Resin for decorative sheets containing ionomer

Abstract

To provide a resin for a decorative sheet using an ionomer which has remarkably excellent chemical resistance, and has good chemical resistance, wear resistance and heat resistance.SOLUTION: There is provided a resin for a decorative sheet containing an ionomer in which in a copolymer (P) containing a structural unit (A) derived from ethylene and / or α-olefin having 3 to 20 carbon atoms, and a structural unit (B) derived from a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group as essential components, at least a part of the carboxyl group and / or the dicarboxylic acid anhydride is converted into metal-containing carboxylate containing at least one kind of metal ions selected from the groups 1, 2 and 12 in the periodic table, and a phase angle δ at an absolute value G* of 0.1 MPa of a complex elastic modulus measured by a rotary type rheometer is 50-75 degrees.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin for decorative sheets with good chemical resistance and a decorative panel using the resin for decorative sheets, and more specifically, to an ionomer suitable as a resin that can provide a decorative sheet with a good balance of chemical resistance, heat resistance and abrasion resistance. [Background technology]

[0002] In recent years, ionomers have been widely used as resins for decorative sheets. These ionomers are obtained by neutralizing the acidic portion of an ionic copolymer consisting of an olefin such as ethylene and an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, or maleic acid with metal ions such as sodium or zinc (Patent Document 1).

[0003] Conventionally, surface materials for interior building materials (doors, windows, floors, walls, etc.), exterior and interior materials for automobiles, and surface materials for everyday goods have been required to have heat resistance, scratch resistance, and chemical resistance, and it is known that films containing ionomers are used as such surface materials. More specifically, a decorative sheet having a film containing ionomers as a transparent resin layer is used as the surface material.

[0004] Currently, commercially available ionomers include "Surlyn®," a sodium and zinc salt of ethylene-methacrylic acid copolymer developed by Dupont, and "Hymiran®," sold by Mitsui Dow Polychemicals.

[0005] The ethylene-unsaturated carboxylic acid copolymers used as base resins in these currently commercially available ionomers all utilize polar group-containing olefin copolymers, which are produced by polymerizing ethylene and polar group-containing monomers such as unsaturated carboxylic acids using high-pressure radical polymerization. The molecular structure of these polar group-containing olefin copolymers produced by high-pressure radical polymerization has many irregular long-chain and short-chain branches, as shown in the image diagram in Figure 1, and has the disadvantage of insufficient chemical resistance, heat resistance, and abrasion resistance.

[0006] Patent Document 2 discloses a method for crosslinking an ionomer by irradiating it with an electron beam, with the aim of improving its heat resistance. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] U.S. Patent No. 3,264,272 [Patent Document 2] Japanese Patent Publication No. 2020-050724 [Overview of the project] [Problems that the invention aims to solve]

[0008] While these methods have yielded ionomers with excellent heat resistance, the focus has essentially been on heat resistance and abrasion resistance, with no mention of chemical resistance, which is essential for decorative sheets. Furthermore, electron beam crosslinking increases costs. Given the above situation, there has been a need for an ionomer and a decorative sheet resin that possess excellent chemical resistance on its own, as well as a good balance of abrasion resistance, heat resistance, and chemical resistance.

[0009] In view of the circumstances of the prior art, this application aims to provide a resin for decorative sheets using an ionomer that has significantly superior chemical resistance and good chemical resistance, abrasion resistance, and heat resistance. [Means for solving the problem]

[0010] To solve the above problems, the inventors have found that a specific ionomer having a linear structure such that the phase angle δ at the absolute value of the complex modulus G* = 0.1 MPa, measured with a rotary rheometer, is 50 to 75 degrees, exhibits superior chemical resistance, abrasion resistance, and heat resistance compared to conventional ionomers based on polar group-containing olefin copolymers produced by high-pressure radical polymerization. This demonstrates the effect of improving the physical properties required for resins used in decorative sheets.

[0011] In other words, the present invention relates to a copolymer (P) containing a structural unit (A) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms and a structural unit (B) derived from a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group as essential constituent units, wherein at least a portion of the carboxyl group and / or dicarboxylic acid anhydride group is converted into a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table, and the absolute value of the complex modulus G measured with a rotational rheometer * This is a resin for decorative sheets containing an ionomer characterized by having a phase angle δ of 50 to 75 degrees at 0.1 MPa. Furthermore, in one aspect of the present invention, the copolymer (P) 13 The number of methyl branches calculated by 13C-NMR is 50 or less per 1,000 carbon atoms. In one aspect of the present invention, the copolymer (P) contains 1 to 20 mol% of the structural unit (B) in the copolymer. In one aspect of the present invention, the structural unit (A) is a structural unit derived from ethylene. In one aspect of the present invention, the copolymer (P) is produced using a transition metal catalyst containing a transition metal of groups 8 to 11 of the periodic table. Furthermore, in one aspect of the present invention, the transition metal catalyst is a transition metal catalyst consisting of a phosphorusulfonic acid or phosphorphenol ligand and nickel or palladium. In one aspect of the present invention, the copolymer (P) has a crystallinity of 50% or less, preferably 10% or less. Furthermore, one aspect of the present invention is a resin composition for decorative sheets, characterized by containing the resin for decorative sheets. Another aspect of the present invention is a resin layer for decorative sheets using the resin for decorative sheets or the resin composition for decorative sheets. Yet another aspect of the present invention is a decorative sheet composed of a laminate comprising at least a base layer and the resin layer, and a decorative panel composed of a laminate comprising a decorative panel base and the decorative sheet. [Effects of the Invention]

[0012] According to the present invention, by using an ionomer with a substantially linear structure, it is possible to provide a resin for decorative sheets that has significantly better chemical resistance compared to conventional ionomers with a multi-branched structure, and that also exhibits a well-balanced combination of chemical resistance, abrasion resistance, and heat resistance. [Brief explanation of the drawing]

[0013] [Figure 1] This is a schematic diagram illustrating the molecular structure of a highly branched olefin copolymer polymerized by a high-pressure radical polymerization process. [Figure 2] This is a conceptual diagram of the molecular structure of a linear olefin copolymer polymerized using a metal catalyst. [Modes for carrying out the invention]

[0014] The present invention relates to a resin for decorative sheets, comprising an ionomer 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, wherein at least a portion of the carboxyl groups and / or dicarboxylic acid anhydride groups are converted into a metal-containing carboxylate containing at least one metal ion selected from Group 1, 2, or 12 of the periodic table, and the phase angle δ at the absolute value of the complex modulus of elasticity G* = 0.1 MPa, as measured by a rotational rheometer, is 50 to 75 degrees.

[0015] The present invention's resin for decorative sheets and related ionomers will be described in detail item by item below. In this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid. In this specification, "~" indicating a numerical range is used to mean that the values ​​written before and after it are included as the lower and upper limits. In this specification, copolymer means a binary or more copolymer containing at least one unit (A) and at least one unit (B). Furthermore, in this specification, "ionomer" means a binary or more copolymer ionomer comprising the structural unit (A) and a structural unit (B') in which at least a portion of the structural unit (B) is converted to a metal-containing carboxylate salt, and which may further contain the structural unit (B).

[0016] 1. Ionomer The ionomer of the present invention is characterized in that it contains as essential structural units (A) a structural unit derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms and a structural unit (B) derived from a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group, and the copolymer (P) obtained by random copolymerizing these substantially in a linear manner is used as the base resin, and at least a portion of the carboxyl group and / or dicarboxylic acid anhydride group of the structural unit (B) is converted into a metal-containing carboxylate salt containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table.

[0017] (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.

[0018] 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. In addition to ethylene derived from petroleum raw materials, ethylene derived from non-petroleum raw materials such as plant raw materials can be used. Furthermore, the structural unit (A) may be of one type or multiple types. Examples of combinations of the two include ethylene-propylene, ethylene-1-butene, ethylene-1-hexene, ethylene-1-octene, propylene-1-butene, propylene-1-hexene, and propylene-1-octene. Examples of combinations of the three include ethylene-propylene-1-butene, ethylene-propylene-1-hexene, ethylene-propylene-1-octene, propylene-1-butene-hexene, and propylene-1-butene-1-octene.

[0019] In the present invention, the structural unit (A) preferably contains ethylene as an essential component, and may further contain one or more α-olefins having 3 to 20 carbon atoms as needed. The amount of ethylene in structural unit (A) may be 50-100 mol%, 70-100 mol%, or 90-100 mol% of the total moles of structural unit (A). From the standpoint of chemical resistance, the preceding structural unit (A) may be a structural unit derived from ethylene.

[0020] (2) Structural unit (B) Structural unit (B) is a structural unit derived from a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group. Note that structural unit (B) has the same structure as the structural unit derived from a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group, and as described in the manufacturing method below, it does not necessarily have to be produced using a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group.

[0021] Examples of structural units derived from monomers having a carboxyl group include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornenedicarboxylic acid, and bicyclo[2,2,1]hepta-2-ene-5,6-dicarboxylic acid. Examples of structural units derived from monomers having a dicarboxylic acid anhydride group include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic 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. Structural units derived from monomers having a carboxyl group and / or a dicarboxylic acid anhydride group are preferably derived from acrylic acid, methacrylic acid, or 5-norbornene-2,3-dicarboxylic acid anhydride, in terms of ease of industrial availability, and may be particularly derived from acrylic acid. Furthermore, the structural unit derived from a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group may be one type or multiple types.

[0022] 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.

