JP7540212B2 - Ethylene-based ionomer for tubes and molded body thereof - Google Patents

Description

The present invention relates to an ethylene-based ionomer for tubes that uses a new ionomer and has an excellent balance of flexibility, abrasion resistance, and transparency, and to a molded article made from the same.

Because tubes are hollow, light, and strong, they have been used since ancient times as a means of transporting liquids or gases in a certain direction, in addition to being used as structural components. In particular, when it comes to transporting fluids, plastic tubes are used, which are made of a flexible material that can be bent to a certain degree of freedom, as they are important for ease of handling. Water hoses are one of the most familiar examples. Various resins are known as materials for tubes.

Ethylene-based ionomers are resins that use ethylene-unsaturated carboxylic acid copolymers as a base resin and are intermolecularly bonded with metal ions such as sodium and zinc (Patent Document 1). They are characterized by their toughness, elasticity, flexibility, abrasion resistance, transparency, etc.
Currently, known ethylene-based ionomers available on the market include "Surlyn (registered trademark)", a sodium salt or zinc salt of ethylene-methacrylic acid copolymer developed by DuPont, and "Himilan (registered trademark)" sold by Mitsui-Dow Polychemicals Co. In addition, a rubber/resin composite hose (Patent Document 2) is an example of an ionomer actually used in the form of a tube.

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

Meanwhile, methods have been sought for producing polar group-containing olefin copolymers having a linear molecular structure, as shown in the image diagram of FIG. 2, by using a polymerization method using a catalyst. However, polar group-containing monomers are generally catalyst poisons and therefore difficult to polymerize. In fact, it has been considered difficult for many years to obtain polar group-containing olefin copolymers having desired physical properties in an industrially inexpensive and stable manner.
However, in recent years, the applicants of the present application have proposed a method for industrially and inexpensively obtaining polar group-containing olefin copolymers having a substantially linear molecular structure in a stable manner by using a new catalyst and a new production method.
The applicants of the present application have reported that they have succeeded in producing a copolymer of ethylene and t-butyl acrylate using a late transition metal catalyst as a production method for a polar group-containing olefin copolymer that serves as a base resin for an ethylene-based ionomer, and modifying the resulting polar group-containing olefin copolymer by heat or acid treatment to form an ethylene-acrylic acid copolymer, which is then reacted with a metal ion to produce a binary ionomer (Patent Document 3).

U.S. Pat. No. 3,264,272 JP 2011-255649 A JP 2016-79408 A

Currently, the product performance required for tubes used in dishwashers and the like includes "flexibility" to increase the degree of freedom in handling since they are installed in a limited space, "abrasion resistance" to prevent wear even with repeated rubbing, and "transparency" to check the fluid flowing through the tube. However, the ionomer described in Patent Document 1 does not have sufficient resistance to impact, and the inventors have found that it also has poor abrasion resistance. Patent Document 2 discloses that the use of ionomers and resins containing ionomers in manufacturing multi-layer hoses improves adhesion to rubber, but the characteristics and effects of the ionomers are only related to adhesion, and there is no description focusing on the mechanical physical properties of the ionomer itself, nor is there any mention of the use of a single layer of ionomers.
In view of the above-mentioned state of the art, the present application has an object to provide an ethylene-based ionomer for tubes having an excellent balance of flexibility, abrasion resistance, and transparency, and a molded article thereof.

As a result of extensive investigations conducted by the present inventors to solve the above problems, it was discovered that a specific ionomer resin has an effect far superior to expectations in terms of the physical properties required for a tube.
The ethylene-based ionomer of Patent Document 3 is a novel ethylene-based ionomer that has not been seen before, in which the base resin has a substantially linear molecular structure and also functions as an ionomer, and its physical properties, etc. are significantly different from those of conventional ethylene-based ionomers having a multi-branched molecular structure, and its unique characteristics and suitable applications are also unknown. The present invention is based on the discovery that a resin composition containing a substantially linear ethylene-based ionomer has an excellent effect in improving the physical properties required for a tube.

That is, according to the first aspect of the present invention, there is provided an ethylene-based ionomer for tubes, which is an ionomer obtained by converting at least a part of the carboxyl groups and/or dicarboxylic anhydride groups in a copolymer (P) containing, as essential constituent units, structural units (A) derived from ethylene and/or an α-olefin having 3 to 20 carbon atoms and structural units (B) derived from a monomer having a carboxyl group and/or a dicarboxylic anhydride group, 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 which is characterized in having the following properties (a) to (e):
(a) The phase angle δ at the absolute value of the complex elastic modulus G ^* =0.1 MPa measured with a rotational rheometer is 50 to 75 degrees.
(b) The melt flow rate (MFR) at a temperature of 190° C. and a load of 2.16 kg is 0.1 to 15 g/10 min.
(c) The tensile modulus is 20 to 350 MPa.
(d) The abrasion resistance in an abrasion test is less than 10 mg.
(e) The haze is 0.1 to 30%.

According to a second aspect of the present invention, there is provided an ethylene-based ionomer for tubes, characterized in that the ionomer is obtained by converting at least a part of the carboxyl groups and/or dicarboxylic anhydride groups in a copolymer (P) containing, as essential constituent units, structural units (A) derived from ethylene and/or an α-olefin having 3 to 20 carbon atoms, structural units (B) derived from a monomer having a carboxyl group and/or a dicarboxylic anhydride group, and structural units (C) which are compounds other than the structural units (A) and (B) and have one or more carbon-carbon double bonds in their molecular structure, 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 ionomer has the following properties (a) to (e):
(a) The phase angle δ at the absolute value of the complex elastic modulus G ^* =0.1 MPa measured with a rotational rheometer is 50 to 75 degrees.
(b) The melt flow rate (MFR) at a temperature of 190° C. and a load of 2.16 kg is 0.1 to 15 g/10 min.
(c) The tensile modulus is 20 to 350 MPa.
(d) The abrasion resistance in an abrasion test is less than 10 mg.
(e) The haze is 0.1 to 30%.

According to a third aspect of the present invention, there is provided an ethylene-based ionomer for tubes according to the first or second aspect, characterized in that the number of methyl branches of the copolymer (P) in the ionomer calculated by ^13C -NMR is 50 or less per 1,000 carbons.

Further, according to a fourth aspect of the present invention, there is provided an ethylene-based ionomer for tubes according to the first or second aspect, characterized in that the number of methyl branches of the copolymer (P) in the ionomer calculated by ^13C -NMR is 5 or less per 1,000 carbons.

The fifth aspect of the present invention provides an ethylene-based ionomer for tubes, characterized in that the copolymer (P) in the ionomer contains 2 to 20 mol % of the structural unit (B) in the copolymer, in any one of the first to fourth aspects.

The sixth aspect of the present invention provides an ethylene-based ionomer for tubes according to any one of the first to fifth aspects, characterized in that the structural unit (A) in the ionomer is a structural unit derived from ethylene.

The seventh aspect of the present invention provides an ethylene-based ionomer for tubes according to any one of the first to sixth aspects, characterized in that the copolymer (P) in the ionomer is produced using a transition metal catalyst containing a transition metal of Groups 8 to 11 of the periodic table.

The eighth aspect of the present invention provides an ethylene-based ionomer for tubes, which is the seventh aspect of the invention, characterized in that the transition metal catalyst is a transition metal catalyst consisting of a phosphorus sulfonic acid or phosphorus phenol ligand and nickel or palladium.

According to the ninth aspect of the present invention, there is provided a copolymer (P) comprising, as essential constituent units, structural units (A) derived from ethylene and/or an α-olefin having 3 to 20 carbon atoms and structural units (B) derived from a monomer having a carboxyl group and/or a dicarboxylic anhydride group, wherein at least a part of the carboxyl groups and/or dicarboxylic anhydride groups in the copolymer (P) is converted to a metal-containing carboxylate containing at least one metal ion selected from Groups 1, 2, and 12 of the Periodic Table;
An ethylene-based ionomer resin composition for tubes is provided, which contains an ionomer characterized in that the phase angle δ at an absolute value of complex elastic modulus G ^* =0.1 MPa measured with a rotational rheometer is 50 degrees to 75 degrees.

Furthermore, according to the tenth aspect of the present invention, there is provided a molded article having a tubular shape, which is made using the ethylene-based ionomer for tubes according to any one of the first to eighth aspects of the present invention or the ethylene-based ionomer resin composition for tubes according to the ninth aspect of the present invention.

Furthermore, according to the eleventh aspect of the present invention, there is provided a hose in which two or more tubular structures are laminated, at least one layer being the molded article of the tenth aspect of the present invention.

The present invention provides an ethylene-based ionomer for tubes and a molded article thereof that has an excellent balance of flexibility, abrasion resistance, and transparency. The ionomer according to the present invention, which has a substantially linear structure, is useful because it can provide tubes that have an excellent balance of flexibility, abrasion resistance, and transparency compared to conventional materials.

FIG. 2 is an image of the molecular structure of a hyperbranched olefin copolymer polymerized by a high-pressure radical polymerization process. FIG. 1 is an image of the molecular structure of a linear olefin copolymer polymerized using a metal catalyst.

The present invention relates to an ethylene-based ionomer for tubes having an excellent balance of flexibility, abrasion resistance, and transparency, and a molded article thereof, which uses an ionomer characterized in that the essential structural units are structural units (A) derived from ethylene and/or an α-olefin having 3 to 20 carbon atoms, and structural units (B) derived from a monomer having a carboxyl group and/or a dicarboxylic anhydride group, and optionally also contain a structural unit (C) which is a compound having one or more carbon-carbon double bonds in its molecular structure, and which is copolymerized, preferably randomly, in a substantially linear manner to form a copolymer (P) as a base resin, and at least a portion of the carboxyl group and/or dicarboxylic anhydride group of the structural unit (B) is converted to a metal-containing carboxylate containing at least one metal ion selected from Groups 1, 2, or 12 of the periodic table.

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

The ionomer of the present invention is characterized in that it contains, as essential constituent units, a structural unit (A) derived from ethylene and/or an α-olefin having 3 to 20 carbon atoms, and a structural unit (B) derived from a monomer having a carboxyl group and/or a dicarboxylic anhydride group, and optionally also contains, as a constituent unit, a structural unit (C) which is a compound having one or more carbon-carbon double bonds in its molecular structure, and uses as a base resin a copolymer (P) in which these are copolymerized, preferably randomly copolymerized, in a substantially linear manner, and that at least a portion of the carboxyl groups and/or dicarboxylic anhydride groups of the structural unit (B) are converted to a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table.

