in a 0.55 mm thick, 6 cm long x 5 cm wide heat press mold, preheated for 5 minutes in a hot press machine at a surface temperature of 180°C, then the residual gas in the molten resin was removed by repeatedly applying and removing pressure, and further pressurized to 4.9 MPa and held for 5 minutes. After that, the sample 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 with a thickness of approximately 0.55 mm and dimensions of 6 cm long x 5 cm wide. 2) Preparation of the sample environment The fabricated press plates were vacuum-dried at 60°C for four days to obtain completely dry samples. After measuring the surface resistivity in the completely dry state, the samples were left in a constant temperature and humidity chamber at 23°C and 50% RH, allowing them to absorb moisture over controlled periods, and the surface resistivity in the moisture-absorbing state was measured. 3) Surface resistivity measurement Measurements were performed using a high-resistivity meter, the HighResta UP (MCP-HT450), manufactured by Mitsubishi Chemical Analytech Co., Ltd., combined with a URS probe (MCP-HTP14) and a UFL register table. The prepared and environmentally adjusted press samples were placed on the UFL register table, and the URS probe was pressed against them to perform the evaluation at a measurement voltage of 250V.

[0097] (3) The absolute value G of the complex modulus of elasticity * = Phase angle δ(G) at 0.1 MPa * (Measurement of 0.1 MPa) 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.

[0098] (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.

[0099] (5) Method for measuring structural units derived from carboxyl groups and / or dicarboxylic acid anhydride group monomers, and the number of branches per 1,000 carbon atoms. Structural units derived from carboxyl groups and / or dicarboxylic acid anhydride group monomers in copolymers, 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.

[0100] 1) Sample pretreatment If the sample contained 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 contained a carboxyl group, esterification treatment, such as methyl esterification using diazomethane or trimethylsilyl (TMS) diazomethane, was performed as appropriate.

[0101] 2) Calculation of structural units derived from monomers having a carboxyl group and / or a dicarboxylic acid anhydride group <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

[0102] <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

[0103] <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

[0104] Furthermore, when 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 multicomponent copolymer, but the amount is less than 0.1 mol%, taking significant figures into consideration.

[0105] 3) Calculation of the number of branches per 1,000 carbon atoms When branching is present in a multi-component copolymer, there are isolated types where the branch is located on the main chain alone, and complex types (facing types where branches face each other via the main chain, branched-branch types where branches are located 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.

[0106] [ka]

[0107] 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 multicomponent 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.

[0108] (6) Measurement of wear 1) Method for preparing abrasion test samples The sample was placed in a 150mm x 150mm, 1mm thick heat press mold and preheated in a heat press at a surface temperature of 180°C for 5 minutes. The sample was then melted by repeatedly applying and removing pressure, and any residual gases were removed. Further pressurization was applied to 4.9 MPa and held for 3 minutes. Subsequently, the sample was gradually cooled at a rate of 10°C / min while maintaining the 4.9 MPa pressure. Once the temperature had dropped to near room temperature, the molded plate was removed from the mold. The resulting molded plate was conditioned for more than 48 hours in an environment with a temperature of 23±2°C and a humidity of 50±5°C. After conditioning, the pressed plate was cut into a circle with a diameter of approximately 115 mm, and a hole with a diameter of approximately 6.5 mm was drilled in the center to serve as an abrasion test sample.

[0109] 2) Abrasion test conditions Using the above test specimens, the amount of wear loss (mg) was measured under the following conditions in accordance with JIS K7204-1999. • Equipment: Taber abrasion tester (rotary abrasion tester) - manufactured by Toyo Seiki Co., Ltd. Manufactured by ·Wear wheel: CS-17 • Rotation speed: 60 rpm • Number of tests: 1000 rotations • Load: 4.9N

[0110] <(Production Example 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]