[0023] (3) Other structural units (C) The copolymer (P) according to the present invention may contain a structural unit (C) other than the structural units (A) and (B). As the monomer that provides the structural unit (C), any monomer can be used as long as it is not included in the monomers that provide the structural units (A) and (B). The monomer that provides the structural unit (C) is not limited as long as it is a compound having one or more carbon-carbon double bonds in its molecular structure, and examples thereof include an acyclic monomer represented by the following general formula (1) and a cyclic monomer represented by the following general formula (2).

[0024] ·Acyclic monomer [Chemical formula] [In general formula (1), T 1 ~T 3 are each independently a substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an ester group having 2 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, a halogen atom, or a cyano group, T 4 is a substituent selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an ester group having 2 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, a halogen atom, or a cyano group.]

[0025] T 1 ~T 4The carbon skeletons of the hydrocarbon groups, substituted alkoxy groups, substituted ester groups, alkoxy groups, aryl groups, ester groups, and silyl groups may have branching, rings, and / or unsaturated bonds. T 1 ~T 4 The number of carbon atoms in the hydrocarbon group related to this can be as follows: the lower limit is 1 or more, the upper limit is 20 or less, or it may be 10 or less. T 1 ~T 4 The number of carbon atoms in the substituted alkoxy group can be as follows: the lower limit is 1 or more, the upper limit is 20 or less, or it may be 10 or less. T 1 ~T 4 The number of carbon atoms in the substituted ester group can be as follows: the lower limit is 2 or more, the upper limit is 20 or less, and it may also be 10 or less. T 1 ~T 4 The number of carbon atoms in the alkoxy group can be as follows: the lower limit is 1 or more, the upper limit is 20 or less, or it may be 10 or less. T 1 ~T 4 The number of carbon atoms in the aryl group can be 6 or more at the lower limit, 20 or less at the upper limit, or 11 or less. T 1 ~T 4 The number of carbon atoms in the ester group can be as follows: the lower limit is 2 or more, the upper limit is 20 or less, and it may also be 10 or less. T 1 ~T 4 The number of carbon atoms in the silyl group can be 3 or more at the lower limit and 18 or less at the upper limit, or 12 or less. Examples of silyl groups include trimethylsilyl, triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, and triphenylsilyl.

[0026] In the ionomer of the present invention, in terms of ease of manufacture, T 1 and T 2 T may be a hydrogen atom, 3T may be a hydrogen atom or a methyl group. 1 ~T 3 However, all of them may be hydrogen atoms. Furthermore, in terms of chemical resistance, T 4 This may be an ester group having 2 to 20 carbon atoms.

[0027] Atypical monomers include, specifically, (meth)acrylic acid esters and the like. 4 Examples include cases where the group is an ester group with 2 to 20 carbon atoms. T 4 If the group is an ester group with 2 to 20 carbon atoms, the acyclic monomer is defined as follows: Structural formula: CH2=C(R 21 )CO2(R 22 Examples of compounds represented by ) are shown here. 21 R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and may have branching, rings, and / or unsaturated bonds. 22 R is a hydrocarbon group having 1 to 20 carbon atoms, and may have branching, ring, and / or unsaturated bonds. 22 Heteroatoms may be included at any position within the material. Structural formula: CH2=C(R 21 )CO2(R 22 As a compound represented by ), R 21 However, examples include compounds that are hydrogen atoms or hydrocarbon groups having 1 to 5 carbon atoms. Also, R 21 Acrylic acid ester or R, where is a hydrogen atom 21 Examples include methacrylate esters, which have a methyl group. Structural formula: CH2=C(R 21 )CO2(R 22Specific examples of compounds represented by ) include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, and benzyl (meth)acrylate. Specific examples of compounds include methyl acrylate, ethyl acrylate, n-butyl acrylate (nBA), isobutyl acrylate (iBA), t-butyl acrylate (tBA), and 2-ethylhexyl acrylate, and in particular n-butyl acrylate (nBA), isobutyl acrylate (iBA), and t-butyl acrylate (tBA). The acyclic monomer may be one type or multiple types.

[0028] • 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 R 11 and R 12 These may each integrate to form a divalent organic group, R 9 or R 10 And, R 11 or R 12 These elements may form a ring with each other. Furthermore, n represents 0 or a positive integer, and if n is 2 or greater, R 5 ~R 8These elements may be identical or different within each repeating unit.

[0029] Examples of cyclic monomers include norbornene-based olefins, such as norbornene, vinylnorbornene, ethylidenenorbornene, norbornadiene, tetracyclododecene, and tricyclo[4.3.0.1 2,5 ], tricyclo[4.3.0.1 2,5 Examples include compounds having a cyclic olefin skeleton such as deca-3-ene, 2-norbornene (NB), and tetracyclo[6.2.1.1 3,6 .0 2,7 Dodeca-4-en may also be used.

[0030] (4) Metal ions Examples of metal ions for carboxylic acid bases include divalent metal ions selected from groups 1, 2, or 12 of the periodic table. Specifically, these include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), and zinc (Zn) ions. From the viewpoint of ease of handling, sodium (Na), magnesium (Mg), calcium (Ca), or zinc (Zn) ions may be particularly preferred. Carboxylic acid bases can be obtained, for example, by hydrolyzing or thermally decomposing the ester groups of a copolymer, or by reacting them with a compound containing the metal ions while hydrolyzing or thermally decomposing them, thereby converting the ester group portion of the copolymer into a metal-containing carboxylate salt. Furthermore, the metal ion may be one type or multiple types.

[0031] (5) Copolymer (P) The copolymer (P) that serves as the base resin for the ionomer used in the present invention is characterized in that it contains structural units (A) derived from ethylene and / or α-olefins having 3 to 20 carbon atoms, and structural units (B) derived from monomers having carboxyl groups and / or dicarboxylic acid anhydride groups as essential constituent units, and optionally includes arbitrary structural units (C), and each of these structural units is substantially copolymerized in a linear manner, preferably randomly copolymerized. "Substantially linear" means that the copolymer does not have branching or the frequency of branching structures is small, and the copolymer can be considered linear. Specifically, it means that the phase angle δ of the copolymer is 50 degrees or more.

[0032] The copolymer according to the present invention must contain at least one type of structural unit (A) and at least one type of structural unit (B), and a total of at least two types of monomer units, and may also contain other structural units (C). The structural units and quantities of structural units of the copolymer related to this invention will be described. A single structural unit in a copolymer is defined as a structure derived from one molecule each of ethylene and / or an α-olefin having 3 to 20 carbon atoms (A), a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group (B), and any monomer (C). The amount of structural units is the ratio of each structural unit, expressed in mol%, when the total amount of structural units in the copolymer is considered to be 100 mol%.

[0033] Structural unit content of ethylene and / or α-olefin (A) having 3 to 20 carbon atoms: The amount of structural unit (A) related to the present invention is selected from a lower limit of 60.0 mol% or more, preferably 70.0 mol% or more, more preferably 80.0 mol% or more, even more preferably 85.0 mol% or more, even more preferably 90.0 mol% or more, and particularly preferably 95.0 mol% or more, and an upper limit of 99.0 mol% or less, preferably 98.0 mol% or less, more preferably 97.0 mol% or less, and even more preferably 96.5 mol% or less. If the amount of structural units derived from ethylene and / or α-olefins (A) having 3 to 20 carbon atoms is less than 60.0 mol%, the toughness of the copolymer will be poor, and if it is more than 99.0 mol%, the crystallinity of the copolymer will be high, which may result in poor transparency.

[0034] • Structural unit amount of monomer (B) having a carboxyl group and / or a dicarboxylic anhydride group: The amount of structural unit (B) related to the present invention is selected from a lower limit of 1.0 mol% or more, preferably 2.0 mol% or more, more preferably 3.0 mol% or more, even more preferably 3.5 mol or more, an upper limit of 20.0 mol% or less, preferably 15.0 mol% or less, more preferably 10.0 mol% or less, even more preferably 8.0 mol% or less, particularly preferably 6.0 mol% or less, and most preferably 5.3 mol% or less. If the amount of structural units derived from monomer (B) having a carboxyl group and / or dicarboxylic acid anhydride group is less than 1.0 mol%, the copolymer may not have sufficient adhesion to highly polar dissimilar materials, and if it is more than 20.0 mol%, the copolymer may not be able to obtain sufficient mechanical properties. Furthermore, the monomers having a carboxyl group and / or a dicarboxylic acid anhydride group used may be used individually or in combination of two or more types.

[0035] • Structural unit amounts of other monomers (C): The amount of structural units (C) related to the present invention is selected from an upper limit of 20.0 mol% or less, preferably 15.0 mol% or less, more preferably 10.0 mol% or less, even more preferably 5.0 mol% or less, and particularly preferably 3.0 mol% or less, with no particular limit on the lower limit, which may be 0 mol%. When the amount of structural units derived from any monomer (C) is 20.0 mol% or less, sufficient mechanical properties of the copolymer are easily obtained. Furthermore, any monomer (C) used may be used alone or in combination of two or more types.

[0036] Number of branches per 1,000 carbon atoms in copolymer (P): In the copolymer of the present invention, in order to achieve a high elastic modulus and sufficient mechanical properties, 13 The number of methyl branches calculated by 13C-NMR may have an upper limit of 50 or less, 5.0 or less, 1.0 or less, or 0.5 or less per 1,000 carbon atoms, and there is no particular lower limit; the fewer the better. Similarly, the number of ethyl branches may have an upper limit of 3.0 or less, 2.0 or less, 1.0 or less, or 0.5 or less per 1,000 carbon atoms, and there is no particular lower limit; the fewer the better. Furthermore, the number of butyl branches may have an upper limit of 7.0 or less, 5.0 or less, 3.0 or less, or 0.5 or less per 1,000 carbon atoms, and there is no particular lower limit; the fewer the better.