(1) Structural unit (A)
The structural unit (A) is at least one structural unit selected from the group consisting of structural units derived from ethylene and structural units derived from an α-olefin having 3 to 20 carbon atoms.
The α-olefin according to the present invention is an α-olefin having 3 to 20 carbon atoms and represented by the structural formula CH ₂ ═CHR ¹⁸ (R ¹⁸ is a hydrocarbon group having 1 to 18 carbon atoms, which may have a linear structure or may be branched). The number of carbon atoms of the α-olefin is more preferably 3 to 12.

Specific examples of the structural unit (A) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, and 4-methyl-1-pentene, and may be ethylene. As the ethylene, ethylene derived from a petroleum raw material or a non-petroleum raw material such as a plant raw material can be used.
The structural unit (A) may be of one type or of multiple types.
Examples of combinations of the two include ethylene-propylene, ethylene-1-butene, ethylene-1-hexene, ethylene-1-octene, propylene-1-butene, propylene-1-hexene, and propylene-1-octene.
Examples of combinations of the three include ethylene-propylene-1-butene, ethylene-propylene-1-hexene, ethylene-propylene-1-octene, propylene-1-butene-hexene, and propylene-1-butene-1-octene.

In the present invention, the structural unit (A) preferably contains ethylene as an essential component and may further contain one or more α-olefins having 3 to 20 carbon atoms, if necessary.
The amount of ethylene in the structural unit (A) may be 65 to 100 mol % or 70 to 100 mol % based on the total moles of the structural unit (A).
From the standpoint of impact resistance, the structural unit (A) may be a structural unit derived from ethylene.

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

Examples of structural units derived from monomers having a carboxyl group include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, and bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid. Examples of structural units derived from monomers having a dicarboxylic acid anhydride group include unsaturated dicarboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, tetracyclo[6.2.1.1 ^3,6 . ^{0 2,7} ]dodec-9-ene-4,5-dicarboxylic anhydride, and 2,7-octadien-1-ylsuccinic anhydride. Specific compounds include acrylic acid, methacrylic acid, 5-norbornene-2,3-dicarboxylic anhydride, and in particular acrylic acid.
Furthermore, the structural unit derived from a monomer having a carboxyl group and/or a dicarboxylic anhydride group may be of one type or of multiple types.

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

(3) Other structural units (C)
The copolymer (P) according to the present invention may contain a structural unit (C) other than the structural units represented by the structural unit (A) and the structural unit (B). Any monomer that gives the structural unit (C) can be used as long as it is not the same as the monomer that gives the structural unit (A) and the structural unit (B). The arbitrary monomer that gives the structural unit (C) is not limited as long as it is a compound having one or more carbon-carbon double bonds in the molecular structure, and examples thereof include acyclic monomers represented by general formula (1) and cyclic monomers represented by general formula (2).
Compared with a binary copolymer consisting of only the structural unit (A) and the structural unit (B), a ternary or higher multi-component copolymer containing the structural unit (C) component can be used as the base resin of the ionomer to obtain an ionomer having a lower elastic modulus and higher transparency. By selecting any monomer that gives the structural unit (C), the physical properties of the ionomer resin can be controlled more precisely, so the copolymer (P) according to the present invention is preferably one that contains the structural unit (C) as a constituent unit. The structural unit (C) may be based on one type of monomer, or may be a combination of two or more types of monomers.

［一般式（１）中、Ｔ^１～Ｔ^３はそれぞれ独立して、水素原子、炭素数１～２０の炭化水素基、水酸基で置換された炭素数１～２０の炭化水素基、炭素数１～２０のアルコキシ基で置換された炭素数２～２０の炭化水素基、炭素数２～２０のエステル基で置換された炭素数３～２０の炭化水素基、ハロゲン原子で置換された炭素数１～２０の炭化水素基、炭素数１～２０のアルコキシ基、炭素数６～２０のアリール基、炭素数２～２０のエステル基、炭素数炭素数３～２０のシリル基、ハロゲン原子、又は、シアノ基からなる群より選択される置換基であり、
Ｔ^４は、水酸基で置換された炭素数１～２０の炭化水素基、炭素数１～２０のアルコキシ基で置換された炭素数２～２０の炭化水素基、炭素数２～２０のエステル基で置換された炭素数３～２０の炭化水素基、ハロゲン原子で置換された炭素数１～２０の炭化水素基、炭素数１～２０のアルコキシ基、炭素数６～２０のアリール基、炭素数２～２０のエステル基、炭素数炭素数３～２０のシリル基、ハロゲン原子、又は、シアノ基からなる群より選択される置換基である。] ・Acyclic monomers

[In general formula (1), T ¹ to T ³ each independently represent a substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an ester group having 2 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, a halogen atom, or a cyano group;
^T4 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.

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

The carbon skeleton of the hydrocarbon group, substituted alkoxy group, substituted ester group, alkoxy group, aryl group, ester group and silyl group for T ¹ to T ⁴ may have a branch, a ring and/or an unsaturated bond.
The carbon number of the hydrocarbon group for T ¹ to T ⁴ may be 1 or more as long as the lower limit is 1, and may be 20 or less as the upper limit, or may be 10 or less.
The lower limit of the number of carbon atoms in the substituted alkoxy group for T ¹ to T ⁴ may be 1 or more, and the upper limit may be 20 or less, or may be 10 or less.
The lower limit of the number of carbon atoms in the substituted ester group for T ¹ to T ⁴ may be 2 or more, and the upper limit may be 20 or less, or may be 10 or less.
The lower limit of the number of carbon atoms in the alkoxy group for T ¹ to T ⁴ may be 1 or more, and the upper limit may be 20 or less, or may be 10 or less.
The lower limit of the number of carbon atoms in the aryl group for T ¹ to T ⁴ may be 6 or more, and the upper limit may be 20 or less, or may be 11 or less.
The lower limit of the number of carbon atoms in the ester group for T ¹ to T ⁴ may be 2 or more, and the upper limit may be 20 or less, or may be 10 or less.
The number of carbon atoms in the silyl group for ^T1 to ^T4 may be 3 or more as the lower limit, and 18 or less as the upper limit, or may be 12 or less. Examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triisopropylsilyl group, a dimethylphenylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group.

In the ionomer of the present invention, from the viewpoint of ease of production, T ¹ and T ² may be hydrogen atoms, T ³ may be a hydrogen atom or a methyl group, or all of T ¹ to T ³ may be hydrogen atoms.
From the standpoint of impact resistance, ^T4 may be an ester group having 2 to 20 carbon atoms.

Specific examples of the non-cyclic monomer include those in which T ⁴ is an ester group having 2 to 20 carbon atoms, including (meth)acrylic esters.
When ^T4 is an ester group having 2 to 20 carbon atoms, examples of the acyclic monomer include compounds represented by the structural formula: CH ₂ ═C(R ²¹ )CO ₂ (R ²² ). Here, R ²¹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, which may have a branch, a ring, and/or an unsaturated bond. R ²² is a hydrocarbon group having 1 to 20 carbon atoms, which may have a branch, a ring, and/or an unsaturated bond. Furthermore, R ²² may contain a heteroatom at any position.
Examples of compounds represented by the structural formula CH ₂ ═C(R ²¹ )CO ₂ (R ²² ) include compounds in which R ²¹ is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, as well as acrylic esters in which R ²¹ is a hydrogen atom and methacrylic esters in which R ²¹ is a methyl group.
Specific examples of the compound represented by the structural formula CH ₂ ═C(R ²¹ )CO ₂ (R ²² ) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, and benzyl (meth)acrylate.
Specific compounds include methyl acrylate, ethyl acrylate, n-butyl acrylate (nBA), isobutyl acrylate (iBA), t-butyl acrylate (tBA), and 2-ethylhexyl acrylate, and in particular may be n-butyl acrylate (nBA), isobutyl acrylate (iBA), and t-butyl acrylate (tBA).
The non-cyclic monomer may be of one type or of multiple types.

［一般式（２）中、Ｒ^１～Ｒ^１２は、それぞれ同一でも異なっていてもよく、水素原子、ハロゲン原子、及び、炭素数１～２０の炭化水素基からなる群より選ばれるものであり、Ｒ^９及びＲ^１０、並びに、Ｒ^１１及びＲ^１２は、各々一体化して２価の有機基を形成してもよく、Ｒ^９又はＲ^１０と、Ｒ^１１又はＲ^１２とは、互いに環を形成していてもよい。
また、ｎは、０又は正の整数を示し、ｎが２以上の場合には、Ｒ^５～Ｒ^８は、それぞれの繰り返し単位の中で、それぞれ同一でも異なっていてもよい。］ Cyclic monomers

[In general formula (2), R ¹ to R ¹² may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 20 carbon atoms; R ⁹ and R ¹⁰ , and R ¹¹ and R ¹² may each be bonded together to form a divalent organic group; and R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring together.
Furthermore, n represents 0 or a positive integer, and when n is 2 or more, R ⁵ to R ⁸ may be the same or different in each repeating unit.]

Examples of the cyclic monomer include norbornene-based olefins, such as norbornene, vinylnorbornene, ethylidenenorbornene, norbornadiene, tetracyclododecene, tricyclo[4.3.0.1 ^2,5 ]dec-3-ene, and other compounds having a cyclic olefin skeleton, and may also be 2-norbornene (NB) and tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene.

(4) Copolymer (P)
The copolymer (P) which is the base resin of the ionomer used in the present invention has a structural unit (A) derived from ethylene and/or an α-olefin having 3 to 20 carbon atoms, a carboxyl group and/or a dicarboxylic anhydride. and a structural unit (B) derived from a monomer having a group as an essential structural unit, and optionally further comprising an arbitrary structural unit (C) other than the above-mentioned (A) and (B), The term "substantially linear" refers to a copolymer that has no branches or has a branch structure that appears at a low frequency. Specifically, it refers to a state in which the phase angle δ of the copolymer is 50 degrees or more under the conditions described below.