[0111] <(Production Example 2, Production Example 3, Production Example 4): Production of Copolymer for Ionomer Precursor Resin> Using the transition metal complex (B-27DM / Ni complex) prepared in Production Example 1, ethylene / t-butyl acrylate / 2-norbornene (Production Example 2), ethylene / t-butyl acrylate / i-butyl acrylate (Production Example 3), and ethylene / t-butyl acrylate copolymer (Production Example 4) were produced. The production of the copolymer was carried out referring to Production Example 1 or Production Example 3 described in JP-A-2016-79408. Table 1 shows the production conditions and production results, such as the metal catalyst species, metal catalyst amount, trioctylaluminum (TNOA) amount, toluene amount, comonomer species, comonomer amount, ethylene partial pressure, polymerization temperature, polymerization time, etc., which were appropriately changed, and Table 2 shows the physical properties of the obtained copolymer. In Table 2, since the melting point of the resin satisfies the relational expression 50 < Tm < -3.74×[Z] + 130 regarding the randomness of the copolymer, it can be determined that the resins of Production Examples 2 to 4 are all resins with high randomness.

[0112]

Table 1

[0113]

Table 2

[0114] <(Production Example 5, Production Example 6, Production Example 7): Production of Ionomer Precursor Resin> Internal volume 1.6 m 3 In a SUS316L autoclave equipped with stirring blades, 100 kg of one of the resins obtained from Production Example 2, Production Example 3, or Production Example 4, 2.0 kg of p-toluenesulfonic acid monohydrate, and 173 L of toluene were added and stirred at 105°C for 4 hours. 173 L of deionized water was added and stirred, and after standing, the aqueous layer was removed. Thereafter, the addition and removal of deionized water was repeated until the pH of the removed aqueous layer was 5 or higher. The remaining solution was put into a twin-screw extruder with a 42 mmφ vent device (L / D=42), and the solvent was removed by venting to a vacuum. Furthermore, resin pellets were obtained by cooling the resin, which was continuously extruded in the form of strands from the die at the tip of the extruder, in water and cutting it with a cutter. In the IR spectrum of the obtained resin, 850 cm⁻¹ originated from the t-Bu group. -1 The disappearance of the nearby peak and the 1730 cm peak originating from the carbonyl group of the ester -1 The decrease in the surrounding peaks and the 1700 cm⁻¹ originating from the carbonyl group of the carboxylic acid (dimer) -1 An increase in the peak in the vicinity was observed. This confirmed the decomposition of t-Bu ester and the formation of carboxylic acid, leading to the production examples 5, 6, and 7. The physical properties of the obtained precursor resins are shown in Table 3. The physical properties of a commercially available carboxylic acid-containing resin (comparative product), brand name: REXPEARL EAA, grade AS211S, manufactured by Nippon Polyethylene Co., Ltd., are also shown in Table 3.

[0115] [Table 3]

[0116] <Manufacturing of potassium ionomer (manufacturing examples 8-19)> 1) Preparation of a potassium ion source A potassium ion source was prepared by adding 22g of metallocene plastomer kernel (manufactured by Nippon Polyethylene Co., Ltd., brand: KS571) and 18g of potassium carbonate to a Toyo Seiki Co., Ltd. Laboplast Mill: Roller Mixer R60, which was fitted with a small 60ml capacity mixer, and mixing at 180°C and 40rpm for 3 minutes.

[0117] 2) Preparation of potassium ionomers 40g of ionomer precursor resin (Production Examples 5-7, Comparative Sample 1) was added to a Toyo Seiki Co., Ltd. Laboplast Mill: Roller Mixer R60 equipped with a 60ml capacity mini mixer, and kneaded at 190°C and 40rpm for 3 minutes until dissolved. Then, a potassium ion source was added to achieve the desired degree of neutralization, and kneading was carried out at 250°C and 40rpm for 5 minutes. The IR spectrum of the obtained potassium ionomer was examined, and a 1700cm² ion 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 peaks in the vicinity were increasing. The reaction was considered complete when the ratio of the areas of these two peaks stopped fluctuating, and an ionomer with a degree of neutralization based on the amount of potassium ions introduced was obtained. The physical properties of the obtained potassium ionomer are shown in Table 4. The amount of structural units (mol%) of comonomer 1, i.e., structural units (B), that were neutralized with potassium was calculated by dividing the product of the amount of comonomer 1 in the ionomer precursor resin described in Tables 2 and 3 and the degree of neutralization described in Table 4 by 100.