[0037] Method for measuring the amount of structural units and branching number derived from monomers having carboxyl groups and / or dicarboxylic acid anhydride groups, and acyclic monomers in copolymers: The amount of structural units derived from monomers having carboxyl groups and / or dicarboxylic acid anhydride groups, and acyclic monomers in the copolymer of the present invention, and the number of branches per 1,000 carbon atoms. 13 It can be determined using 1C-NMR spectroscopy. 13 1C-NMR is measured using the following method. 200-300 mg of the sample is placed in 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. 13 Set the C signal to 1.98 ppm, and the other 13 The chemical shift of the signal due to C is based on this. obtained 13 In 1C-NMR, by identifying signals specific to monomers or branches in a copolymer and comparing their intensities, the amount of structural units of each monomer and the number of branches in the copolymer can be analyzed. The location of the signals specific to monomers or branches can be determined by referring to known data or by independently identifying them depending on the sample. Such analytical techniques are generally possible for those skilled in the art.

[0038] • Weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn): The weight-average molecular weight (Mw) of the copolymer according to the present invention is typically 1,000 or more at the lower limit, preferably 6,000 or more, more preferably 10,000 or more, and typically 2,000,000 or less at the upper limit, preferably 1,500,000 or less, even more preferably 1,000,000 or less, particularly suitable for 800,000 or less, and most preferably 100,000 or less. If Mw is less than 1,000, the copolymer's physical properties such as mechanical strength and impact resistance are insufficient, and if Mw exceeds 2,000,000, the copolymer's melt viscosity becomes extremely high, which can make molding and processing difficult.

[0039] The ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) (Mw / Mn) of the copolymer related to the present invention is usually in the range of 1.5 to 4.0, preferably 1.6 to 3.5, more preferably 1.7 to 3.7, and even more preferably 1.9 to 2.4. If Mw / Mn is less than 1.5, the copolymer will not have sufficient processability, including molding, and if it exceeds 4.0, the copolymer may have poor mechanical properties. In this invention, (Mw / Mn) may be expressed as the molecular weight distribution parameter.

[0040] 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.

[0041] An example of a GPC measurement method related to the present invention is as follows: (Measurement conditions) Model used: Waters 150C Detector: FOXBORO MIRAN1A IR detector (measurement wavelength: 3.42 μm) Measurement temperature: 140℃ Solvent: Orthodichlorobenzene (ODCB) Columns: Showa Denko AD806M / S (3 pieces) Flow rate: 1.0mL / min Injection volume: 0.2mL (Sample preparation) The sample is prepared by creating a 1 mg / mL solution using ODCB (containing 0.5 mg / mL of BHT (2,6-di-t-butyl-4-methylphenol)) and dissolving it at 140°C for approximately 1 hour. (Calculation of molecular weight (M)) The calibration is performed using the standard polystyrene method, and the conversion from retention capacity to molecular weight is performed using a calibration curve prepared in advance using standard polystyrene. Examples of standard polystyrenes used include those manufactured by Tosoh Corporation (F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000) and monodisperse polystyrene manufactured by Showa Denko (S-7300, S-3900, S-1950, S-1460, S-1010, S-565, S-152, S-66.0, S-28.5, S-5.05, each in a 0.07 mg / ml solution). A calibration curve is created by injecting 0.2 mL of each solution, dissolved in ODCB (containing 0.5 mg / mL BHT) to a concentration of 0.5 mg / mL. The calibration curve is obtained by approximating it using the least squares method, using a cubic equation, or by approximating it using a quartic equation with the logarithm of the elution time and molecular weight. The viscosity formula [η] = K × Mα used for conversion to molecular weight (M) is as follows. Polystyrene (PS): K = 1.38 × 10 -4 α=0.7 Polyethylene (PE): K = 3.92 × 10 -4 , α=0.733 Polypropylene (PP): K = 1.03 × 10 -4 α = 0.78

[0042] • Melting point (Tm, °C): The melting point of the copolymer according to the present invention is indicated by the maximum peak temperature of the endothermic curve measured by differential scanning calorimeter (DSC). The maximum peak temperature refers to the temperature of the peak with the greatest height from the baseline when multiple peaks are shown in the endothermic curve obtained when heat flow (mW) is plotted on the vertical axis and temperature (°C) on the horizontal axis in a DSC measurement, or the temperature of that peak if there is only one peak. The melting point is preferably 50°C to 140°C, more preferably 60°C to 138°C, and most preferably 70°C to 135°C. If it is lower than this range, the heat resistance will not be sufficient, and if it is higher than this range, the adhesive properties may be poor. In this invention, the melting point can be determined from the absorption curve obtained by, for example, using DSC (DSC7020) manufactured by SII Nanotechnology Co., Ltd., packing approximately 5.0 mg of the sample into an aluminum pan, raising the temperature to 200°C at 10°C / min, holding it isothermally at 200°C for 5 minutes, then lowering the temperature to 20°C at 10°C / min, holding it isothermally at 20°C for 5 minutes, and then raising the temperature again to 200°C at 10°C / min.

[0043] • Crystallinity (%): In the copolymer of the present invention, the degree of crystallinity observed by differential scanning calorimetry (DSC) is not particularly limited, but is preferably greater than 0%. It is more preferably greater than 5%, and even more preferably 7% or more. If the degree of crystallinity is 0%, the toughness of the copolymer may not be sufficient. The degree of crystallinity is also an indicator of transparency, and transparency is preferable, but there is no particular upper limit to the degree of crystallinity. In the present invention, the degree of crystallinity can be determined, for example, by calculating the heat of fusion (ΔH) from the endothermic peak area obtained by DSC measurement using the same procedure as for measuring the melting point, and then dividing that heat of fusion by the heat of fusion of perfect high-density polyethylene (HDPE), which is 293 J / g.

[0044] • Molecular structure of copolymers: The molecular chain end of the copolymer according to the present invention may be an ethylene and / or α-olefin structural unit (A) having 3 to 20 carbon atoms, a monomer structural unit (B) having a carboxyl group and / or a dicarboxylic acid anhydride group, or any monomer structural unit (C).

[0045] Furthermore, copolymers related to the present invention include random copolymers, block copolymers, and graft copolymers of ethylene and / or α-olefin structural units having 3 to 20 carbon atoms (A), monomer structural units having a carboxyl group and / or a dicarboxylic acid anhydride group (B), and structural units of any monomer (C). Among these, a random copolymer that can contain a large amount of structural unit (B) may also be used. An example of the molecular structure of a typical ternary copolymer (1) is shown below. A random copolymer is a copolymer in which the structural units of ethylene and / or α-olefins having 3 to 20 carbon atoms (A), the monomer structural units having a carboxyl group and / or a dicarboxylic acid anhydride group (B), and the structural units of any monomer (C) shown in molecular structure example (1) below, are found at any given molecular chain position, and the probability of finding each structural unit is independent of the type of adjacent structural units. As shown below, in the example molecular structure of the copolymer (1), structural units of ethylene and / or α-olefins having 3 to 20 carbon atoms (A), structural units of monomers having a carboxyl group and / or a dicarboxylic acid anhydride group (B), and structural units of any monomer (C) form a random copolymer. [ka]

[0046] For reference, an example of the molecular structure (2) of a copolymer into which a monomer structural unit (B) having a carboxyl group and / or a dicarboxylic acid anhydride group has been introduced by graft modification is also shown. In this example, a portion of the copolymer, which is copolymerized with a monomer structural unit (A) of ethylene and / or an α-olefin having 3 to 20 carbon atoms and a monomer structural unit (C) of any monomer, is graft-modified with a monomer structural unit (B) having a carboxyl group and / or a dicarboxylic acid anhydride group. [ka]

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

[0049] Furthermore, from the viewpoint of having a linear molecular structure, it is preferable that the copolymer related to the present invention is manufactured in the presence of a transition metal catalyst. It is known that the molecular structure of copolymers differs depending on the manufacturing method, such as polymerization by high-pressure radical polymerization or polymerization using metal catalysts. While these differences in molecular structure can be controlled by selecting a manufacturing method, the molecular structure can also be estimated by measuring the complex modulus of elasticity using a rotational rheometer, as described in Japanese Patent Publication No. 2010-150532.

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

[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 in a hot press machine at a surface temperature of 180°C for 5 minutes. After that, residual gas in the molten resin was removed by repeatedly applying and removing pressure, and then pressurized to 4.9 MPa and held for 5 minutes. Subsequently, the sample was transferred to a press machine at a surface temperature of 25°C and cooled by holding at a pressure of 4.9 MPa for 3 minutes to create a press plate made from the sample with a thickness of approximately 1.0 mm. A 25 mm diameter circular press plate was processed from the sample and used as the sample. Dynamic viscoelasticity was measured under the following conditions in a nitrogen atmosphere using a Rheometrics ARES type rotary rheometer as the device for measuring dynamic viscoelastic properties. • Plate: φ25mm parallel plate ·Temperature: 160℃ Distortion level: 10% • Measurement angular frequency range: 1.0 × 10 -2 ~1.0×10 2 rad / s ·Measurement interval: 5 points / decade Absolute value G of complex elastic modulus * (Pa) common logarithm logG * Plot the phase angle δ against it, and logG * Let the value of δ (degrees) at the point corresponding to logG = 5.0 be δ(G * = 0.1 MPa). When there is no point corresponding to logG * = 5.0 among the measurement points, use two points around logG * = 5.0 to obtain the δ value at logG * = 5.0 by linear interpolation. Also, when all measurement points are logG * < 5, use the values of three points with larger logG * values to obtain the δ value at logG * = 5.0 by extrapolation using a quadratic curve.