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

Amount of structural units of ethylene and/or α-olefin having 3 to 20 carbon atoms (A):
The structural unit amount of the structural unit (A) according to the present invention is selected from the following: the lower limit is 60.0 mol% or more, preferably 70.0 mol% or more, more preferably 80.0 mol% or more, even more preferably 85.0 mol% or more, still more preferably 90.0 mol% or more, and particularly preferably 92.0 mol% or more, and the upper limit is 97.9 mol% or less, preferably 97.5 mol% or less, more preferably 97.0 mol% or less, and even more preferably 96.5 mol% or less.
If the amount of structural units derived from ethylene and/or an α-olefin (A) having 3 to 20 carbon atoms is less than 60.0 mol %, the toughness of the copolymer will be inferior, and if it is more than 97.9 mol %, the crystallinity of the copolymer will be high, and the transparency may be deteriorated.

Amount of structural units of monomer (B) having a carboxyl group and/or a dicarboxylic anhydride group:
The amount of the structural unit (B) according to the present invention is selected from the following: the lower limit is 2.0 mol% or more, preferably 2.9 mol% or more, and more preferably 3.5 mol% or more, and the upper limit is 20.0 mol% or less, preferably 15.0 mol% or less, more preferably 10.0 mol% or less, even more preferably 8.0 mol% or less, particularly preferably 6.0 mol% or less, and most preferably 5.6 mol% or less.
If the amount of structural units derived from the monomer (B) having a carboxyl group and/or a dicarboxylic anhydride group is less than 2.0 mol %, the copolymer may not have sufficient adhesion to a different material having high polarity, whereas if the amount of structural units derived from the monomer (B) having a carboxyl group and/or a dicarboxylic anhydride group is more than 20.0 mol %, the copolymer may not have sufficient mechanical properties.
Furthermore, the monomer having a carboxyl group and/or a dicarboxylic anhydride group to be used may be used alone or in combination of two or more kinds.

Amount of structural units of optional monomer (C):
When the structural unit (C) is introduced into the copolymer (P), the structural unit amount of the structural unit (C) according to the present invention is selected from the following: the lower limit is 0.001 mol% or more, preferably 0.010 mol% or more, more preferably 0.020 mol% or more, even more preferably 0.1 mol% or more, still more preferably 2.0 mol% or more, and particularly preferably 2.3 mol% or more, and the upper limit is 20.0 mol% or less, preferably 15.0 mol% or less, more preferably 10.0 mol% or less, even more preferably 5.0 mol% or less, and particularly preferably 2.9 mol% or less.
If the amount of the structural unit derived from any monomer (C) is less than 0.001 mol %, the flexibility of the copolymer is insufficient, whereas if it exceeds 20.0 mol %, the copolymer may not have sufficient mechanical properties.
Furthermore, any of the monomers used may be used alone or in combination of two or more kinds.

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

Method for measuring the amount of structural units derived from monomers having a carboxy group and/or a dicarboxylic anhydride group and non-cyclic monomers in a copolymer, and the number of branches:
The amount of structural units derived from the monomer having a carboxy group and/or a dicarboxylic anhydride group and the noncyclic monomer in the copolymer of the present invention, and the number of branches per 1,000 carbons can be determined using ¹³ C-NMR spectrum. ¹³ C-NMR is measured by the following method.

200 to 300 mg of a sample is placed in an NMR sample tube with an inner diameter of 10 mm together with 2.4 ml of a mixed solvent of o-dichlorobenzene (C ₆ H ₄ Cl ₂ ) and deuterated bromide benzene (C ₆ D ₅ Br) (C ₆ H ₄ Cl ₂ /C ₆ D ₅ Br = 2/1 (volume ratio)) and hexamethyldisiloxane, a chemical shift standard substance, and the tube is purged with nitrogen, sealed, and heated to dissolve to prepare a homogeneous solution to be used as the NMR measurement sample.
The NMR measurement is carried out at 120° C. using an AV400M NMR apparatus manufactured by Bruker Japan Ltd. equipped with a 10 mmφ cryoprobe.
¹³ C-NMR is measured by the inverse gate decoupling method at a sample temperature of 120° C., a pulse angle of 90°, a pulse interval of 51.5 seconds, and an accumulation number of 512 or more.
The chemical shifts are set to 1.98 ppm for the ¹³ C signal of hexamethyldisiloxane, and the chemical shifts of other ¹³ C signals are based on this.
In the obtained ^13C -NMR, signals specific to the monomers or branches of the multicomponent copolymer are identified, and the intensities are compared to analyze the amount of structural units of each monomer in the multicomponent copolymer and the number of branches. The positions of the signals specific to the monomers or branches can be referred to publicly known materials, or can be independently identified depending on the sample. Such an analysis method is commonly known to those skilled in the art.

Weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn):
The weight average molecular weight (Mw) of the copolymer according to the present invention has a lower limit of usually 1,000 or more, preferably 6,000 or more, and more preferably 10,000 or more, and an upper limit of usually 2,000,000 or less, preferably 1,500,000 or less, further preferably 1,000,000 or less, particularly preferably 800,000 or less, and most preferably 100,000 or less.
If the Mw is less than 1,000, the physical properties such as mechanical strength and impact resistance of the copolymer will be insufficient, whereas if the Mw exceeds 2,000,000, the melt viscosity of the copolymer will be so high that molding of the copolymer may become difficult.

The ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the copolymer according to the present invention is usually in the range of 1.5 to 4.0, preferably 1.6 to 3.5, and more preferably 1.9 to 2.3. If Mw/Mn is less than 1.5, various processability including molding of the copolymer may be insufficient, and if it exceeds 4.0, the mechanical properties of the copolymer may be poor.
In this specification, (Mw/Mn) may be expressed as a molecular weight distribution parameter.

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

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

Melting point (Tm, ° C.):
The melting point of the copolymer according to the present invention is indicated by the maximum peak temperature of the endothermic curve measured by a differential scanning calorimeter (DSC). When multiple peaks are shown in the endothermic curve obtained by DSC measurement, with heat flow (mW) on the vertical axis and temperature (°C) on the horizontal axis, the maximum peak temperature refers to the temperature of the peak with the maximum height from the baseline among the multiple peaks, and when there is only one peak, it refers to the temperature of that peak.
The melting point is preferably 50° C. to 140° C., more preferably 60° C. to 138° C., and most preferably 70° C. to 135° C. If it is lower than this range, the heat resistance is insufficient, and if it is higher than this range, the adhesiveness may be poor.
In the present invention, the melting point can be determined from an absorption curve obtained by, for example, using a DSC (DSC7020) manufactured by SII Nanotechnology Inc., packing about 5.0 mg of a sample into an aluminum pan, heating the sample to 200° C. at 10° C./min, holding the sample isothermally at 200° C. for 5 minutes, lowering the sample to 20° C. at 10° C./min, holding the sample isothermally at 20° C. for 5 minutes, and then heating the sample again to 200° C. at 10° C./min.

Crystallinity (%):
In the copolymer of the present invention, the crystallinity observed by differential scanning calorimetry (DSC) is not particularly limited, but is preferably more than 0% and not more than 50%, more preferably more than 0% and not more than 40%, particularly preferably more than 5% and not more than 40%, and most preferably 17% or more and not more than 38%.
If the crystallinity is 0%, the toughness of the copolymer is insufficient, and if the crystallinity is higher than 30%, the transparency of the copolymer may be poor. Note that the crystallinity is an index of transparency, and it can be determined that the lower the crystallinity of a copolymer, the more excellent its transparency.
In the present invention, the crystallinity can be determined, for example, by determining the heat of fusion (ΔH) from the area of the melting endothermic peak obtained by DSC measurement using the same procedure as in the measurement of the melting point, and dividing the heat of fusion by the heat of fusion of 293 J/g of perfect crystals of high density polyethylene (HDPE).

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

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

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

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

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

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

Absolute value of complex elastic modulus G ^* = Phase angle δ at 0.1 MPa:
In the copolymer of the present invention, the phase angle δ at the absolute value of the complex elastic modulus G ^* = 0.1 MPa measured using a rotational rheometer may have a lower limit of 50 degrees or more, 51 degrees or more, 54 degrees or more, 56 degrees or more, or 58 degrees or more, and an upper limit of 75 degrees or less, or 70 degrees or less.
More specifically, when the phase angle δ (G ^* = 0.1 MPa) at the absolute value of the complex modulus G ^* = 0.1 MPa measured using a rotational rheometer is 50 degrees or more, this indicates that the molecular structure of the copolymer is a linear structure that does not contain any long chain branches or a substantially linear structure that contains a small amount of long chain branches that does not affect the mechanical strength.
Furthermore, if the phase angle δ (G ^* = 0.1 MPa) at the absolute value of the complex modulus G ^* = 0.1 MPa measured using a rotational rheometer is lower than 50 degrees, the molecular structure of the copolymer will contain excessive long chain branches and will have poor mechanical strength.
The phase angle δ at the absolute value G ^* =0.1 MPa of the complex modulus measured by a rotational rheometer is affected by both the molecular weight distribution and the long chain branching. However, it is an index of the amount of long chain branching only for copolymers with Mw/Mn≦4, more preferably Mw/Mn≦3, and the more long chain branches contained in the molecular structure, the smaller the δ(G ^* =0.1 MPa) value becomes. Note that if the Mw/Mn of a copolymer is 1.5 or more, the δ(G ^* =0.1 MPa) value will not exceed 75 degrees even if the molecular structure does not contain long chain branches.

The method for measuring the complex elastic modulus is as follows.
The sample is placed in a 1.0 mm thick mold for hot pressing, preheated for 5 minutes in a hot press machine with a surface temperature of 180 ° C., and then repeatedly pressurized and depressurized to remove residual gas in the molten resin, and then pressurized at 4.9 MPa and held for 5 minutes. The sample is then transferred to a press machine with a surface temperature of 25 ° C., and cooled by holding at a pressure of 4.9 MPa for 3 minutes to create a press plate made of a sample with a thickness of about 1.0 mm. The press plate made of the sample is processed into a circular shape with a diameter of 25 mm to form a sample, and a Rheometrics ARES type rotational rheometer is used as a measuring device for dynamic viscoelastic properties to measure dynamic viscoelasticity under the following conditions in a nitrogen atmosphere.
Plate: φ25mm parallel plate Temperature: 160℃
Distortion: 10%
Measurement angular frequency range: 1.0×10 ⁻² to 1.0×10 ² rad/s
Measurement interval: 5 points/decade
The phase angle δ is plotted against the common logarithm logG ^* of the absolute value G ^* (Pa) of the complex elastic modulus, and the value of δ (degrees) at the point corresponding to logG ^* = 5.0 is taken as δ (G ^* = 0.1 MPa). When there is no point corresponding to logG ^* = 5.0 among the measurement points, the δ value at logG ^* = 5.0 is obtained by linear interpolation using two points around logG ^* = 5.0. In addition, when all the measurement points are logG ^* < 5, the δ value at logG ^* = 5.0 is obtained by extrapolating the δ value using a quadratic curve using the values of the three points from the largest logG ^* value.