[0118] [Table 4]

[0119] <Mixing with polyvalent hydroxy compounds> 40g of the prepared potassium ionomer (Production Examples 8-19) was placed in a Toyo Seiki Co., Ltd. Laboplast Mill: Roller Mixer R60, equipped with a 60ml capacity mini mixer, and mixed at 190°C and 40rpm for 3 minutes until dissolved. Subsequently, 2g of glycerin was added as a polyvalent hydroxy compound, and the mixture was further mixed at 190°C and 40rpm for 3 minutes to obtain a resin composition consisting of potassium ionomer and glycerin.

[0120] [Examples 1-8, Comparative Examples 1-4] For the resin composition composed of the above potassium ionomer and glycerin, the wear amount and surface resistivity were measured by the method described above. The results are shown in Table 5.

[0121]

Table 5

[0122] <Discussion of Examples / Comparative Examples> Examples 1 to 8 are resin compositions that satisfy the constituent requirements related to the present invention. It can be confirmed that the wear amount is less than that of Comparative Examples 2, 3, and 4 in which a carboxylic acid-containing resin that does not satisfy the condition that the phase angle δ at G = 0.1 MPa is 50 degrees to 75 degrees is blended. On the other hand, for the antistatic performance, the level equivalent to that of the comparative examples is maintained. * Comparative Example 1 satisfies the constituent requirements for the phase angle δ, but since the structural unit amount of the structural unit (B) neutralized with potassium does not satisfy the condition of being 1.5 mol% or more, the value of the surface resistivity is large and the antistatic property is poor. Comparative Example 1 satisfies the constituent requirements for the phase angle δ, but since the structural unit amount of the structural unit (B) neutralized with potassium does not satisfy the condition of being 1.5 mol% or more, the value of the surface resistivity is large and the antistatic property is poor.

[0123] From the good results of each of the above examples and the comparison with each comparative example, the significance, rationality of the configuration (invention specific matters) of the present invention, and the superiority over the prior art are clarified.

Industrial Applicability

[0124] The resin composition (antistatic resin composition) containing the potassium ionomer according to the present invention is excellent in terms of strength compared to the conventional resin composition (antistatic resin composition) containing a potassium ionomer, and can be applied to uses that could not be applied with conventional products. The present invention can be effectively used for various molded products such as automotive parts, power tool housings, machine parts, electrical and electronic parts, household and office supplies, building material-related parts, furniture parts, packaging materials, etc.< / e> < / e> < / e>

Claims

1. An antistatic resin composition comprising a potassium ionomer (I) and a polyvalent hydroxy compound (II), characterized in that the potassium ionomer (I) is an ionomer that satisfies the following requirements. An ionomer characterized in that, in 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, at least a portion of the carboxyl groups and / or dicarboxylic acid anhydride groups are converted to potassium ion-containing carboxylate salts, the proportion of the structural units (B) converted to potassium ion-containing carboxylate salts in the copolymer (P) is 1.5 mol% or more, and 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.

2. The copolymer (P) １３ The antistatic resin composition 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 copolymer (P) １３ The antistatic resin composition according to claim 1, characterized in that the number of methyl branches calculated by C-NMR is 5 or less per 1,000 carbon atoms.

4. The antistatic resin composition according to any one of claims 1 to 3, characterized in that the copolymer (P) contains 2 to 20 mol% of the structural unit (B) in the copolymer.

5. The antistatic resin composition according to any one of claims 1 to 4, characterized in that the structural unit (A) is a structural unit derived from ethylene.

6. The antistatic resin composition according to any one of claims 1 to 5, 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.

7. The antistatic resin composition according to any one of claims 1 to 6, characterized in that the transition metal catalyst is a transition metal catalyst comprising a phosphorusulfonic acid or phosphorphenol ligand and nickel or palladium.

8. The compositional ratios of the potassium ionomer (I) and the polyvalent hydroxy compound (II) are, Potassium ionomer (I): 80% or more by weight, and 99.9% or less by weight Polyhydric hydroxy compound (II): 0.1% or more by weight, and 20% or less by weight The antistatic resin composition according to any one of claims 1 to 7, characterized in that it is within the range of .

9. A molded article characterized by being formed by molding an antistatic resin composition according to any one of claims 1 to 8.

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