[0052] ·Regarding the production of the copolymer From the viewpoint of making the molecular structure of the copolymer linear, it is preferably produced in the presence of a transition metal catalyst.

[0053] ·Polymerization catalyst The type of polymerization catalyst used for the production of the copolymer according to the present invention is not particularly limited as long as it can copolymerize structural unit (A), structural unit (B), and optional structural unit (C). For example, transition metal compounds of Groups 5 to 11 having a chelating ligand can be mentioned. Specific examples of preferred transition metals include vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, manganese atom, iron atom, platinum atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom, copper atom, etc. Among these, preferably, transition metals of Groups 8 to 11, more preferably transition metals of Group 10, and particularly preferably nickel (Ni) and palladium (Pd). These metals may be single or used in combination of a plurality. The chelating ligand contains a ligand having at least two atoms selected from the group consisting of P, N, O, and S, and is bidentate or multidentate, and is electronically neutral or anionic. The structure of the chelating ligand is exemplified in a review by Brookhart et al. (Chem. Rev., 2000, 100, 1169). Preferred chelating ligands include bidentate anionic P, O ligands. Examples of bidentate anionic P, O ligands include phosphinosulfonic acid, phosphinocarboxylic acid, phosphinophenol, and phosphinoenolate. Other chelating ligands include bidentate anionic N, O ligands. Examples of bidentate anionic N, O ligands include salicylaldiminato and pyridinecarboxylic acid. Other chelating ligands include diimine ligands, diphenoxide ligands, and diamide ligands, etc.

[0054] The structure of the metal complex obtained from the chelating ligand is represented by the following structural formula (a) or (b) coordinated with an arylphosphine compound, arylarsine compound or arylantimony compound which may have a substituent. [Chemical formula] [Chemical formula] [In structural formula (a) and structural formula (b), M represents a transition metal belonging to any of Groups 5 to 11 of the periodic table of the elements, that is, various transition metals as described above. X 1 represents oxygen, sulfur, -SO3-, or -CO2-. Y 1 represents carbon or silicon. n represents an integer of 0 or 1. E 1 represents phosphorus, arsenic or antimony. R 53 and R 54Each of these independently represents a hydrocarbon group which may contain hydrogen or a heteroatom having 1 to 30 carbon atoms. R 55 Each of these independently represents a hydrocarbon group which may contain hydrogen, a halogen, or a heteroatom having 1 to 30 carbon atoms. R 56 and R 57 Each of these independently contains hydrogen, a halogen, a hydrocarbon group which may contain a heteroatom having 1 to 30 carbon atoms, OR 52 CO2R 52 CO2M', C(O)N(R 51 )2, C(O)R 52 , SR 52 SO2R 52 SOR 52 OSO2R 52 , P(O)(OR 52 ) 2-y (R 51 ) y , CN, NHR 52 , N(R 52 )2, Si(OR 51 ) 3-x (R 51 ) x , OSi(OR 51 ) 3-x (R 51 ) x , NO2, SO3M', PO3M'2, P(O)(OR 52 ) Represents 2M' or epoxy-containing groups. R 51 This represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. R 52 This represents a hydrocarbon group having 1 to 20 carbon atoms. M' represents alkali metals, alkaline earth metals, ammonium, quaternary ammonium, or phosphonium, x is an integer from 0 to 3, and y is an integer from 0 to 2. Note, R 56 and R 57 These elements may be linked together to form an alicyclic ring, an aromatic ring, or a heterocycle containing a heteroatom selected from oxygen, nitrogen, or sulfur. In this case, the number of ring members is 5 to 8, and the ring may or may not have substituents. L1 This represents the ligand coordinated to M. Also, R 53 and L 1 They may join together to form a ring.

[0055] More preferably, it is a transition metal complex represented by the following structural formula (c). [ka] [In structural formula (c), M represents a transition metal belonging to one of groups 5 through 11 of the periodic table, i.e., the various transition metals mentioned above. X 1 represents oxygen, sulfur, -SO3-, or -CO2-. Y 1 represents carbon or silicon. n represents an integer, either 0 or 1. E 1 This represents phosphorus, arsenic, or antimony. R 53 and R 54 Each of these independently represents a hydrocarbon group which may contain hydrogen or a heteroatom having 1 to 30 carbon atoms. R 55 Each of these independently represents a hydrocarbon group which may contain hydrogen, a halogen, or a heteroatom having 1 to 30 carbon atoms. R 58 , R 59 , R 60 and R 61 Each of these independently contains hydrogen, a halogen, a hydrocarbon group which may contain a heteroatom having 1 to 30 carbon atoms, OR 52 CO2R 52 CO2M', C(O)N(R 51 )2, C(O)R 52 , SR 52 SO2R 52 SOR 52 OSO2R 52 , P(O)(OR 52 ) 2-y (R 51 ) y , CN, NHR52 , N(R 52 )2, Si(OR 51 ) 3-x (R 51 ) x , OSi(OR 51 ) 3-x (R 51 ) x , NO2, SO3M', PO3M'2, P(O)(OR 52 ) Represents 2M' or epoxy-containing groups. R 51 This represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. R 52 This represents a hydrocarbon group having 1 to 20 carbon atoms. M' represents alkali metals, alkaline earth metals, ammonium, quaternary ammonium, or phosphonium, x is an integer from 0 to 3, and y is an integer from 0 to 2. Note, R 58 ~R 61 Multiple groups appropriately selected from these may be linked together to form an alicyclic ring, an aromatic ring, or a heterocycle containing a heteroatom selected from oxygen, nitrogen, or sulfur. In this case, the number of ring members is 5 to 8, and the ring may or may not have substituents. L 1 This represents the ligand coordinated to M. Also, R 53 and L 1 They may join together to form a ring.

[0056] 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).

[0057] • Polymerization method for copolymers: The polymerization method for copolymers related to the present invention is not limited. Polymerization methods include slurry polymerization, in which at least a portion of the resulting polymer becomes a slurry in the medium; bulk polymerization, which uses the liquefied monomer itself as the medium; gas-phase polymerization, which is carried out in vaporized monomer; and high-pressure ionic polymerization, in which at least a portion of the resulting polymer dissolves in monomer liquefied at high temperature and pressure. The polymerization method can be batch polymerization, semi-batch polymerization, or continuous polymerization. Furthermore, living polymerization may be performed, or polymerization may be carried out while simultaneously undergoing chain transfer. Furthermore, during polymerization, a so-called chain shuttling agent (CSA) may be used in combination to perform chain shuttling reactions or coordinated chain transfer polymerization (CCTP). Specific manufacturing processes and conditions are disclosed, for example, in Japanese Patent Publication No. 2010-260913 and Japanese Patent Publication No. 2010-202647.

[0058] 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.

[0059] 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.

[0060] When hydrolyzing or thermally decomposing as described above, conventionally known acid-base catalysts may be used as additives to promote the reaction. There are no particular restrictions on the acid-base catalyst, but for example, alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; alkali metal or alkaline earth metal carbonates such as sodium bicarbonate and sodium carbonate; solid acids such as montmorillonite; inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid; and organic acids such as formic acid, acetic acid, benzoic acid, citric acid, p-toluenesulfonic acid, trifluoroacetic acid, and trifluoromethanesulfonic acid can be used as appropriate. From the viewpoints of reaction acceleration effect, cost, and equipment corrosivity, sodium hydroxide, potassium hydroxide, sodium carbonate, p-toluenesulfonic acid, and trifluoroacetic acid are preferred, and p-toluenesulfonic acid and trifluoroacetic acid are more preferred.

[0061] (6) Ionomer The ionomer according to the present invention has at least a portion of the carboxyl groups and / or dicarboxylic acid anhydride groups of the copolymer structural unit (B) of the present invention converted to a metal-containing carboxylate containing at least one metal ion selected from Group 1, 2, or 12 of the periodic table, and the absolute value of the complex modulus G measured with a rotational rheometer * The phase angle δ at 0.1 MPa is between 50 and 75 degrees, indicating that it is an ionomer with a substantially linear structure.

[0062] • Structure of ionomers Since the ionomers related to the present invention have a substantially linear structure, similar to the copolymers related to the present invention, the absolute value of the complex modulus G measured with a rotational rheometer *The phase angle δ at 0.1 MPa is characterized by being in the range of 50 to 75 degrees. * If the temperature (=0.1 MPa) is below 50 degrees Celsius, the molecular structure of the ionomer will exhibit a structure with excessive long-chain branching, resulting in inferior mechanical strength. Furthermore, even if the molecular structure does not contain long-chain branching, δ(G * The value (=0.1MPa) will never exceed 75 degrees. In the present invention, from the viewpoint of improving mechanical strength, the lower limit of the phase angle δ is preferably 51 degrees or more, more preferably 54 degrees or more, even more preferably 56 degrees or more, and even more preferably 58 degrees or more. The upper limit is not particularly limited, and the closer it is to 75 degrees, the better.

[0063] • Metal ions The metal ions contained in the ionomer related to the present invention may include metal ions used in conventionally known ionomers. Preferably, the metal ions are metal ions from Group 1, Group 2, or Group 12 of the periodic table, and Li + na + , K + , Rb + Be 2+ Mg 2+ Ca 2+ Sr 2+ Ba 2+ Ra 2+ Zn 2+ More preferably, at least one selected from the group consisting of the following is preferred. Particularly preferred is Na + , K + Mg 2+ Ca 2+ Ba 2+ and Zn 2+ More preferably, Na + Mg + and Zn 2+ At least one species is selected from the group consisting of the following: These metal ions can be mixed in any way of their type, with two or more types included as needed.