Production of the Copolymer The copolymer according to the present invention is preferably produced in the presence of a transition metal catalyst, in order to make the molecular structure of the copolymer linear.
Polymerization Catalyst The type of polymerization catalyst used in the production of the copolymer of the present invention is not particularly limited as long as it is capable of copolymerizing the structural unit (A), the structural unit (B), and the optional structural unit (C). For example, a Group 5 to 11 transition metal compound having a chelating ligand can be used.
Specific examples of preferred transition metals include vanadium atoms, niobium atoms, tantalum atoms, chromium atoms, molybdenum atoms, tungsten atoms, manganese atoms, iron atoms, platinum atoms, ruthenium atoms, cobalt atoms, rhodium atoms, nickel atoms, palladium atoms, and copper atoms. Among these, preferred are transition metals in Groups 8 to 11, more preferred are transition metals in Group 10, and particularly preferred are nickel (Ni) and palladium (Pd). These metals may be used alone or in combination.
Chelating ligands have at least two atoms selected from the group consisting of P, N, O, and S, and include ligands that are bidentate or multidentate, and are electronically neutral or anionic. Exemplary chelating ligand structures are given in the review by Brookhart et al. (Chem. Rev., 2000, 100, 1169).
The chelating ligand preferably includes a bidentate anionic P, O ligand. Examples of the bidentate anionic P, O ligand include phosphorus sulfonic acid, phosphorus carboxylic acid, phosphorus phenol, and phosphorus enolate. Other examples of the chelating ligand include a bidentate anionic N, O ligand. Examples of the bidentate anionic N, O ligand include salicylaldiminate and pyridine carboxylic acid. Other examples of the chelating ligand include a diimine ligand, a diphenoxide ligand, and a diamide ligand.

［構造式（ａ）、及び構造式（ｂ）において、
Ｍは、元素の周期表の第５～１１族のいずれかに属する遷移金属、即ち前述したような種々の遷移金属を表す。
Ｘ^１は、酸素、硫黄、－ＳＯ_３－、又は－ＣＯ_２－を表す。
Ｙ^１は、炭素又はケイ素を表す。
ｎは、０又は１の整数を表す。
Ｅ^１は、リン、砒素又はアンチモンを表す。
Ｒ^５３及びＲ^５４は、それぞれ独立に、水素又は炭素数１ないし３０のヘテロ原子を含有してもよい炭化水素基を表す。
Ｒ^５５は、それぞれ独立に、水素、ハロゲン、又は炭素数１ないし３０のヘテロ原子を含有してもよい炭化水素基を表す。
Ｒ^５６及びＲ^５７は、それぞれ独立に、水素、ハロゲン、炭素数１ないし３０のヘテロ原子を含有してもよい炭化水素基、ＯＲ^５２、ＣＯ_２Ｒ^５２、ＣＯ_２Ｍ’、Ｃ（Ｏ）Ｎ（Ｒ^５１）_２、Ｃ（Ｏ）Ｒ^５２、ＳＲ^５２、ＳＯ_２Ｒ^５２、ＳＯＲ^５２、ＯＳＯ_２Ｒ^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、ＮＯ_２、ＳＯ_３Ｍ’、ＰＯ_３Ｍ’_２、Ｐ（Ｏ）（ＯＲ^５２）_２Ｍ’又はエポキシ含有基を表す。
Ｒ^５１は、水素又は炭素数１ないし２０の炭化水素基を表す。
Ｒ^５２は、炭素数１ないし２０の炭化水素基を表す。
Ｍ’は、アルカリ金属、アルカリ土類金属、アンモニウム、４級アンモニウム又はフォスフォニウムを表し、ｘは、０から３までの整数、ｙは、０から２までの整数を表す。
なお、Ｒ^５６とＲ^５７が互いに連結し、脂環式環、芳香族環、又は酸素、窒素、若しくは硫黄から選ばれるヘテロ原子を含有する複素環を形成してもよい。この時、環員数は５～８であり、該環上に置換基を有していても、有していなくてもよい。
Ｌ^１は、Ｍに配位したリガンドを表す。
また、Ｒ^５３とＬ^１が互いに結合して環を形成してもよい。］ The structure of the metal complex obtained from the chelating ligand is represented by the following structural formula (a) or (b) in which an arylphosphine compound, an arylarsine compound or an arylantimony compound which may have a substituent is coordinated.

[In the structural formula (a) and the 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, -SO ₃ - or -CO ₂ -.
^Y1 represents carbon or silicon.
n represents an integer of 0 or 1.
^E1 represents phosphorus, arsenic or antimony.
R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom.
Each R ⁵⁵ independently represents hydrogen, a halogen, or a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom.
R ⁵⁶ and R ⁵⁷ are each independently hydrogen, halogen, a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom, OR ⁵² , CO ₂ R ⁵² , CO ₂ M', C(O)N(R ⁵¹ ) ₂ , C(O)R ⁵² , SR ⁵² , SO ₂ R ⁵² , SOR ⁵² , OSO ₂ R 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 , NO ₂ , SO ₃ M', PO ₃ M' ₂ , P(O)(OR ⁵² ) ₂ M′ or an epoxy-containing group.
R ⁵¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
R ⁵² represents a hydrocarbon group having 1 to 20 carbon atoms.
M′ represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium; x represents an integer of 0 to 3; and y represents an integer of 0 to 2.
R ⁵⁶ and R ⁵⁷ may be bonded to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, or sulfur, in which case the ring has 5 to 8 members and may or may not have a substituent on the ring.
^L1 represents a ligand coordinated to M.
In addition, R ⁵³ and L ¹ may be bonded to each other to form a ring.

［構造式（ｃ）において、
Ｍは、元素の周期表の第５～１１族のいずれかに属する遷移金属、即ち前述したような種々の遷移金属を表す。
Ｘ^１は、酸素、硫黄、－ＳＯ_３－、又は－ＣＯ_２－を表す。
Ｙ^１は、炭素又はケイ素を表す。
ｎは、０又は１の整数を表す。
Ｅ^１は、リン、砒素又はアンチモンを表す。
Ｒ^５３及びＲ^５４は、それぞれ独立に、水素又は炭素数１ないし３０のヘテロ原子を含有してもよい炭化水素基を表す。
Ｒ^５５は、それぞれ独立に、水素、ハロゲン、又は炭素数１ないし３０のヘテロ原子を含有してもよい炭化水素基を表す。
Ｒ^５８、Ｒ^５９、Ｒ^６０及びＲ^６１は、それぞれ独立に、水素、ハロゲン、炭素数１ないし３０のヘテロ原子を含有してもよい炭化水素基、ＯＲ^５２、ＣＯ_２Ｒ^５２、ＣＯ_２Ｍ’、Ｃ（Ｏ）Ｎ（Ｒ^５１）_２、Ｃ（Ｏ）Ｒ^５２、ＳＲ^５２、ＳＯ_２Ｒ^５２、ＳＯＲ^５２、ＯＳＯ_２Ｒ^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、ＮＯ_２、ＳＯ_３Ｍ’、ＰＯ_３Ｍ’_２、Ｐ（Ｏ）（ＯＲ^５２）_２Ｍ’又はエポキシ含有基を表す。
Ｒ^５１は、水素又は炭素数１ないし２０の炭化水素基を表す。
Ｒ^５２は、炭素数１ないし２０の炭化水素基を表す。
Ｍ’は、アルカリ金属、アルカリ土類金属、アンモニウム、４級アンモニウム又はフォスフォニウムを表し、ｘは、０から３までの整数、ｙは、０から２までの整数を表す。
なお、Ｒ^５８～Ｒ^６１から適宜選択された複数の基が互いに連結し、脂環式環、芳香族環、又は酸素、窒素、若しくは硫黄から選ばれるヘテロ原子を含有する複素環を形成してもよい。このとき、環員数は５～８であり、該環上に置換基を有していても、有していなくてもよい。
Ｌ^１は、Ｍに配位したリガンドを表す。
また、Ｒ^５３とＬ^１が互いに結合して環を形成してもよい。］ More preferably, the complex serving as the polymerization catalyst is a transition metal complex represented by the following structural formula (c).

[In structural formula (c),
M represents a transition metal belonging to any of Groups 5 to 11 of the periodic table of the elements, that is, various transition metals as described above.
X ¹ represents oxygen, sulfur, -SO ₃ - or -CO ₂ -.
^Y1 represents carbon or silicon.
n represents an integer of 0 or 1.
^E1 represents phosphorus, arsenic or antimony.
R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom.
Each R ⁵⁵ independently represents hydrogen, a halogen, or a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom.
R ⁵⁸ , R ⁵⁹ , R ⁶⁰ and R ⁶¹ each independently represent hydrogen, halogen, a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom, OR ⁵² , CO ₂ R ⁵² , CO ₂ M′, C(O)N(R ⁵¹ ) ₂ , C(O)R ⁵² , SR ⁵² , SO ₂ R ⁵² , SOR ⁵² , OSO ₂ R 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 , NO ₂ , SO ₃ M', PO ₃ M' ₂ , P(O)(OR ⁵² ) ₂ M' or an epoxy-containing group.
R ⁵¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
R ⁵² represents a hydrocarbon group having 1 to 20 carbon atoms.
M′ represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium; x represents an integer of 0 to 3; and y represents an integer of 0 to 2.
In addition, a plurality of groups appropriately selected from R ⁵⁸ to R ⁶¹ may be bonded to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, or sulfur, in which the number of ring members is 5 to 8, and the ring may or may not have a substituent.
^L1 represents a ligand coordinated to M.
In addition, R ⁵³ and L ¹ may be bonded to each other to form a ring.

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

・Copolymer polymerization method:
The polymerization method for the copolymer according to the present invention is not limited.
Examples of the polymerization method include slurry polymerization in which at least a portion of the produced polymer becomes a slurry in a medium, bulk polymerization in which the liquefied monomer itself is used as the medium, gas phase polymerization in vaporized monomer, and high pressure ionic polymerization in which at least a portion of the produced polymer is dissolved in monomer liquefied at high temperature and pressure.
The polymerization method may be any of batch polymerization, semi-batch polymerization, and continuous polymerization.
Furthermore, living polymerization may be carried out, or polymerization may be carried out while simultaneously causing chain transfer.
Furthermore, during the polymerization, a so-called chain shuttling agent (CSA) may be used in combination to carry out a chain shuttling reaction or coordinate chain transfer polymerization (CCTP).
Specific manufacturing processes and conditions are disclosed in, for example, Japanese Patent Application Laid-Open No. 2010-260913 and Japanese Patent Application Laid-Open No. 2010-202647.

Method for introducing carboxyl groups and/or dicarboxylic anhydride groups into copolymers:
The method of introducing a carboxyl group and/or a dicarboxylic anhydride group into the copolymer according to the present invention is not particularly limited. A carboxyl group and/or a dicarboxylic anhydride group can be introduced by various methods within the scope of the present invention.
Examples of methods for introducing a carboxyl group and/or a dicarboxylic anhydride group include a method of directly copolymerizing a comonomer having a carboxyl group and/or a dicarboxylic anhydride group, and a method of copolymerizing another monomer having a functional group that generates a carboxyl group, and then introducing a carboxyl group and/or a dicarboxylic anhydride group by modification.

Methods for introducing carboxyl groups and/or dicarboxylic anhydride groups by modification include, for example, when introducing carboxylic acid, a method in which an acrylic acid ester is copolymerized as a precursor and then hydrolyzed to convert it to a carboxylic acid, or a method in which t-butyl acrylate is copolymerized as a precursor and then thermally decomposed to convert it to a carboxylic acid.

As an additive for promoting the reaction during the hydrolysis or thermal decomposition, a conventionally known acid/base catalyst may be used. The acid/base catalyst is not particularly limited, but examples thereof include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, alkali metals such as sodium hydrogencarbonate and sodium carbonate, carbonates of alkaline earth metals, 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, paratoluenesulfonic acid, trifluoroacetic acid, and trifluoromethanesulfonic acid.
From the viewpoints of reaction promotion effect, cost, equipment corrosivity, etc., sodium hydroxide, potassium hydroxide, sodium carbonate, paratoluenesulfonic acid, and trifluoroacetic acid are preferred, and paratoluenesulfonic acid and trifluoroacetic acid are more preferred.

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

- Structure of the ionomer The ionomer of the present invention has a substantially linear structure like the copolymer of the present invention, and is characterized in that the phase angle δ at the absolute value of the complex modulus G ^* = 0.1 MPa measured with a rotational rheometer is 50 to 75 degrees.
When the phase angle δ (G ^* =0.1 MPa) is lower than 50 degrees, the molecular structure of the ionomer contains excessive long chain branches, resulting in poor mechanical strength. As mentioned above, if Mw/Mn≦4, the value of the phase angle δ is an index of the amount of long chain branches. If the Mw/Mn of an ionomer is 1.5 or more, the value of δ (G ^* =0.1 MPa) will not exceed 75 degrees even if the molecular structure does not contain long chain branches.
In the ionomer of the present invention, from the viewpoint of improving the 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 still more preferably 58 degrees or more. The upper limit is not particularly limited, and the closer to 75 degrees the better.

Melting point of ionomer (Tm, °C)
The melting point (Tm, °C) of the ionomer according to the present invention is preferably 50° C. to 140° C., more preferably 60° C. to 138° C., and most preferably 70° C. to 135° C. If it is lower than this range, the heat resistance is insufficient, and if it is higher than this range, the adhesiveness may be poor.
Of the ionomers related to the present invention, ionomers based on a binary copolymer consisting of only the structural unit (A) and the structural unit (B) preferably have a melting point of 90° C. or higher, more preferably 95° C. or higher, and even more preferably 100° C. or higher. Ionomers based on a ternary or higher multicomponent copolymer preferably have a melting point of less than 100° C., more preferably less than 95° C., and even more preferably less than 90° C.

Crystallinity (%):
In the ionomer of the present invention, the crystallinity observed by differential scanning calorimetry (DSC) is not particularly limited, but is preferably more than 0% and not more than 30%, more preferably more than 0% and not more than 25%, particularly preferably more than 5% and not more than 25%, and most preferably 7% or more and not more than 24%.
If the crystallinity is 0%, the toughness of the ionomer is insufficient, and if the crystallinity is higher than 30%, the transparency of the copolymer may be poor. Note that the crystallinity is an index of transparency, and it can be determined that the lower the crystallinity of the ionomer, the more excellent its transparency.

Metal ions The metal ions contained in the ionomer of the present invention are not particularly limited and may include metal ions used in conventionally known ionomers. The metal ions are preferably metal ions of Group 1, 2, or 12 of the periodic table, more preferably at least one selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ and Zn ²⁺ . Particularly preferred are at least one selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ and Zn ²⁺ , and even more preferably at least one selected from the group consisting of Na ⁺ and Zn ²⁺ .
Two or more of these metal ions may be mixed as necessary.

・Neutralization degree (mol%)
The content of the metal ions is preferably an amount that neutralizes at least a part or all of the carboxyl groups and/or dicarboxylic anhydride groups in the copolymer as the base polymer, and the preferred degree of neutralization (average The degree of neutralization is preferably 5 to 95 mol %, more preferably 10 to 90 mol %, further preferably 20 to 80 mol %, and most preferably 10 to 40 mol %.
The degree of neutralization is determined from the ratio of the total molar amount of the valence x molar amount of the metal ion to the total molar amount of the carboxyl groups that may be contained in the carboxyl groups and/or dicarboxylic anhydride groups in the copolymer. It is possible.
When a dicarboxylic anhydride group forms a carboxylate, it opens its ring to form a dicarboxylic acid. Therefore, the total molar amount of the carboxyl groups is calculated assuming that there are 2 mol of carboxyl groups per 1 mol of dicarboxylic anhydride groups. In addition, for example, 1 mol of a divalent metal ion such as Zn ²⁺ can form a salt with 2 mol of carboxyl groups, and the total molar amount of molecules with a degree of neutralization is calculated by 2×mol amount.
When the degree of neutralization is high, the ionomer has a high tensile strength and a high tensile stress at break, and a small tensile strain at break, but the ionomer tends to have a small melt flow rate (MFR). Ionomers with appropriate MFR can be obtained, but the tensile modulus and tensile stress at break tend to be low, and the tensile strain at break tends to be high.
The degree of neutralization can be calculated from the amount of carboxyl groups and/or dicarboxylic anhydride groups and the molar ratio of the added metal ions.

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

When an ionomer is produced after introducing a carboxyl group and/or a dicarboxylic anhydride group into a polymer, the production method is, for example, as follows. That is, a metal ion source is produced by kneading a metal salt with a substance that captures metal ions, such as an ethylene/methacrylic acid (MAA) copolymer, optionally with heating, and then the metal ion source is added to the ionomer base resin in an amount that results in the desired degree of neutralization, and the ionomer can be obtained by kneading.

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

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

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

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

The reaction time varies depending on the heating temperature and the reactivity of the ester group portion, 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.

In the above steps, the reaction atmosphere is not particularly limited, but it is generally preferable to carry out the steps under a flow of inert gas. Examples of inert gases that can be used include nitrogen, argon, and carbon dioxide atmospheres. Small amounts of oxygen and air may be present.

There are no particular limitations on the reactor used in the above steps, but any method that can substantially uniformly stir the copolymer may be used. A glass vessel or autoclave (AC) equipped with a stirrer may be used, or any conventionally known kneading machine may be used, such as a Brabender plastograph, a single-screw or twin-screw extruder, a high-intensity screw-type kneader, a Banbury mixer, a kneader, or a roll.

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

・MFR:
In the ionomer of the present invention, the melt flow rate (MFR) at a temperature of 190° C. and a load of 2.16 kg is 0.1 to 15 g/10 min, and preferably 0.5 to 10 g/10 min.
When the MFR is within this range, drawdown is prevented and the resin pressure during extrusion molding is appropriately suppressed, resulting in better moldability and making it easier to obtain a perfectly round tube.

Tensile modulus:
In the ionomer of the present invention, the tensile modulus is 20 to 350 MPa, and preferably 20 to 300 MPa.
When the tensile modulus is within this range, the ionomer can be produced without difficulty in designing in terms of the modulus of elasticity, and the rigidity of the tube does not become too high, further improving the degree of freedom in handling.

・Wear loss in wear test:
In the ionomer of the present invention, the amount of wear in an abrasion test is less than 10 mg, and preferably 9 mg or less.
If the amount of wear in the wear test is less than 10 mg, breakage is unlikely to occur even when repeated rubbing and compression forces are applied, and a good tube can be obtained from the standpoint of avoiding the generation of wear debris due to repeated rubbing, etc., which would pollute the usage environment, or the creation of holes in the tube.

Hayes:
In the ionomer of the present invention, the haze is 0.1 to 30%, preferably 0.1 to 20%.
If the haze of the ionomer is 30% or less, the transparency is not reduced and the ionomer can be used without being restricted in the environment or application, which is preferable. On the other hand, an ionomer having a haze of less than 0.1% is difficult to produce, and an ionomer having a lower limit of 0.1% can be produced without using special conditions, so it is sufficiently practical.

2. Resin Composition The ionomer of the present invention may be used alone or as a resin composition containing other resin components. Hereinafter, in the present invention, when the term "resin composition containing an ionomer" is used for a molded product, it includes the ionomer alone or a composition containing other resin components or additives. The other resin components that can be blended in the ionomer resin composition of the present invention are not particularly limited as long as they are compatible with the ionomer and do not impair the effects of the present invention. For example, high density polyethylene, medium density polyethylene, low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, other ionomers, etc. can be mentioned. Two or more types of materials can also be used in combination. The blending amount of these resin components is not particularly limited as long as it is within a range that does not impair the effects of the present invention.
The resin composition of the present invention is characterized by containing the specific ionomer according to the present application, and the content thereof can be selected preferably from the range of 1 to 100% by weight in combination with the intended use and other conditions.
The content of the ionomer of the present invention in the resin composition is preferably 10% by weight or more, more preferably 30% by weight or more, even more preferably 50% by weight or more, and particularly preferably 60% by weight or more. The upper limit can be arbitrarily selected from 100% by weight or less to 90% by weight or less, 70% by weight or less, 50% by weight or less, or 40% by weight or less.
The higher the content of the specific ionomer according to the present invention in the resin composition, the more fully it becomes possible to exhibit the excellent physical properties and the like that are achieved by using the ionomer, but the blending amount can be selected as desired from the standpoint of other processability, required physical properties, cost, and the like.