[0064] ·Neutralization degree (mol%) The metal ion content is preferably such that it contains an amount that neutralizes at least some or all of the carboxyl groups and / or dicarboxylic acid anhydride groups in the copolymer as the base polymer, and the preferred degree of neutralization (average degree of neutralization) is 1 to 90 mol%, more preferably 5 to 85 mol%, and even more preferably 10 to 80 mol%. The degree of neutralization can be determined from the ratio of the total amount of moles of metal ions (valence × moles) to the total amount of carboxyl groups that may be contained in the copolymer and / or dicarboxylic acid anhydride groups. Since the dicarboxylic acid anhydride group undergoes ring-opening to form a dicarboxylic acid when forming a carboxylate salt, the total amount of carboxyl groups is calculated by assuming that 1 mole of dicarboxylic acid anhydride group contains 2 moles of carboxyl groups. Also, for example, Zn 2+ For divalent metal ions such as these, assuming that 1 mole can form a salt with 2 moles of carboxyl groups, the total mole amount of molecules with a degree of neutralization is calculated using 2 × moles. Higher neutralization levels result in higher tensile strength and tensile fracture stress of the ionomer, and lower tensile fracture strain, but tend to lower the melt flow rate (MFR) of the ionomer. On the other hand, lower neutralization levels yield an ionomer with a moderate MFR, but tend to result in lower tensile modulus and tensile fracture stress, and higher tensile fracture strain. If the degree of neutralization is lower than 1 mol%, the toughness (strength and impact resistance) of the ionomer may be insufficient, and if the degree of neutralization is higher than 90 mol%, the heat resistance may be insufficient.

[0065] • Chemical resistance of ionomers: In the ionomer of the present invention, a low mass increase rate in the immersion test described in JIS K7114 (2001) is preferable, as this ensures sufficient impact resistance of the ionomer. The mass increase rate, which is the evaluation criterion for chemical resistance, is considered for each solvent, as the practical frequency of use and expected applications differ for each solvent. Ammonia is reactive and has a small molecular weight, so its effect on the ionomer relative to its quantity is greater than that of other solvents. Ethanol is used for disinfection, so it is used frequently in practice and the amount of contact is large; therefore, it is preferable that these solvents have higher resistance, i.e., a low mass increase rate, than other solvents. Specifically, in the case of toluene, it is preferable that the amount be less than 30%, more preferably less than 20%, and even more preferably less than 15%. In the case of ammonia, it is preferable that the amount be less than 10%, more preferably less than 5%, and even more preferably less than 3.5%. In the case of ethyl acetate, it is preferable that the amount be less than 5%, more preferably less than 4.0%, and even more preferably less than 3.5% or more. In the case of ethanol, it is preferable that the amount be less than 1.5%, more preferably less than 1.3%, and even more preferably less than 1.0%. In the case of FuelC, it is preferable that the content be less than 40%, more preferably less than 30%, and even more preferably less than 25% or more.

[0066] • Abrasion resistance of ionomers In the ionomer of the present invention, the wear loss amount specified in JIS K7204-1999 is preferably less than 15 mg, more preferably less than 7.0 mg, and even more preferably less than 5.0 mg, in order to ensure sufficient wear resistance of the ionomer.

[0067] • Crystallinity of the ionomer (%): In the ionomer of the present invention, the degree of crystallinity observed by differential scanning calorimetry (DSC) is preferably greater than 0%, more preferably greater than 5%, and even more preferably 7% or higher, from the viewpoint of sufficient toughness of the ionomer. From the viewpoint of transparency of the ionomer, the upper limit is preferably 50% or less, more preferably 40% or less, and even more preferably 35% or less. The degree of crystallinity serves as an indicator of transparency, and the lower the degree of crystallinity of the ionomer, the better its transparency can be judged to be.

[0068] The ionomer of the present invention is preferable to have at least one of the following properties: chemical resistance, abrasion resistance, and heat resistance, in order to be superior in terms of chemical resistance, abrasion resistance, and heat resistance.

[0069] • Method for manufacturing ionomers The ionomers according to the present invention may also be obtained by a conversion step in which a copolymer of ethylene and / or α-olefin / unsaturated carboxylic acid having 3 to 20 carbon atoms, obtained by the method of introducing carboxyl groups and / or dicarboxylic acid anhydride groups into the copolymer as described above, is treated with a metal salt containing at least one metal ion selected from Group 1, 2, or 12 of the periodic table to convert it into a metal-containing carboxylate salt. Alternatively, the ionomers according to the present invention may also be obtained by a heating conversion step in which an ethylene and / or α-olefin / unsaturated carboxylic acid ester copolymer having 3 to 20 carbon atoms is heated and at least some of the ester groups in the copolymer are converted into a metal-containing carboxylate salt containing at least one metal ion selected from Group 1, 2, or 12 of the periodic table.

[0070] When an ionomer is produced by introducing carboxyl groups and / or dicarboxylic acid anhydride groups into a polymer, the production method is as follows, for example: A metal ion source is prepared by heating and kneading a metal salt with a metal ion-capturing substance such as ethylene / (meth)acrylic acid ((M)AA) copolymer, and then the metal ion source is added to the ionomer precursor resin in an amount that results in a desired degree of neutralization and kneaded to obtain the ionomer.

[0071] Furthermore, in the heating conversion step, (i) the ethylene and / or C3-C20 α-olefin / unsaturated carboxylic acid ester copolymer may be heated to obtain an ethylene and / or C3-C20 α-olefin / unsaturated carboxylic acid copolymer by hydrolysis or thermal decomposition, and then reacted with a compound containing a metal ion of group 1, 2, or 12 of the periodic table to convert the carboxylic acid in the ethylene and / or C3-C20 α-olefin / unsaturated carboxylic acid copolymer into the metal-containing carboxylate salt; or (ii) the ethylene and / or C3-C20 α-olefin / unsaturated carboxylic acid ester copolymer may be heated to hydrolyze or thermal decompose the ester groups of the copolymer, and reacted with a compound containing a metal ion of group 1, 2, or 12 of the periodic table to convert the ester group portion in the ethylene and / or C3-C20 α-olefin / unsaturated carboxylic acid ester copolymer into the metal-containing carboxylate salt.

[0072] Furthermore, the compounds containing metal ions may also be oxides, hydroxides, carbonates, bicarbonates, acetates, formates, etc., of metals from Group 1, 2, or 12 of the periodic table. Compounds containing metal ions may be supplied to the reaction system in granular or fine powder form, or they may be dissolved or dispersed in water or an organic solvent before being supplied to the reaction system. Alternatively, a masterbatch may be prepared using an ethylene / unsaturated carboxylic acid copolymer or an olefin copolymer as the base polymer and supplied to the reaction system. To ensure the reaction proceeds smoothly, it is preferable to prepare a masterbatch and supply it to the reaction system.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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. Small amounts of oxygen or air may be present.

[0077] There are no particular restrictions on the reactor used in the above process; any method that can stir the copolymer substantially uniformly is acceptable. A glass container or autoclave (AC) equipped with a stirrer may be used, or any conventionally known kneader such as a Brabender plastograph, a single-screw or twin-screw extruder, a heavy-duty screw kneader, a Banbury mixer, a kneader, or a roll can be used.

[0078] Whether a metal ion has been introduced into an ionomer-based resin and it has become an ionomer can be confirmed by measuring the IR spectrum of the obtained resin and examining the decrease in the peak originating from the carbonyl group of the carboxylic acid (dimer). Similarly, the degree of neutralization can be confirmed by examining the decrease in the peak originating from the carbonyl group of the carboxylic acid (dimer) and the increase in the peak originating from the carbonyl group of the carboxylic acid base, in addition to the calculation from the molar ratio mentioned above.

[0079] • Additives The ionomers related to the present invention may contain additives such as conventionally known antioxidants, ultraviolet absorbers, lubricants, antistatic agents, colorants, pigments, crosslinking agents, foaming agents, nucleating agents, flame retardants, conductive materials, and fillers, to the extent that they do not depart from the spirit of the present invention. These additives can be appropriately selected from materials used in decorative sheets and constitute a resin composition for decorative sheets.

[0080] • Decorative sheet One aspect of the present invention is a decorative sheet comprising a laminate comprising at least a base sheet layer and a resin layer for decorative sheets (the resin layer of the present invention) using a resin or resin composition containing the above-mentioned ionomer. By incorporating the resin layer of the present invention, the decorative sheet can be provided with good chemical resistance, abrasion resistance, and heat resistance. The decorative sheet may further have laminates such as a pattern layer, an adhesive layer, a surface protection layer, a primer layer, etc. The resin layer of the present invention is usually provided between the adhesive layer and the surface protection layer.

[0081] <Base sheet> Various materials can be used as the base sheet, such as resin films, paper, and resin-impregnated paper. Resin films formed from thermoplastic resins are preferably used. Specific examples of thermoplastic resins include polyolefin resins such as polyethylene and polypropylene, acrylic resins such as acrylic acid esters and methacrylic acid esters, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and ethylene-acrylic acid ester copolymer.

[0082] The base sheet may contain various additives as needed, such as colorants, fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, UV absorbers, and light stabilizers. Furthermore, the base sheet may be subjected to corona discharge treatment on its surface according to known methods and conditions to improve the adhesion of the ink forming the pattern layer, if necessary. The thickness of the base sheet can be set appropriately depending on the application and method of use of the final product, but it is generally preferable to be in the range of 50 to 250 μm.