Additives The ionomer according to the present invention may contain additives such as conventionally known antioxidants, ultraviolet absorbers, lubricants, antistatic agents, antiblocking agents, colorants, pigments, crosslinking agents, foaming agents, nucleating agents, flame retardants, conductive materials, and fillers, as long as the additives do not deviate from the spirit and scope of the present invention.

The ionomer used in the present invention may be mixed with various additives and polymer components to be added or blended as necessary using a Henschel mixer, super mixer, tumbler mixer, etc., and then heated and kneaded in a single-screw or twin-screw extruder, kneader, etc., and pelletized.

3. Molded product The ionomer according to the present invention can be effectively used for molded products, particularly tubes, because it gives a cured product with an excellent balance of flexibility, abrasion resistance, and transparency. Here, the term "tube" refers to a long and thin hollow body with at least one end open, including cylinders, hoses, pipes, and the like. The length and thickness (caliber) of the tube are not particularly limited within the range generally recognized as tubular, but the length is usually greater than the thickness. The shape of the tube cross section is not particularly limited, but is preferably circular because it is not biased in the pressure applied and has excellent strength. In addition, the tube does not need to be of a constant thickness, and may have a mechanism such as a bellows structure depending on the application, but it is preferable that the thickness is constant within the same tube in order to ensure uniform pressure when transporting a fluid.

The molded article containing the ionomer of the present invention is preferably a hose. The cylindrical molded article containing the ionomer of the present invention can be used as a hose as it is, but it may also be made into a composite hose by providing it with layers of at least one different material. Hoses currently used to transport fluids are generally composite hoses in which resin and rubber form multiple layers. One aspect of the present invention is a composite hose in which the molded article containing the ionomer forms one of the layers, particularly the resin layer.

Now, we will explain the structure of the hose. Most of the hoses currently in common use include an inner layer that contains a resin layer and a rubber layer, an outer layer to increase durability, and sometimes a reinforcing layer to maintain strength. Normally, a hose is constructed by laminating a resin layer, a rubber layer, a reinforcing layer, and an outer layer in that order from the inside of the hose. An adhesive layer may be provided between each layer to increase the adhesion between the layers. In applications where transparency is important, it is preferable that these layers also have transparency.

Materials used for the rubber layer include, for example, epoxidized rubber, natural rubber, butadiene rubber, polyisoprene rubber, butyl rubber, chlorinated polyethylene, chlorinated butyl rubber, brominated butyl rubber, chloroprene rubber, acrylic rubber, chlorosulfonated polyethylene, styrene-butadiene copolymer rubber (SBR), ethylene-propylene copolymer rubber, styrene-isoprene copolymer rubber, acrylonitrile-butadiene rubber (NBR) or hydrogenated products thereof, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer rubber, and other copolymer rubbers. These rubbers may be blends of multiple types, and may contain commonly used additives.

There are no particular restrictions on the material used for the outer layer, but a rubber layer is preferred. In addition, since this layer comes into contact with the outside, it is also desirable for the material to have excellent impact resistance, moisture resistance, heat resistance, weather resistance, etc., such as silicone or fluororesin, depending on the application.

A reinforcing layer may be used to maintain strength and further increase pressure resistance. The reinforcing layer may be a film-like resin layer, or may have a mesh-like structure made of fiber or metal reinforcing threads. From the viewpoint of prioritizing the transparency of the composite hose as a whole, a mesh-like structure with a roughness that does not affect transparency is preferable. Examples of materials for the reinforcing threads include polyamide fiber, polyester fiber, aramid fiber, carbon fiber, brass-plated wire, and zinc-plated wire.

The thickness of the tubular molded article containing the ionomer of the present invention can be set appropriately depending on the application, and is not particularly limited. Note that "thickness" here can mean both the inner diameter and the outer diameter, and which one is meant can be used depending on the situation. In the case of a hose, since it is used for household faucets and other items with a fixed diameter, the thickness can be similar to that of a typical hose available on the market. The thickness of the tubular molded article containing the ionomer of the present invention can be set appropriately depending on the application. It is usually 0.3 to 30 mm, preferably 0.5 to 25 mm, and more preferably 0.7 to 20 mm. In the case of a composite hose, it can also be set appropriately depending on the thickness of the other layers.

The tubular molded body containing the ionomer according to the present invention can be manufactured by a method known to those skilled in the art. If it is to be used as a short hose, it can be obtained by rolling a sheet whose length and width are adjusted to the desired length and diameter, and fusing the ends. Injection molding, extrusion molding, or hollow molding are used as a method for manufacturing a hose of any length. Each molding method can be molded according to a conventional method. In the extrusion molding method, a hose is manufactured by extruding molten resin into a circular mold while cooling it. In the extrusion molding method, a single-screw or multi-screw extruder can be used, and a composite hose can be molded by multi-layer extrusion using multiple extruders. The extrusion molding method is suitable for manufacturing a composite hose as a straight tube with a simple shape. The hollow molding method is a method in which a hollow body called a parison is formed and then molded by air pressure from inside, and is convenient for manufacturing tubes with complex structures that are difficult to manufacture by the extrusion molding method, as well as manufacturing tubular molded bodies with one end closed. There are no limitations on the molding temperature, as long as it is higher than the melting point of the ionomer resin of the present invention and lower than the decomposition starting temperature, regardless of the molding method.

The tubular molded article containing the ionomer of the present invention can be used as a single layer by itself, or as a multilayer in combination with other materials to form a tube. Applications of the tube include hoses directly connected to water supply, tubes for consumer products such as dishwashers, infusion tubes in the medical field such as for intravenous drips, and piping for refrigerants, oils, various chemicals, various gases, etc. in automobiles, ships, machine tools, etc.

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

<Measurement and Evaluation>
(1) Measurement of the phase angle δ (G ^{* = 0.1 MPa) at the absolute value of the complex elastic modulus G * =} 0.1 MPa 1) Preparation and measurement of the sample The sample was placed in a 1.0 mm thick heat press mold, preheated for 5 minutes in a heat press machine with a surface temperature of 180 ° C., and then repeatedly pressurized and depressurized to degas the residual gas in the molten resin, and further pressurized at 4.9 MPa and held for 5 minutes. Then, it was transferred to a press machine with a surface temperature of 25 ° C., and cooled by holding it at a pressure of 4.9 MPa for 3 minutes to produce a press plate made of a sample with a thickness of about 1.0 mm. The press plate made of the sample was processed into a circular shape with a diameter of 25 mm to serve as a sample, and a Rheometrics ARES type rotational rheometer was used as a measuring device for dynamic viscoelastic properties, and dynamic viscoelasticity was measured under the following conditions in a nitrogen atmosphere.
Plate: φ25mm (diameter) parallel plate Temperature: 160℃
Distortion: 10%
Measurement angular frequency range: 1.0×10 ⁻² to 1.0×10 ² 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 elastic modulus, and the value of δ (degrees) at the point corresponding to logG ^* = 5.0 was taken as δ (G ^* = 0.1 MPa). When there was no point corresponding to logG ^* = 5.0 among the measurement points, the δ value at logG ^* = 5.0 was obtained by linear interpolation using two points around logG ^* = 5.0. In addition, when all the measurement points were logG ^* < 5, the δ value at logG ^* = 5.0 was obtained by extrapolating the δ value using a quadratic curve using the values of the three points from the largest logG ^* value.

(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 from the ratio of Mw to Mn, Mw/Mn, by determining the number average molecular weight (Mn) by gel permeation chromatography (GPC).
The measurements were carried out according to the following procedures and conditions.

1) Sample pretreatment When a sample contains a carboxylic acid group, the sample is subjected to an esterification treatment such as methyl esterification using diazomethane, trimethylsilyl (TMS) diazomethane, etc., before being used for measurement. When a sample contains a carboxylate group, the sample is subjected to an acid treatment to modify the carboxylate group to a carboxylic acid group, and then the above-mentioned esterification treatment is performed before being used for measurement.

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

3) Measurement One Showdex HT-G and two Showa Denko high temperature GPC columns HT-806M were connected to a Waters Alliance GPCV2000 model, and measurements were performed using o-dichlorobenzene as an eluent at a temperature of 145° C. and a flow rate of 1.0 mL/min.

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

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

(4) Tensile Modulus of Elasticity A sample was prepared into a sheet having a thickness of 1 mm by the method described in JIS K7151 (1995) (cooling method A), and this was punched out to prepare a small 5B-type test piece described in JIS K7162 (1994). A tensile test was carried out at a temperature of 23° C. in accordance with JIS K7161 (1994) to measure the tensile modulus of elasticity. The test speed was 10 mm/min.

(5) Melting point and crystallinity The melting point is indicated by the peak temperature of the endothermic curve measured by a differential scanning calorimeter (DSC). The measurement was performed using a DSC (DSC7020) manufactured by SII Nano Technology Co., Ltd. under the following measurement conditions.
About 5.0 mg of the sample was packed in an aluminum pan, heated to 200° C. at 10° C./min, held at 200° C. for 5 minutes, and then cooled to 30° C. at 10° C./min. After holding at 30° C. for 5 minutes, the sample was heated again at 10° C./min. The maximum peak temperature in the absorption curve was taken as the melting point Tm, and the heat of fusion (ΔH) was calculated from the area of the melting endothermic peak. The heat of fusion was divided by the heat of fusion of 293 J/g for a completely crystalline high density polyethylene (HDPE) to calculate the crystallinity (%).

(6) Method for measuring the amount of structural units derived from monomers having a carboxy group and/or a dicarboxylic anhydride group, and non-cyclic monomers, and the number of branches per 1,000 carbons The amount of structural units derived from monomers having a carboxy group and/or a dicarboxylic anhydride group, and non-cyclic monomers in the multicomponent copolymer of the present invention, and the number of branches per 1,000 carbons, are determined using ¹³ C-NMR spectrum. ¹³ C-NMR was measured by the following method.
200 to 300 mg of the sample was placed in an NMR sample tube with an inner diameter of 10 mm together with 2.4 ml of a mixed solvent of o-dichlorobenzene (C ₆ H ₄ Cl ₂ ) and deuterated bromide benzene (C ₆ D ₅ Br) (C ₆ H ₄ Cl ₂ /C ₆ D ₅ Br = 2/1 (volume ratio)) and hexamethyldisiloxane as a chemical shift standard substance, and the tube was purged with nitrogen, sealed, and heated to dissolve to prepare a homogeneous solution for use as an NMR measurement sample.
The NMR measurement was carried out at 120° C. using an AV400M NMR apparatus manufactured by Bruker Japan Ltd. equipped with a 10 mmφ cryoprobe.
¹³ C-NMR was measured by the inverse gate decoupling method at a sample temperature of 120° C., a pulse angle of 90°, a pulse interval of 51.5 seconds, and an accumulation number of 512 or more.
The chemical shifts were set to 1.98 ppm for the ¹³ C signal of hexamethyldisiloxane, and the chemical shifts of other ¹³ C signals were based on this.

1) Pretreatment of sample When a sample contains a carboxylate group, the sample is subjected to an acid treatment to convert the carboxylate group into a carboxyl group, and then used for measurement. When a sample contains a carboxyl group, an esterification treatment such as methyl esterification using diazomethane or trimethylsilyl (TMS) diazomethane may be appropriately performed.

2) Calculation of the amount of structural units derived from monomers having a carboxy group and/or a dicarboxylic anhydride group and non-cyclic monomers <E/tBA>
The quaternary carbon signal of the t-butyl acrylate group of tBA is detected at 79.6 to 78.8 in the ¹³ C-NMR spectrum. Using these signal intensities, the amount of comonomer was calculated from the following formula.
Total amount of tBA (mol%) = I(tBA) x 100/[I(tBA) + I(E)]
Here, I(tBA) and I(E) are quantities represented by the following formulas.
I(tBA)=I _79.6-78.8
I(E)=(I _180.0~135.0 +I _120.0~5.0 -I(tBA)×7)/2

<E/tBA/iBA>
The quaternary carbon signal of the t-butyl acrylate group of tBA is at 79.6 to 78.8 ppm in the ¹³ C-NMR spectrum, the methylene signal of the isobutoxy group of iBA is at 70.5 to 69.8 ppm, and the methyl signal of the isobutoxy group is at The comonomer amount was calculated from these signal intensities according to the following formula:
Total amount of tBA (mol%) = I (tBA) × 100/[I (tBA) + I (iBA) + I (E)]
Total amount of iBA (mol%) = I (iBA) × 100 / [I (tBA) + I (iBA) + I (E)]
Here, I(tBA), I(iBA), and I(E) are quantities represented by the following formulas, respectively.
I(tBA)=I _{79.6 to 78.8}
I(iBA)=(I _70.5~69.8 +I _19.5~18.9 )/3
I(E)=(I _180.0~135.0 +I _120.0~5.0 -I(iBA)×7−I(tBA)×7)/2

<E/tBA/NB>
The quaternary carbon signal of the t-butyl acrylate group of tBA is detected at 79.6 to 78.8 ppm in the ¹³ C-NMR spectrum, and the methine carbon signal of NB is detected at 41.9 to 41.1 ppm. These signal intensities The amount of comonomer was calculated from the following formula.
Total amount of tBA (mol%) = I (tBA) × 100/[I (tBA) + I (NB) + I (E)]
Total amount of NB (mol%) = I (NB) × 100/[I (tBA) + I (NB) + I (E)]
Here, I(tBA), I(NB), and I(E) are quantities represented by the following formulas, respectively.
I(tBA)=I _{79.6 to 78.8}
I(NB)=(I _41.9~41.1 )/2
I (E) = (I _{180.0 ~ 135.0} + I _{120.0 ~ 5.0} - I (NB) x 7 - I (tBA) x 7)/2

When the amount of structural units of each monomer is indicated by "<0.1" including an inequality sign, this means that it is present as a structural unit in the multicomponent copolymer, but the amount is less than 0.1 mol%, taking into account significant digits.

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

The number of branches per 1,000 carbons is calculated by substituting either I(B1), I(B2), or I(B4) below into the I (branch) term in the following formula. B1 represents methyl branches, B2 represents ethyl branches, and B4 represents butyl branches. The number of methyl branches is calculated using I(B1), the number of ethyl branches using I(B2), and the number of butyl branches using I(B4).
Number of branches (per 1,000 carbons) = I (branches) x 1000/I (total)
Here, I(total), I(B1), I(B2), and I(B4) are quantities expressed by the following formulas.
I (total) = I _{180.0 ~ 135.0} + I _{120.0 ~ 5.0}
I (B1) = (I _{20.0 ~ 19.8} + I _{33.2 ~ 33.1} + I _{37.5 ~ 37.3} ) / 4
I (B2) = I _{8.6 ~ 7.6} + I _{11.8 ~ 10.5}
I (B4) = I _{14.3 ~ 13.7} - I _{32.2 ~ 32.0}
Here, I is the integrated intensity, and the subscript number of I indicates the range of chemical shifts. For example, I _180.0-135.0 indicates the integrated intensity of the ¹³ C signal detected between 180.0 ppm and 135.0 ppm.
The attribution was based on the non-patent literature Macromolecules 1984, 17, 1756-1761 and Macromolecules 1979, 12, 41.
In addition, when each branch number is indicated by "<0.1" including an inequality sign, it means that it is present as a structural unit in the multi-component copolymer, but the amount is less than 0.1 mol% taking into account significant figures. In addition, "not detected" means that it is below the detection limit.

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

(8) Measurement of wear amount 1) Method of preparing a wear test sample The sample was placed in a mold for hot pressing with dimensions: 150 mm x 150 mm, thickness 1 mm, and preheated for 5 minutes in a hot press machine with a surface temperature of 180 ° C., and then the sample was melted and the residual gas in the sample was degassed by repeatedly applying pressure and reducing pressure, and the sample was further pressurized at 4.9 MPa and held for 3 minutes. Then, under a pressure of 4.9 MPa, the sample was gradually cooled at a rate of 10 ° C./min, and the molded plate was removed from the mold when the temperature had dropped to near room temperature. The obtained molded plate was conditioned for 48 hours or more in an environment of a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5 ° C. The press plate after conditioning was cut into a circle with a diameter of about 115 mm, and a hole with a diameter of about 6.5 mm was drilled in the center to prepare a wear test sample.

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

(9) Haze 1) Method of preparing a press plate of a sample The sample was placed in a mold for hot pressing with dimensions: 50 mm x 60 mm, thickness: 0.5 mm, preheated for 5 minutes in a hot press machine with a surface temperature of 180°C, and then repeatedly pressurized and depressurized to remove residual gas from the sample, and further pressurized to 4.9 MPa and held for 3 minutes. Thereafter, the sample was transferred to a press machine with a surface temperature of 25°C, and cooled by holding at a pressure of 4.9 MPa for 3 minutes to produce a press plate with a thickness of about 0.5 mm.
2) Haze Measurement Conditions Using the above test pieces, the haze was measured in accordance with JIS K 7136-2000.

<Synthesis of Metal Complexes>
(1) Synthesis of B-27DM/Ni Complex The B-27DM/Ni complex was prepared according to Synthesis Example 4 described in WO 2010/050256, using the following 2-bis(2,6-dimethoxyphenyl)phosphano-6-pentafluorophenylphenol ligand (B-27DM). A nickel complex (B-27DM/Ni) was synthesized in which B-27DM and Ni(COD) ₂ reacted in a 1:1 ratio using bis(1,5-cyclooctadiene)nickel(0) (referred to as Ni(COD) ₂ ) in accordance with Example 1 of WO 2010/050256.

以下のスキームに従って配位子Ｂ－４２３を合成した。
なお、以降の化学式中、－ＯＭＯＭとはメトキシメトキシ基（－ＯＣＨ_２ＯＣＨ_３）を表す。

(2) Synthesis of B-423/Ni complex 1) Synthesis of ligand B-423: 2-bis(2,6-dimethoxyphenyl)phosphano-6-(2,6-diisopropylphenyl)phenol

Ligand B-423 was synthesized according to the following scheme.
In the following chemical formulas, --OMOM represents a methoxymethoxy group (--OCH ₂ OCH ₃ ).

(i) Synthesis of Compound 2 Compound 2 was synthesized according to Patent Document WO2010/050256.

(ii) Synthesis of Compound 3 To a solution of compound 2 (2.64 g, 10.0 mmol) in THF (5.0 ml) was added iso-PrMgCl (2 M, 5.25 ml) at 0° C. The reaction mixture was stirred at 25° C. for 1 hour, and then PCl ₃ (618 mg, 4.50 mmol) was added at −78° C.
The reaction mixture was warmed to 25° C. over 3 hours to give a yellow suspension. The solvent was removed under reduced pressure to give a yellow solid. This mixture was used in the next reaction without purification.

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

(iv) Synthesis of Compound 7 Compound 5 (5.00 g, 27.5 mmol), compound 6 (4.42 g, 18.3 mmol), Pd ₂ (dba) ₃ (168 mg, 0.183 mmol), s-Phos (2-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl) (376 mg, 0.916 mmol), and K ₃ PO ₄ (7.35 g, 34.6 mmol) were weighed into a reaction vessel, and toluene (40 ml) was added. This solution was reacted at 110°C for 12 hours to obtain a black suspension.
_H2O (50 ml) was added, and the mixture was extracted with EtOAc (55 ml x 3). The organic layer was washed with brine (20 ml) and dried over _Na2SO4 . The organic layer was filtered _, the solvent was removed under reduced pressure, and the mixture was purified with a silica gel column to obtain 1.3 g of an oily substance.