[0083] <Pattern layer> The pattern layer applies desired patterns and designs to the decorative sheet. There are no restrictions on the type of pattern; any pattern can be applied, such as wood grain, stone, sand, tile, brick, fabric, leather, geometric shapes, letters, symbols, abstract patterns, etc. The method for forming the pattern layer is not particularly limited. For example, it can be formed on the surface of a substrate sheet by a printing method using an ink obtained by dissolving a known coloring agent, such as a dye, inorganic or organic pigment, or fluorescent pigment, together with a binder resin in a solvent or dispersed in a dispersion medium.

[0084] Printing methods used to form the pattern layer include, for example, inkjet printing, gravure printing, offset printing, screen printing, flexographic printing, and electrostatic printing. Furthermore, when forming a solid-color pattern layer covering the entire surface, various coating methods such as gravure coating, gravure reverse coating, roll coating, knife coating, air knife coating, die coating, lip coating, comma coating, kiss coating, flow coating, and dip coating can also be used. In addition to these methods, other methods such as hand-drawing, suminagashi (marbling), photography, transfer, laser beam drawing, electron beam drawing, partial deposition of metals, and etching can also be used, and multiple image formation methods may be combined. The thickness of the pattern layer is not particularly limited and can be set appropriately according to the product characteristics, but the layer thickness during coating is generally around 0.1 to 10 μm.

[0085] <Adhesive layer> The adhesive layer is laminated between the pattern layer and the resin layer of the present invention, and is a layer that adheres the two together. The adhesive used in the adhesive layer can be appropriately selected depending on the components that make up the pattern layer or the resin layer of the present invention. For example, various adhesives including polyurethane resins, polyacrylic resins, polycarbonate resins, epoxy resins, etc., can be used. The means for exhibiting adhesive strength are also not limited. In addition to reaction-curing type adhesives, hot-melt type, ionizing radiation curing type, ultraviolet curing type adhesives, etc. may also be used. Furthermore, if necessary, known easy-adhesion treatments such as corona discharge treatment, plasma treatment, degreasing treatment, and surface roughening treatment can be applied to the bonding surface. While it is preferable to use a transparent resin for the adhesive layer, it may be semi-transparent rather than completely transparent, as long as the pattern layer is visible.

[0086] The adhesive layer can be formed, for example, by applying an adhesive to the pattern layer, allowing it to dry, and then laminating the resin of the present invention. The method of applying the adhesive is not particularly limited, and methods such as roll coating or other methods mentioned as methods for forming the pattern layer can be used. The thickness of the adhesive layer varies depending on the transparent protective layer, the type of adhesive used, etc., but it is generally around 0.1 to 30 μm.

[0087] <Transparent surface protective layer> A transparent surface protective layer may be formed on the resin layer of the present invention. The components of the resin forming the transparent surface protective layer are not particularly limited, but it is preferable that it contains an ionizing radiation-curable resin or a two-component curable urethane resin. An ionizing radiation-curable resin or a two-component curable urethane resin is preferred because it has properties that easily enhance abrasion resistance, impact resistance, stain resistance, scratch resistance, weather resistance, etc.

[0088] As ionizing radiation-curable resins, resins that can undergo polymerization and crosslinking reactions upon irradiation with ionizing radiation such as ultraviolet light and electron beams can be used. For example, compounds having radically polymerizable unsaturated groups such as (meth)acryloyl groups and (meth)acryloyloxy groups, or cationic polymerizable functional groups such as epoxy groups in their molecules can be used. Specific examples include polymers of monofunctional monomers such as methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and phenoxyethyl (meth)acrylate; polymers of polyfunctional monomers such as diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and dipentaerythritol tetra(meth)acrylate; and (meth)acrylate-modified resins such as isoprene (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, urethane (meth)acrylate, melamine (meth)acrylate, and silicone (meth)acrylate.

[0089] Methods known to those skilled in the art can be used to cure ionizing radiation-curable resins. Typically, the curing reaction is carried out using ultraviolet light or electron beams. For example, ultraviolet sources such as mercury lamps, carbon arc lamps, black lights, and metal halide lamps, and electron sources such as Cockcroft-Walton type, Van de Graft type, resonant transformer type, insulated core transformer type, Dynamitron type, and high-frequency type electron beam accelerators can be used.

[0090] The two-component curing urethane resin is not particularly limited, but among them, those containing a polyol component having a hydroxyl group and an isocyanate component as the main component can be used.

[0091] The transparent surface protective layer can be formed, for example, by applying an ionizing radiation-curable resin or a two-component urethane-based resin onto a transparent resin layer using a known coating method such as gravure coating or roll coating, and then curing the resin. The thickness of the transparent surface protective layer is not particularly limited and can be set appropriately according to the characteristics of the final product, but is usually 0.1 to 50 μm, preferably about 1 to 20 μm.

[0092] <Primer layer> A primer layer may be laminated between the surface protective layer and the resin layer of the present invention. The primer layer serves to improve the adhesion between the two. The primer layer is mainly composed of a binder resin and may contain additives such as UV absorbers and light stabilizers as needed. Suitable binder resins include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, styrene resins, urethane-acrylic copolymers, vinyl chloride-vinyl acetate copolymers, chlorinated propylene resins, nitrocellulose resins, and cellulose acetate resins. These may be used individually or in combination. The thickness of the primer layer is preferably 1 μm to 10 μm.

[0093] <<Processing>> The decorative sheet may be further processed on the transparent surface protective layer side by embossing, antiviral treatment, etc. Embossing is performed to impart a desired texture, such as a wood grain pattern, to the decorative sheet. For example, after heating and softening the transparent protective layer, the texture is imparted by pressing and shaping it with an embossing plate having the desired shape of raised and recessed pattern, and then cooling and fixing it. Embossing can be performed using a known sheet-fed or rotary embossing machine. Antiviral processing can be performed by incorporating an antiviral agent into the layer laminated on the outermost surface of the decorative sheet. Suitable antiviral agents include inorganic antiviral agents formed by incorporating silver, copper, or zinc ions into materials such as zeolite, apatite, or zirconia; organic antiviral agents such as 2-(4-thiazolyl)-benzimidazole, 10,10-oxybisphenoxanodine, and pyridine-2-thiol oxide; and resins into which cationic polymers are kneaded. Inorganic antiviral agents with added silver are preferred for their antiviral effect.

[0094] • Decorative laminate One aspect of the present invention is a decorative panel comprising a laminate comprising a decorative panel base material and a decorative sheet of the present invention. The base material of the decorative panel is appropriately selected according to the application. Examples include wood fiberboard, particleboard, plywood, cork sheet, cork-containing composite base material, thermoplastic resin board, etc. These decorative panel base materials may be used individually or in combination of two or more types, laminated and bonded with an adhesive as necessary. Furthermore, the shape of the base material is not particularly limited, and various materials such as flat plates, curved plates, three-dimensional articles, sheets, etc., can be used in any shape and thickness. The lamination method for bonding the decorative sheet and the decorative panel substrate is not limited, and methods known to those skilled in the art, such as bonding them together with an adhesive, can be employed. The adhesive can be appropriately selected from known adhesives depending on the type of material to be bonded. [Examples]

[0095] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The physical properties in the examples and comparative examples were measured and evaluated using the methods described below. Additionally, "no data" in the table means no measurement was taken, and "not detected" means the value was below the detection limit.

[0096] <Measurement and Evaluation> (1) Measurement of the phase angle δ (G*=0.1MPa) at the absolute value of the complex modulus G*=0.1MPa. 1) Sample preparation and measurement The sample was placed in a 1.0 mm thick heat press mold and preheated in a hot press machine at a surface temperature of 180°C for 5 minutes. After that, residual gas in the molten resin was removed by repeatedly applying and removing pressure, and then it was further pressurized to 4.9 MPa and held for 5 minutes. After that, it was transferred to a press machine at a surface temperature of 25°C and cooled by holding it at a pressure of 4.9 MPa for 3 minutes to produce a press plate made from the sample with a thickness of approximately 1.0 mm. A 25 mm diameter circular press plate was processed from the sample and used as the sample. Dynamic viscoelasticity was measured under the following conditions in a nitrogen atmosphere using a Rheometrics ARES type rotary rheometer as the device for measuring dynamic viscoelastic properties. • Plate: φ25mm (diameter) Parallel plate ·Temperature: 160℃ Distortion level: 10% • Measurement angular frequency range: 1.0 × 10⁻² to 1.0 × 10² rad / s • Measurement interval: 5 points / decade The phase angle δ was plotted against the common logarithm logG* of the absolute value G*(Pa) of the complex modulus of elasticity, and the value of δ (degrees) at the point corresponding to logG*=5.0 was defined as δ(G*=0.1MPa). When there was no point corresponding to logG*=5.0 among the measurement points, the value of δ at logG*=5.0 was obtained by linear interpolation using two points around logG*=5.0. Furthermore, when all measurement points were logG*<5, the value of δ at logG*=5.0 was obtained by extrapolating using a quadratic curve with the values ​​of the three points with the largest logG* values.

[0097] (2) Measurement of weight-average molecular weight (Mw) and molecular weight distribution parameter (Mw / Mn) The weight-average molecular weight (Mw) was determined by gel permeation chromatography (GPC). The molecular weight distribution parameter (Mw / Mn) was calculated by determining the number-average molecular weight (Mn) using GPC, and then determining the ratio of Mw to Mn, Mw / Mn. The measurements were performed according to the following procedures and conditions.

[0098] 1) Sample pretreatment If the sample contained a carboxylic acid group, it was subjected to esterification treatment, such as methyl esterification using diazomethane or trimethylsilyl (TMS) diazomethane, before being used for measurement. If the sample contained a carboxylic acid base, it was treated with acid to convert the carboxylic acid base into a carboxylic acid group, and then subjected to the above-mentioned esterification treatment before being used for measurement.