(v) Synthesis of Compound 8 To a solution of Compound 7 (6.5 g, 22 mmol) in THF (40 ml), n-BuLi (2.5 M, 9.15 ml) was added dropwise at 0° C., the temperature was raised to 30° C., and the mixture was stirred for 1 hour. This reaction solution was cooled to −78° C., CuCN (2.1 g, 23 mmol) was added, and the mixture was stirred at 30° C. for 1 hour.
The reaction solution was cooled to -78°C, and a solution of compound 3 (6.7 g, 20 mmol) in THF (40 ml) was added, followed by stirring at 30°C for 12 hours to obtain a white suspension. When H ₂ O (50 ml) was added to the suspension, a white precipitate was generated. The white precipitate was collected by filtration and dissolved in dichloromethane (20 ml), and ammonia water (80 ml) was added and stirred for 3 hours. The product was extracted with dichloromethane (50 ml x 3), dehydrated with Na ₂ SO ₄ , and then concentrated to obtain a yellow oily substance. This oily substance was purified using a silica gel column to obtain 2.9 g of compound 8.

(vi) Synthesis of B-423 To a solution of compound 8 (2.9 g, 4.8 mmol) in dichloromethane (20 ml) was added HCl/EtOAc (4 M, 50 ml) at 0° C., and the mixture was stirred at 30° C. for 2 hours to obtain a pale yellow solution.
After the solvent was removed under reduced pressure, dichloromethane (50 ml) was added. The mixture was washed with saturated NaHCO ₃ aqueous solution (100 ml) to obtain 2.5 g of B-423.
The NMR assignment values of the obtained ligand B-423 are shown below.
[NMR]
^1H NMR ( _CDCl3 , δ, ppm): 7.49 (t, 1H), 7.33 (t, 1H), 7.22 (m, 4H), 6.93 (d, 1H), 6.81 (t, 1H), 6.49 (dd, 4H), 6.46 (br, 1H), 3.56 (s, 12H), 2.63 (se pt, 2H), 1.05 (d, 6H), 1.04 (d, 6H);
³¹ P NMR (CDCl ₃ , δ, ppm): -61.6 (s).

2) Synthesis of B-423/Ni Complex The B-423/Ni complex was synthesized using bisacetylacetonatonickel(II) (referred to as Ni(acac) ₂ ) in a 1:1 reaction between B-423 and Ni(acac) _{2 using the B-423 ligand in accordance with Example 1 of WO 2010/050256. A nickel complex (B-423/Ni) was synthesized in which B-423 and Ni(acac)2} reacted in a 1:1 ratio.

(Production Examples 1 to 3): Production of ionomer-based resin precursors
Using a transition metal complex (B-27DM/Ni complex or B-423/Ni complex), ethylene/acrylic acid tBu copolymer, ethylene/acrylic acid tBu/acrylic acid ester copolymer, and ethylene/acrylic acid tBu/norbornene copolymer were produced. The copolymers were produced with reference to Production Example 1 or Production Example 3 described in JP 2016-79408 A, and the production conditions and production results, which were appropriately changed such as the metal catalyst type, metal catalyst amount, trioctyl aluminum (TNOA) amount, toluene amount, comonomer type, comonomer amount, ethylene partial pressure, polymerization temperature, and polymerization time, are shown in Table 1, and the physical properties of the obtained copolymers are shown in Table 2. However, "not detected" in the table means below the detection limit.

<(Resin 1 to Resin 3): Production of Ionomer-Based Resins>
In a 500 ml separable flask, 40 g of the copolymers of Production Examples 1 to 3, 0.8 g of paratoluenesulfonic acid monohydrate, and 185 ml of toluene were added and stirred at 105° C. for 4 hours. 185 ml of ion-exchanged water was added, stirred, allowed to stand, and then the aqueous layer was extracted. Thereafter, the addition and extraction of ion-exchanged water was repeated until the pH of the extracted aqueous layer reached 5 or more. The solvent was distilled off under reduced pressure from the remaining solution, and the solution was dried until it reached a constant weight.
In the IR spectrum of the obtained resin, the disappearance of the peak at around 850 cm ⁻¹ due to the tBu group, the decrease of the peak at around 1730 cm ⁻¹ due to the carbonyl group of the ester, and the increase of the peak at around 1700 cm ⁻¹ due to the carbonyl group of the carboxylic acid (dimer) were observed.
As a result, decomposition of t-Bu ester and generation of carboxylic acid were confirmed, and ionomer base resins 1 to 3 were obtained. The physical properties of the obtained resins are shown in Table 3. In the table, "not detected" means below the detection limit.

<Examples 1 to 4: Production of ionomers>
1) Preparation of Zn ion source A Zn ion source was prepared by adding 21.8 g of ethylene/methacrylic acid (MAA) copolymer (manufactured by Mitsui DuPont Polychemicals Co., Ltd., brand: Nucrel N1050H) to a Labo Plastomill: Roller Mixer R60 type manufactured by Toyo Seiki Co., Ltd. equipped with a small mixer with a capacity of 60 ml, and kneading the mixture at 180° C. and 40 rpm for 3 minutes.

2): Preparation of ionomers 40 g of resins 1 to 3 were added to a Labo Plastomill (Roller Mixer R60) manufactured by Toyo Seiki Co., Ltd., equipped with a small mixer with a capacity of 60 ml, and dissolved by kneading for 3 minutes at 160°C and 40 rpm. Then, a Zn ion source was added so as to achieve a desired degree of neutralization, and kneading was performed for 5 minutes at 250°C and 40 rpm.
In the IR spectrum of the obtained resin, the peak at about 1700 cm ⁻¹ derived from the carbonyl group of the carboxylic acid (dimer) was decreased, and the peak at about 1560 cm ⁻¹ derived from the carbonyl group of the carboxylate salt group was increased. It was confirmed that an ionomer with the desired degree of neutralization had been produced from the decrease in the peak at about 1700 cm ⁻¹ derived from the carbonyl group of the carboxylic acid (dimer). The physical properties of the obtained ionomer are shown in Tables 4 and 5.

Comparative Example 1: E/MAA-based binary ionomer An ionomer resin (HIMILAN HIM1555, manufactured by Dow Mitsui Polychemicals Co., Ltd.), which 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 4 and 5.

Comparative Example 2: E/MAA-based binary ionomer An ionomer resin (HIMILAN HIM1605, manufactured by Dow Mitsui Polychemicals Co., Ltd.), which is a copolymer of ethylene, methacrylic acid, and sodium methacrylate and produced by a high-pressure radical process, was used as a reference ionomer. The physical properties are shown in Tables 4 and 5.

<Consideration of the results of the Examples and Comparative Examples>
[evaluation]
As described above, from the results shown in Table 5, when Examples 1 to 4 are compared with Comparative Examples 1 and 2, the ethylene-based ionomers that do not satisfy the specific requirements for the ethylene-based ionomer for tubes of the present invention are inferior to the ethylene-based ionomers of Examples 1 to 4 in terms of the balance of flexibility, abrasion resistance, and transparency.
Compared with these comparative examples, it was confirmed that the ethylene-based ionomer for tubes and the molded article thereof according to the present invention have a good balance of flexibility, abrasion resistance, and transparency, as shown in Examples 1 to 4.

According to the present invention, it is possible to provide an ethylene-based ionomer tube suitable for use in dishwashers and the like.
That is, molded articles using the ethylene-based ionomer of the present invention have an excellent balance of flexibility, abrasion resistance and transparency, and are therefore of great industrial utility.

Claims (10)

An ethylene-based ionomer for tubes, the ionomer being a copolymer comprising, as essential constituent units, a structural unit (A) derived from ethylene and/or an α-olefin having 3 to 20 carbon atoms, a structural unit (B) derived from a monomer having a carboxyl group and/or a dicarboxylic anhydride group, and a structural unit (C) which is a compound having one or more carbon-carbon double bonds in its molecular structure other than the structural units (A) and (B), wherein the structural unit (A) is a copolymer (P) essentially containing ethylene , and at least a part of the carboxyl groups and/or dicarboxylic anhydride groups are converted to a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table, and the ionomer has the following properties (a) to (e):
(a) The phase angle δ at the absolute value of the complex elastic modulus G ^* =0.1 MPa measured with a rotational rheometer is 50 to 75 degrees.
(b) The melt flow rate (MFR) at a temperature of 190° C. and a load of 2.16 kg is 0.1 to 15 g/10 min.
(c) The tensile modulus is 20 to 350 MPa.
(d) The amount of wear in an abrasion test is less than 10 mg.
(e) The haze is 0.1 to 30%. 2. The ethylene-based ionomer for tubes according to claim 1 , wherein the number of methyl branches of the copolymer (P) calculated by ¹³ C-NMR is 50 or less per 1,000 carbons. 2. The ethylene-based ionomer for tubes according to claim 1 , wherein the number of methyl branches of the copolymer (P) calculated by ¹³ C-NMR is 5 or less per 1,000 carbons. The ethylene-based ionomer for tubes according to any one of claims 1 to 3 , characterized in that the copolymer (P) contains 2 to 20 mol % of the structural unit (B) in the copolymer. The ethylene-based ionomer for a tube according to any one of claims 1 to 4 , characterized in that the structural unit (A) is a structural unit derived from ethylene. The ethylene-based ionomer for tubes according to any one of claims 1 to 5, characterized in that the copolymer (P) is produced using a transition metal catalyst containing a transition metal of Groups 8 to 11 of the periodic table. 7. The ethylene-based ionomer for tubes according to claim 6 , wherein the transition metal catalyst is a transition metal catalyst comprising a phosphorus sulfonic acid or phosphorus phenol ligand and nickel or palladium. A copolymer comprising, as essential constituent units, structural units (A) derived from ethylene and/or an α-olefin having 3 to 20 carbon atoms, structural units (B) derived from a monomer having a carboxyl group and/ or a dicarboxylic anhydride group, and structural units (C) which are compounds having one or more carbon-carbon double bonds in the molecular structure other than the structural units (A) and (B), wherein at least a part of the carboxyl groups and/or dicarboxylic anhydride groups in the copolymer (P) essentially containing ethylene as the structural unit (A) is converted to a metal-containing carboxylate containing at least one metal ion selected from Groups 1, 2, and 12 of the periodic table,
The ethylene-based ionomer resin composition for tubes contains an ionomer characterized in that the phase angle δ at an absolute value of complex elastic modulus G ^* =0.1 MPa measured with a rotational rheometer is 50 degrees to 75 degrees. A molded article, which is made of the ethylene-based ionomer for tubes according to any one of claims 1 to 7 or the ethylene-based ionomer resin composition for tubes according to claim 8 , and has a tubular shape. A hose in which two or more tubular structures are laminated, at least one of the layers being the molded article according to claim 9 .