[0099] 2) Preparation of sample solution 3 mg of the sample and 3 mL of o-dichlorobenzene were weighed into a 4 mL vial, sealed with a screw cap and a Teflon® septum, and then shaken at 150°C for 2 hours using a Senshu Scientific SSC-7300 high-temperature shaker. After shaking, the absence of insoluble components was visually confirmed.

[0100] 3) Measurement One Showdex HT-G and two Showdex HT-806M high-temperature GPC columns were connected to a Waters Alliance GPCV2000 column. Measurements were performed using o-dichlorobenzene as the eluent at a temperature of 145°C and a flow rate of 1.0 mL / min.

[0101] 4) Calibration curve Column calibration was performed by measuring monodisperse polystyrene (S-7300, S-3900, S-1950, S-1460, S-1010, S-565, S-152, S-66.0, S-28.5, S-5.05, each at 0.07 mg / ml solution), n-eicosane, and n-tetracontane under the same conditions as above, and elution time and the logarithm of molecular weight were approximated by a quartic equation. The following formula was used to convert between polystyrene molecular weight (MPS) and polyethylene molecular weight (MPE). MPE = 0.468 × MPS

[0102] (3) Melt Flow Rate (MFR) MFR was measured according to Table 1-Condition 7 of JIS K-7210 (1999), under conditions of a temperature of 190°C and a load of 21.18 N (= 2.16 kg). In the table, "<0.01" means that the resin did not flow under the test conditions and measurement was not possible.

[0103] (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.

[0104] (5) Method for measuring the amount of structural units and the number of branches per 1,000 carbon atoms derived from monomers having a carboxyl group and / or a dicarboxylic acid anhydride group, and acyclic monomers. The amount of structural units derived from monomers having carboxyl groups and / or dicarboxylic acid anhydride groups, and acyclic monomers in the copolymer of the present invention, and the number of branches per 1,000 carbon atoms. 13 It can be determined using 1C-NMR spectroscopy. 13 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.

[0105] 1) Sample pretreatment If the sample contains a carboxylic acid base, it was treated with acid to convert the carboxylic acid base into a carboxyl group before being used for measurement. If the sample contains a carboxyl group, esterification treatment, such as methyl esterification using diazomethane or trimethylsilyl (TMS) diazomethane, may be performed as appropriate.

[0106] 2) Calculation of structural unit amounts derived from monomers having carboxyl groups and / or dicarboxylic acid anhydride groups, and acyclic monomers. <e tba> The quaternary carbon signal of the t-butyl acrylate group of tBA is 13 It is detected in the 1C-NMR spectrum between 79.6 and 78.8. Using these signal intensities, the amount of comonomer was calculated from the following formula. Total amount of tBA (mol%) = I(tBA) × 100 / [I(tBA) + I(E)] Here, I(tBA) and I(E) are quantities given by the following equations, respectively. I(tBA)=I 79.6~78.8 I(E)=(I 180.0~135.0 +I 120.0~5.0 -I(tBA×7) / 2

[0107] Furthermore, if the structural unit amount of each monomer is indicated with an inequality sign, such as "<0.1", it means that it exists as a constituent unit in the copolymer, but the amount is less than 0.1 mol%, taking significant figures into consideration.

[0108] 3) Calculation of the number of branches per 1,000 carbon atoms Copolymers include isolated types, where branches exist individually in the main chain, and complex types (facing types, where branches face each other via the main chain; branched-branch types, where branches exist within the branched chain; and chained types). The following are examples of ethyl branched structures. In the examples of the opposite type, R represents an alkyl group.

[0109] [ka]

[0110] The number of branches per 1,000 carbon atoms can be determined by substituting one of the following I(B1), I(B2), or I(B4) into the I(branching) term in the following equation. B1 represents methyl branching, B2 represents ethyl branching, and B4 represents butyl branching. The number of methyl branchings is determined using I(B1), the number of ethyl branchings is determined using I(B2), and the number of butyl branchings is determined using I(B4). Number of branches (per 1,000 carbon atoms) = I (number of branches) × 1000 / I (total) Here, I(total), I(B1), I(B2), and I(B4) are quantities expressed by the following formulas. I(total)=I 180.0~135.0 +I 120.0~5.0 I(B1)=(I 20.0~19.8 +I 33.2~33.1 +I 37.5~37.3 ) / 4 I(B2)=I 8.6~7.6 +I 11.8~10.5 I(B4)=I 14.3~13.7 -I 32.2~32.0 Here, I is the integral intensity, and the subscript number of I indicates the range of the chemical shift. For example, I 180.0~135.0 It was detected between 180.0 ppm and 135.0 ppm. 13 This shows the integrated intensity of the C signal. Attributions are based on the non-patent literature Macromolecules 1984, 17, 1756-1761 and Macromolecules 1979, 12, 41. Note that when the number of branches is indicated with an inequality sign, such as "<0.1", it means that the component exists as a constituent unit in the copolymer, but the amount is less than 0.1 mol%, taking significant figures into consideration. Also, "not detected" means that it is below the detection limit.

[0111] (6) Infrared absorption spectrum The sample was melted at 180°C for 3 minutes, and then compressed to produce a film with a thickness of approximately 50 μm. This film was analyzed by Fourier transform infrared spectroscopy to obtain an infrared absorption spectrum. Product Name: FT / IR-6100, manufactured by JASCO Corporation. Measurement method: transmission method Detector: TGS (Triglycine sulfate) Cumulative number of times: 16-512 Resolution: 4.0cm -1 Measurement wavelength: 5000~500cm -1

[0112] (7) Measurement of the mass increase rate 1) Chemical resistance test sample 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. Residual gas in the molten resin was then removed by repeatedly applying and removing pressure, and the mold 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. 2) Chemical resistance test conditions Using the above test specimens, the mass change rate (%) was measured under the following conditions in accordance with JIS K 7114-2001. FuelC refers to JIS fuel oil C with isooctane / toluene = 1:1 (by weight). • Immersion time: Toluene, ammonia water, ethyl acetate, ethanol. 72 hours. FuelC 168 hours ·Soaking temperature: Toluene, aqueous ammonia, ethyl acetate, ethanol 23℃ FuelC 60℃ • Container: 240ml glass bottle • Immersion solvent volume: 200 ml The mass increase rate (%) was calculated using the following formula. • Mass increase rate (%) = (Sample weight after immersion m2 - Sample weight before immersion m1) / Sample weight before immersion m1

[0113] (8) 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 at 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 115mm, and a hole with a diameter of approximately 6.5mm was drilled in the center to serve as an abrasion test sample.

[0114] 2) Abrasion test conditions Using the above test pieces, the amount of wear loss (mg) was measured under the following conditions in accordance with JIS K 7204-1999. · Apparatus: Taber abrasion tester (Rotary abrasion tester), manufactured by Toyo Seiki Seisakusho Co., Ltd. · Abrasion wheel: CS-17 · Rotation speed: 60 rotations / min · Number of test rotations: 1000 rotations · Load: 4.9 N

[0115] <Synthesis of metal complex> Synthesis of B-423 / Ni complex The B-423 / Ni complex was synthesized using the following 2-bis(2,6-dimethoxyphenyl)phosphano-6-(2,6-diisopropylphenyl)phenol ligand (B-423) according to Synthesis Example 1 described in Patent 2019 / 156764. According to Example 1 of Patent 2019 / 156764, a nickel complex (B-423 / Ni) in which B-423 and Ni(COD)2 reacted in a 1:1 ratio was synthesized using bis(1,5-cyclooctadiene)nickel(0) (referred to as Ni(COD)2). [Chemical formula]

[0116] <(Production Examples 1 to Production Examples 4): Production of ionomer-based resin precursor> An ethylene / t-butyl acrylate copolymer was produced using a transition metal complex (B-423 / Ni complex). The copolymer was produced referring to Production Example 1 or Production Example 3 described in JP-A-2016-79408, and the production conditions and production results were appropriately changed, such as the metal complex species, the amount of metal complex, the amount of aluminum compound (trioctylaluminum (TNOA)), the amount of toluene, the comonomer species, the amount of comonomer, the ethylene partial pressure, the polymerization temperature, and the polymerization time. Table 1 shows the production conditions and Table 2 shows the physical properties of the obtained copolymer.

[0117]

Table 1

[0118]

Table 2

[0119] <(Resin 1 - Resin 2): Production of Ionomer - based Resin> 40 g of the copolymers obtained in Production Examples 1 and 2, 0.8 g of p - toluenesulfonic acid monohydrate, and 185 ml of toluene were charged into a 500 - ml separable flask, and the mixture was stirred at 105 °C for 4 hours. 185 ml of ion - exchanged water was added, stirred, allowed to stand, and then the aqueous layer was withdrawn. Thereafter, the addition and withdrawal of ion - exchanged water were repeated until the pH of the withdrawn aqueous layer became 5 or more. The solvent was distilled off under reduced pressure from the remaining solution, and drying was carried out until a constant weight was obtained. In the IR spectrum of the obtained resin, the disappearance of the peak near 850 cm -1 derived from the tBu group, the decrease in the peak near 1730 cm -1 derived from the carbonyl group of the ester, and the increase in the peak near 1700 cm -1 derived from the carbonyl group of the carboxylic acid (dimer) were observed. Thereby, the decomposition of the t - Bu ester and the formation of the carboxylic acid were confirmed, and ionomer - based resins 1 and 2 were obtained. The physical properties of the obtained resins are shown in Table 3.

[0120]

Table 3

[0121] 〈Examples 1 - 9: Production of Ionomer〉 1) Preparation of Na ion source 22 g of an ethylene / methacrylic acid (MAA) copolymer (brand name: Nucrel N1050H, manufactured by Mitsui - Dow Polychemical Co., Ltd.) and 18 g of sodium carbonate were charged into a Toyo Seiki Co., Ltd. - manufactured Laboplastmill: Roller Mixer R60 type equipped with a 60 - ml small mixer, and kneaded at 180 °C and 40 rpm for 3 minutes to prepare a Na ion source.

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

[0123] 3) Preparation of ionomers 40g each of resins 1 to 6 were added to a Toyo Seiki Co., Ltd. Laboplast Mill: Roller Mixer R60, equipped with a 60ml capacity mini mixer, and mixed at 160°C and 40rpm for 3 minutes until dissolved. Subsequently, a Na ion source and a Zn ion source were added to achieve the desired degree of neutralization, and the mixture was kneaded at 250°C and 40rpm for 5 minutes. In the IR spectrum of the obtained resin, a 1700 cm⁻¹ spectrum originating from the carbonyl group of the carboxylic acid (dimer) was observed. -1 The peak in the vicinity decreases, and the 1560 cm peak originates from the carbonyl group of the carboxylic acid base. -1 The peak in the vicinity was increasing. This was due to the carbonyl group of the carboxylic acid (dimer) at 1700 cm². -1 The decrease in the surrounding peaks confirmed that the desired degree of neutralization of the ionomer was achieved. The physical properties of the obtained ionomer are shown in Tables 4 and 5.

[0124] [Table 4]

[0125] [Table 5]

[0126] (Comparative Example 1): Ionomer-based resin E / AA Resin 1, an ionomer-based resin, was used as a 0% neutralized ionomer. The physical properties are shown in Tables 6 and 7.

[0127] (Comparative Example 2): Ionomer-based resin E / AA Resin 2, which is an ionomer-based resin, was used as a 0% neutralized ionomer. The physical properties are shown in Tables 6 and 7.

[0128] (Comparative Example 3): E / MAA-based binary ionomer An ionomer resin (brand name: HIMILAN HIM1605, manufactured by Mitsui Dow Chemical Co., Ltd.) that is a copolymer of ethylene, methacrylic acid, and sodium methacrylate and is produced by a high-pressure radical process was used as a reference ionomer. The physical properties are shown in Tables 6 and 7.

[0129] (Comparative Example 4): E / MAA-based binary ionomer An ionomer resin (brand name: HIMILAN HIM1707, manufactured by Mitsui Dow Chemical Co., Ltd.) that is a copolymer of ethylene, methacrylic acid, and sodium methacrylate and is produced by a high-pressure radical process was used as a reference ionomer. These ionomers have a phase angle δ of 46 - 47° and a structure containing excessive long-chain branches. The physical properties are shown in Tables 6 and 7.

[0130] (Comparative Example 5): E / MAA-based binary ionomer An ionomer resin (brand name: HIMILAN HIM1650, manufactured by Mitsui Dow Chemical Co., Ltd.) that is a copolymer of ethylene, methacrylic acid, and zinc methacrylate and is produced by a high-pressure radical process was used as a reference ionomer. The physical properties are shown in Tables 6 and 7.

[0131]

Table 6

[0132]

Table 7

[0133] The evaluation criteria in Tables 5 and 7 will be explained. 1) Chemical resistance For toluene, a mass increase rate of less than 15% was marked with ○, 15% to less than 20% with △, and 20% or more with ×. For aqueous ammonia, a mass increase rate of less than 3.5% was marked with ○, 3.5% to less than 5% with △, and 5% or more with ×. For ethyl acetate, a mass increase rate of less than 4.5% was marked with ○, 4.5% to less than 6% with △, and 6% or more with ×. For ethanol, a mass increase rate of less than 1% was marked with ○, 1% to less than 1.5% with △, and 1.5% or more with ×. For Fuel C, a mass increase rate of less than 25% was marked with ○, 25% to less than 40% with △, and 40% or more with ×.

[0134] 2) Abrasion resistance A wear loss of less than 5 mg was marked with ○, 5 mg to 10 mg was marked with △, and 10 mg or more was marked with ×.

[0135] 3) Heat resistance A melting point of 95°C or higher was marked with ○, 93°C or higher but less than 95°C was marked with △, and less than 93°C was marked with ×.

[0136] <Discussion of the results from the examples and comparative examples> [Comparison of the ionomer of the present invention with conventional ionomers] Examples 1-9 are ionomers consisting of a base resin produced with a specific transition metal catalyst and a metal ion source; therefore, their molecular structure is substantially linear, and the phase angle δ (G* = 0.1 MPa) is 50° or greater. On the other hand, Comparative Examples 1 and 2 use base resin 1 or 2 as is; their molecular structure is substantially linear, and the phase angle δ (G* = 0.1 MPa) is 50° or greater, but the degree of metal ion neutralization is 0%. Comparative Examples 3-5 are commercially available ionomers consisting of a base resin produced by a high-pressure radical method and a metal ion source; therefore, their molecular structure has many long-chain branches, and the phase angle δ (phase angle δ (G* = 0.1 MPa)) at the absolute value of the complex modulus G* = 0.1 MPa is less than 50°. Example 6 and Comparative Example 5, Example 8 and Comparative Example 3, and Example 9 and Comparative Example 4 all have similar structural unit (B) content, metal species, and degree of neutralization, allowing for direct comparison and evaluation. Therefore, the comparisons are explained below.

[0137] The ionomers of Examples 6, 8, and 9 and the ionomers of Comparative Examples 5, 3, and 4 show that the mass change rate during FuelC immersion is lower for Examples 6, 8, and 9 than for Comparative Examples 5, 3, and 4, resulting in significantly less wear and a higher melting point. Therefore, the ionomers of Examples 6, 8, and 9 have superior chemical resistance, wear resistance, and heat resistance compared to the ionomers of Comparative Examples 5, 3, and 4. This indicates that the linear ionomer of the present invention, having a phase angle δ (G* = 0.1 MPa) of 50° or more, exhibits superior chemical resistance, abrasion resistance, and heat resistance compared to conventional multi-branched ionomers.

[0138] [Regarding the metal ion species and degree of neutralization of the ionomer in this invention] Comparative Example 1 is the base resin of Examples 1-6, and Comparative Example 2 is the base resin of Examples 7-9, both corresponding to a 0% degree of neutralization by metal ions. Examples 1-9, where the degree of neutralization is not 0%, exhibit significantly less wear than Comparative Examples 1 and 2, where the degree of neutralization is 0%. This indicates that the ionomer of the present invention, having a substantially linear structure, exhibits excellent chemical resistance, wear resistance, and heat resistance regardless of the type of metal.

[0139] [Regarding the composition, degree of neutralization, and metal ion species of the ionomer in this invention] Examples 1 to 9 are ionomers with different base resin compositions, degrees of neutralization, and metal ion species, but all of them have higher melting points, significantly lower mass change rates, and less wear compared to the conventional ionomers in the comparative example. This indicates that the ionomer of the present invention, which has a substantially linear structure, exhibits relatively superior chemical resistance, abrasion resistance, and heat resistance, regardless of the composition of the base resin, degree of neutralization, and type of metal ion.

[0140] The reason why the ionomer of this invention exhibits superior abrasion resistance and chemical resistance compared to conventional ionomers is likely due to the significant difference in molecular structure. As shown in Figure 2, the ionomer of this invention has a substantially linear molecular structure, while conventional ionomers have a highly branched molecular structure with many long-chain branches, as shown in Figure 1. Compared to a linear molecular structure, a highly branched molecular structure has a large number of molecular chain ends within the molecule. Abrasion tests involve deforming and breaking the surface using an abrasion wheel with irregularities. Since the molecular chain ends are the triggers for fracture when deformation is applied, it is thought that the linear structure, which has fewer molecular chain ends, has superior abrasion resistance compared to the highly branched structure, which has many molecular chain ends. Chemical resistance depends on how easily solvents penetrate the material. A highly branched structure, with its numerous molecular ends, allows molecules to move more easily, thus facilitating solvent penetration. For this reason, linear structures with fewer molecular ends are considered to have superior chemical resistance and abrasion resistance compared to highly branched structures with many molecular ends.< / e>

Claims

1. 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 are converted into a metal-containing carboxylate containing at least one metal ion selected from Group 1, 2, or 12 of the periodic table, and the absolute value of the complex modulus G measured with a rotational rheometer ＊ A resin composition for decorative sheets, characterized by containing a resin for decorative sheets that includes an ionomer characterized in that the phase angle δ at 0.1 MPa is 50 to 75 degrees.

2. The copolymer (P) １３ The resin composition for decorative sheets 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 resin composition for decorative sheets according to claim 1 or 2, characterized in that the copolymer (P) contains 1 to 20 mol% of the structural unit (B) in the copolymer.

4. The resin composition for decorative sheets according to any one of claims 1 to 3, characterized in that the structural unit (A) is a structural unit derived from ethylene.

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

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

7. The resin composition for decorative sheets according to any one of claims 1 to 6, characterized in that the copolymer (P) has a degree of crystallinity of 50% or less.

8. The resin composition for decorative sheets according to any one of claims 1 to 6, characterized in that the copolymer (P) has a degree of crystallinity of 10% or more.

9. A resin layer for decorative sheets using the resin composition for decorative sheets described in any one of claims 1 to 8.

10. A decorative sheet comprising a laminate comprising at least a base layer and the resin layer described in claim 9.

11. A decorative panel comprising a laminate comprising a decorative panel base material and a decorative sheet according to claim 10.

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